WO1996030429A1 - Agents tensio-actifs, adhesifs et pansements formes a partir de ceux-ci - Google Patents
Agents tensio-actifs, adhesifs et pansements formes a partir de ceux-ci Download PDFInfo
- Publication number
- WO1996030429A1 WO1996030429A1 PCT/GB1996/000782 GB9600782W WO9630429A1 WO 1996030429 A1 WO1996030429 A1 WO 1996030429A1 GB 9600782 W GB9600782 W GB 9600782W WO 9630429 A1 WO9630429 A1 WO 9630429A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- adhesive
- salt
- polymer
- compounds
- Prior art date
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 32
- 239000000853 adhesive Substances 0.000 title claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 title abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 18
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000002998 adhesive polymer Substances 0.000 description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- -1 phenylene radical Chemical class 0.000 description 7
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000011953 free-radical catalyst Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- JELFVXVEOTVGKC-UHFFFAOYSA-N 3-dodecoxycarbonylbut-3-enoic acid Chemical compound CCCCCCCCCCCCOC(=O)C(=C)CC(O)=O JELFVXVEOTVGKC-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940082500 cetostearyl alcohol Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- UBHWBODXJBSFLH-UHFFFAOYSA-N hexadecan-1-ol;octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO.CCCCCCCCCCCCCCCCCCO UBHWBODXJBSFLH-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OULAJFUGPPVRBK-UHFFFAOYSA-N tetratriacontyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO OULAJFUGPPVRBK-UHFFFAOYSA-N 0.000 description 2
- VTNBTUFKJGHHSM-UHFFFAOYSA-N 2,5-dioxofuran-3-sulfonic acid Chemical compound OS(=O)(=O)C1=CC(=O)OC1=O VTNBTUFKJGHHSM-UHFFFAOYSA-N 0.000 description 1
- FIQBJLHOPOSODG-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]benzoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=CC=C1C(O)=O FIQBJLHOPOSODG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical class CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 231100000606 suspected carcinogen Toxicity 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/48—Surfactants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/58—Adhesives
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
Definitions
- This invention concerns polymerisable compounds exhibiting surfactant properties, adhesives containing such compounds and adhesive containing products.
- European Patent 0099675 describes polymerisable surfactants of the general formula
- R is H or CH 3 .
- x is an integer from 2 to 20, y is an integer from 0 to 5.
- A is an alkylene, alkenylene or phenylene radical such that A (COOH) 2 is a dibasic acid capable of forming an anhydride A(CO) 2 O.
- R is a C 10 to C 14 alkyl radical and M is hydrogen, ammonia or an alkai metal in emulsion polymerisable reactions with one or more copolymerisable acrylic monomers to make emulsion polymers which have adhesive properties and are suitable for application to the skin.
- Sodium mono-lauryl itaconoxypropane sulphonate is a surfactant according to the formula claimed in EP 0194881 which is used in the manufacture of an emulsion adhesive polymer as claimed in EP 194881 B1.
- a pressure sensitive adhesive as disclosed in EP 194881 can be used for adhesive surgical and medical dressings.
- the surfactant sodium mono-lauryl itaconoxypropane sulphate for use in the manufacture of an adhesive is the product of a two stage synthesis. Firstly monolauryl itaconate is produced by the reaction of intaconic anhydride with lauryl alcohol. Thereafter the ester is sulphopropylated using propane sultone.
- the present invention thus provides a compound having the formula (I):
- A is an alkenylene radical such that A(CO 2 H) 2 is a dibasic acid capable of forming an anhydride A (CO) 2 O
- Apt salts of compounds of formula (I) are water soluble and include the ammonium, water soluble alkyl substituted ammonium and alkali metal salts thereof.
- a preferred salt of the compounds of formula (I) is the ammonium salt.
- Compounds of general formula (I) having low cloud points can be converted to salts to increase their efficiency.
