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WO1996006878A1 - Derivatized polyester compounds and uses thereof - Google Patents

Derivatized polyester compounds and uses thereof Download PDF

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Publication number
WO1996006878A1
WO1996006878A1 PCT/US1995/010789 US9510789W WO9606878A1 WO 1996006878 A1 WO1996006878 A1 WO 1996006878A1 US 9510789 W US9510789 W US 9510789W WO 9606878 A1 WO9606878 A1 WO 9606878A1
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WO
WIPO (PCT)
Prior art keywords
hair
compound
skin
formula
polyester
Prior art date
Application number
PCT/US1995/010789
Other languages
French (fr)
Inventor
David J. Grillo
Rocco V. Burgo
Robert W. Siegfried
Anna M. Howe
Thomas Grebenar, Jr.
Original Assignee
Inolex Investment Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Inolex Investment Corporation filed Critical Inolex Investment Corporation
Priority to AU33724/95A priority Critical patent/AU3372495A/en
Publication of WO1996006878A1 publication Critical patent/WO1996006878A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85—Polyesters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/74—Biological properties of particular ingredients
    • A61K2800/75—Anti-irritant

Definitions

  • the invention generally relates to polyester resins and formulations thereof. More specifically, the invention is directed to polyester resins derivatized with various functional groups, and to hair-care and skin-care formulations incorporating the derivatized polyester resins. BACKGROUND OF THE INVENTION
  • ingredients may either perform a specific function on the hair and skin such as
  • polymers of many types have been used over the past twenty years to perform some of these functions. These polymers include polyvinyl pyrrolidone derivatives, hydroxyl ethyl cellulose copolymers and derivatives, polysaccharides, polyethers and derivatives, and many others.
  • Polyester polyols have historically had limited use in personal care formulations. This is at least partly because most polyesters have limited performance properties in personal care product formulations, and they can be difficult to incorporate into stable formulations
  • Polyester polyols are used for non-personal care applications such as the diol component in polyurethanes, plasticizers for industrial applications and specific polymer additives including adhesion promoters, carrier vehicles and stabilizers. Though some classes of polyester polyols have been introduced for personal care application, they have not been derivatized in the ways disclosed herein, nor have efforts been made to derivatize polyester polyols specifically for the personal care applications as disclosed herein.
  • the invention is directed to compounds of the formula
  • R 1 is -N(R 5 ) (R 6 ) or -OR 7 ;
  • R 2 is independently C 2 -C 10 aliphatic;
  • R 3 is independently C 2 -C 10 aliphatic having 0-5 oxygen atoms as ether groups;
  • R 4 is R 1 ;
  • p is an integer between 3-100, inclusive;
  • R 5 is H or C 1 -C 10 aliphatic;
  • R 6 is -R 8 -N(R 9 ) 2 (R 1. ),
  • R 14 or -CH 2 CH (OH) CH 2 -NH-polysiloxane R 14 ;
  • R 11 is R 12 or C 1 -C 22 ;
  • R 12 is lithium, sodium, calcium, magnesium, ammonium monoalkylammonium, dialkylammonium, trialkylammonium, or
  • R 13 is C 1 -C 22 aliphatic
  • R 14 is halide, sulfate, phosphate, citrate, lactate, malate, fatty carboxylate or polymeric carboxylate
  • R 15 is C 1 -C 22 hydrocarbon
  • n is an integer between 1 and 5, inclusive
  • a further aspect of the invention is the product resulting from the reaction between at least one of a botanical derivative, an essential oil or a polysiloxane, and the polyester of the formula
  • R 1 is -OH or -O-R 3 -OH;
  • R 2 is independently C 2 -C 10
  • polyesters By derivatizing the polyesters with various functional moieties, they can be altered into materials which have wide- ranging physical and performance properties. Physical propertie can be varied widely in terms of solubility, viscosity, melting point, HLB value, hydrophilicity/hydrophobicity, hydrolytic stability, emulsion stability, surfactancy and others.
  • Performance properties of the derivatized polyesters include film-forming, moisture retention, emolliency, adhesion,
  • the derivatized polyesters can also be used to delive other functional ingredients with enhanced efficacy, where these properties are valued in skin-care and hair-care formulations.
  • compositions of the invention include derivatized polyester molecules and formulations comprising those derivatize polyester molecules, particularly in hair-care and skin-care formulations.
  • the polyester molecule of the invention terminates with endgroups, designated R 1 and R 4 , that contain functional groups, where the R 1 or R 4 groups are also known as functionalized endgroups, as described in detail below.
  • R 1 or R 4 groups are also known as functionalized endgroups, as described in detail below.
  • the preferred R 2 and R 3 groups are aliphatic, and not aromatic.
  • the polyesters of the invention having a polyester chain and functionalized endgroups are denoted herein as derivatized polyesters.
  • Preferred derivatized polyesters of the invention have the formula (II)
  • the derivatized polyesters have functional groups present only as part of the endgroups, as shown in Formula (II). However, in another embodiment of the invention, functional groups may be additionally present at one or more points along the polyester chain. In a preferred embodiment,
  • the polyester chain is linear, e.g., there are no crosslinks present, as shown in formula (II).
  • crosslinks may be present which provide for the joining together of two or more polyester chains through R 2 and/or R 3 groups.
  • Formula (Ila) represents a polyester resin of the invention which clearly indicates, with groups R 1S and R 18 , that the derivatized polyesters may have functional groups along the polyester chain, or cites for
  • an R 2 group of the invention has between 2 and 10 aliphatic carbon atoms, inclusive, where said aliphatic carbon atoms are present in a linear, branched and/or cyclic arrangement.
  • the R 2 group is a hydrocarbon, that is, it contains only hydrogen and carbon atoms.
  • the R 2 groups may additionally contain oxygen atoms, where said oxygen atoms are present in the form of one or more ether
  • R 2 group contains one or more oxygen atoms
  • Any of the exemplary R 2 hydrocarbon groups listed below may additionally contain not more than 5 oxygen atoms.
  • Exemplary hydrocarbon R 2 groups have molecular formulas selected from the group C 2 H 4 , C 3 H 6 , C 4 H 8 , C 5 H 10 , C 6 H 12 , C 7 H 14 , C 8 H 16 , C 9 H 18 and C 10 H 22 .
  • the carbon atoms are arranged in a straight chain, that is, R 2 is selected from the group having the formula (-CH 2 -) a , wherein a is 2 to 10,
  • An especially preferred straight chain R 2 group is butyl, -CH 2 -CH 2 - CH 2 -CH 2 -.
  • R 2 may also be a branched chain hydrocarbon group, where exemplary, non-limiting branched chain hydrocarbon groups include 1-methylethyl (-CH (CH 3 ) -CH 2 -), 1-methylpropyl (-CH(CH 3 )- CH 2 -CH 2 -), 2-methylpropyl ( -CH 2 -CH (CH 3 ) -CH 2 - ), 1, 2-dimethylethyl (-CH(CH3) -CH(CH3)-), 1-ethylethyl (-CH (CH 2 CH 3 ) -CH 2 - ), 1- methylbutyl (-CH(CH 3 ) -CH 2 -CH 2 -CH 2 - ), 2-methylbutyl (CH 2 -CH (CH 3 ) - CH 2 -CH 2 -), 1-ethylpropyl (-CH (CH 2 CH 3 ) -CH 2 -CH 2 -), 2-ethylpropyl (-CH 2 CH 3 ) -CH
  • R 2 may also contain a cyclic hydrocarbon group, where exemplary non-limiting R 2 groups with a cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl groups.
  • R 2 may also contain one or more bicyclic arrangement of carbon atoms.
  • a single R 2 group may contain both a cyclic arrangement of carbon atoms and acyclic carbon atoms.
  • R 2 group may be substituted with m R 18 groups, where m is up to 5, and where the R 18 substituent is attached to the R 2 group in lieu of one of the hydrogen atoms otherwise present in the R 2 group.
  • the R 3 group of the invention has between 2 and 10 aliphatic carbon atoms, inclusive, and between 0 and 5 oxygen atoms, inclusive, and may have any of the atomic arrangements previously set forth for the R 2 groups.
  • Preferred R 3 groups include butyl (-CH 2 -CH 2 -CH 2 -CH 2 -), hexyl (-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - CH 2 -), 2-methylpropyl (-CH 2 -CH (CH 3 ) -CH 2 -), 1-methylethyl
  • Ethylene oxide derivatives are a preferred R group of the invention, where said ethylene oxide derivatives are recognized by having a formula corresponding to
  • R 3 group may be substituted with n R 16 groups, where n is up to 5, and where the R 16 substituent is attached to the R 3 group in lieu of one of the hydrogen atoms otherwise present in the R 3 group.
  • the addition of functionality to the polyester chain o the invention provides for a molecule having unique and desirable properties which are particularly valuable in hair-care and skin- care formulations.
  • the functionality is added to one or both of the ends of the polyester chain.
  • An R 2 or R 3 group closest to an end of the polyester chain will be denoted herein as a terminal R 2 or R 3 group, while all other R 2 and R 3 groups will be denoted as internal R 2 or R 3 groups.
  • functionality is preferably identical.
  • the functionality at each end the
  • the polyester chain is joined to functionality at one or more sites other than, or in addition to, the ends of the polyester chain.
  • the polyester molecules of the invention may have functional groups appended to the polyester chain at sites along the chain. More specifically, any R 2 and/or R 3 group of the polyester chain may be joined to one or more functional groups of the invention. In instances where at least one functionality is appended to at least one internal R 2 or R 3 group, then the polyester chain may terminate at both ends with either carboxylic acid or hydroxyl groups.
  • the polyester molecules of the invention necessarily have at least one functional group, where said functional groups will be described next.
  • the functional groups of the invention are selected to result in polyester derivatives having nonionic, anionic, cationic and zwitterionic character.
  • functional groups groups are hydrocarbon groups, which may be saturated or unsaturated.
  • Other exemplary nonionic groups come from essential oils, botanical extracts or have a polysiloxane structure.
  • exemplary anionic groups include the carboxylate, sulfonate and sulfate groups, which have associated therewith a neutralizing group of opposite charge, i.e., a counterion.
  • Exemplary cationic groups include ammonium, sulfoxonium and phosphonium, which have associated therewith a neutralizing group of opposite charge, i.e., a counterion.
  • Exemplary zwitterionic groups have both positively and negatively charged moieties present as part of the functional group.
  • zwitterionic group is the - + N(R 9 ) 2 - (CH 2 ) 1-3 -COO- group, where the nitrogen atom bears a positive charge and the carboxylate group bears a neutralizing negative charge.
  • Another functional group is the amine oxide functional group, represented by -N(R 9 ) 2 -O.
  • the amine terminus of the polyamino acid chain is joined to the polyester chain, and the carboxyl terminus is present as either a carboxylate salt or carboxylic ester.
  • an exemplary nonionic endgroup is a hydrocarbon chain.
  • Said hydrocarbon chain may have from 1 to 22 aliphatic carbon atoms, joined together by single and/or double bonds.
  • Preferred hydrocarbon chains have none or minimal branching, and are available as the hydrocarbon portion of natural or synthetic fatty acids.
  • the condensation of a fatty acid with a hydroxyl group from the polyester chain of the invention provides a convenient means of providing for polyester molecules having nonionic endgroups that comprise a hydrocarbon chain.
  • Exemplary fatty acids which may be used to introduce exemplary nonionic hydrocarbon endgroups to the polyester
  • molecules of the invention include fatty acids available from, for example, tallow, coconut oil, palm oil, palm kernel oil, canola oil, soybean oil, tall oil, peanut oil, cottonseed oil, rapeseed oil, cod liver oil, castor oil, sunflower oil, olive oil, safflower oil and carobseed oil.
  • Polyester chains may be reacted with essential oils or botanical extracts to provide derivatized polyesters of the invention.
  • An exemplary reaction between an essential oil or a botanical extract and a polyester chain may be conducted by contacting the reactants, optionally in the presence of a catalyst, and heating until at least some condensation reaction has occurred between the reactants.
  • the polyester chain and/or the essential oil or botanical extract may be chemically modified so as to provide a preferred means of linking the polyester chain to the functional group.
  • Exemplary essential oils are obtained from, for example, camphor, vanilla bean, mint, eucalyptus, pine, rose, jasmine, garlic, orange, lemon, lime, grapefruit, mandarin, almond, anise, avocado, bayberry, bergamot, mace, nutmeg, menthol, turpentine, gardenia, lilac, clove, and ylang ylang.
  • Exemplary botanical derivatives are extracts of, for example, comfrey, chamomile, algae, cucumber, arnica, nettle, kelp, hypericum, mimosa bark, hawkweed, myrtle, English oak, horsetail, spiraea, quince, rosemary, pansy, yeast, sage,
  • Polyester chains may be reacted with polysilicone and/or polysiloxane incorporating materials, to provide a
  • polysiloxane incorporating materials include the repeating unit - (Si(R) 2 O)-, where a preferred R group is C 1 -C 4 alkyl, and
  • a convenient polysiloxane material for preparing polysiloxane derivatized polyesters of the invention have a primary amine terminus, e.g., amodimethicone, having the structure HO [Si (CH 3 ) 2 -O] - [Si (OH) (CH 2 CH 2 -NH-CH 2 CH 2 -NH 2 ) ] x -H, where x is a positive integer ⁇ 1.
  • the polysiloxane materials may also have hydroxy termination to enable them to enter into
  • R 12 exemplary, non-limiting, positively charged counterions R 12 include sodium (Na + ), lithium (Li * ), calcium
  • RNH 3 + dialkylammonium (R 2 NH 2 + ), trialkylammonium (R 3 NH + ) and tetraalkylammonium (R 4 N + ) wherein an alkyl group R attached to a nitrogen atom of an alkylammonium group has from 1 to 20 carbon atoms, inclusive, and has 0-3 hydroxyl groups, inclusive.
  • said cationic endgroup which may be present in the derivatized polyesters of the invention, said cationic endgroup is characterized in having a positive charge, and is preferably selected from the group consisting of ammonium (including mono-, di- and trialkylammonium), sulfoxonium (-S(R) 2 -O + ) sulfonium (-S(R) 2 + ) and phosphonium (-P(R) 3 + ).
  • the R groups which are bonded to the N, S or P atom of the ammonium, sulfonium or phosphonium group, respectively, may have from 1 to 22 carbon atoms, where those carbon atoms may be present in aliphatic or aromatic arrangements, and where those R groups may additionally contain hydroxyl functionality.
  • R groups bonded to a nitrogen atom of an ammonium group preferably have 1 to 3 carbon atoms, and 0-3 hydroxyl substituents.
  • R 14 Exemplary, non-limiting, negatively charged counterions R 14 include organic and inorganic counterions, where inorganic counterions include halide (specifically fluoride, chloride, bromide or iodide), sulfate and phosphate, and where organic counterions include carboxylates such as citrate, lactate, malate, fatty acid carboxylate and carboxylates bonded to polymeric materials.
  • inorganic counterions include halide (specifically fluoride, chloride, bromide or iodide), sulfate and phosphate
  • organic counterions include carboxylates such as citrate, lactate, malate, fatty acid carboxylate and carboxylates bonded to polymeric materials.
  • said zwitterionic endgroup is characterized in having a positively charged site covalently bonded to a negatively charged site, in other words, the zwitterionic group is
  • An exemplary zwitterionic functional group is the betaine group, where an exemplary betaine is (- + N(R 9 ) 2 - (CH 2 ) 1 - 3 -COO-).
  • the group which links the cationic ammonium group to the anionic carboxylate group preferably has 1 carbon, so as to form - + NR 2 -CH 2 -COO-, however additional carbon atoms may be present.
  • the R groups which are bound to the ammonium nitrogen atom, i.e., the R 9 groups are independently selected from alkyl groups having 1 to 3 carbon atoms, where those carbon atoms may be optionally substituted with up to 3 hydroxyl groups.
  • Another exemplary endgroup is the amine oxide group (- + N(R 9 ) 2 -O-), where the R groups bonded to the nitrogen atom of the amine oxide are independently selected from alkyl groups having 1 to 3 carbon atoms, where those carbon atoms may be optionally substituted with up to 3 hydroxyl groups.
  • Another exemplary functional group is a polyamino acid chain.
  • a convenient source for a polyamino acid chain is
  • polyamino acid chain through its amine terminus, i.e., its terminal -NH 2 group, to the polyester chain.
  • the other end of the polyamino acid chain i.e., the carboxyl terminus, may be in the carboxylic acid, carboxylate or
  • the esterifying alcohol has from 1 to 22 carbon atoms.
  • the pH of the formulation into which the derivatized polyester having a polyamino acid chain is
  • the polyamino acid chain may have one or more positively or negatively charged groups.
  • proteins include, for example, keratin, collagen, silk, wheat, oat bran, zein, pea, milk, lentil, tobacco, egg yolk, soy, elastin, gelatin, and fibronectin.
  • polyester chain Preferably, a linear aliphatic dicarboxylic acid molecule , HOOC-R 2 -COOH, which may be simply called the diacid, is reacted with an excess of a dihydric compound, HO-R 3 - OH, which may be simply called the diol, under thermal conditions to form a polyester polyol. More specifically, the diacid is added to the diol and the mixture heated to between about 140°C and 240°C to form the polyester chain by condensation
  • a strong acid such as toluenesulfonic acid or methanesulfonic acid, or an organometallic compound, such as an organotin compound, may be added to catalyze the reaction.
  • condensation reaction is continuously separated from the forming polyester according to distillation techniques well known in the art.
  • polyester The number average molecular weight of the polyester chain, after its synthesis and before being
  • derivatized polyesters preferably ranges from about 2,000 to about 10,000.
  • a convenient means to quantitatively monitor the progress, or extent, of the reaction is to periodically pull aliquots of the reaction mixture and measure the acid number, or acid value, of the aliquots. It is preferred for the preparation of many of the derivatized polyesters of the invention that the polyester chain having a low acid number, preferably less than 2.
  • Acid numbers also known as acid values, may be determined as follows. 2-10 g of a sample is weighed and placed into a 200 to 300 mL Erlenmeyer flask, and an ethanol/benzene (1/1) mixture is added to dissolve the resin. If the resin is not readily dissolved, a small amount of acetone may be added. The resultant solution is titrated with a preliminarily
  • the above-mentioned KOH solution is prepared as follows. First, 1.5 g of KOH is dissolved in about 3 mL of water, and 200 mL of alcohol are added thereto, followed by stirring. After standing, a uniform clear solution is formed.
  • the concentration of the KOH solution is determined by titration with a standardized 1/10 N HCl solution.
  • Diacid molecules which may be employed to prepare the polyester chain of the invention include succinic acid, methylmalonic acid, fumaric acid, maleic acid, acetylene dicarboxylic acid, glutaric acid, ethylmalonic acid,
  • dimethylmalonic acid methylsuccinic acid, citraconic acid, glutaconic acid, itaconic acid, mesaconic acid, 2,2- dimethylsuccinic acid, 2-methylglutaric acid, trans-beta- hydromuconic acid, trans-trans-muconic acid, pimelic acid, butylmalonic acid, diethylmalonic acid, 2, 2-dimethylglutaric acid, 2 -ethyl-2-methylsuccinic acid, 3-methyladipic acid, cyclopentanedicarboxylic acid, suberic acid,
  • cyclohexanedicarboxylic acid azelaic acid, 5-norbornene-2, 3- dicarboxylic acid, sebacic acid, camphoric acid, 1,1- cyclohexanediacetic acid, cyclohexylsuccinic acid, benzylmalonic acid, undecanedioic acid, 1,10-decanedicarboxylic acid, and trans-traumatic acid.
