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WO1988009783A1 - Absorbeurs polymeres de lumiere ultraviolette - Google Patents

Absorbeurs polymeres de lumiere ultraviolette Download PDF

Info

Publication number
WO1988009783A1
WO1988009783A1 PCT/AU1988/000180 AU8800180W WO8809783A1 WO 1988009783 A1 WO1988009783 A1 WO 1988009783A1 AU 8800180 W AU8800180 W AU 8800180W WO 8809783 A1 WO8809783 A1 WO 8809783A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
ultraviolet light
compounds
copolymer
acrylic acid
Prior art date
Application number
PCT/AU1988/000180
Other languages
English (en)
Inventor
Vicki Lee Ker
Jeffrey Wayne Langley
Graham John Hamilton Melrose
Jeffrey Mark Stewart
Original Assignee
Biopolymers Limited
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 Biopolymers Limited filed Critical Biopolymers Limited
Publication of WO1988009783A1 publication Critical patent/WO1988009783A1/fr

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Classifications

    • 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
    • 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
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety

Definitions

  • the present invention relates to polymeric ultraviolet light-absorbing compounds and processes for their production and relates particularly but not exclusively to polymeric ultraviolet light-absorbing compounds being copolymers of acrylic acid with the ultraviolet light-absorbing monomers of the invention and with other ultraviolet light-absorbing compounds. It is desirable that such compounds have a spreadability and lubricity which is conducive to their rubbing into the SKin either alone or when formulated in sunscreen lotions, creams or suspensions; as well these compounds should desirably have relatively low skin permeability and relatively low water solubility; all these properties make these polymeric compounds suitable as sunscreen agents either alone or when formulated in sunscreen lotions, creams or suspensions.
  • a sunscreen agent should have the property of absorbing ultraviolet light and especially, in the region 300-310nm since this is a particularly damaging radiation to the human skin.
  • many publications and patents for reviews see Bailey and Vogi, J Macromol. Sci. - Rev., 1976, C14(2), 257-93 and Tirrell, Polymer News, 1981, 7, 104-110) relate to such ultraviolet light-absorbing agents which are polymeric in order to achieve lower water solubility (which reduces losses of the agents after application and then, swimming) and/or skin permeability (which reduces the possibility of dermal toxicity or allergy).
  • copolymers of acrylic acid with ultraviolet light-absorbing monomers do not have these intractable properties and particularly, have a spreadability and lubricity which favours their formulation in creams lotions or suspensions and even, may be rubbed into the skin alone to form efficacious, sun-protecting barriers.
  • acrylic acid may be copolymerised with new, ultraviolet light-absorbing comonomers.
  • the present invention therefore provides ultraviolet light-absorbing compounds, of general formula (I):
  • R represents -(alk) n O- or -(CH 2 CH 2 O)- n in which alk is a divalent straight or branched alkyl, aryl or alkaryl radical having 1 to 20 carbon atoms and n is from 1 to 1000
  • R' represents -OH, NH 2 , -NHR" or -NR" 2 in which R" represents a straight or branched alkyl, aryl or alkylaryl radical having from 1 to 20 carbon atoms.
  • the invention also provides a process for the manufacture of compounds of formula (I) as hereinbefore defined which comprises reacting a compound of formula (II)
  • n is from 1 to 10 and particularly preferred compounds of formula (I) are those in which
  • R is -CH 2 CH 2 O- and R' is 2-OH or
  • R is -CH 2 CH 2 O- and R' is 4-N(CH 3 ) 2 .
  • compositions of formula (I) include 2-acryloxypolyoxyethylene salicylate, 2-acryloxyethyl-4-N,N'-dimethylamino- benzoate, 4-acryloxy-2-hydroxybenzophenone.
  • the invention also provides polymeric compounds, being copolymers of acrylic acid and/or methacrylic acid with compounds of general formula (I) and/or with any other one or a number of ultraviolet light-absorbing monomers.
  • Such other ultraviolet light-absorbing monomers include vinyl or acrylate derivatives of 2-acrylyloxydibenzoylmethane, 2-hydroxy-4'-vinyl- dibenzoylmethane, oxalanilides, hydroxy benzoyl benzoic acids, 6-aza1,2-dinydro-3H-1,4-benzodiazepine, 5-styrylpyrazoles, 7-azobenzimidazoles, benzal-3-alkyl-2H-benzothiazoloazines, p- or m- hydroxycinnamic acids, hydroxyphenylcarbamates, 4-methyl-N-(2-hydroxy- benzylidene)aniline, 4-hydroxy-N-(2-hydroxybenzylidene)aniline, N-(3-hydroxybenzylidene)aniline, (4-hydroxybenzaldelhyde) phenylhydrazone, benzaldehyde-4-hydroxyphenyl- hydrazone, N-(4-hydroxybenzylidene
  • this application is not limited to copolymerisation of the abovementioned monomers with acrylic acid and/or methacrylic acid and includes the covalent bonding to those monomers of one or more known ultraviolet chromophores which have been suitably functional ised to enable bonding.
  • non-ultraviolet light-absorbing monomers are net needed or used in these polymeric compounds, but they may be included so long as they do not unduly detract from the desired properties. Because the various polymeric compounds which are provided by this invention are often similar in structure, conveniently, they may be often blended without undue incompatibilities in creams, lotions or suspensions to resultant, wide and/or uniform ultraviolet light-absorption across the spectrum.
  • the polymeric compounds of the invention are ultraviolet light-absorbing, have attractive spreadability and lubricity on the skin and usually, relatively low skin permeability or/and relatively low water solubility which are desirable when used alone, or as an ingredient for a sunscreen preparation.