- the water insoluble compounds of the invention can be used as intermediates to form the water soluble compounds of the invention by ion exchange.
- the compound of formula (I) itself is water soluble.
- Aptly y has a value of less than 80.
- Preferred values for y are from 10 to 50 or from 50 to 80.
- the favoured values for y are 20 to 30.
- Favoured values for x are 10 to 17 and more favourably 15 o 17.
- the compounds of formula (I) of the present invention can be prepared by a process which comprises reacting a dibasic acid anhydride of the formula A(CO) 2 O wherein A is as defined in relation to the compound of formula (I) with a compound of the formula (II):
- a favoured ethoxylated alcohol is cetostearyl alcohol having an average of 25 moles of oxyethylene groups per molecule and is available under the Trade Mark LUTENSOL AT25 from BASF
- Suitable dibasic anhydrides include maleic anhydride, sulphomaleic anhydride and itaconic anhydride.
- the reaction between the fatty acid/alcohol and the anhydride may be performed by fusing the reagents at temperatures above their melting points.
- the reaction may also be performed in a suitable aprotic solvent. More than one molar equivalent of the anhydride may be used.
- the reagents are heated to 70°C for 30 mins.
- the salts may then be formed by reaction of aqueous solutions of formula (I) with appropriate bases. They may either be generated in situ when needed for the relevant emulsion polymerisation processes or stored as solutions.
- the surfactant system of the present invention provides an advantage over the prior art in that the one step reaction for preparation is simpler than that required for the surfactants disclosed and used in EP 0099675 and EP 194881
- Water soluble compounds of the invention are surfactants.
- the ammonium and alkali metal salt compounds in particular have good surfactant properties
- the ammonium salt is especially favoured for this purpose.
- the surfactant compounds of the present invention can be used in emulsion polymerisation, when they will become part of the resulting polymer molecule
- the invention provides a polymer which comprises residues of a compound of formula (I) or a salt thereof
- Apt acrylic monomers include alkyl esters or amides of acrylic and methacrylic acids and hydroxylated derivatives thereof
- a polymer produced by emulsion polymerisation using a surfactant of the present invention may be an adhesive polymer, advantageously an acrylic adhesive polymer
- Apt acrylic monomers for such adhesive polymers include those listed above.
- a skin friendly adhesive suitable for use with medical and surgical dressings comprising a polymer of the invention.
- an adhesive polymer which comprises residues of one or more acrylic monomers and residues of one or more compounds of formula (I) or a salt thereof.
- Adhesive polymers of this type may be pressure sensitive adhesive polymers.
- the water soluble compounds of the invention can be readily copolymerised with one or more acrylic monomers by emulsion polymerisation and thus form adhesive materials suitable for use on skin.
- ammonium salt of the invention to form an adhesive polymer of the invention is specially advantageous in that on heating the polymer in a dry form, ammonia is liberated and the adhesive polymer is converted to the acid form.
- the acid form of the adhesive polymer of the invention is generally less sensitive to water than analogous polymers containing salts of the acid.
- the adhesive polymer of the invention may suitably contain 0.2 to 5% by weight of residues of a compound of formula (I) or a salt thereof, for example 1%.
- the acrylic polymer component consists mainly of acrylic residues for which the monomer is an alkyl ester of acrylic or methacrylic acid in which the alkyl residue contains 2 to 10 carbon atoms.
- Favoured pressure sensitive adhesive forming alkyl acrylate monomers are alkyl esters of acrylic acid in which the alkyl group contains 3 to 12 carbon atoms and preferably 4 to 9 carbon atoms.
- Alkyl acrylate monomers of this type include n-butyl acrylate, 2-ethylhexyl acrylate and other octyl acrylates.
- Favourably monomers include n-butyl acrylate and 2-ethylhexyl acrylate.
- a suitable pressure sensitive adhesive polymer may comprise
- acrylic residues will consist of a mixture of two monomer species, often in equal proportions.