  • Diol molecules which may be used to prepare the polyester chain of the invention include compounds with the molecular formulas C 2 H 6 O 2 , e.g., 1, 2-ethanediol (HO-CH 2 -CH 2 -OH); C 3 H 8 O 2 , e.g., 1,2-propanediol and 1,3-propanediol; C 4 H 10 O 2 , e.g., 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2 -methyl-1,3-propanediol; C 4 H 8 O 2 , e.g., 2-butene-1,4-diol, 2- methylene-1,3-propanediol; C 4 H 6 O 2 , e.g., 2-butyne-1,4-diol;
  • C 5 H 12 O 2 e.g., 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol;
  • C 5 H 10 O 2 e.g., 1,2-cyclopentanediol (cis and trans), 1, 3-cyclopentanediol (cis and trans);
  • C 6 H 14 O 2 e.g., 3,3- dimethyl-1, 2 -butanediol, 2 -ethyl-2-methyl-1,3-propanediol, 1,2- hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2- methyl-2,4-pentanediol, 2, 3-dimethyl-2, 3-butanediol;
  • C 6 H 12 O 2 e.g., 1,
  • C 9 H 20 O 2 e.g., 2 -butyl-2-ethyl-1, 3-propanediol, 1,2-nonanediol;
  • C 9 H 14 O 2 e.g., 5-norbornene-2, 2-dimethanol;
  • C 10 H 22 O 2 e.g., 1,2- decanediol, 1,10-decanediol;
  • C 10 H 18 O 2 e.g., 1,5-decalindiol, trans, trans-2, 6-methyl-2, 6-octadiene-1, 8-diol, 3,6-dimethyl-4- octyne-3, 6-diol, trans-p-menth-6-ene-2, 8-diol, 1,2,3,5- pinanediol;
  • C 10 H 16 O 2 e.g., (2-endo-3-exo-)-bicyclo [2.2.2] oct-5- ene-2,
  • diol compounds contain at least one ether group in the chain of atoms which link the two hydroxyl groups of the diol.
  • exemplary ether containing diols include ethylene glycols of the general formula HO- (CH 2 - CH 2 -O-) b CH 2 -CH 2 -OH, where b is between 1 and 5.
  • a preferred diol with an ether group is diethylene glycol.
  • polyester chain In the preparation of the polyester chain, one may use a single isomeric diol, or one may use a mixture of diols. For example, one may use diethylene glycol in admixture with ethylene glycol. In addition, if a partially crosslinked polyester chain is desired, then one may add some polyol, i.e., a polyhydric molecule, i.e.,. a molecule with at least three hydroxyl groups, to the reaction mixture which will additionally comprise diol and diacid.
  • a polyhydric molecule i.e.,. a molecule with at least three hydroxyl groups
  • Exemplary polyols include glycerol, 1,2,4-butanetriol, 1,1,1-tris (hydroxymethyl) ethane, 2 -ethyl-2- (hydroxymethyl)-1,3- propanediol, 1,2,3-trihydroxyhexane, 1,2,6-trihydroxyhexane, 1, 2, 3 -heptanetriol, erythritol, threitol, pentaerythritol, adonitol, arabitol, xylitol, dulcitol, iditol, mannitoi, sorbitol and dipentaerythritol.
  • the polyol contributes less than 20% of the hydroxyl functionality present in the reaction mixture used to prepare the polyester chain.
  • polyol contributes more than about 20% of the hydroxyl functionality, then an unacceptable portion of the product is an insoluble gel, ill-suited for use in skin-care and hair-care formulations.
  • polyols may also be employed in the
  • polyesters having functional groups bonded to internal R 2 or R 3 groups it is typically necessary to protect those additional hydroxyl groups, that is, those hydroxyl groups other than the two hydroxyl groups necessary for the formation of the polyester chain.
  • a protected hydroxyl group it is meant a hydroxyl group which has been chemically modified so that it will not enter into condensation polymerization reactions.
  • Protecting groups for hydroxyl functionality are well known in the art, and are
  • deprotecting the hydroxyl group so that the hydroxyl group is susceptible to functionalization so as to allow the formation of a derivatized polyester having functionality along the chain rather than, or in addition to, functionality at the termini of the chain.
  • Methods for deprotecting hydroxyl groups are well- known in the art.
  • polycarboxylic acid compounds i.e., molecules having more than two carboxylic acid groups, may be employed to introduce either crosslinking or internal functionality to the polyester chain. It is generally preferred to use polyhydric rather than
  • polycarboxylic acid compounds merely because a greater array of polyhydric compounds are readily available at a reasonable cost.
  • the polyester polyol In the preparation of the derivatized polyesters of the invention, it is convenient to react a low acid number polyester chain, hereinafter the polyester polyol, prepared as described above, with a diamine (III) to provide an intermediate polyester amidoalkylamine.
  • a polyester amidoalkylamine is very readily converted to the derivatized polyesters of the invention.
  • the polyester polyol preferably having an acid number or value of less than 2
  • R 8 having two amine groups linked with a chain, designated R 8 , where R 8 has 1 to 3 carbon atoms, hereinafter "the diamine”.
  • One of the two amine groups of the diamine is a tertiary amine group, where the tertiary amine is, in addition to being covalently bonded to the R 8 group, is bonded to two groups R 9 .
  • Each R 9 group is independently selected from the group consisting of C 1 -C 3 radicals having 0-3 hydroxyl
  • R 9 radicals include methyl, ethyl, propyl, hydroxymethyl, 2 -hydroxyethyl and 3-hydroxypropyl .
  • the other of the two amine groups of the diamine is either a primary or secondary amine group, represented by the formula H- N(R 5 )-R 8 , wherein R 5 can be hydrogen or a C 1 to C 10 radical.
  • the diamine of formula (III) can be represented as shown below:
  • the preparation of the derivatized polyesters of the invention preferably proceeds through a polyester amidoalkylamine intermediate of formula (IV), prepared by the condensation reaction of (I) and (III):
  • reaction to prepare the intermediate (IV) is preferably carried out by adding the diamine to the polyester polyol in a ratio such that the desired average degree of
  • polyester amidoalkylamine polymerization of the product polyester amidoalkylamine.
  • 3 moles of diamine are added to one mole of polyester polyol which has a number average molecular weight of 5,000, a mixture of one mole polyester polyol and three moles of polyester amidoalkylamine is obtained, where the
  • molecular weight of the polyester amidoalkylamine is (number average molecular weight of the polyester polyol + molecular weight of the diamine) / (moles of polyester polyol + moles of diamine), or in the instant case, (5,000+ MW of diamine) / (1+3).
  • amidoalkylamine intermediate of formula (IV) is typically less than the value of p for the starting polyester.
  • the intermediate (IV) typically has a number average molecular weight of between about 500 and 5,000.
  • the diamine may be added to the polyester polyol with stirring under an inert atmosphere, for example, under a nitrogen or argon atmosphere, and the mixture may be heated to between about 100°C and 160°C. This reaction temperature is maintained until it has been determined that the diamine has been
  • the determination is made by titration of an aliquot of the reaction mixture.
  • the polyester amidoalkylamine intermediate (IV) is readily converted to derivatized polyesters of the invention.
  • the intermediate (IV) can be combined with water and heated to a temperature between about 60°C and 90°C to provide a dispersion.
  • approximately one mole of proton acid, HR 14 is slowly added to the dispersion for each mole of intermediate (IV), until a clear solution or a turbid dispersion is obtained.
  • HR 14 proton acid
  • the intermediate (IV) is also a convenient precursor to cationic polyester derivatives having terminal trialkylammonium groups.
  • the intermediate (IV) may be dissolved or
  • the resulting quaternary ammonium compound has the formula (II) wherein R 1 is -N(R 5 ) (R 6 ), R 6 is -R 8 -N (R 9 ) 2 (R 10 ), R 10 is -R 9 R 14 , and R 4 is R 1 or -OR 7 .
  • the intermediate (IV) is also a convenient precursor for the preparation of zwitterionic polyester derivatives.
  • the intermediate (IV) may be dissolved or dispersed in a solvent, preferably water and/or propylene glycol.
  • R 6 is -R 8 -N(R 9 ) 2 (R 10 )
  • R 10 is -CH 2 -COO-
  • R 4 is R 1 or -OR 7 .
  • the intermediate (IV) can be reacted with
  • the intermediate (IV) wherein R 14 is preferably a halide, is dissolved in water and/or propylene glycol and heated to between about 40°C and about 90°C.
  • the secondary intermediate (V) has the formula shown below:
  • polyamino acid refers to a chain of amino acids, having one terminal -NH 2 group and one terminal -COOH group, as occurs naturally in, for example, protein.
  • a protein hydrolysate derived from animal or vegetable sources is slowly added, with stirring, to an aqueous solution of the secondary intermediate (V) maintained at a temperature of about 40°C to about 90°C.
  • the amine terminus of the protein hydrolysate reacts with terminal -CH 2 -Cl group of the intermediate (V) so as to displace the chloride group with the amine group, and thus join the polyamine acid chain of the protein hydrolysate to the polyester chain.
  • the product of this reaction has the formula (II) wherein R 1 is N(R 5 ) (R 6 ), R 6 is -R 8 -N(R 9 ) 2 (R 10 ), and R 10 is -CH 2 -CH (OH) -CH 2 -polyamino acid-COO-.
  • the protein hydrolysate is preferably reacted with R 15 - OH prior to its reaction with the secondary intermediate (V).
  • the secondary intermediate (V) is also a convenient precursor to derivatized polyesters having polysiloxane
  • an aqueous solution or dispersion of the intermediate (V) is heated to between about 40°C and 90°C, and slowly treated with an amine functionalized silicone-containing molecule.
  • a representative amine functionalized silicone is amodimethacone.
  • Additional representative amine functional silicones have the formula H 2 N- (Si (CH 3 ) 2 -O) g -H wherein g is an integer from about 2 to about 50.
  • the polysiloxane derivatized polyesters so made have the formula (II) wherein R 1 is N(R 5 ) (R 6 ), R 6 is -R 8 -N(R 9 ) 2 (R 10 ), and R 10 is CH 2 -CH (OH) -CH 2 -NH-polysiloxane R 14 .
  • the first step consists of the reaction of a diol with an excess of diacid, with heating and stirring, to form a polyester diacid, i.e., a polyester chain having carboxylic acid endgroups.
  • the diacid is added to the diol and the two component are reacted together at a temperature of about 140°C to about 240°C.
  • the water of reaction is continuously removed by
  • a strong acid such as toluenesulfonic acid or methanesulfonic acid, or an organometallic catalyst such as a tin catalyst, may be added to further drive the reaction.
  • the pressure is then reduced in the reaction vessel, and the reaction mixture maintained at about 240°C until titration of an aliquot of the reaction mixture indicates that the acid number has reached the theoretically desired acid value.
  • the number average molecular weight of the polyester diacid so obtained is approximately about 2,000 to about 10,000.
  • the polyester acid is neutralized with two equivalents of base.
  • bases for the neutralization include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, monoalkylamine such as ethanolamine, dialkylamine such as diethanolamine, and trialkylamine such as triethanolamine.
  • the polyester diacid is combined with water at a temperature of about 60°C to about 90°C to provide a solution or, more
  • the product of this reaction has the formula (II) wherein R 1 is -OR 7 , R 7 is R 12 , and R 12 is selected from the group consisting of sodium, lithium, calcium, magnesium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium and
  • tetraalkylammonium wherein an alkyl portion of an ammonium group has 1-20 carbon atoms and 0-3 hydroxyl groups.
  • nonionic polyester derivatives of the invention two alternative schemes may be followed.
  • diacid and diol are reacted as previously described for the preparation of polyester diol, however the reaction is conducted in the presence of at least one monocarboxylic acid having the formula R 13 -COOH.
  • R 13 is a C 1 to C 22 , saturated or unsaturated, straight chain or branched hydrocarbon group.
  • R 13 examples include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl and decyl through behenyl.
  • Additional, non-limiting examples of R 13 -COOH include the fatty acids obtained from the splitting of coconut, palm, soy and other natural oils. Where the R 13 -COOH is derived from natural oils, the R 13 radical may be substituted with one or more hydroxyl groups.
  • R 13 -COOH may also be a silicone carboxylic acid, having a polysiloxane chain terminated with one or more carboxylic acid groups.
  • At least one diacid and at least one monoacid are added to at least one diol, and the mixture heated to about 140°C to about 240°C.
  • the water of reaction, produced by the resulting condensation reaction is continuously removed by distillation.
  • a strong acid such as toluenesulfonic acid or methanesulfonic acid, or an organometallic catalyst such as a tin catalyst, may be added.
  • the pressure is then reduced until a derivatized
  • polyester having an acid value of less than 2 is obtained.
  • the product has a number average molecular weight of about 2,000 to about 10,000.
  • a mixture of diacid, diol and a natural triglyceride are prepared.
  • exemplary, non-limiting natural triglycerides include coconut oil, palm oil, soy oil and other natural oils.
  • the reaction temperature and course of the reaction are identical to that previously described in connection with the first approach to the preparation of the nonionic derivatized polyesters of the
  • polyester resins according to the present invention provides unique materials that are useful in skin-care and hair-care formulations.
  • Compounds described within this disclosure may be used in hair-care and skin-care
  • Hair-care and skin-care systems utilizing compounds described within this disclosure as formulation aids may include, for example: surfactant systems; oil-in-water cream and liquid emulsions; water-in-oil cream and liquid emulsions; aqueous, hydro-alcoholic and alcoholic gel systems; aqueous, hydro-alcoholic and alcoholic suspension systems; solid suspension or emulsion systems; and aerosol systems.
  • Hair care formulations utilizing compounds described within this disclosure may include, for example: cleansing, rinsing, conditioning, styling, bleaching, coloring and setting compositions such as gels, liquids, mousses, sprays, lotions, glazes, creams, hydro-alcoholic systems and shampoos.
  • formulations utilizing compounds described within this disclosure may include, for example: facial, hand and body moisturizing creams, liquids, pastes, and lotions; facial and body sunscreen creams, lotions, solids, pastes and liquids; facial treatment creams, lotions, pastes and liquids; underarm antiperspirant and deodorant sprays, liquids, creams and solids; facial, body and hand cleansing creams, gels, lotions, liquids and mousses;
  • foaming bath gels liquids, salts, oils and powders
  • aqueous, alcoholic and hydro-alcoholic toners astringents pre-shaves, after-shaves and after-bath products
  • eyelash and mascara lip color sticks and glosses
  • liquid and cream foundation make-up preparations aqueous, alcoholic and hydro-alcoholic toners, astringents pre-shaves, after-shaves and after-bath products.
  • foam volume texture and endurance enhancement are achieved upon incorporation of amine oxide and betaine functionalized polyester resins into skin-care and hair-care formulations.
  • Detergency in skin, hair, hand and body cleansing systems is provided by the incorporation therein of anionic, zwitterionic and polyamino acid containing derivatized polyesters.
  • mitigation of the irritation potential of primary surfactants can be achieved by incorporation of nonionic and zwitterionic derivatized polyesters.
  • the viscosity of skin- and hair-care formulations can be adjusted through the addition of
  • zwitterionic, nonionic and polyamino acid derivatized polyester compounds An enhancement in the electrolyte tolerance of primary surfactants is observed upon incorporation of anionic or zwitterionic polyesters into hair- and skin-care formulations having primary surfactants. Improved wetting and dispersion of particulate matter is provided to skin- and hair-care
  • a modification in the cloud point or critical micelle concentration of a nonionic surfactant, and/or a modification in the critical micelle concentration of an ionic surfactant, including an anionic surfactant, in a hair-care or skin-care formulation is provided by the addition thereto of a zwitterionic or nonionic derivatized polyester.
  • Improved solubilization of lipophilic materials is imparted to hair-care and skin-care formulations by incorporating therein either nonionic or a betaine derivatized polyester of the invention.
  • Nonionic, anionic, and cationic derivatized polyesters provide
  • improved hair shine and tactile feel enhancement is provided to hair-care formulations by the addition of a derivatized polyester having nonionic,
  • cationic, betaine, polysiloxane or polyamino acid functional groups An improvement in hair manageability is observed upon incorporation of cationic, anionic, nonionic, polysiloxane or polyamino acid functionalized polyester into a hair-care
  • quaternary ammonium groups, nonionic, polysiloxane and polyamino acid derivatized polyesters into hair-care formulations provides products that, when applied to hair, impart enhancement of hair body, greater perceived thickness, improvement of wet and dry combability, enhancement of hair styling ability and style retention.
  • Another aspect of the invention is the neutralization of static charge on hair with less hair flyaway due to combing, which is observed upon application of hair-care formulations incorporating cationic, and particularly quaternary ammonium containing, derivatized polyesters. Dry and damaged hair moisture normalization is observed upon application to hair of a hair-care product incorporating polyesters with cationic, nonionic and polyamino acid functional groups.
  • Repair of hair split ends may be achieved by applying to hair having spit ends a hair-care product incorporating polyester molecules of the invention having cationic, and particularly quaternary ammonium groups, nonionic, polyamino acid or polysiloxane functional groups.
  • skin-care sensory enhancement through contribution of a moist, soft tactile feel and visual smoothness is provided to skin having applied thereto a skin-care formulation that incorporated derivatized polyester compounds having cationic, nonionic, anionic, polysiloxane or polyamino acid functional groups. Normalization of the moisture content of the stratum corneum of skin, and enhancement in the ability of the stratum corneum to retain moisture is observed when a skin-care product having cationic, nonionic or polyamino acid derivatized polyester compounds incorporated therein is applied to the skin.
  • nonionic derivatized polyester compounds to topical skin-care preparations confers water resistance barrier properties to the topical skin-care
  • a sufficient amount refers to an amount of the referred to compound which can provide the indicated performance property to the skin-care or hair-care formulation. This amount will vary, depending on the derivatized polyester employed and the hair- or skin-care properties desired.
  • the amounts of the derivatized polyester generally present in the skin-care and hair-care formulations of the invention are indicated in the following Table A.
  • the invention provides a method for improving the endurance and volume of foam, and modifying the texture of foam, by the addition of a sufficient amount of polyester betaine and/or polyester amine oxide (see Examples 6 and 13 for the preparation of betaine and amine oxide functionalized polyesters, respectively) as a modifier of the foaming characteristics of primary anionic surfactant systems when aerated during use in systems designed to function, for example, as human hair
  • the invention provides a method of providing detergent cleansing function to systems designed to function as human hair shampoos, body cleansers, bubble baths, hand cleansers and facial skin cleansers through the addition of a sufficient amount of polyester betaine, polyester dicarboxylate, polyester protein derivative and/or polyester amine oxide (where representative examples thereof may be prepared according to Examples 6, 9, 11 and 13, respectively) so that particulate debris, skin oils, body sweat and make-up residue can be wetted, emulsified and rinsed from relevant body surfaces.
  • the invention provides a method to mitigate and minimize the irritating effects of primary anionic surfactant systems upon human skin and eyes through addition of a sufficient amount of polyester betaine polyester dicarboxylate, polyester protein derivative and/or polyester amine oxide (where
  • representative examples thereof may be prepared according to Examples 6, 9, 11 and 13, respectively) to systems designed to function as human hair shampoos, body cleansers, bubble baths, hand cleansers and facial skin cleansers.