  • the invention is not limited by the choice of copolymeri sing monomer, but when compounds of formula I in which R' is -2-OH are used, we have discovered that the invention additionally provides a polymeric compound which has been observed to often reduce any dermal irritation/inflammation attributable to any other ingredients of a base-cream or lotion or suspension for example, in vhich it may be formulated.
  • the invention provides a process for producing ultraviolet absorbing polymers by copolymeri sing at least one ultraviolet absorbing monomer, including compounds of formula I, with acrylic acid and/or metnacrylic acid.
  • the special properties of the copolymers of the invention allow spreadability and lubricity even at high content (up to about 90% molar) of the ultraviolet light-absorbing monomers.
  • This high content is very desirable as it maximises absorption and thus minimises the amount of ultraviolet light-absorber needed in a formulation or polymer blend to achieve the desired level of utlraviolet light-absorption.
  • the invention also provides ultraviolet light-absorbing formulations which include, in addition to the usual carriers and excipients known for such formulations, compounds of formula I or one or more of the ultraviolet light-absorbing copolymers of the invention.
  • Such formulations find use in protecting surfaces (including skin) from the effects of ultraviolet light.
  • copolymers of the invention may also be formulated into polymer blends with other non ultraviolet light-absorbing polymers.
  • Example 1 (a) 2-acryloxyethyl salicylate and (b) analogue: 2-acryloxypolyoxyethylene salicylate
  • Example 4 (a) and (b) Copolymers of acrylic acid and 2-acryl oxyethyl salicylate: (c) acrylic acid and 2-acryloxylpolyoxyethylene salicylate; (d) and (e) Copolymers of Methacrylic acid/acrylic acid and 2-acryloxyethyl salicylate
  • the 80% salicylate copolymer is a white powdery solid; soluble in chloroform, toluene, ethyl acetate, 2-butanone, acetone; insoluble in petrol, water, sea water, ethanoi. 'H n.m.r. (CDCl 3 ): ⁇ 0.6-3.3 (hump,
  • the salicylate benzophenone terpolymer is a cream to pale yellow powder; soluble in ethyl acetate, acetone; slightly soluble in toluene; insoluble in water, sea water, petroT and methanol.
  • 'H n.m.r. (CDCl 3 ): ⁇ 1.0-3.3 (hump, -CH 2 CH-); 4.4 (bs, -OCH 2 CH 2 O-) ; 6.3-8.0 (m, ArH); 10.4 (bs, -OH); 12.2 (bs, -OH).
  • U.V. (43.2mgl -1 ) ⁇ -CHCl 3 , max. (A max ): 320 (0.540); 268 (1.186); 244nm (1.061).
  • Crodamol PC (20g; a propylene glycol fatty acid ester), crodamol CAP (20g; mixed fatty acid esters), crillet 3 (2g; sorbitan monostearate), cetyl alcohol (2g), stearic acid (6g) and super heartolan (2g; lanolin alcohols) were heated until the mixture was homogeneous then al lowed to cool.
  • Triethanolamine (3g) and glycerol (6g) were dissolved in water (110ml).
  • PART C Dcwicil 200 (20mg; preservative) was dissolved in water (20ml) and to this was added collasol (6g; collagen). Part A dig) and Part B (25ml) were heated to 60° then B added to A and then allowed to cool with constant stirring. Then, Part C (5ml) was added with stirring.
  • the resulting sunscreen lotion was tested for its sunscreen factor according to Australian Standard 2604 "Sunscreen Products -'Evaluation and Classification" of 1986, and gave a sunscreen protecting factor score on average of 9. Similar results were recorded when the copolymer within the formulation (example 8(b)) was rubbed into the skin - neat and dry, without being dispersed into the base formulation.
  • Triethanolamine (0.39g) and glycerol (0.45g) were dissolved in water (10.5ml); terpolymer (1.5g; example 6) was dry ground then ground further with the above solution.
  • Part A (3.31g) and the above (9.61g) were heated to 60-70°; Part A was then added to Part B with stirring. The resulting mixture was allowed to cool with stirring (temp, below 30°).
  • Part C (1.48g) was then added with stirring.
  • Salicylic acid (16.4mg) was combined with labelled acid (2.5mg).
  • the methyl ester was prepared according to the method of "Vogel's Textbook of Practical Organic Chemistry", Longmans, 4th ed. in 30% yield after preparative thin layer chromatography (p.t.l.c).
  • Salicylic acid (65.4mg) was combined with labelled acid (22.3mg).
  • the polymer was prepared essentially as described in examples 1(a) and 4(b) above and purified by spray precipitation.
  • the intermediate esters were purified by the p.t.l.c. and obtained in 67% and 37% yield respectively.
  • the polymer was isolated in 16% yield. 5% formulations were prepared of the above materials in the base described above.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention se rapporte à des composés polymères absorbant la lumière ultraviolette, à des composés permettant leur production, et notamment mais pas exclusivement à des composés polymères absorbant la lumière ultraviolette, lesquels sont des copolymères d'acide acrylique avec les monomères de l'invention absorbant la lumière ultraviolette, et avec d'autres composés absorbant la lumière ultraviolette. Les composés absorbant la lumière ultraviolette ont pour formule générale (I): dans laquelle R représente -(alk)nO- ou -(CH2 CH2O)-n dans lequel alk est un radical d'alkyle, d'aryle ou d'alkaryle droit ou ramifié, bivalent, ayant 1 à 20 atomes de carbone, et n va de 1 à 1000 R' représente -OH, NH2, -NHR'' ou -NR''2 dans lequel R'' représente un radical d'alkyle, d'aryle ou d'alkylarile droit ou ramifié ayant de 1 à 20 atomes de carbone. Les polymères ont une aptitude à l'enduction et une onctuosité qui facilite leur pénétration dans la peau, soit seuls soit lorsqu'ils sont formulés dans des lotions, des crèmes ou des suspensions d'écrans de protection solaire.
PCT/AU1988/000180 1987-06-09 1988-06-06 Absorbeurs polymeres de lumiere ultraviolette WO1988009783A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPI2368 1987-06-09
AUPI236887 1987-06-09