  • the invention provides a method to modify the viscosity and rheology of aqueous systems, aqueous phases of emulsion systems and/or surfactant systems through the addition of a sufficient amount of polyester betaine, polyester/botanical condensate, polyester dicarboxylate, polyester amine oxide and/or a nonionic polyester alkylate (where representative examples thereof may be prepared according to Examples 6, 7, 8, 13 and 14, respectively) to systems designed to function, for example:
  • shampoos body cleansers, bubble baths, hand cleansers, facial skin cleansers, facial moisturizers, body moisturizers, hand barrier and moisturizing preparations, and make-up preparations.
  • the invention provides a method for extending the concentration of electrolytes which can be combined with primary anionic surfactant systems before foaming, detergent, stability or viscosity characteristics of the primary anionic surfactants are adversely affected.
  • the method comprises the addition of a sufficient amount of polyester betaine, polyester dicarboxylate and/or polyester amine oxide (where representative examples of which may be prepared according to Examples 6, 9 and 13,
  • surfactant systems designed for use, for example, as human hair shampoos, body cleansers, bubble baths, hand cleansers, hair conditioners, and facial skin cleansers.
  • the invention provides a method for wetting and/or dispersing particulate matter in aqueous systems, aqueous and oil phases of emulsion systems and anhydrous systems through addition of a sufficient amount of polyester betaine, polyester
  • dicarboxylate, polyester amine oxide and/or nonionic polyester alkylate where representative examples thereof may be prepared according to Examples 6, 9, 13 and 14
  • This method would apply, for example, to systems designed for use as human hair shampoos, body shampoos, facial and body masks, facial and body moisturizers, make-up preparations, bath and body oils, antiperspirant and deodorant systems, sunscreen preparations and bubble baths.
  • the invention provides a method for reducing the concentration at which primary anionic surfactants may change from a spherical or micellar gel structure to lamellar gel structure or otherwise become visually hazy (or reach their critical micelle concentration) by addition of a sufficient amount of polyester betaine, polyester dicarboxylate and/or polyester amine oxide (where representative examples thereof may be prepared according to Examples 6, 8 and 13, respectively) to systems designed for use as human hair shampoos, body cleansers, bubble baths, hand cleansers and facial skin cleansers.
  • the invention provides a method for solubilizing lipophilic materials into aqueous systems, surfactant systems, or aqueous phases of emulsion systems so that the lipophilic
  • micro emulsion which is clear and/or
  • polyester betaine polyester dicarboxylate and/or nonionic polyester alkylate
  • the invention provides a method of emulsifying or aiding in the emulsification of lipophilic materials into water or hydrophilic materials, or emulsifying or aiding in the
  • the method involves addition of a sufficient amount of polyesteramine, polyesteramine salt, polyester ammonium salt, polyester betaine, polyester dicarboxylate and/or nonionic polyester alkylate (where representative examples thereof may be prepared according to Examples 2, 3, 4, 5, 6, 7, 8 and 14, respectively) to a system designed to perform, for example, as human hair conditioner or rinse, body or facial moisturizer, hand protectant or moisturizer, suncare or skin protectant
  • the invention provides a method of enhancing or adding visual shine to hair and/or enhancing the tactile feel of hair to the extent that it is perceived as healthy, moist and attractive through the addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester betaine, polyester/botanical condensate, polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where
  • representative examples thereof may be prepared according to Examples, 2, 3, 4, 5, 6, 7, 8 and 14) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
  • the invention provides a method of improving hair manageability through the deposition and/or attachment on hair and/or through addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester/botanical condensate,
  • polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4, 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
  • the invention provides a method of enhancing the tactile sense that hair has body and/or perceived thickness through the deposition and/or attachment on hair of, or addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester/botanical condensate, polyester/protein
  • polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
  • the invention provides a method of improving the wet and dry combability of hair through the deposition and/or attachment on hair, or addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester/botanical condensate, polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where
  • representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
  • the invention provides a method of incorporating the capability of forming hair into specific configurations or styles and/or retaining the configuration or style when formed by providing a means for individual hairs to adhere to one another at locations of contact through addition of a sufficient amount of a polyesteramine, polyester ammonium salt, polyester/botanical condensate, polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where
  • representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
  • the invention provides a method to neutralize the static electrical charge on hair and "fly-away” or repulsion of individual hairs as a result of static electrical charge build-up on hair through the deposition and/or attachment on hair, or addition of a sufficient amount of polyesteramine and/or polyester ammonium salt (where representative examples thereof may be prepared according to Examples 2 or 4, and 5,
  • the invention provides a method to normalize the moisture content or moisture absorbed onto hair keratin through the deposition and/or attachment on hair of, or addition of a sufficient amount of polyesteramine, polyester/botanical
  • polyester alkylate (where representative examples thereof may be prepared according to Examples: 2 or 4, 7, 11 and 14,
  • the invention provides a method of repairing hair split ends or temporarily facilitating the adhesion of hair tips that have separated into visibly differentiated segments within the area roughly approximating the tip of a hair through the
  • polyesteramine terephthalate
  • polyester ammonium salt terephthalate
  • polyester/botanical condensate polyester/protein condensate
  • polyester/silicone condensate and/or nonionic
  • polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair gels, hair creams, hair hot oil treatments, hair ambient temperature oil treatments or hair sprays.
  • the invention provides a method of contributing a moist soft tactile feeling on skin and/or visual skin smoothness through the deposition and/or attachment on the surface of skin, or addition of a sufficient amount of polyesteramine,
  • polyesteramine salt polyester/botanical condensate, polyester dicarboxylate, polyester/protein condensate, polyester/siloxane condensate and/or nonionic polyester alkylate (where
  • moisturizers suncare preparations, antiperspirant preparations or deodorant preparations.
  • the invention provides a method of normalizing the moisture content of the stratum corneum of human skin through deposition and/or attachment on the surface of skin, or addition of a sufficient amount of polyesteramine, polyesteramine salt, polyester/botanical condensate, polyester dicarboxylate,
  • polyester/protein condensate, polyester/siloxane condensate and/or nonionic polyester alkylate (where representative example thereof may be prepared according to Examples 2 or 4, 3, 7, 9, 11, 12 and 14, respectively) to systems designed to function, for example, as human facial moisturizers, body moisturizers, make-up preparations dusting powders, after-bath veils, facial masks, body masks, facial scrubs, body scrubs, facial cleansers, body cleansers, hand protectants and moisturizers, suncare
  • the invention provides a method of modification of the application characteristics or the apparent relative friction on the surface of skin during application and rub-in and/or the relative tactile impression of wetness, dryness and/or sliminess during rub-in of products designed to function as human facial moisturizers, body moisturizers, make-up preparations, dusting powders, after-bath veils, facial masks, body masks, facial scrubs, body scrubs, facial cleansers, body cleansers, hand protectants and moisturizers, suncare preparations,
  • polyesteramine polyesteramine salt, polyester/botanical condensate, polyester diacid, polyester dicarboxylate and/or polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4, 3, 7, 8, 9 and 14, respectively).
  • the invention provides a method to confer resistance to rinse off or wash off by water or human perspiration of
  • formulation ingredients or entire formulations through deposition and/or attachment on the surface of skin or inclusion in a formulation or part, or parts of a formulation of a sufficient amount of polyester/botanical condensate and/or nonionic
  • polyester alkylate (where representative examples thereof may be prepared according to Examples 7 and 14, respectively) to systems designed to function, for example, as human sunscreen
  • polyester/silcone condensates are particularly desirable components in skin-care and hair-care products because the condensates do not build up on skin or hair with repeated usage of skin- and hair-care formulations incorporating the polyester/silicone condensates.
  • Example 2 Into an apparatus like the one used in Example 1, 4500 g (0.9 moles) of the polyester of Example 1 and 408.5 g (4.0 moles) of dimethylaminopropylamine (DMAPA) were placed. The mixture was heated under atmospheric pressure with nitrogen purge to 120°C and held for twelve hours at these conditions. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the mixture (stripping) for four hours to remove any residual amine and trace odor compounds. After stripping, the mixture was brought to atmospheric pressure and 4900 g (4.9 moles) of poly (propylene glycol adipate) amidopropyldimethylamine with a number average molecular weight of 1000 were obtained.
  • DMAPA dimethylaminopropylamine
  • Example 2 Into an apparatus like the one used in Example 1, 4900 g (4.9 moles) of the polyester of Example 2 and 4575 g of pure water were placed. The mixture was heated to 60°C and 470 g of 31% by weight of aqueous hydrochloric acid (4 moles) was slowly added over a one-hour period. Additional hydrochloric acid was then added as necessary to bring the pH of the solution to 6.0 at 25°C. About 5000 g of poly (propylene glycol
  • Example 2 Into an apparatus like the one used in Example 1, 4500 g (0.9 moles) of poly (diethylene glycol adipate) diol with a molecular weight of 5000 (obtained in a manner similar to the procedure set forth in Example 1) and 1038 g (10.2 moles) of dimethylaminopropylamine (DMAPA) were placed. The mixture was heated under atmospheric pressure with nitrogen purge to 120°C, and held for twelve hours at these conditions. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the mixture for four hours to remove any residual amine and odor bodies. After sparging, the mixture was brought to atmospheric pressure and 5500 g (11.0 moles) of
  • poly (diethylene glycol adipate) amidopropyldimethylamine with a number average molecular weight of 500 was obtained.
  • MCH monochlorohydrin
  • Example 2500 g (5.0 moles) of the polyesteramide product of Example 4 4575 g (60 moles) of propylene glycol and 612 g (5.25 moles) of sodium monochloroacetate (SMCA) were added. The mixture was heated to 90°C and held at that temperature for six hours. The product was then vacuum-filtered through a bed of diatomaceous earth. This removes some of the sodium chloride that was formed as a byproduct of the reaction. About 10,500 g of poly (diethylene glycol adipate) amidopropylbetaine were obtained.
  • SMCA sodium monochloroacetate
  • Example 2 Into an apparatus like the one used in Example 1, 5,000 g (1.0 mole) of the polyester of Example 1 and 439 g (0.5 moles) of olive oil (a botanical extract) were placed. The mixture was heated to 220°C and held at that temperature for sixteen hours. The mixture was then cooled to 120°C. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the mixture for four hours to remove any residual odor bodies. About 5400 g of derivatized polyester containing some glycerin crosslinks and olive fatty acid termination were
  • Example 2 Into an apparatus like the one used in Example 1, 5,000 g (1.0 mole) of the polyester of Example 1 and 292 g (2 moles) of adipic acid were placed. The mixture was heated with nitrogen purge to 220°C and held at these conditions for sixteen hours. The pressure was then reduced and the mixture was heated under vacuum for 20 hours until 36 g (2 moles) of water were distilled off. 5256 g of poly (propylene glycol adipate) diacid with a molecular weight of 5250 were obtained.
  • Example 8 Into an apparatus like the one used in Example 1, 5256 g (1.0 mole) of the derivatized polyester product of Example 8 were placed. The polyester was heated to 120°C. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the polyester for four hours to remove any residual odor compounds. Then 5000 g of pure water and 110 g (2 moles) of a 30% by weight solution of ammonia were added with stirring. This resulted in the formation of 10,300 g of a 50% by weight aqueous solution of ammonium poly (propylene glycol adipate) dicarboxylate.
  • Example 2 Into an apparatus like the one used in Example 1, 5000 g (10 moles) of the polyester of Example 4, 5000 g of propylene glycol (65.8 moles), and 1177 g (10 moles) of 31% by weight aqueous hydrochloric acid were placed. The mixture was heated with stirring to 60°C and held under these conditions for one hour until the neutralization of the polyester of Example 4 was complete. 925 g (10 moles) of epichlorohydrin were added and the mixture was held at 60°C for 5 hours.
  • Example 2 Into an apparatus like the one used in Example 1, 4900 g (4.9 moles) of the polyester of Example 2 and 4575 g of pure water were placed. The mixture was heated to 60°C and 272 g of 50% by weight aqueous hydrogen peroxide (4 moles) was slowly added over a one-hour period. About 9,500 g of poly (propylene glycol adipate) amidopropyldimethylamine oxide were obtained.
  • Example 2 Into an apparatus like the one used in Example 1, 5000 g (1.0 moles) of the polyester of Example 1 and 416 g
  • Legends A through Y represent polymer names
  • Legends AA through GG represent trade names with corresponding supplier's addresses.
  • Polyesters which are liquids at room temperature were agitated to ensure homogeneity. Polyesters which are solid at room temperature were warmed above their melting point (ca. 50°C) and agitated until homogeneous. Into 1.5 oz. screw-top glass jars, polyester (solute) and solvent (water, ethanol or
  • isopropanol were weighed in amounts required to provide 20 grams in each vial of mixtures at concentrations of 5, 25, and 50 percent by weight.
  • the jars were capped with polyethylene lids, warmed to 30°C, and shaken vigorously for thirty to sixty
  • the specific gravity of the derivatized polyesters was determined by using a Gardner gallon weight cup. Polyesters which were liquid at room temperature were agitated to ensure
  • Derivatized polyesters which were liquid at room temperature were agitated to ensure homogeneity, and their pH measured using a Brinkmann 632 pH-Meter equipped with combination glass electrode. Solid polyesters were warmed above their melting point (ca. 50°C), agitated until homogeneous, and then diluted to 10% by volume in deionized water, before measuring their pH. All measurements were carried out at 25°C, with the results provided in TABLE V.
  • the viscosity of selected derivatized polyesters was measured at various temperatures using a Brookfield RV coaxial cylinder viscometer (No. 24 spindle, RPM adjusted as necessary).
  • the sample chamber was fitted with a small sample adapter, which was jacketed, and through which flowed heat transfer fluid from a controlled temperature bath. The viscosity measurement so obtained are recorded in TABLE VI.
  • polyesters Approximately a 10% w/w mixture was made of respective polyesters in deionized water. The polyester was mixed into the water using an electric rotating stirrer equipped with a
  • Worsted wool challis (6" x 2.75") (Test Fabrics, Inc.)
  • Polyesters M, B, U and V and Polyester I appear to perform on a competitive level with ingredients commonly used for their ability to adhere to skin and hair.
  • Polyester I appears to retain moisture on leather comparatively better than other film forming agents typically used in skin- and hair-care applications. Polyesters M and V appear to be similar in their moisture retention ability as other film forming agents commonly used in skin- and hair-care
  • polyesters U and V When applied to leather, polyesters U and V appear to absorb moisture from the atmosphere comparatively better than other film forming agents typically used in skin- and hair-care applications.
  • Polyesters M and I appear to improve the visual shine of hair tresses and perform better than competitive ingredients used in hair-care products for that purpose.
  • PROCEDURE
  • Rate resistance on a scale of 1 to 10 (with 1 being optimum, or least resistant to combing). After 2 hours of drying at ambient temperature and humidity, pass comb through tress 20 times making a comparative evaluation of relative resistance to combing. Rate resistance on a scale of 1 to 10 (as before). While dry combing, make a comparative
  • Polyesters B and I appear to improve the combability of hair tresses to the same extent as competitive ingredients typically utilized in hair conditioning preparations for
  • Polyester M appears to perform better than many competitive additives as far as providing good hair tress combability.
  • section "3" material polyyester O
  • the resulting product is a clear, high foaming conditioning shampoo which conditioned without causing build-up of conditioner on hair.
  • Polyester O is a conditioning agent which adds body to hair and improves its manageability.
  • the resulting product is a cleansing gel for direct use on skin.
  • the resulting product provides moderate hold utilizing minimal volatile organic compounds (VOC).
  • VOC minimal volatile organic compounds
  • the resulting product is an after-shampoo leave-on conditioner for sun and wind damaged hair.
  • Polyester S boosts foam, mitigates the irritation potential of TEA lauryl sulfate and helps build viscosity.
  • Polyester Q enhances detergency while minimizing irritation .
  • the resulting product is a thin lotion that would be compatible for use in a glass bottle.
  • the inclusion of Polyester V adds a moist emollient feel to the skin following application and is expected to increase the substantivity of the alpha hydroxy acid. Polyester V is also expected to act as a buffer for lactic acid, thereby increasing the efficacy of the AHA and mitigating it's irritation potential.
  • the resulting product is a thixotropic lotion which leaves a non-greasy and moist feeling on the skin following application and has good body.
  • Polyester B adds a moist
  • the resulting product is a light cream which leaves a non-greasy and perceptible moist film on the skin following application.
  • Polyester U adds a substantive moist film on the skin.
  • the resulting product is a viscous lotion which leaves a non-greasy and moist feeling on the skin following application.
  • Polyester U adds a moist emollient skin feel.

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Abstract

Polyester resins made from aliphatic dicarboxylic acid and dihydric compounds are modified to provide derivatized polyesters having functional groups. The functional groups include anionic, cationic, quaternary ammonium, zwitterionic, polyamine acid chain, nonionic, essential oils, botanical derivatives or silicone-based polymers. These derivatized polyesters have use as formulation aids and conditioning agents in hair and skin personal care products.

Description

DERTVATIZED POLYESTER COMPOUNDS AND USES THEREOF
FIELD OF THE INVENTION
The invention generally relates to polyester resins and formulations thereof. More specifically, the invention is directed to polyester resins derivatized with various functional groups, and to hair-care and skin-care formulations incorporating the derivatized polyester resins. BACKGROUND OF THE INVENTION
Personal care product formulations utilize many
different classes of ingredients to provide a desired performance when used on the human body. These ingredients may either perform a specific function on the hair and skin such as
cleaning, moisturizing, adding shine, styling, lubricating and protecting, or they may provide a way for other ingredients to be used within the formulation, such as by providing emulsification, thickening, preservation and delivery. Polymers of many types have been used over the past twenty years to perform some of these functions. These polymers include polyvinyl pyrrolidone derivatives, hydroxyl ethyl cellulose copolymers and derivatives, polysaccharides, polyethers and derivatives, and many others.
Polyester polyols have historically had limited use in personal care formulations. This is at least partly because most polyesters have limited performance properties in personal care product formulations, and they can be difficult to incorporate into stable formulations
Polyester polyols are used for non-personal care applications such as the diol component in polyurethanes, plasticizers for industrial applications and specific polymer additives including adhesion promoters, carrier vehicles and stabilizers. Though some classes of polyester polyols have been introduced for personal care application, they have not been derivatized in the ways disclosed herein, nor have efforts been made to derivatize polyester polyols specifically for the personal care applications as disclosed herein.
SUMMARY OF THE INVENTION
The invention is directed to compounds of the formula
Figure imgf000004_0001
wherein R1 is -N(R5) (R6) or -OR7; R2 is independently C2-C10 aliphatic; R3 is independently C2-C10 aliphatic having 0-5 oxygen atoms as ether groups; R4 is R1; p is an integer between 3-100, inclusive; R5 is H or C1-C10 aliphatic; R6 is -R8 -N(R9)2(R1.),
-polyamino acid-C (=O) OR11, -R8-P(R15)3 R14 or -R8-S(R15)2 R14 ; R7 is H, R12, -R3-OC(=O) -R13, -R3-OSO2O- R12 or -R3-SO3- R12 ; R8 is C1-C3; R9 is independently C1-C3 having 0-3 -OH substituents; R10 is -H R14, -R9 R14, -O-, - (CH2)1_3-C(=O)O-,
-CH2CH(OH)CH2-NH-polyamino acid-COO-, -CH2CH (OH) CH2-NH-polyamino acid-COOR15 R14 or -CH2CH (OH) CH2-NH-polysiloxane R14 ; R11 is R12 or C1 -C22 ; R12 is lithium, sodium, calcium, magnesium, ammonium monoalkylammonium, dialkylammonium, trialkylammonium, or
tetralkylammonium, where an alkyl portion of an ammonium group has 1-20 carbon atoms and 0-3 hydroxyl groups; R13 is C1-C22 aliphatic; R14 is halide, sulfate, phosphate, citrate, lactate, malate, fatty carboxylate or polymeric carboxylate; R15 is C1-C22 hydrocarbon; R16 is -O(C=O)R1, H, or -O [C (=O) -R2 (R18) m-C (=O) O- R3(R16)n-O]pC(=O) -R2(R18)m-C(=O) -R1; n is an integer between 1 and 5, inclusive; R18 is -C(=O)R1, H, or -C (=O) O-R3-O [C (=O) -R2 (R18)m- C(=O)O-R3(R16)n-O]pC(=O) -R2(R18)m-C(=O) -R1; and m is an integer between 1 and 5, inclusive; with the proviso that when R is either -OH or -O-R3-OH, then R4 is neither -OH nor -O-R3-OH.
A further aspect of the invention is the product resulting from the reaction between at least one of a botanical derivative, an essential oil or a polysiloxane, and the polyester of the formula
Figure imgf000005_0001
wherein R1 is -OH or -O-R3-OH; R2 is independently C2-C10
aliphatic; R is independently C2-C10 aliphatic having 0-5 oxygen atoms as ether groups; R4 is -OH or -O-R3-0H; p is an integer between 3-100, inclusive; R16 is -O(C=O)R1, H, or
-O[C(=O)-R2(R18)m-C(=O)O-R3(R16)n-O]pC(=O)-R2(R18)m,-C(=O)-R1; n is an integer between 1 and 5, inclusive; R18 is -C(=O)OR1, H, or
-C(=O)O-R3-O[C(=O)-R2(R18)m-C(=O)O-R3(R16)n-O]pC(=O)-R2(R18)m-C(=O)- R1 ; and m is an integer between 1 and 5, inclusive.
By derivatizing the polyesters with various functional moieties, they can be altered into materials which have wide- ranging physical and performance properties. Physical propertie can be varied widely in terms of solubility, viscosity, melting point, HLB value, hydrophilicity/hydrophobicity, hydrolytic stability, emulsion stability, surfactancy and others.
Performance properties of the derivatized polyesters include film-forming, moisture retention, emolliency, adhesion,
stabilization and others which are desirable in personal care products. The derivatized polyesters can also be used to delive other functional ingredients with enhanced efficacy, where these properties are valued in skin-care and hair-care formulations.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The compositions of the invention include derivatized polyester molecules and formulations comprising those derivatize polyester molecules, particularly in hair-care and skin-care formulations. The derivatized polyester molecules contain a plurality of ester (-O-C(=O)-) groups linked together by R2 and R3 groups, where an R2 group links the carbon atoms of two ester groups, and an R3 group links the (non-carbonyl) oxygen atoms of two ester groups. In other words, the polyester molecules have repeating units of -C(=O) -R2-C (=O)O-R3-O- where the number of repeating units may be denoted as p and wherein p is an integer between 3 and 100, inclusive, so as to form what will be denoted herein as a polyester chain, where a preferred polyester chain is represented by formula (I)
Figure imgf000006_0001
The polyester molecule of the invention terminates with endgroups, designated R1 and R4, that contain functional groups, where the R1 or R4 groups are also known as functionalized endgroups, as described in detail below. The preferred R2 and R3 groups are aliphatic, and not aromatic. The polyesters of the invention having a polyester chain and functionalized endgroups are denoted herein as derivatized polyesters.
Preferred derivatized polyesters of the invention have the formula (II)
Figure imgf000007_0001
In a preferred embodiment, the derivatized polyesters have functional groups present only as part of the endgroups, as shown in Formula (II). However, in another embodiment of the invention, functional groups may be additionally present at one or more points along the polyester chain. In a preferred
embodiment, the polyester chain is linear, e.g., there are no crosslinks present, as shown in formula (II). However, in another embodiment of the invention, crosslinks may be present which provide for the joining together of two or more polyester chains through R2 and/or R3 groups. Formula (Ila) represents a polyester resin of the invention which clearly indicates, with groups R1S and R18, that the derivatized polyesters may have functional groups along the polyester chain, or cites for
crosslinking.
Figure imgf000008_0001
In a preferred embodiment, an R2 group of the invention has between 2 and 10 aliphatic carbon atoms, inclusive, where said aliphatic carbon atoms are present in a linear, branched and/or cyclic arrangement. In one preferred embodiment, the R2 group is a hydrocarbon, that is, it contains only hydrogen and carbon atoms. However, in another embodiment of the invention, the R2 groups may additionally contain oxygen atoms, where said oxygen atoms are present in the form of one or more ether
(-C-O-C-), hydroxyl (C-OH), carbonyl (-C(-O)-), ester (-O-C(-O)-) or carboxylic acid (-C(=O)OH) groups. In instances where an R2 group contains one or more oxygen atoms, there are preferably not more than 5 of said oxygen atoms present in the R2 group. Any of the exemplary R2 hydrocarbon groups listed below may additionally contain not more than 5 oxygen atoms.
Exemplary hydrocarbon R2 groups have molecular formulas selected from the group C2H4, C3H6, C4H8, C5H10, C6H12, C7H14 , C8H16, C9H18 and C10H22. In a preferred embodiment, the carbon atoms are arranged in a straight chain, that is, R2 is selected from the group having the formula (-CH2-)a, wherein a is 2 to 10,
inclusive, and includes ethyl (a=2), propyl (a=3), butyl (a=4), pentyl (a=5), hexyl (a=6), heptyl (a=7), octyl (a=8), nonyl (a=9) and decyl (a=10). An especially preferred straight chain R2 group is butyl, -CH2-CH2- CH2-CH2-. R2 may also be a branched chain hydrocarbon group, where exemplary, non-limiting branched chain hydrocarbon groups include 1-methylethyl (-CH (CH3) -CH2-), 1-methylpropyl (-CH(CH3)- CH2-CH2-), 2-methylpropyl ( -CH2-CH (CH3) -CH2- ), 1, 2-dimethylethyl (-CH(CH3) -CH(CH3)-), 1-ethylethyl (-CH (CH2CH3) -CH2- ), 1- methylbutyl (-CH(CH3) -CH2-CH2-CH2- ), 2-methylbutyl (CH2-CH (CH3) - CH2-CH2-), 1-ethylpropyl (-CH (CH2CH3) -CH2-CH2-), 2-ethylpropyl (-CH2-CH(CH2CH3) -CH2-), 1, 2-dimethylpropyl (-CH (CH3) -CH (CH3) -CH2-), 1,3-dimethylpropyl ( -CH (CH3) -CH2-CH (CH3) - ), 2, 2-dimethylpropyl (-CH2-C(CH3)2-CH2-), and so forth.
R2 may also contain a cyclic hydrocarbon group, where exemplary non-limiting R2 groups with a cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl groups. R2 may also contain one or more bicyclic arrangement of carbon atoms. A single R2 group may contain both a cyclic arrangement of carbon atoms and acyclic carbon atoms.
An R2 group may be substituted with m R18 groups, where m is up to 5, and where the R18 substituent is attached to the R2 group in lieu of one of the hydrogen atoms otherwise present in the R2 group. The R18 group may be -C(=O)R1, which is the case when a functional group is appended to the polyester chain, or R18 may be -C (=O) O-R3-O [C (=O) -R2 (R18)m-C (=O) O-R3 (R16) n-O] pC (=O) - R2 (R18)m-C(=O) -R1. which is the case when R18 is a site of
crosslinking to another polyester chain and/or derivatized polyester.
The R3 group of the invention has between 2 and 10 aliphatic carbon atoms, inclusive, and between 0 and 5 oxygen atoms, inclusive, and may have any of the atomic arrangements previously set forth for the R2 groups. Preferred R3 groups include butyl (-CH2-CH2-CH2-CH2-), hexyl (-CH2-CH2-CH2-CH2-CH2-CH2- CH2-), 2-methylpropyl (-CH2-CH (CH3) -CH2-), 1-methylethyl
(-CH(CH3) -CH2-), 2,2-dimethylpropyl (-CH2-C (CH3) 2-CH2-), diethyl ether (-CH2-CH2-O-CH2-CH2-) and di (1-methylethyl) ether (-CH(CH3)- CH2-O-CH(CH3) -CH2-). Ethylene oxide derivatives are a preferred R group of the invention, where said ethylene oxide derivatives are recognized by having a formula corresponding to
(-CH(R) -CH2-O-)b-CH(R)-CH2-) wherein b is either 1, 2, 3, 4 or 5, and R is either methyl, ethyl, propyl, butyl or pentyl.
An R3 group may be substituted with n R16 groups, where n is up to 5, and where the R16 substituent is attached to the R3 group in lieu of one of the hydrogen atoms otherwise present in the R3 group. The R16 group may be -OC(=O)R1, which is the case when a functional group is appended to the polyester chain, or R16 may be -O [C(=O) -R2 {R18)m-C(=O) O-R3 (R16)n-O]pC (=O) -R2 (R18)m-C (=O) - R1, which is the case when R16 is a site of crosslinking to another polyester chain and/or derivatized polyester.
The addition of functionality to the polyester chain o the invention provides for a molecule having unique and desirable properties which are particularly valuable in hair-care and skin- care formulations. Preferably, the functionality is added to one or both of the ends of the polyester chain. An R2 or R3 group closest to an end of the polyester chain will be denoted herein as a terminal R2 or R3 group, while all other R2 and R3 groups will be denoted as internal R2 or R3 groups. In instances where functionality is added to both ends of the polyester chain, said functionality is preferably identical. In other words, for polyester molecules having functionality at each end, the
functionality present at one end is preferably the same as the functionality present at the other end. In instances where functionality is only present at one of the two ends of the polyester molecule, then the non-functionalized end will be either a carboxylic acid group (-C(=O)OH) or a hydroxyl group (-OH).
In one embodiment of the invention, the polyester chain is joined to functionality at one or more sites other than, or in addition to, the ends of the polyester chain. In other words, the polyester molecules of the invention may have functional groups appended to the polyester chain at sites along the chain. More specifically, any R2 and/or R3 group of the polyester chain may be joined to one or more functional groups of the invention. In instances where at least one functionality is appended to at least one internal R2 or R3 group, then the polyester chain may terminate at both ends with either carboxylic acid or hydroxyl groups. The polyester molecules of the invention necessarily have at least one functional group, where said functional groups will be described next.
The functional groups of the invention are selected to result in polyester derivatives having nonionic, anionic, cationic and zwitterionic character. Exemplary nonionic
functional groups groups are hydrocarbon groups, which may be saturated or unsaturated. Other exemplary nonionic groups come from essential oils, botanical extracts or have a polysiloxane structure. Exemplary anionic groups include the carboxylate, sulfonate and sulfate groups, which have associated therewith a neutralizing group of opposite charge, i.e., a counterion.
Exemplary cationic groups include ammonium, sulfoxonium and phosphonium, which have associated therewith a neutralizing group of opposite charge, i.e., a counterion. Exemplary zwitterionic groups have both positively and negatively charged moieties present as part of the functional group. An exemplary
zwitterionic group is the -+N(R9) 2- (CH2) 1-3-COO- group, where the nitrogen atom bears a positive charge and the carboxylate group bears a neutralizing negative charge. Another functional group is the amine oxide functional group, represented by -N(R9)2-O. Yet another functional group of the invention, which may be considered zwitterionic, but actually imparts unique properties to a derivatized polyester, is a polyamino acid chain.
Preferably, the amine terminus of the polyamino acid chain is joined to the polyester chain, and the carboxyl terminus is present as either a carboxylate salt or carboxylic ester.
Turning now to a more detailed description of the nonionic endgroups of the invention, an exemplary nonionic endgroup is a hydrocarbon chain. Said hydrocarbon chain may have from 1 to 22 aliphatic carbon atoms, joined together by single and/or double bonds. Preferred hydrocarbon chains have none or minimal branching, and are available as the hydrocarbon portion of natural or synthetic fatty acids. The condensation of a fatty acid with a hydroxyl group from the polyester chain of the invention provides a convenient means of providing for polyester molecules having nonionic endgroups that comprise a hydrocarbon chain. Exemplary fatty acids, which may be used to introduce exemplary nonionic hydrocarbon endgroups to the polyester
molecules of the invention include fatty acids available from, for example, tallow, coconut oil, palm oil, palm kernel oil, canola oil, soybean oil, tall oil, peanut oil, cottonseed oil, rapeseed oil, cod liver oil, castor oil, sunflower oil, olive oil, safflower oil and carobseed oil.
Polyester chains may be reacted with essential oils or botanical extracts to provide derivatized polyesters of the invention. An exemplary reaction between an essential oil or a botanical extract and a polyester chain may be conducted by contacting the reactants, optionally in the presence of a catalyst, and heating until at least some condensation reaction has occurred between the reactants. Alternatively, the polyester chain and/or the essential oil or botanical extract may be chemically modified so as to provide a preferred means of linking the polyester chain to the functional group. Exemplary essential oils are obtained from, for example, camphor, vanilla bean, mint, eucalyptus, pine, rose, jasmine, garlic, orange, lemon, lime, grapefruit, mandarin, almond, anise, avocado, bayberry, bergamot, mace, nutmeg, menthol, turpentine, gardenia, lilac, clove, and ylang ylang. Exemplary botanical derivatives are extracts of, for example, comfrey, chamomile, algae, cucumber, arnica, nettle, kelp, hypericum, mimosa bark, hawkweed, myrtle, English oak, horsetail, spiraea, quince, rosemary, pansy, yeast, sage,
watercress, witch hazel, horse chestnut, yarrow, ivy, jojoba, lavender, henna, geranium, fennel and dandelion.
Polyester chains may be reacted with polysilicone and/or polysiloxane incorporating materials, to provide a
preferred derivatized polyester of the invention. The
polysiloxane incorporating materials include the repeating unit - (Si(R)2O)-, where a preferred R group is C1-C4 alkyl, and
particularly methyl. A convenient polysiloxane material for preparing polysiloxane derivatized polyesters of the invention have a primary amine terminus, e.g., amodimethicone, having the structure HO [Si (CH3) 2-O] - [Si (OH) (CH2CH2-NH-CH2CH2-NH2) ] x-H, where x is a positive integer ≥ 1. The polysiloxane materials may also have hydroxy termination to enable them to enter into
condensation reactions with polyol.
Turning now to the anionic functional endgroup which may be present in the derivatized polyester of the invention, said anionic endgroup is characterized in having a negative charge, and is preferably selected from the group consisting of carboxylate (-C(=O)O-), sulfonate (-SO2-O-) and sulfate
(-O-S)2-O-). Said anionic functional group is present with an associated, positively charged counterion, which will be
designated R12. Exemplary, non-limiting, positively charged counterions R12 include sodium (Na+), lithium (Li*), calcium
(Ca+2), magnesium (Mg+2), ammonium (NH4 +) , monoalkylammonium
(RNH3 +), dialkylammonium (R2NH2 +), trialkylammonium (R3NH+) and tetraalkylammonium (R4N+) wherein an alkyl group R attached to a nitrogen atom of an alkylammonium group has from 1 to 20 carbon atoms, inclusive, and has 0-3 hydroxyl groups, inclusive.
Turning now to the cationic functional endgroup which may be present in the derivatized polyesters of the invention, said cationic endgroup is characterized in having a positive charge, and is preferably selected from the group consisting of ammonium (including mono-, di- and trialkylammonium), sulfoxonium (-S(R)2-O+) sulfonium (-S(R)2 +) and phosphonium (-P(R)3 +). The R groups which are bonded to the N, S or P atom of the ammonium, sulfonium or phosphonium group, respectively, may have from 1 to 22 carbon atoms, where those carbon atoms may be present in aliphatic or aromatic arrangements, and where those R groups may additionally contain hydroxyl functionality. R groups bonded to a nitrogen atom of an ammonium group preferably have 1 to 3 carbon atoms, and 0-3 hydroxyl substituents. Said cationic functional group is present with an associated, negatively charged counterion, which will be designated R14 Exemplary, non-limiting, negatively charged counterions R14 include organic and inorganic counterions, where inorganic counterions include halide (specifically fluoride, chloride, bromide or iodide), sulfate and phosphate, and where organic counterions include carboxylates such as citrate, lactate, malate, fatty acid carboxylate and carboxylates bonded to polymeric materials.
Turning now to the zwitterionic functional endgroup which may be present in the derivatized polyester of the
invention, said zwitterionic endgroup is characterized in having a positively charged site covalently bonded to a negatively charged site, in other words, the zwitterionic group is
characterized in being dipolar. An exemplary zwitterionic functional group is the betaine group, where an exemplary betaine is (-+N(R9)2- (CH2) 1-3-COO-). The group which links the cationic ammonium group to the anionic carboxylate group preferably has 1 carbon, so as to form -+NR2-CH2-COO-, however additional carbon atoms may be present. The R groups which are bound to the ammonium nitrogen atom, i.e., the R9 groups, are independently selected from alkyl groups having 1 to 3 carbon atoms, where those carbon atoms may be optionally substituted with up to 3 hydroxyl groups.
Another exemplary endgroup is the amine oxide group (-+N(R9) 2-O-), where the R groups bonded to the nitrogen atom of the amine oxide are independently selected from alkyl groups having 1 to 3 carbon atoms, where those carbon atoms may be optionally substituted with up to 3 hydroxyl groups.
Another exemplary functional group, is a polyamino acid chain. A convenient source for a polyamino acid chain is
protein, which may or may not be hydrolyzed before incorporation into the derivatized polyesters of the invention. It is
convenient to join the polyamino acid chain through its amine terminus, i.e., its terminal -NH2 group, to the polyester chain. The other end of the polyamino acid chain, i.e., the carboxyl terminus, may be in the carboxylic acid, carboxylate or
carboxylic acid ester form. When present in the carboxylic acid ester form, the esterifying alcohol has from 1 to 22 carbon atoms. Depending on the pH of the formulation into which the derivatized polyester having a polyamino acid chain is
introduced, and depending on the exact amino acids which form the polyamino acid chain, the polyamino acid chain may have one or more positively or negatively charged groups.
Exemplary amino acid chains are obtained by the
hydrolysis of proteins, where exemplary proteins include, for example, keratin, collagen, silk, wheat, oat bran, zein, pea, milk, lentil, tobacco, egg yolk, soy, elastin, gelatin, and fibronectin.
Turning now to the preparation of the derivatized polyester of the invention, it is convenient to first prepare the polyester chain. Preferably, a linear aliphatic dicarboxylic acid molecule , HOOC-R2-COOH, which may be simply called the diacid, is reacted with an excess of a dihydric compound, HO-R3- OH, which may be simply called the diol, under thermal conditions to form a polyester polyol. More specifically, the diacid is added to the diol and the mixture heated to between about 140°C and 240°C to form the polyester chain by condensation
polymerization, i.e., with the generation of water. A strong acid, such as toluenesulfonic acid or methanesulfonic acid, or an organometallic compound, such as an organotin compound, may be added to catalyze the reaction. The water formed by the
condensation reaction is continuously separated from the forming polyester according to distillation techniques well known in the art.
When it appears that the rate of water evolution is slowing, it is preferred that the pressure inside the reactor be reduced. In this way, the reaction is driven toward the
formation of polyester. The number average molecular weight of the polyester chain, after its synthesis and before being
subjected to reactions which result in the formation of
derivatized polyesters, preferably ranges from about 2,000 to about 10,000.