Publications (1)

Publication Number Publication Date
WO1988009783A1 true WO1988009783A1 (fr) 1988-12-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1988/000180 WO1988009783A1 (fr) 1987-06-09 1988-06-06 Absorbeurs polymeres de lumiere ultraviolette

Country Status (2)

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WO (1) WO1988009783A1 (fr)
ZA (1) ZA883992B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5523152A (en) * 1993-10-27 1996-06-04 Minnesota Mining And Manufacturing Company Organic compounds suitable as reactive diluents, and binder precursor compositions including same
US5580647A (en) * 1993-12-20 1996-12-03 Minnesota Mining And Manufacturing Company Abrasive articles incorporating addition polymerizable resins and reactive diluents
US5667842A (en) * 1993-10-27 1997-09-16 Minnesota Mining And Manufacturing Company Abrasive articles incorporating addition polymerizable resins and reactive diluents, and methods of making said abrasive articles
EP0583888B2 (fr) † 1992-07-30 2001-01-17 Unilever Plc Copolymère susceptible d'être dispersé dans l'eau absorbant la lumière UV
US20190204245A1 (en) * 2017-12-29 2019-07-04 Jeol Ltd. Charged Particle Beam Device and Analysis Method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2116973A1 (de) * 1971-04-07 1972-12-14 Bayer Ag, 5090 Leverkusen Polymerisierbare Anthranilsäureester

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2116973A1 (de) * 1971-04-07 1972-12-14 Bayer Ag, 5090 Leverkusen Polymerisierbare Anthranilsäureester

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMDEX 3 DATABASE, RN 100012-67-7, Benzoic acid, 2 hydroxy, 2-((1-oxo-2-propenyl) oxy) ethyl ester. *
RESEARCH DISCLOSURE, December 1980, Vol. 200, No. 20036, W.P. EWALD et al., "Photopolymerizable Compounds Featuring Novel Co-Initiators", pp 560-5. See Example 10, Table II. *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0583888B2 (fr) † 1992-07-30 2001-01-17 Unilever Plc Copolymère susceptible d'être dispersé dans l'eau absorbant la lumière UV
US5523152A (en) * 1993-10-27 1996-06-04 Minnesota Mining And Manufacturing Company Organic compounds suitable as reactive diluents, and binder precursor compositions including same
US5667842A (en) * 1993-10-27 1997-09-16 Minnesota Mining And Manufacturing Company Abrasive articles incorporating addition polymerizable resins and reactive diluents, and methods of making said abrasive articles
US5710281A (en) * 1993-10-27 1998-01-20 Minnesota Mining And Manufacturing Company Organic compounds suitable as reactive diluents and binder precursor compositions including same
US5709935A (en) * 1993-10-27 1998-01-20 Minnesota Mining And Manufacturing Company Organic compounds suitable as reactive diluents, and binder precursor compositions including same
US5733648A (en) * 1993-10-27 1998-03-31 Minnesota Mining And Manufacturing Company Organic compounds suitable as reactive diluents, and binder precursor compositions including same
US5736747A (en) * 1993-10-27 1998-04-07 Minnesota Mining And Manufacturing Company Organic compounds suitable as reactive diluents, and binder precursor compositions including same
US5580647A (en) * 1993-12-20 1996-12-03 Minnesota Mining And Manufacturing Company Abrasive articles incorporating addition polymerizable resins and reactive diluents
US20190204245A1 (en) * 2017-12-29 2019-07-04 Jeol Ltd. Charged Particle Beam Device and Analysis Method

Also Published As

Publication number Publication date
ZA883992B (en) 1989-02-22

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