A convenient means to quantitatively monitor the progress, or extent, of the reaction, is to periodically pull aliquots of the reaction mixture and measure the acid number, or acid value, of the aliquots. It is preferred for the preparation of many of the derivatized polyesters of the invention that the polyester chain having a low acid number, preferably less than 2.
Acid numbers, also known as acid values, may be determined as follows. 2-10 g of a sample is weighed and placed into a 200 to 300 mL Erlenmeyer flask, and an ethanol/benzene (1/1) mixture is added to dissolve the resin. If the resin is not readily dissolved, a small amount of acetone may be added. The resultant solution is titrated with a preliminarily
standardized KOH/alcohol solution with phenolphthalein as the indicator. The acid value is calculated from the consumption of the KOH/alcohol solution based on the following equation, wherein "N" stands for the normality of the KOH/alcohol solution:
Acid value = [vol (mL) of KOH/alcohol] x [N] x [56.1] /sample weight,
The above-mentioned KOH solution is prepared as follows. First, 1.5 g of KOH is dissolved in about 3 mL of water, and 200 mL of alcohol are added thereto, followed by stirring. After standing, a uniform clear solution is formed.
The concentration of the KOH solution is determined by titration with a standardized 1/10 N HCl solution.
Diacid molecules which may be employed to prepare the polyester chain of the invention include succinic acid, methylmalonic acid, fumaric acid, maleic acid, acetylene dicarboxylic acid, glutaric acid, ethylmalonic acid,
dimethylmalonic acid, methylsuccinic acid, citraconic acid, glutaconic acid, itaconic acid, mesaconic acid, 2,2- dimethylsuccinic acid, 2-methylglutaric acid, trans-beta- hydromuconic acid, trans-trans-muconic acid, pimelic acid, butylmalonic acid, diethylmalonic acid, 2, 2-dimethylglutaric acid, 2 -ethyl-2-methylsuccinic acid, 3-methyladipic acid, cyclopentanedicarboxylic acid, suberic acid,
cyclohexanedicarboxylic acid, azelaic acid, 5-norbornene-2, 3- dicarboxylic acid, sebacic acid, camphoric acid, 1,1- cyclohexanediacetic acid, cyclohexylsuccinic acid, benzylmalonic acid, undecanedioic acid, 1,10-decanedicarboxylic acid, and trans-traumatic acid.
Diol molecules which may be used to prepare the polyester chain of the invention include compounds with the molecular formulas C2H6O2, e.g., 1, 2-ethanediol (HO-CH2-CH2-OH); C3H8O2, e.g., 1,2-propanediol and 1,3-propanediol; C4H10O2, e.g., 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2 -methyl-1,3-propanediol; C4H8O2, e.g., 2-butene-1,4-diol, 2- methylene-1,3-propanediol; C4H6O2, e.g., 2-butyne-1,4-diol;
C5H12O2, e.g., 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol; C5H10O2, e.g., 1,2-cyclopentanediol (cis and trans), 1, 3-cyclopentanediol (cis and trans); C6H14O2, e.g., 3,3- dimethyl-1, 2 -butanediol, 2 -ethyl-2-methyl-1,3-propanediol, 1,2- hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2- methyl-2,4-pentanediol, 2, 3-dimethyl-2, 3-butanediol; C6H12O2, e.g., 1,2-cyclohexanediol (cis and trans), 1, 3-cyclohexane diol (cis and trans), 1, 4-cyclohexane diol (cis and trans), 5-hexene- 1,2-diol; C6H10O2, e.g., trans-2-cyclohexene-1,4-diol, 1,5- hexadiene-3 ,4-diol, 3-hexyne-2, 5-diol; C6H8O2, e.g., cis-3,5- cyclohexadiene-1, 2-diol; C7H16)2, e.g., 2, 2-diethyl-1,3- propanediol, 2,4-dimethyl-2, 4-pentanediol, 1,7-heptanediol, 2- methyl-2-propyl-1, 3 -propanediol; C8H16O2, e.g., cis-1,2- cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2- cyclooctanediol (cis and trans), 1-4-cyclooctanediol, cis-1,5- cyclooctanediol, 7-octene-1,2-diol; C8H18O2, e.g., 2,5-dimethyl- 2,5-hexamediol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 1,8- octanediol, 2,2-2-trimethyl-1, 3-pentanediol; C8H14O2, e.g., 3- cyclohexene-1,-1-dimethanol, 2,5-dimethyl-3-hexyne-2, 5-diol;
C9H20O2, e.g., 2 -butyl-2-ethyl-1, 3-propanediol, 1,2-nonanediol; C9H14O2, e.g., 5-norbornene-2, 2-dimethanol; C10H22O2, e.g., 1,2- decanediol, 1,10-decanediol; C10H18O2, e.g., 1,5-decalindiol, trans, trans-2, 6-methyl-2, 6-octadiene-1, 8-diol, 3,6-dimethyl-4- octyne-3, 6-diol, trans-p-menth-6-ene-2, 8-diol, 1,2,3,5- pinanediol; C10H16O2, e.g., (2-endo-3-exo-)-bicyclo [2.2.2] oct-5- ene-2, 3-dimethanol. Additionally preferred diol compounds contain at least one ether group in the chain of atoms which link the two hydroxyl groups of the diol. Exemplary ether containing diols include ethylene glycols of the general formula HO- (CH2- CH2-O-)bCH2-CH2-OH, where b is between 1 and 5. A preferred diol with an ether group is diethylene glycol.
In the preparation of the polyester chain, one may use a single isomeric diol, or one may use a mixture of diols. For example, one may use diethylene glycol in admixture with ethylene glycol. In addition, if a partially crosslinked polyester chain is desired, then one may add some polyol, i.e., a polyhydric molecule, i.e.,. a molecule with at least three hydroxyl groups, to the reaction mixture which will additionally comprise diol and diacid. Exemplary polyols include glycerol, 1,2,4-butanetriol, 1,1,1-tris (hydroxymethyl) ethane, 2 -ethyl-2- (hydroxymethyl)-1,3- propanediol, 1,2,3-trihydroxyhexane, 1,2,6-trihydroxyhexane, 1, 2, 3 -heptanetriol, erythritol, threitol, pentaerythritol, adonitol, arabitol, xylitol, dulcitol, iditol, mannitoi, sorbitol and dipentaerythritol. Preferably, the polyol contributes less than 20% of the hydroxyl functionality present in the reaction mixture used to prepare the polyester chain. When polyol contributes more than about 20% of the hydroxyl functionality, then an unacceptable portion of the product is an insoluble gel, ill-suited for use in skin-care and hair-care formulations.
In addition to their utility in providing crosslinks to the polyester chain, polyols may also be employed in the
preparation of polyesters having functional groups bonded to internal R2 or R3 groups. However, in such instances, it is typically necessary to protect those additional hydroxyl groups, that is, those hydroxyl groups other than the two hydroxyl groups necessary for the formation of the polyester chain. By reference to a protected hydroxyl group, it is meant a hydroxyl group which has been chemically modified so that it will not enter into condensation polymerization reactions. Protecting groups for hydroxyl functionality are well known in the art, and are
described, for example, in Greene et al. Protective Groups in
Organic Synthesis; John Wiley & Sons; New York, 1991. After the preparation of a polyester chain incorporating a polyol with protected hydroxyl functionality, it will be necessary to
"deprotect" the hydroxyl group so that the hydroxyl group is susceptible to functionalization so as to allow the formation of a derivatized polyester having functionality along the chain rather than, or in addition to, functionality at the termini of the chain. Methods for deprotecting hydroxyl groups are well- known in the art.
It should be understood that the foregoing discussion in regard to the utility of polyhydric compounds in the preparation of derivatized polyesters of the invention will equally apply to the use of polycarboxylic acid compounds. Thus, polycarboxylic acid compounds, i.e., molecules having more than two carboxylic acid groups, may be employed to introduce either crosslinking or internal functionality to the polyester chain. It is generally preferred to use polyhydric rather than
polycarboxylic acid compounds merely because a greater array of polyhydric compounds are readily available at a reasonable cost.
In the preparation of the derivatized polyesters of the invention, it is convenient to react a low acid number polyester chain, hereinafter the polyester polyol, prepared as described above, with a diamine (III) to provide an intermediate polyester amidoalkylamine. A polyester amidoalkylamine is very readily converted to the derivatized polyesters of the invention. To prepare the intermediate polyester amidoalkylamine, the polyester polyol, preferably having an acid number or value of less than 2, is reacted with a molecule (III) having two amine groups linked with a chain, designated R8, where R8 has 1 to 3 carbon atoms, hereinafter "the diamine". One of the two amine groups of the diamine is a tertiary amine group, where the tertiary amine is, in addition to being covalently bonded to the R8 group, is bonded to two groups R9. Each R9 group is independently selected from the group consisting of C1-C3 radicals having 0-3 hydroxyl
groups. Exemplary, non-limiting R9 radicals include methyl, ethyl, propyl, hydroxymethyl, 2 -hydroxyethyl and 3-hydroxypropyl . The other of the two amine groups of the diamine is either a primary or secondary amine group, represented by the formula H- N(R5)-R8, wherein R5 can be hydrogen or a C1 to C10 radical. The diamine of formula (III) can be represented as shown below:
Figure imgf000022_0001
The preparation of the derivatized polyesters of the invention preferably proceeds through a polyester amidoalkylamine intermediate of formula (IV), prepared by the condensation reaction of (I) and (III):
Figure imgf000022_0002
The reaction to prepare the intermediate (IV) is preferably carried out by adding the diamine to the polyester polyol in a ratio such that the desired average degree of
polymerization of the product polyester amidoalkylamine is obtained. For example, when 3 moles of diamine are added to one mole of polyester polyol which has a number average molecular weight of 5,000, a mixture of one mole polyester polyol and three moles of polyester amidoalkylamine is obtained, where the
molecular weight of the polyester amidoalkylamine is (number average molecular weight of the polyester polyol + molecular weight of the diamine) / (moles of polyester polyol + moles of diamine), or in the instant case, (5,000+ MW of diamine) / (1+3).
It is typically observed that reaction of the diamine (III) with the polyester chain results in cleaving of the
polyester chain. Thus, the value for p in the polyester
amidoalkylamine intermediate of formula (IV) is typically less than the value of p for the starting polyester. The intermediate (IV) typically has a number average molecular weight of between about 500 and 5,000.
The diamine may be added to the polyester polyol with stirring under an inert atmosphere, for example, under a nitrogen or argon atmosphere, and the mixture may be heated to between about 100°C and 160°C. This reaction temperature is maintained until it has been determined that the diamine has been
incorporated to its maximum possible extent. The determination is made by titration of an aliquot of the reaction mixture.
After the reaction is deemed complete, any residual amine and other volatile compounds contributing to the product odor are removed by steam distillation under low pressure conditions.
The polyester amidoalkylamine intermediate (IV) is readily converted to derivatized polyesters of the invention. For example, the intermediate (IV) can be combined with water and heated to a temperature between about 60°C and 90°C to provide a dispersion. Then, approximately one mole of proton acid, HR14, is slowly added to the dispersion for each mole of intermediate (IV), until a clear solution or a turbid dispersion is obtained. By this procedure, a derivatized polyester having the formula (II) wherein R1 is N(R5) (R6), R6 is -R8-N(R9) 2 (R10), R10 is -H R14, and R1 is R4 or OR7 is produced.
The intermediate (IV) is also a convenient precursor to cationic polyester derivatives having terminal trialkylammonium groups. Thus, the intermediate (IV) may be dissolved or
dispersed in a solvent, preferably water and/or propylene glycol. Alkyl halide of formula R9-R14 is then added to the mixture with stirring and heating to a temperature of about 70°C to about 120°C. Heating and stirring is maintained until the level of unreacted intermediate (IV) is below a desired level. Then the resulting quaternary ammonium compound is isolated by filtration. The resulting quaternary ammonium compound has the formula (II) wherein R1 is -N(R5) (R6), R6 is -R8-N (R9) 2 (R10), R10 is -R9 R14, and R4 is R1 or -OR7.
The intermediate (IV) is also a convenient precursor for the preparation of zwitterionic polyester derivatives. Thus, the intermediate (IV) may be dissolved or dispersed in a solvent, preferably water and/or propylene glycol. Sodium
monochloroacetate is then added to the solution or dispersion, and the mixture heated with stirring at a temperature of about 70°C to about 120°C. Heating and stirring is maintained until the level of unreacted intermediate (IV) is below a desired level. Then the resulting betaine is isolated by filtration. The resulting betaine has the formula (II) wherein R1 is
N(R5) (R6), R6 is -R8-N(R9)2(R10), R10 is -CH2-COO-, and R4 is R1 or -OR7.
The intermediate (IV) can be reacted with
epichlorohydrin to provide a secondary intermediate (V) which is also quite useful in the preparation of derivatized polyesters of the invention. Thus, the intermediate (IV), wherein R14 is preferably a halide, is dissolved in water and/or propylene glycol and heated to between about 40°C and about 90°C.
Epichlorohydrin in then added, and the mixture allowed to react for about 3 to 6 hours, at which time titration of an aliquot typically indicates that the reaction is complete. The secondary intermediate (V) has the formula shown below:
Figure imgf000025_0001
The preparation of a derivatized polyester of the invention having polyamino acid endgroups may be accomplished by use of the secondary intermediate (V). As used herein, polyamino acid refers to a chain of amino acids, having one terminal -NH2 group and one terminal -COOH group, as occurs naturally in, for example, protein. Thus, a protein hydrolysate derived from animal or vegetable sources is slowly added, with stirring, to an aqueous solution of the secondary intermediate (V) maintained at a temperature of about 40°C to about 90°C. The amine terminus of the protein hydrolysate reacts with terminal -CH2-Cl group of the intermediate (V) so as to displace the chloride group with the amine group, and thus join the polyamine acid chain of the protein hydrolysate to the polyester chain. The product of this reaction has the formula (II) wherein R1 is N(R5) (R6), R6 is -R8-N(R9)2(R10), and R10 is -CH2-CH (OH) -CH2-polyamino acid-COO-. To obtain this product wherein R10 is -CH2-CH (OH) -CH2-polyamino acid- COOR15 R4, the protein hydrolysate is preferably reacted with R15- OH prior to its reaction with the secondary intermediate (V).
The secondary intermediate (V) is also a convenient precursor to derivatized polyesters having polysiloxane
endgroups. Thus, an aqueous solution or dispersion of the intermediate (V) is heated to between about 40°C and 90°C, and slowly treated with an amine functionalized silicone-containing molecule. A representative amine functionalized silicone is amodimethacone. Additional representative amine functional silicones have the formula H2N- (Si (CH3) 2-O) g-H wherein g is an integer from about 2 to about 50. The polysiloxane derivatized polyesters so made have the formula (II) wherein R1 is N(R5) (R6), R6 is -R8-N(R9)2(R10), and R10 is CH2-CH (OH) -CH2-NH-polysiloxane R14.
In the preparation of anionic derivatized polyesters of the invention, a two step synthesis is preferably employed. The first step consists of the reaction of a diol with an excess of diacid, with heating and stirring, to form a polyester diacid, i.e., a polyester chain having carboxylic acid endgroups.
Preferably the diacid is added to the diol and the two component are reacted together at a temperature of about 140°C to about 240°C. The water of reaction is continuously removed by
distillation. When the maximum temperature is reached, a strong acid such as toluenesulfonic acid or methanesulfonic acid, or an organometallic catalyst such as a tin catalyst, may be added to further drive the reaction. The pressure is then reduced in the reaction vessel, and the reaction mixture maintained at about 240°C until titration of an aliquot of the reaction mixture indicates that the acid number has reached the theoretically desired acid value. The number average molecular weight of the polyester diacid so obtained is approximately about 2,000 to about 10,000.
In the second step towards preparation of the anionic derivatized polyesters, the polyester acid is neutralized with two equivalents of base. Exemplary, non-limiting bases for the neutralization include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, monoalkylamine such as ethanolamine, dialkylamine such as diethanolamine, and trialkylamine such as triethanolamine.
More specifically, and according to a preferred method, the polyester diacid is combined with water at a temperature of about 60°C to about 90°C to provide a solution or, more
typically, a dispersion. Two moles of base are added per mole of polyester diacid until a clear solution or turbid dispersion is obtained. The product of this reaction has the formula (II) wherein R1 is -OR7, R7 is R12, and R12 is selected from the group consisting of sodium, lithium, calcium, magnesium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium and
tetraalkylammonium wherein an alkyl portion of an ammonium group has 1-20 carbon atoms and 0-3 hydroxyl groups.
In the preparation of nonionic polyester derivatives of the invention, two alternative schemes may be followed. In the first, diacid and diol are reacted as previously described for the preparation of polyester diol, however the reaction is conducted in the presence of at least one monocarboxylic acid having the formula R13-COOH. R13 is a C1 to C22, saturated or unsaturated, straight chain or branched hydrocarbon group.
Exemplary, non-limiting examples of R13 include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl and decyl through behenyl. Additional, non-limiting examples of R13-COOH include the fatty acids obtained from the splitting of coconut, palm, soy and other natural oils. Where the R13-COOH is derived from natural oils, the R13 radical may be substituted with one or more hydroxyl groups. R13-COOH may also be a silicone carboxylic acid, having a polysiloxane chain terminated with one or more carboxylic acid groups. More specifically, and according to a preferred embodiment, at least one diacid and at least one monoacid are added to at least one diol, and the mixture heated to about 140°C to about 240°C. The water of reaction, produced by the resulting condensation reaction, is continuously removed by distillation. When the maximum temperature is reached, a strong acid such as toluenesulfonic acid or methanesulfonic acid, or an organometallic catalyst such as a tin catalyst, may be added. The pressure is then reduced until a derivatized
polyester having an acid value of less than 2 is obtained. The product has a number average molecular weight of about 2,000 to about 10,000.
In a second approach to the preparation of nonionic derivatized polyesters having at least one R13 endgroup, a mixture of diacid, diol and a natural triglyceride are prepared. Exemplary, non-limiting natural triglycerides include coconut oil, palm oil, soy oil and other natural oils. The reaction temperature and course of the reaction are identical to that previously described in connection with the first approach to the preparation of the nonionic derivatized polyesters of the
invention. Owing to the presence of glycerin in the
triglyceride, there is likely to be some crosslinking of the polyester chain through the glycerin groups.
The derivatization of polyester resins according to the present invention provides unique materials that are useful in skin-care and hair-care formulations. Compounds described within this disclosure may be used in hair-care and skin-care
preparations as a formulation aid for the purposes of, for example: foam volume, texture and endurance enhancement;
detergency; irritation mitigation; viscosity modification;
enhancement of electrolyte tolerance; wetting and dispersion of particulate material; reduction of cloud point; solubilzation; and emulsification or co-emulεification. Hair-care and skin-care systems utilizing compounds described within this disclosure as formulation aids may include, for example: surfactant systems; oil-in-water cream and liquid emulsions; water-in-oil cream and liquid emulsions; aqueous, hydro-alcoholic and alcoholic gel systems; aqueous, hydro-alcoholic and alcoholic suspension systems; solid suspension or emulsion systems; and aerosol systems.
Compounds described within this disclosure may be used in hair-care preparations for the purposes of, for example:
enhancing the manageability of hair; improving the appearance of hair; improving the tactile quality of hair by making hair feel softer and smoother; imparting body or apparent thickness to thin hair; minimizing tangling of hair by improving hairs' wet and dry combability; improving or facilitating the ability to form hair into specific styles and retaining those styles during normal activities; neutralizing the static electricity generated by combing hair; reducing "flyaway" or the tendency for individual hairs to repel each other and resist styling; adding shine and gloss co dull hair; aiding in normalizing the moisture content of dry or damaged hair; and helping repair or hold together split hair ends. Hair care formulations utilizing compounds described within this disclosure may include, for example: cleansing, rinsing, conditioning, styling, bleaching, coloring and setting compositions such as gels, liquids, mousses, sprays, lotions, glazes, creams, hydro-alcoholic systems and shampoos.
Compounds described within this disclosure may be used in skin-care preparations for the purposes of, for example:
providing a moist and soft tactile feeling on the surface of skin; aiding in normalizing the moisturization of the stratum corneum of skin; enhancing the smooth visual appearance and minimizing the obviousness of skin wrinkles; enhancing the ability of the skin stratum corneum to retain moisture; forming a porous non-greasy barrier film to the surface of the skin and modifying the application characteristics of preparations intended to be applied to the skin surface. Skin-care
formulations utilizing compounds described within this disclosure may include, for example: facial, hand and body moisturizing creams, liquids, pastes, and lotions; facial and body sunscreen creams, lotions, solids, pastes and liquids; facial treatment creams, lotions, pastes and liquids; underarm antiperspirant and deodorant sprays, liquids, creams and solids; facial, body and hand cleansing creams, gels, lotions, liquids and mousses;
foaming bath gels, liquids, salts, oils and powders; aqueous, alcoholic and hydro-alcoholic toners, astringents pre-shaves, after-shaves and after-bath products; eyelash and mascara; lip color sticks and glosses; and liquid and cream foundation make-up preparations.
In preferred embodiments of the invention, foam volume texture and endurance enhancement are achieved upon incorporation of amine oxide and betaine functionalized polyester resins into skin-care and hair-care formulations. Detergency in skin, hair, hand and body cleansing systems is provided by the incorporation therein of anionic, zwitterionic and polyamino acid containing derivatized polyesters.
In further preferred embodiments of the invention, mitigation of the irritation potential of primary surfactants can be achieved by incorporation of nonionic and zwitterionic derivatized polyesters. The viscosity of skin- and hair-care formulations can be adjusted through the addition of
zwitterionic, nonionic and polyamino acid derivatized polyester compounds. An enhancement in the electrolyte tolerance of primary surfactants is observed upon incorporation of anionic or zwitterionic polyesters into hair- and skin-care formulations having primary surfactants. Improved wetting and dispersion of particulate matter is provided to skin- and hair-care
formulations having incorporated therein zwitterionic, nonionic or anionic functionalized polyester compounds of the invention.
According to further preferred embodiments of the invention, a modification in the cloud point or critical micelle concentration of a nonionic surfactant, and/or a modification in the critical micelle concentration of an ionic surfactant, including an anionic surfactant, in a hair-care or skin-care formulation is provided by the addition thereto of a zwitterionic or nonionic derivatized polyester. Improved solubilization of lipophilic materials is imparted to hair-care and skin-care formulations by incorporating therein either nonionic or a betaine derivatized polyester of the invention. Nonionic, anionic, and cationic derivatized polyesters provide
emulsification and co-emulsification properties to skin-care and hair-care formulations.
According to the invention, improved hair shine and tactile feel enhancement is provided to hair-care formulations by the addition of a derivatized polyester having nonionic,
cationic, betaine, polysiloxane or polyamino acid functional groups. An improvement in hair manageability is observed upon incorporation of cationic, anionic, nonionic, polysiloxane or polyamino acid functionalized polyester into a hair-care
formulation. Incorporation of cationic, and particularly
quaternary ammonium groups, nonionic, polysiloxane and polyamino acid derivatized polyesters into hair-care formulations provides products that, when applied to hair, impart enhancement of hair body, greater perceived thickness, improvement of wet and dry combability, enhancement of hair styling ability and style retention. Another aspect of the invention is the neutralization of static charge on hair with less hair flyaway due to combing, which is observed upon application of hair-care formulations incorporating cationic, and particularly quaternary ammonium containing, derivatized polyesters. Dry and damaged hair moisture normalization is observed upon application to hair of a hair-care product incorporating polyesters with cationic, nonionic and polyamino acid functional groups. Repair of hair split ends may be achieved by applying to hair having spit ends a hair-care product incorporating polyester molecules of the invention having cationic, and particularly quaternary ammonium groups, nonionic, polyamino acid or polysiloxane functional groups.
Also according to the invention, skin-care sensory enhancement through contribution of a moist, soft tactile feel and visual smoothness is provided to skin having applied thereto a skin-care formulation that incorporated derivatized polyester compounds having cationic, nonionic, anionic, polysiloxane or polyamino acid functional groups. Normalization of the moisture content of the stratum corneum of skin, and enhancement in the ability of the stratum corneum to retain moisture is observed when a skin-care product having cationic, nonionic or polyamino acid derivatized polyester compounds incorporated therein is applied to the skin.
Also according to the invention, desirable
modifications in the application characteristics of topical skin- care and cosmetic preparations is achieved when cationic, nonionic or anionic derivatized polyester compounds are
incorporated into said topical skin-care and cosmetic
preparations. The addition of nonionic derivatized polyester compounds to topical skin-care preparations confers water resistance barrier properties to the topical skin-care
preparations.
As used herein, the term "a sufficient amount" refers to an amount of the referred to compound which can provide the indicated performance property to the skin-care or hair-care formulation. This amount will vary, depending on the derivatized polyester employed and the hair- or skin-care properties desired. The amounts of the derivatized polyester generally present in the skin-care and hair-care formulations of the invention are indicated in the following Table A.
Figure imgf000033_0001
The invention provides a method for improving the endurance and volume of foam, and modifying the texture of foam, by the addition of a sufficient amount of polyester betaine and/or polyester amine oxide (see Examples 6 and 13 for the preparation of betaine and amine oxide functionalized polyesters, respectively) as a modifier of the foaming characteristics of primary anionic surfactant systems when aerated during use in systems designed to function, for example, as human hair
shampoos, body cleansers, bubble baths, hand cleansers and facial skin cleansers.
The invention provides a method of providing detergent cleansing function to systems designed to function as human hair shampoos, body cleansers, bubble baths, hand cleansers and facial skin cleansers through the addition of a sufficient amount of polyester betaine, polyester dicarboxylate, polyester protein derivative and/or polyester amine oxide (where representative examples thereof may be prepared according to Examples 6, 9, 11 and 13, respectively) so that particulate debris, skin oils, body sweat and make-up residue can be wetted, emulsified and rinsed from relevant body surfaces.
The invention provides a method to mitigate and minimize the irritating effects of primary anionic surfactant systems upon human skin and eyes through addition of a sufficient amount of polyester betaine polyester dicarboxylate, polyester protein derivative and/or polyester amine oxide (where
representative examples thereof may be prepared according to Examples 6, 9, 11 and 13, respectively) to systems designed to function as human hair shampoos, body cleansers, bubble baths, hand cleansers and facial skin cleansers.
The invention provides a method to modify the viscosity and rheology of aqueous systems, aqueous phases of emulsion systems and/or surfactant systems through the addition of a sufficient amount of polyester betaine, polyester/botanical condensate, polyester dicarboxylate, polyester amine oxide and/or a nonionic polyester alkylate (where representative examples thereof may be prepared according to Examples 6, 7, 8, 13 and 14, respectively) to systems designed to function, for example:
shampoos, body cleansers, bubble baths, hand cleansers, facial skin cleansers, facial moisturizers, body moisturizers, hand barrier and moisturizing preparations, and make-up preparations.
The invention provides a method for extending the concentration of electrolytes which can be combined with primary anionic surfactant systems before foaming, detergent, stability or viscosity characteristics of the primary anionic surfactants are adversely affected. The method comprises the addition of a sufficient amount of polyester betaine, polyester dicarboxylate and/or polyester amine oxide (where representative examples of which may be prepared according to Examples 6, 9 and 13,
respectively) to surfactant systems designed for use, for example, as human hair shampoos, body cleansers, bubble baths, hand cleansers, hair conditioners, and facial skin cleansers.
The invention provides a method for wetting and/or dispersing particulate matter in aqueous systems, aqueous and oil phases of emulsion systems and anhydrous systems through addition of a sufficient amount of polyester betaine, polyester
dicarboxylate, polyester amine oxide and/or nonionic polyester alkylate (where representative examples thereof may be prepared according to Examples 6, 9, 13 and 14) to the systems in which particulate matter is to be added or to a portion of the system to which particulate matter is added to facilitate incorporation into the final system. This method would apply, for example, to systems designed for use as human hair shampoos, body shampoos, facial and body masks, facial and body moisturizers, make-up preparations, bath and body oils, antiperspirant and deodorant systems, sunscreen preparations and bubble baths.
The invention provides a method for reducing the concentration at which primary anionic surfactants may change from a spherical or micellar gel structure to lamellar gel structure or otherwise become visually hazy (or reach their critical micelle concentration) by addition of a sufficient amount of polyester betaine, polyester dicarboxylate and/or polyester amine oxide (where representative examples thereof may be prepared according to Examples 6, 8 and 13, respectively) to systems designed for use as human hair shampoos, body cleansers, bubble baths, hand cleansers and facial skin cleansers.
The invention provides a method for solubilizing lipophilic materials into aqueous systems, surfactant systems, or aqueous phases of emulsion systems so that the lipophilic
material exists as a micro emulsion which is clear and/or
homogeneously dispersed in the system being utilized, through the addition of a sufficient amount of polyester betaine, polyester dicarboxylate and/or nonionic polyester alkylate (where
representative examples thereof may be prepared according to
Examples 6, 9 and 14). This method would apply, for example, to systems designed to function as human hair shampoos, body
cleansers, bubble baths, hand cleansers, facial skin cleansers, facial and body moisturizers, make-up preparations,
antiperspirant and deodorant systems and sunscreen preparations.
The invention provides a method of emulsifying or aiding in the emulsification of lipophilic materials into water or hydrophilic materials, or emulsifying or aiding in the
emulsification of water or hydrophilic materials into lipophilic materials so that a suspension of acceptable stability is
obtained. The method involves addition of a sufficient amount of polyesteramine, polyesteramine salt, polyester ammonium salt, polyester betaine, polyester dicarboxylate and/or nonionic polyester alkylate (where representative examples thereof may be prepared according to Examples 2, 3, 4, 5, 6, 7, 8 and 14, respectively) to a system designed to perform, for example, as human hair conditioner or rinse, body or facial moisturizer, hand protectant or moisturizer, suncare or skin protectant
preparation, make-up preparation as an antiperspirant or
deodorant preparation. The invention provides a method of enhancing or adding visual shine to hair and/or enhancing the tactile feel of hair to the extent that it is perceived as healthy, moist and attractive through the addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester betaine, polyester/botanical condensate, polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where
representative examples thereof may be prepared according to Examples, 2, 3, 4, 5, 6, 7, 8 and 14) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
The invention provides a method of improving hair manageability through the deposition and/or attachment on hair and/or through addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester/botanical condensate,
polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4, 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
The invention provides a method of enhancing the tactile sense that hair has body and/or perceived thickness through the deposition and/or attachment on hair of, or addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester/botanical condensate, polyester/protein
condensate, polyester/silicone condensate and/or nonionic
polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
The invention provides a method of improving the wet and dry combability of hair through the deposition and/or attachment on hair, or addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester/botanical condensate, polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where
representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
The invention provides a method of incorporating the capability of forming hair into specific configurations or styles and/or retaining the configuration or style when formed by providing a means for individual hairs to adhere to one another at locations of contact through addition of a sufficient amount of a polyesteramine, polyester ammonium salt, polyester/botanical condensate, polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where
representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
The invention provides a method to neutralize the static electrical charge on hair and "fly-away" or repulsion of individual hairs as a result of static electrical charge build-up on hair through the deposition and/or attachment on hair, or addition of a sufficient amount of polyesteramine and/or polyester ammonium salt (where representative examples thereof may be prepared according to Examples 2 or 4, and 5,
respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair gels or hair creams.
The invention provides a method to normalize the moisture content or moisture absorbed onto hair keratin through the deposition and/or attachment on hair of, or addition of a sufficient amount of polyesteramine, polyester/botanical
condensate, polyester/protein condensate and/or nonionic
polyester alkylate (where representative examples thereof may be prepared according to Examples: 2 or 4, 7, 11 and 14,
respectively) to systems designed to function as human hair shampoos, hair conditioners, hair rinses, hair gels, hair creams, hair hot oil treatments or hair ambient temperature oil
treatments.
The invention provides a method of repairing hair split ends or temporarily facilitating the adhesion of hair tips that have separated into visibly differentiated segments within the area roughly approximating the tip of a hair through the
deposition and/or attachment on those split hair segments, or addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester/botanical condensate, polyester/protein condensate, polyester/silicone condensate and/or nonionic
polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair gels, hair creams, hair hot oil treatments, hair ambient temperature oil treatments or hair sprays. The invention provides a method of contributing a moist soft tactile feeling on skin and/or visual skin smoothness through the deposition and/or attachment on the surface of skin, or addition of a sufficient amount of polyesteramine,
polyesteramine salt, polyester/botanical condensate, polyester dicarboxylate, polyester/protein condensate, polyester/siloxane condensate and/or nonionic polyester alkylate (where
representative examples thereof may be prepared according to Examples 2 or 4, 3, 7, 9, 11, 12 and 14, respectively) to systems designed to function, for example, as human facial moisturizers, body moisturizers, make-up preparations, dusting powders, after- bath veils, facial masks, body masks, facial scrubs, body scrubs, facial cleansers, body cleansers, hand protectants and
moisturizers, suncare preparations, antiperspirant preparations or deodorant preparations.
The invention provides a method of normalizing the moisture content of the stratum corneum of human skin through deposition and/or attachment on the surface of skin, or addition of a sufficient amount of polyesteramine, polyesteramine salt, polyester/botanical condensate, polyester dicarboxylate,
polyester/protein condensate, polyester/siloxane condensate and/or nonionic polyester alkylate (where representative example thereof may be prepared according to Examples 2 or 4, 3, 7, 9, 11, 12 and 14, respectively) to systems designed to function, for example, as human facial moisturizers, body moisturizers, make-up preparations dusting powders, after-bath veils, facial masks, body masks, facial scrubs, body scrubs, facial cleansers, body cleansers, hand protectants and moisturizers, suncare
preparations, antiperspirant preparations or deodorant
preparations. The invention provides a method of modification of the application characteristics or the apparent relative friction on the surface of skin during application and rub-in and/or the relative tactile impression of wetness, dryness and/or sliminess during rub-in of products designed to function as human facial moisturizers, body moisturizers, make-up preparations, dusting powders, after-bath veils, facial masks, body masks, facial scrubs, body scrubs, facial cleansers, body cleansers, hand protectants and moisturizers, suncare preparations,
antiperspirant preparations or deodorant preparations through deposition and/or attachment on the surface of skin, or addition of a sufficient amount of polyesteramine, polyesteramine salt, polyester/botanical condensate, polyester diacid, polyester dicarboxylate and/or polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4, 3, 7, 8, 9 and 14, respectively).
The invention provides a method to confer resistance to rinse off or wash off by water or human perspiration of
formulation ingredients or entire formulations through deposition and/or attachment on the surface of skin or inclusion in a formulation or part, or parts of a formulation of a sufficient amount of polyester/botanical condensate and/or nonionic
polyester alkylate (where representative examples thereof may be prepared according to Examples 7 and 14, respectively) to systems designed to function, for example, as human sunscreen
preparations, facial moisturizers, body moisturizers, make-up preparations, skin protectant preparations or hand-barrier products.
The polyester/silcone condensates are particularly desirable components in skin-care and hair-care products because the condensates do not build up on skin or hair with repeated usage of skin- and hair-care formulations incorporating the polyester/silicone condensates.
The following examples are provided to better disclose and teach the preparation of the derivatized polyester compounds of the present invention, and their use in hair care and skin care personal products. These examples are for illustrative purposes only, and it must be acknowledged that minor variations and changes can be made without materially affecting the spirit and scope of the invention as recited in the claims that follow.
EXAMPLE 1
Into a heated, agitated three-neck flask (12 liter) with vapor column, distillate take-off through a total condenser, and vacuum capability, were placed 5200 g (35.6 moles) of adipic acid and 2810 g (37.0 moles) of propylene glycol. The mixture was heated to 220°C with removal of water. The pressure was then reduced and the mixture was held at that temperature for 20 hours until 1282 g (71.2 moles) of water was distilled off. 6728 g of poly (propylene glycol adipate)diol were obtained.
EXAMPLE 2
Into an apparatus like the one used in Example 1, 4500 g (0.9 moles) of the polyester of Example 1 and 408.5 g (4.0 moles) of dimethylaminopropylamine (DMAPA) were placed. The mixture was heated under atmospheric pressure with nitrogen purge to 120°C and held for twelve hours at these conditions. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the mixture (stripping) for four hours to remove any residual amine and trace odor compounds. After stripping, the mixture was brought to atmospheric pressure and 4900 g (4.9 moles) of poly (propylene glycol adipate) amidopropyldimethylamine with a number average molecular weight of 1000 were obtained.
EXAMPLE 3
Into an apparatus like the one used in Example 1, 4900 g (4.9 moles) of the polyester of Example 2 and 4575 g of pure water were placed. The mixture was heated to 60°C and 470 g of 31% by weight of aqueous hydrochloric acid (4 moles) was slowly added over a one-hour period. Additional hydrochloric acid was then added as necessary to bring the pH of the solution to 6.0 at 25°C. About 5000 g of poly (propylene glycol
adipate) amidopropyldimethylamine hydrochloride were obtained.
EXAMPLE 4
Into an apparatus like the one used in Example 1, 4500 g (0.9 moles) of poly (diethylene glycol adipate) diol with a molecular weight of 5000 (obtained in a manner similar to the procedure set forth in Example 1) and 1038 g (10.2 moles) of dimethylaminopropylamine (DMAPA) were placed. The mixture was heated under atmospheric pressure with nitrogen purge to 120°C, and held for twelve hours at these conditions. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the mixture for four hours to remove any residual amine and odor bodies. After sparging, the mixture was brought to atmospheric pressure and 5500 g (11.0 moles) of
poly (diethylene glycol adipate) amidopropyldimethylamine with a number average molecular weight of 500 was obtained.
EXAMPLE 5
Into an apparatus like the one used in Example 1, 2500 g (5.0 moles) of the polyeεteramide product of Example 4, 4575 g (60 moles) of propylene glycol and 580 g (5.25 moles) of
monochlorohydrin (MCH, also known as 2, 3-dihydroxy-1- chloropropane) were placed. The mixture was heated to 90°C and held at that temperature for six hours. The product was then vacuum-filtered through a bed of diatomaceous earth to provide about 10,500 g of poly (diethylene glycol
adipate) amidopropyl (dihydroxypropyl) dimethylammonium chloride.
EXAMPLE 6
Into an apparatus like the one used in Example 1, 2500 g (5.0 moles) of the polyesteramide product of Example 4, 4575 g (60 moles) of propylene glycol and 612 g (5.25 moles) of sodium monochloroacetate (SMCA) were added. The mixture was heated to 90°C and held at that temperature for six hours. The product was then vacuum-filtered through a bed of diatomaceous earth. This removes some of the sodium chloride that was formed as a byproduct of the reaction. About 10,500 g of poly (diethylene glycol adipate) amidopropylbetaine were obtained.
EXAMPLE 7
Into an apparatus like the one used in Example 1, 5,000 g (1.0 mole) of the polyester of Example 1 and 439 g (0.5 moles) of olive oil (a botanical extract) were placed. The mixture was heated to 220°C and held at that temperature for sixteen hours. The mixture was then cooled to 120°C. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the mixture for four hours to remove any residual odor bodies. About 5400 g of derivatized polyester containing some glycerin crosslinks and olive fatty acid termination were
obtained.
EXAMPLE 8
Into an apparatus like the one used in Example 1, 5,000 g (1.0 mole) of the polyester of Example 1 and 292 g (2 moles) of adipic acid were placed. The mixture was heated with nitrogen purge to 220°C and held at these conditions for sixteen hours. The pressure was then reduced and the mixture was heated under vacuum for 20 hours until 36 g (2 moles) of water were distilled off. 5256 g of poly (propylene glycol adipate) diacid with a molecular weight of 5250 were obtained.
EXAMPLE 9
Into an apparatus like the one used in Example 1, 5256 g (1.0 mole) of the derivatized polyester product of Example 8 were placed. The polyester was heated to 120°C. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the polyester for four hours to remove any residual odor compounds. Then 5000 g of pure water and 110 g (2 moles) of a 30% by weight solution of ammonia were added with stirring. This resulted in the formation of 10,300 g of a 50% by weight aqueous solution of ammonium poly (propylene glycol adipate) dicarboxylate.
EXAMPLE 10
Into an apparatus like the one used in Example 1, 5000 g (10 moles) of the polyester of Example 4, 5000 g of propylene glycol (65.8 moles), and 1177 g (10 moles) of 31% by weight aqueous hydrochloric acid were placed. The mixture was heated with stirring to 60°C and held under these conditions for one hour until the neutralization of the polyester of Example 4 was complete. 925 g (10 moles) of epichlorohydrin were added and the mixture was held at 60°C for 5 hours.
EXAMPLE 11
Into an apparatus like the one used in Example 1,
12,100 g (10 moles) of the polyester of Example 10 and 5000 g (10 moles) of wheat protein hydrolysate were placed. The mixture was heated to 75°C and stirred at this temperature for three hours. During this period, sufficient sodium hydroxide was slowly added in order to neutralize the proton liberated during alkylation of the protein. The mixture was then cooled to room temperature and filtered through a bed of diatomaceous earth. 17,000 g of a polyester/protein condensate were obtained.
EXAMPLE 12
Into an apparatus like the one used in Example 1, 12,100 g (10 moles) of the polyester of Example 10 and 5000 g
(10 moles) of amodimethicone were placed. The mixture was heated to 75°C and stirred at this temperature for three hours. During this period, sufficient sodium hydroxide was slowly added in order to neutralize the proton liberated during alkylation of the polyester. The mixture was then cooled to room temperature and filtered through a bed of diatomaceous earth. 17,000 g of a polyester/silicone condensate were obtained.
EXAMPLE 13
Into an apparatus like the one used in Example 1, 4900 g (4.9 moles) of the polyester of Example 2 and 4575 g of pure water were placed. The mixture was heated to 60°C and 272 g of 50% by weight aqueous hydrogen peroxide (4 moles) was slowly added over a one-hour period. About 9,500 g of poly (propylene glycol adipate) amidopropyldimethylamine oxide were obtained.
EXAMPLE 14
Into an apparatus like the one used in Example 1, 5000 g (1.0 moles) of the polyester of Example 1 and 416 g
(2 moles) of coconut fatty acid were placed. The mixture was heated under a nitrogen purge to 220°C. The pressure was then reduced and the mixture was held for 20 hours until 36 g
(2 moles) of water were distilled off. 5256 g of poly (propylene glycol adipate) diyl cocoate with a number average molecular weight of 5250 g were obtained.
The following legends will be used throughout this application: Legends A through Y represent polymer names;
Figure imgf000047_0001
Legends AA through GG represent trade names with corresponding supplier's addresses.
Figure imgf000048_0001
EXAMPLE 15 - PHYSICAL TEST DATA
Example 15A - Solubility Testing
Polyesters which are liquids at room temperature were agitated to ensure homogeneity. Polyesters which are solid at room temperature were warmed above their melting point (ca. 50°C) and agitated until homogeneous. Into 1.5 oz. screw-top glass jars, polyester (solute) and solvent (water, ethanol or
isopropanol) were weighed in amounts required to provide 20 grams in each vial of mixtures at concentrations of 5, 25, and 50 percent by weight. The jars were capped with polyethylene lids, warmed to 30°C, and shaken vigorously for thirty to sixty
seconds. The samples were then allowed to stand until their temperature reached 25°C. The appearance was then noted and recorded in TABLES I, II and III.
Figure imgf000049_0001
Figure imgf000050_0001
Example 15B - Specific Gravity Testing
The specific gravity of the derivatized polyesters was determined by using a Gardner gallon weight cup. Polyesters which were liquid at room temperature were agitated to ensure
homogeneity. Solid polyesters were warmed above their melting point (ca. 50°C) and agitated until homogeneous. The specific gravities of room temperature liquid polyesters were determined at 20°C relative to water at 20°C. The specific gravity of room temperature solid polyesters was determined at 60°C relative to water at 60°C.
Figure imgf000050_0002
Example 15C - pH Testing
Derivatized polyesters which were liquid at room temperature were agitated to ensure homogeneity, and their pH measured using a Brinkmann 632 pH-Meter equipped with combination glass electrode. Solid polyesters were warmed above their melting point (ca. 50°C), agitated until homogeneous, and then diluted to 10% by volume in deionized water, before measuring their pH. All measurements were carried out at 25°C, with the results provided in TABLE V.
Figure imgf000051_0001
Exam ple 15D - Viscosity Measurement
The viscosity of selected derivatized polyesters was measured at various temperatures using a Brookfield RV coaxial cylinder viscometer (No. 24 spindle, RPM adjusted as necessary). The sample chamber was fitted with a small sample adapter, which was jacketed, and through which flowed heat transfer fluid from a controlled temperature bath. The viscosity measurement so obtained are recorded in TABLE VI.
Figure imgf000052_0002
Example 15E - HLB Estimates In order to estimate HLB values, visual
characterizations of dilute dispersions/solutions of the subject derivatized polyesters in deionized water were made, as follows.
Approximately a 10% w/w mixture was made of respective polyesters in deionized water. The polyester was mixed into the water using an electric rotating stirrer equipped with a
propeller-type impeller. Mixtures were heated as necessary up to 60°C or until the polyester was completely dispersed and a homogeneous mixture was achieved. Samples were then cooled to room temperature with continuous mixing. Room temperature samples were visually evaluated and the appropriate HLB value was assigned in accordance with the scheme listed below.
Figure imgf000052_0001
Figure imgf000053_0001
EXAMPLE 16 - SUBSTANTTVTTY ON WORSTED WOOL PURPOSE :
To determine the relative substantivity of various derivatized polyesters and other materials that are typically used in skin- and hair-care preparations because of their perceived substantivity to skin and hair keratin.
MATERIALS :
Worsted wool challis (6" x 2.75") (Test Fabrics, Inc.)
Sirius Red F3BA-N (0.28% solution) (indicator dye)
Beakers
Deionized water
Disposable plastic gloves
#01500 Ultra High Absorbency C fold paper towels from
Scott Paper Co.
Forceps
PROCEDURE:
Using forceps, soak worsted wool patches (6" x 2.75") in 150 mL of 38°C deionized water for 60 seconds. Allow wool patches to drip for 5 seconds following removal from water.
Spread wool patches onto a paper towel. Place 1 g of test material in water (diluted in water to the concentration set forth in the "DILUTION" column of TABLE VIII) on wool, rub the test material into the wool using gloved fingers and let the test material remain on the wool for 60 seconds. Using forceps, soak the wool patch in 150 mL deionized water at 35°C for 30 seconds while constantly agitating. Allow the wool patch to drip for 5 seconds following removal from water. Using forceps, transfer the wool patch to a beaker containing 20 mL of a fresh 0.28% w/w solution of indicator dye maintained at ambient temperature.
Agitate the patch in the indicator solution for 30 seconds.
Allow the wool patch to drip for 5 seconds following removal from indicator dye solution. Using forceps, soak wool patch in 400 mL of 38°C deionized water for 30 seconds while constantly
agitating. Allow wool patch to drip for 5 seconds following removal from water. Spread wool patch onto a paper towel and allow it to air dry. Arrange wool patches in order of least dye uptake (0) to greatest dye uptake (8). J. Soc. Cosmet . Chem. , 44, 221-234 (July-August 1993). The results are provided in TABLE VIII.
Figure imgf000055_0001
CONCLUSION:
The results indicate that a number of derivatized polyesters exhibit electrostatic substantive to wool.
Additionally, Polyesters M, B, U and V and Polyester I appear to perform on a competitive level with ingredients commonly used for their ability to adhere to skin and hair. EXAMPLE 17 - MOISTURE RETENTION PROPERTIES
PURPOSE:
To determine the moisture retention ability of various derivatized polyesters of the invention and other film forming ingredients on water-saturated leather strips when placed in a high humidity chamber (90%).
MATERIALS :
Deionized water
Humidity chamber
Phychrometer
Knife
12" long cowhide (leather) laces
PROCEDURES :
Rough up the leather with a knife. Soak leather in warm deionized water for 24 hours. Immerse the leather strips for 1 minute at ambient temperature in aqueous solutions/ dispersions of the materials listed under the "SAMPLE" column heading of TABLE IX, at the concentrations listed under the "DILUTION" column. Allow excess material to run off of strips for 30 seconds, then record weight (w-1). Place the strips in a humidity chamber for 24 hours, and record the weight of the strips (w-2). Calculate weight change after 24 hours (w-3). Calculate percent weight change after 24 hours (w-4).
Figure imgf000057_0001
Although the percent difference between closely rated samples is not significantly different, the test does serve as a rapid screen to provide a general idea of the relative
performance of these ingredients as agents of moisture retention within this test scheme.
CONCLUSION:
Polyester I appears to retain moisture on leather comparatively better than other film forming agents typically used in skin- and hair-care applications. Polyesters M and V appear to be similar in their moisture retention ability as other film forming agents commonly used in skin- and hair-care
formulations.
EXAMPLE 18 - MOISTURE ABSORPTION PROPERTIES PURPOSE :
To determine the ability of various derivatized polyesters of the invention and other film- forming ingredients to absorb moisture when applied to oven-dried leather strips and placed in a high humidity chamber (90%).
MATERIALS :
12" long cowhide (leather) laces
Humidity chamber
Phychrometer
Knife
Oven (110°C)
PROCEDURE:
Rough up the leather with a knife. Place leather in a
110°C oven for 24 hours. Immerse the leather strips for 1 minute at ambient temperature in aqueous solutions/dispersions of the materials listed under the "SAMPLE" column of TABLE X, at the concentration listed under the "DILUTION" column. Allow excess material to run off of strips for 30 seconds, then the record weight of the strip (w-1). Place the strip in a humidity chamber for 24 hours. Record strip weight after 24 hours (w-2).
Calculate weight change after 24 hours (w-3). Calculate percent weight change after 24 hours (w-4).
Figure imgf000058_0001
CONCLUSION:
When applied to leather, polyesters U and V appear to absorb moisture from the atmosphere comparatively better than other film forming agents typically used in skin- and hair-care applications.
EXAMPLE 19 - VISUAL SHINE OF TREATED HAIR TRESSES PURPOSE :
To use a panel rating. system to compare the visual shine of human hair tresses treated with derivatized polyesters of the invention and materials used commercially to enhance the visual shine of human hair.
MATERIALS :
1 gm tresses (6" long) of hair previously stripped with a 40% ammonium laureth sulfate solution at 40°C.
Disposable plastic gloves
Comb
Deionized water
Beakers
PROCEDURE:
Immerse hair tress in 35°C-40°C deionized water (600 mL) for 30 seconds. Squeegee excess water off tress with gloved fingers. Immerse tress for 30 seconds at room temperature in aqueous solutions/dispersions of the materials listed under the "SAMPLE" column of TABLE XI, at the concentration listed under the "DILUTION" column. Squeegee excess sample off tress with gloved fingers. Immerse hair tress in 35°C-40°C deionized water
(600 mL) for 30 seconds. Squeegee excess water off tress with gloved fingers. Immerse hair tress in 35°C-40°C deionized water (600 mL) for 30 seconds a second time. Squeegee excess water off tress with gloved fingers. Hang tress at ambient temperature and humidity, and pass comb through wet tress 10 times. After 2 hours of drying at ambient temperature and humidity, pass comb through tress 20 times.
Lay hair tresses out m flat tray and have five panelists arrange the tresses in order of greatest to least visual shine (#1 is the greatest shine). Allow panelists to use a lignt source and angle of view m which they can visualize differences. Calculate a composite rating for each sample by a summation of the normalized individual scores. The results are provided m TABLE XI.
Figure imgf000060_0001
CONCLUSION:
Polyesters M and I appear to improve the visual shine of hair tresses and perform better than competitive ingredients used in hair-care products for that purpose.
EXAMPLE 20 - COMBTNC PROPERTIES OF TREA TED HAIR TRESSES PURPOSE:
To determine the comparative effect of various
derivatized polyesters of the invention and competitive hair conditioning ingredients on the wet and dry combability of human hair tresses via a subjective rating system. MATERIALS :
1 gm tresses of (6" long/bleached) human hair previously stripped with a 40% ammonium laureth sulfate solution at 40°C.
Disposable plastic gloves
Comb
Deionized water
Beakers
Cream rinse vehicle of TABLE XII
Figure imgf000061_0001
Process:
1. Combine ingredients and heat to 50°C. Mix at medium speed with a propeller mixer.
2. When the mixture is homogeneous, adjust the pH to 4.9 ± 0.1 with 10% w/v NaOH or 50% w/w citric acid. 3. Empirically adjust for water loss.
PROCEDURE :
Immerse hair tress in 30°C deionized water (300 mL) for 10 seconds. Weigh 10 gm of creme rinse vehicle and rub it into the hair tress with a gloved hand. Completely immerse and rinse hair tress in 30°C deionized water (300 mL). Squeegee excess water off of tress with gloved fingers. Completely immerse and rinse hair tress in 30°C deionized water (300 mL) a second time. Squeegee excess water off of tress with gloved fingers. Hang tress in ambient temperature and humidity, and pass comb through wet tress 10 times while making a comparative evaluation of the relative resistance to combing. Rate resistance on a scale of 1 to 10 (with 1 being optimum, or least resistant to combing). After 2 hours of drying at ambient temperature and humidity, pass comb through tress 20 times making a comparative evaluation of relative resistance to combing. Rate resistance on a scale of 1 to 10 (as before). While dry combing, make a comparative
evaluation of the relative tendency for the hairs to "fly-away" from each other, or be electrostatically repelled, and rate on a scale of 1 to 10 (with 1 being optimum, or least prone to fly- away). Calculate a composite rating by summing the wet, dry and fly-away ratings.
Figure imgf000062_0001
CONCLUSION:
Polyesters B and I appear to improve the combability of hair tresses to the same extent as competitive ingredients typically utilized in hair conditioning preparations for
improvement in combability. Polyester M appears to perform better than many competitive additives as far as providing good hair tress combability. EXAMPLE 21 - 2:1 SHAMPOO WHICH CLEANSES AND CONDITIONS
PROCESS :
With reference to TABLE XIV:
1. Combine ingredients in section "1". Heat mixture to 70°C, while agitating rapidly with a propeller mixer. 2. When the section "1" mixture is clear, cool to <45°C.
3. In the order listed, add the ingredients in section "2" to the clear mixture of section "1" ingredients. Use low speed agitation to minimize foaming.
4. When the mixture of sections "1 and 2" materials is clear and homogeneous, adjust the pH of the system to 7.0 ± 0.1.
5. Add section "3" material (polyester O) to sections "1 and 2", mix until homogeneous.
6. Adjust the viscosity to the desired level with sodium
chloride.
Figure imgf000063_0001
The resulting product is a clear, high foaming conditioning shampoo which conditioned without causing build-up of conditioner on hair. Polyester O is a conditioning agent which adds body to hair and improves its manageability.
Poly (diethylene glycol adipate) amidopropyl betaine
(MW=500) (Polyester R) enhances foaming and mitigates the
irritation of sodium lauryl sulfate.
EXAMPLE 22 2:1 SHOWER GEL WITH SKIN MOISTURIZING PROPERTIES PROCESS :
With reference to TABLE XV: 1. Combine ingredients in section "1" and heat mixture to 70°C while agitating rapidly with a propeller mixer .
2 . When the section "1" mixture is clear, cool it to <45°C.
3. In the order listed, add the ingredients in section "2" to the clear, cooled mixture of section "1" ingredients. Use low speed agitation to minimize foaming.
4. When the mixture of sections "1 and 2" ingredients are clea and homogeneous, adjust the pH of the system to 7.0 ± 0.1.
5. Add section "3" to the mixture of sections "1 and 2"
ingredients, mix until homogeneous.
6. Adjust the viscosity to the desired level with sodium
chloride.
Figure imgf000064_0001
The resulting product is a cleansing gel for direct use on skin. Poly (1,4 butanediol adipate) amidopropyl dimethylamine lactate/citrate/malate (MW=1000) is a water dispersible polyester containing essential fatty moieties which acts as a super fatting agent on skin. Poly (1,4 butanediol adipate) amidopropyl
dimethylamine Lactate/Citrate/Malate (MW=1000) leaves a
perceptible moist emollient feel on skin following showering. EXAMPLE 23 - 50% VOC HAIR SPRAY WITH MODERATE HOLD AND
EXCEPTIONAL HAIR SHINE ENHANCEMENT PROCESS :
With reference to TABLE XVI:
1. Combine the ingredients in section "1" using an explosion proof mixer.
2. Add the ingredients in section "2" to section "1" in order.
Mix until homogeneous using an explosion proof mixer.
Figure imgf000065_0001
The resulting product provides moderate hold utilizing minimal volatile organic compounds (VOC). Poly (polyethylene glycol adipate) diol (MW=1000) acts as an auxiliary film former and reduces the tendency for the primary film former to flake. Polyester M adds shine to hair.
EXAMPLE 24 - CONDITIONING TREATMENT FOR DAMAGED HAIR
PROCESS :
With reference to TABLE XVII:
1. Combine the ingredients in section "1", heating to 70°C.
Agitate rapidly with a propeller mixer.
2. Add section "2" by sprinkling it into section "1" while
creating a vortex with the propeller mixer. When addition is complete, slow mixer to a speed which does not result in vortexing.
3. Combine section "3" heating to 70°C. Mix slowly. 4. When sections "1, 2" and "3" are clear and homogeneous and at 65°C-70°C, slowly pour section "3" into sections "1 and 2". Mix rapidly for 5 minutes, then begin to cool batch. 5. When sections "1, 2 and 3" are homogeneous, adjust the pH of the system to 7.0 ± 0.1 using 50% w/w citric acid.
6. Add section "4" to sections "1, 2 and 3" when the batch is 35°C-40°C. Mix until homogeneous.
Figure imgf000066_0001
The resulting product is an after-shampoo leave-on conditioner for sun and wind damaged hair. Poly (1,2 propanediol adipate) amidopropyl dimethylamino hydroxypropyl collagen
(MW=1000) provides conditioning properties and is reparative to damaged hair.
EXAMPLE 25 - GENERAL PURPOSE SHAMPOO WITH
LOW IRRITATION POTENTIAL PROCESS :
With reference to TABLE XVIII:
1. Combine the ingredients in section "1", heating to 70°C.
Agitate rapidly with a propeller mixer.
2. When section "1" is clear, cool to <45°C.
3. Add the ingredients in section "2" to section "1" in order.
Use low speed agitation to minimize foaming. 4. When sections "1 and 2" are clear and homogeneous, adjust the pH of the system to 7.0 ± 0.1.
5. Add section "3" to sections "1 and 2", mix until
homogeneous.
6. Adjust the viscosity to the desired level with sodium
chloride.
Figure imgf000067_0001
Resulting product is a clear, high foaming shampoo for daily use. Polyester S boosts foam, mitigates the irritation potential of TEA lauryl sulfate and helps build viscosity.
Polyester Q enhances detergency while minimizing irritation .
EXAMPLE 26 - ALPHA HYDROXY ACID (AHA) LOTION PROCESS :
With reference to TABLE XIX:
1. Combine the ingredients in section "1", heating to 80°C.
Use a propeller mixer for agitation.
2. Combine section "2", heating to 80°C. Agitate slowly with a propeller mixer.
3. When sections "1 and 2" are homogeneous and at the
designated temperatures, slowly add "2" to "1". Mix with rapid agitation for 5 minutes, then begin cooling.
4. Reduce mixing speed during cooling to prevent vortexing. 5. At 45°C, adjust for water loss. 6. Mix to room temperature .
Figure imgf000068_0001
The resulting product is a thin lotion that would be compatible for use in a glass bottle. The inclusion of Polyester V adds a moist emollient feel to the skin following application and is expected to increase the substantivity of the alpha hydroxy acid. Polyester V is also expected to act as a buffer for lactic acid, thereby increasing the efficacy of the AHA and mitigating it's irritation potential.
EXAMPLE 27 - MOISTURIZING LOTION WITH
MOIST EMOLLIENT AFTER-FEEL
PROCESS :
With reference to TABLE XX:
1. Combine the ingredients in section "1", heating to 80-85°C.
Agitate rapidly with a propeller mixer.
2. Combine the ingredients in section "2", heating to 80-85°C.
Agitate slowly with a low shear mixer.
3. When sections "1 and 2" are homogeneous and at the
prescribed temperatures, slowly pour section "2" into section "1" . Increase rate of agitation as phases are joined. 4. Maintain the mixture at 80-85°C for 5 to 10 minutes, then begin slowly cooling the batch. Adjust mixer speed so not to entrap air.
5. At 40-45°C, adjust for water loss.
6. Mix to 30-35°C.
7. Adjust pH 6.0 ± 0.2 with 10% w/v NaOH/H2O.
Figure imgf000069_0001
The resulting product is a thixotropic lotion which leaves a non-greasy and moist feeling on the skin following application and has good body. Polyester B adds a moist
emollient feel, enhances the skin moisturizing potential of the lotion and improves skin substantivity. EXAMPLE 28 - MOISTURIZING NIGHT CREAM WITH
PERCEPTIBLE MOIST AFTER-FEEL
PROCESS :
With reference to TABLE XXI:
1. Combine the ingredients in section "1", heating to 80-85°C.
Agitate rapidly with a propeller mixer.
2. Combine the ingredients in section "2", heating to 80-85°C.
Agitate slowly with a low shear mixer. 3. When sections "1 and 2" are homogeneous and at the
prescribed temperatures, slowly pour section "2" into section "1". Increase rate of agitation as phases are joined.
4. Maintain the mixture at 80-85°C for 5 to 10 minutes, then begin slowly cooling the batch. Adjust mixer speed so not to entrap air .
5 . At 40 -45 °C, adjust for water loss.
6 Mix to 30-35°C.
7. Adjust pH 6.0 ± 0.2 with 10% w/v NaOH/H2O.
Figure imgf000070_0001
The resulting product is a light cream which leaves a non-greasy and perceptible moist film on the skin following application. Polyester U adds a substantive moist film on the skin.
EXAMPLE 29 - WATER RESISTANT SUNSCREEN
LOTION WITH A NON-GREASY SKIN FEEL
PROCESS :
With reference to TABLE XXII:
1. Combine the ingredients in section "1", heating to 80-85°C.
Agitate rapidly with a propeller mixer. 2. Combine the ingredients in section "2", heating to 80-85°C. Agitate slowly with a low shear mixer.
3. When sections "1 and 2" are homogeneous and at the
prescribed temperatures, slowly pour section "2" into section "1". Increase rate of agitation as phases are joined.
4. Maintain the mixture at 80-85°C for 5 to 10 minutes, then begin slowly cooling the batch. Adjust mixer speed so not to entrap air.
5. At 40-45°C, adjust for water loss.
6. Mix to 30-35°C.
7. Adjust pH 6.0 ± 0.2 with 10% w/v NaOH/H2O.
Figure imgf000071_0001
The resulting product is a viscous lotion which leaves a non-greasy and moist feeling on the skin following application. Polyester U adds a moist emollient skin feel. Poly (diethylene glycol adipate) amidopropyl dimethylamine cocoate (MW = 1000) lends water resistance to the formulation.
It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims

CLAIMS 1. A compound of the formula (1)
Figure imgf000073_0001
wherein
R1 is -N(R5) (R6) or -OR7;
R2 is independently C2-C10 aliphatic;
R3 is independently C2-C10 aliphatic having 0-5 oxygen atoms as ether groups;
R4 is R1;
p is an integer between 3-100, inclusive;
R is H or C1-C10 aliphatic;
R6 is R8-N(R9)2(R10) polyamino acid-C(=O)OR11,
-R8-P(R15) or -R8-S(R15)2 R14;
R7 is -H, R12, -R3-OC(=O)-R13, -R3-OSO2O- R12 or -R3-SO3- R12 ;
R8 is C1-C3;
R9 is independently C1-C3 having 0-3 -OH substituents;
R10 is -H R 14 -R9 R14, -O-, -(CH 2) 1-3 -C(=O)O-,
-CH2CH(OH)CH2-NH-polyamino acid-COO-,
-CH2CH(OH) CH2-NH-polyamino acid-COOR15 R14, or
-CH2CH(OH) CH2-NH-polysiloxane R14 ;
R11 is R12 or C1-C22 ;
R12 is lithium, sodium, calcium, magnesium, ammonium monoalkylammonium, dialkylammonium, trialkylammonium or tetralkylammonium, where an alkyl portion of an ammonium group has 1-20 carbon atoms and 0-3 hydroxyl groups;
R13 is C1-C22 aliphatic;
R14 is halide, sulfate, phosphate, citrate, lactate, malate, fatty carboxylate or polymeric carboxylate;
R15 is C1-C22 hydrocarbon;
R16 is -O(C=O)R1, H, or
-O[C(=O) -R2(R18)m-C(=O)O-R3 (R16)n-O]pC(=O) -R2 (R18) m-C (=O) -R1;
n is an integer between 1 and 5, inclusive;
R18 is -C(=O)OR1, H, or
-C (=O) O-R3-O [C (=O) -R2 (R18) m-C (=O) O-R3 (R16) n-O] pC (=O) -R2 (R18)m-
C(=O)-R1; and
m is an integer between 1 and 5, inclusive;
with the proviso that when R1 is either -OH or -O-R3-OH, then R4 is neither -OH nor -O-R3-OH.
2. The compound of claim 1 wherein R1 is -N(R5) (R6), R6 is either -polyamino acid-C (=O) OR11 or -R8-N (R9) 2 (R10), and R10 is either CH2CH (OH) CH2-NH-polyamino acid-COO- or CH2CH (OH) CH2-NH- polyamino acid-COOR15 R14.
3. The compound of claim 1 wherein R1 is -N(R5) (R6), R6 is -R8-N(R9)2 (R10) , and R10 is -CH2-CH (OH) CH2-NH-polysiloxane R14.
4. The compound of claim 1 wherein R1 is -OR7, and
R7 is -R3-O-C(=O) -R13.
5. The compound of claim 1 wherein R1 is -N(R5) (R6), R6 is -R6-N(R8)2(R10), and R10 is - (CH2)1 - 3 -C (=O) O- .
6. The compound of claim 1 wherein R1 is -N(R5) (R6), R6 is -N(R9)2(R10] and R 10 is -O-.
7. The compound of claim 1 wherein R is -OR7 and R7 is R12.
8. The compound of claim 1 wherein R1 is -OR7 and R7 isR3-OSO2O- R12.
9. The compound of claim 1 wherein R1 is -OR7 and R7 is
R3 -SO3- R12.
10. The compound of claim 1 wherein R1 is -N(R5) (R5), R6 is -R8-N(R9)2(R10), and R10 is -R9 R14.
11. The compound of claim 1 wherein R1 is -N(R5) (R6), and
R6 is -R8-P(R15)3 R14.
12. The compound of claim 1 wherein R1 is -N(R5 ) (R6), and
R6 is -R8-S(R15)2 R14.
13. The compound of claim 1 wherein R1 is -N(R5) (R6), R6 is -R8-N(R9)2(R10), and R10 is -H R14.
14. The compound of claim 1 wherein p is an integer between 3 and 20, inclusive.
15. The compound of claim 1 wherein both m and n are equal to 1 and both R16 and R1 are -H.
16. The composition according to claim 1, wherein R1 is OR7; R2 is independently C2-C10 aliphatic; R3 is independently C2- C10 aliphatic having 0-5 oxygen atoms as ether groups; R4 is R1; R7 is -H or -R3-O(C=O) -R13; R13 is C1-C22 aliphatic; R16 is H; R18 is H; m=1; n=1; p is an integer between 3 and 20, inclusive, with the proviso that R7 is H at no more than one occurrence in any one molecule of formula (1).
17. The product resulting from the condensation reaction between at least one of a botanical derivative, an essential oil or a polysiloxane, and the polyester of the formula (1)
Figure imgf000076_0001
wherein R1 is -OH or -O-R3-OH;
R2 is independently C2-C10 aliphatic;
R is independently C2-C10 aliphatic having 0-5 oxygen atoms as ether groups;
R4 is -OH or -O-R3-OH;
p is an integer between 3-100, inclusive;
R16 is -O(C=O)R1, H, or
-O[C(=O)-R2(R18)m-C(=O)O-R3(R16)n-O]pC(=O)-R2(R18)m-C(=O)-R1;
n is an integer between 1 and 5, inclusive;
R18 is -C(=O)OR1, H, or -C(=O)O-R3-O[C(=O)-R2(R18)m-C(=O)O-R3(R16)n-O]pC(=O)-R2(R18)m- C(=O)-R1; and
m is an integer between 1 and 5, inclusive.
18. A method of using a compound of formula (1) according to claims 1 or 16, comprising the step of incorporating the compound of formula (1) into a personal care formulation.
19. The method according to claim 18 wherein the compound of formula (1) is incorporated in the personal care formulation to provide a concentration of 0.1 to 20 weight percent of a compound of formula (1), based on the total weight of the formulation.
20. The method according to claim 18 wherein the personal care formulation is in a form selected from the group consisting of a surfactant system, oil-in-water cream emulsion, oil-in-water liquid emulsion, water-in-oil cream emulsion, water-in-oil liquid emulsion, aqueous gel, hydro-alcoholic gel, alcoholic gel, aqueous suspension, hydro-alcoholic suspension, alcoholic suspension, solid suspension and aerosol.
21. The method according to claim 18 wherein the compound of formula (1) functions as a formulation aid in the personal care formulation.
22. The method according to claim 18 wherein the compound of formula (1) functions to enhance the performance of the personal care formulation.
23. The method according to claim 18 wherein the personal care formulation is a skin-care formulation.
24. The method according to claim 23 wherein the skin- care formulation is selected from the group consisting of
moisturizer in the form of a cream, liquid, paste or lotion;
sunscreen in the form of a cream, lotion, solid, paste or liquid; underarm antiperspirant; deodorant in the form of a spray, liquid, cream, or solid; cleanser in the form of a cream, gel, lotion, liquid or mousse; bath foaming preparation in the form of a gel, liquid, salt, oil or powder; aqueous toner; alcoholic toner; hydro-alcoholic toner; astringent pre-shave; astringent after-shave; astringent after-bath; eyelash mascara; lip color stick; lip gloss; make-up foundation in liquid or cream form; and make-up preparation.
25. The method according to claim 23 wherein the compound of formula (1) enhances at least one of protection from skin irritants when the skin-care formulation comprises skin
irritants, visual shine, apparent smoothness, apparent moistness, moisture content, and resistance to washoff of the skin-care formulation, when the skin-care formulation comprising a compound of formula (1) is applied to the skin.
26. The method according to claim 23 wherein the skin- care formulation further comprises skin irritants, and the compound of formula (1) is added to the irritant-containing skin- care formulation to mitigate skin irritation that occurs upon applying the skin-care formulation to the skin.
27. The method according to claim 26 wherein the irritant is a primary surfactant.
28. The method according to claim 27 wherein the irritant is a primary anionic surfactant.
29. The method according to claim 23 wherein the
formulation comprises particulate matter and the compound of formula (1) provides for enhanced dispersion of the particulate matter in the skin-care formulation.
30. The method according to claim 29 wherein the compound of formula (1) is added to an anhydrous composition useful in a skin-care formulation, the anhydrous composition is thereafter combined with water and formed into an emulsion, and particulate matter is added to the emulsion to form the skin-care
formulation.
31. The method according to claim 23 wherein the compound of formula (1) enhances the moist, soft tactile feeling of the skin to which the skin-care formulation is applied.
32. The method according to claim 23 wherein the compound of formula (1) enhances the apparent smoothness of the skin to which the skin-care formulation is applied.
33. The method according to claim 23 further comprising the step of applying the skin-care formulation to skin, wherein friction and a tactile feeling is produced during the applying step, and the compound of formula (1) modifies the friction and tactile feeling.
34. The method according to claim 33 wherein the tactile feeling is the impression of wetness, dryness or sliminess.
35. The method according to claim 23 wherein the skincare formulation incorporating a compound of formula (1) has enhanced resistance to being rinsed away or washed off the skin to which it is applied, upon exposure to perspiration or other aqueous media.
36. The method according to claim 18 wherein the personal care formulation is a hair-care formulation.
37. The method according to claim 36 wherein the haircare formulation is applied to hair for a purpose selected from the group consisting of cleansing the hair, rinsing the hair, conditioning the hair, styling the hair, bleaching the hair, coloring the hair and setting the hair.
38. The method according to claim 36 wherein the haircare formulation has a form selected from the group consisting of gel, liquid, mousse, spray, lotion, glaze and cream.
39. The method according to claim 36 wherein the compound of formula (1) enhances at least one of shine, manageability, apparent thickness, apparent body, combability in a wet or dry state, retention of hair configuration after styling, moisture absorption into the hair, and moisture of the hair, when the hair-care formulation is applied to the hair.
40. The method according to claim 39 wherein the compound of formula (1) enhances the shine of hair to which the hair-care formulation is applied.
41. The method according to claim 39 wherein the compound of formula (1) enhances the manageability of hair to which the hair-care formulation is applied.
42. The method according to claim 39 wherein the compound of formula (1) enhances the apparent body of hair to which the hair-care formulation is applied.
43. The method according to claim 39 wherein the compound of formula (1) enhances the apparent thickness of hair to which the hair-care formulation is applied.
44. The method according to claim 39 wherein the compound of formula (1) enhances the combability of wet hair to which the hair-care formulation is applied.
45. The method according to claim 39 wherein the compound of formula (1) enhances the combability of dry hair to which the hair-care formulation is applied.
46. The method according to claim 39 wherein the compound of formula (1) enhances the style retention of hair that is styled and to which the hair-care formulation comprising the compound of formula (1) is applied.
47. The method according to claim 39 wherein the compound of formula (1) enhances the moisture absorptivity of hair to which the hair-care formulation is applied.
48. The method according to claim 39 wherein the compound of formula (1) enhances the moisture content of hair to which the hair-care formulation is applied.
49. The method according to claim 39 wherein the haircare formulation incorporating a compound of formula (1) has enhanced resistance to being rinsed away or washed off the hair to which it is applied, upon exposure to perspiration or other aqueous media.
PCT/US1995/010789 1994-08-26 1995-08-24 Derivatized polyester compounds and uses thereof WO1996006878A1 (en)

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US5833961A (en) * 1996-06-25 1998-11-10 Inolex Investment Corporation Polyester-based suncreen formulations
US5989527A (en) * 1998-01-26 1999-11-23 Inolex Investment Corporation Compositions and methods for improving the performance of chemical exfoliating agents, sunless tanning agents, skin lightening agents and insect repellents
FR2831430A1 (en) * 2001-10-26 2003-05-02 Oreal Cosmetic or care composition comprises an uncrosslinked film-forming polyorganosiloxane-modified polyester
FR2873570A1 (en) * 2004-08-02 2006-02-03 Oreal Cosmetic composition, useful: e.g. for make-up and/or care of the skin, blush, cheek rouge or eye shadow and anti-dark circle product, comprises organic liquid phase and polyester amide polymer
WO2006013200A1 (en) * 2004-08-02 2006-02-09 L'oreal Cosmetic care and/or makeup composition comprising at least one polyesteramide polymer
US8163274B2 (en) 2004-04-07 2012-04-24 Rocco Burgo Personal care products containing high refractive index esters and methods of preparing the same
US20160244853A1 (en) * 2013-09-30 2016-08-25 Rhodia Poliamida E Especialidades Ltda Chrome tanning process
US20160244854A1 (en) * 2013-09-30 2016-08-25 Rhodia Poliamida E Especialidades Ltda Tanning process for obtaining leather
US10272026B2 (en) 2017-07-31 2019-04-30 L'oreal Water-in-oil emulsion compositions suitable for altering the color of hair

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5833961A (en) * 1996-06-25 1998-11-10 Inolex Investment Corporation Polyester-based suncreen formulations
US5989527A (en) * 1998-01-26 1999-11-23 Inolex Investment Corporation Compositions and methods for improving the performance of chemical exfoliating agents, sunless tanning agents, skin lightening agents and insect repellents
FR2831430A1 (en) * 2001-10-26 2003-05-02 Oreal Cosmetic or care composition comprises an uncrosslinked film-forming polyorganosiloxane-modified polyester
US8163274B2 (en) 2004-04-07 2012-04-24 Rocco Burgo Personal care products containing high refractive index esters and methods of preparing the same
FR2873570A1 (en) * 2004-08-02 2006-02-03 Oreal Cosmetic composition, useful: e.g. for make-up and/or care of the skin, blush, cheek rouge or eye shadow and anti-dark circle product, comprises organic liquid phase and polyester amide polymer
WO2006013200A1 (en) * 2004-08-02 2006-02-09 L'oreal Cosmetic care and/or makeup composition comprising at least one polyesteramide polymer
US20160244853A1 (en) * 2013-09-30 2016-08-25 Rhodia Poliamida E Especialidades Ltda Chrome tanning process
US20160244854A1 (en) * 2013-09-30 2016-08-25 Rhodia Poliamida E Especialidades Ltda Tanning process for obtaining leather
US10731230B2 (en) * 2013-09-30 2020-08-04 Techpolymers Industria E Comercio Ltda Tanning process for obtaining leather
US10844445B2 (en) * 2013-09-30 2020-11-24 Techpolymers Industria E Comercio Ltda Chrome tanning process
US10272026B2 (en) 2017-07-31 2019-04-30 L'oreal Water-in-oil emulsion compositions suitable for altering the color of hair

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