- a combination of 2-ethyl hexyl acrylate and n-butyl acrylate are used.
- Pressure sensitive adhesives of the invention advantageously contain residues of other acrylic monomers.
- Suitable monomers include acrylic esters, comprising monoesters such as optionally hydroxylated or alkoxylated alkyl esters, for example methyl methacrylate, hydroxyethyl methacrylate and n-butyl methacrylate.
- Suitable monomer residues also include acrylic amides, comprising monoamides such as optionally N-alkylated amides, for example acrylamide, methacrylamide, N-tert. butylacrylamide and N-lauryl acryiamide.
- Optional monomers also include ammonium sulphatoethyl methacrylate, monomethacryloyloxyethyl phthalate, acrylic acid and methacrylic acid.
- Such residues may form up to 10% by weight of the polymer, for example up to 8%, aptly 4 to 8%.
- the most apt proportion of such residues will depend to some extent on the particular monomer species, the monomer species of the main components, the emulsion polymerisation conditions and the desired physical properties of the pressure sensitive adhesives.
- a suitable pressure sensitive adhesive polymer compnses 39 to 59% by weight of n-butyl acrylate residues, 39 to 59% by weight of 2-ethylhexyl acrylate residues, 0.3 to 10%, aptly 0.3 to 5% by weight of hydroxyethyl methacrylate residues and 2% to 8% by weight of n-butyl methacrylate residues.
- a favoured pressure sensitive adhesive polymer comprises
- Preferred pressure sensitive adhesive polymers of the invention contain: 44, 50, 1 and 5% by weight respectively of the above residues, the last two being respectively hydroxyethyl methacrylate and n-butyl methacrylate.
- the pressure sensitive adhesives of the invention can be used for adhesive surgical and medical dressings and therefore adhesive surgical and medical dressings comprising flexible substrates carrying an adhesive of this invention are an important aspect of this invention
- the adhesive of the invention may be used to coat fabrics such as non-woven, knitted or woven fabrics; filmic materials, including polymer films such as porous polyvinylchlo ⁇ de film, continuous and perforated films such as polyurethane-containing film; integral nets; and the like to form surgical and medical adhesive dressings.
- filmic materials including polymer films such as porous polyvinylchlo ⁇ de film, continuous and perforated films such as polyurethane-containing film; integral nets; and the like to form surgical and medical adhesive dressings.
- Suitable backing materials for moisture vapour transmitting adhesive dressings are disclosed in British Patent No. 1 ,280,631
- Adhesive polymers of the invention can be prepared by a process which comprises polymerising as an emulsion one or more unsaturated monomers and a water soluble salt of a compound of the formula (I) in the presence of a free radical catalyst.
- the free radical catalyst is generally a conventional aqueous free radical catalyst such as ammonium persulpate, or may be a redox catalyst.
- the emulsion may conveniently be made by initially forming an aqueous solution of a water-soluble salt of the compound of formula (I) in situ from the acid of formula (I) and a suitable basic salifying agent, for example an alkali metal or optionally trialkyl substituted ammonium hydroxide.
- a suitable basic salifying agent for example an alkali metal or optionally trialkyl substituted ammonium hydroxide.
- the optional termonomer in the polymers of the present invention may then be added to the solution, in particular if it is an acrylic amide, and the remaining monomers to be polymerised then added to the salt solution.
- all the monomers may be premixed, in particular if the termonomer is an acrylic ester, and the premix then added to the salt solution.
- the pH of the salt solution is adjusted to approximately pH7 before the addition of remaining or premixed monomers, which are then mixed under high-shear stirring.
- the resulting monomer emulsion typically has a solids content in the range of 15 to 60% by weight and preferably 30 to 50%.
- the resulting monomer emulsion may then be added to an aqueous solution of free-radical catalyst, for example ammonium persulphate, and polymerisation effected by heating, typically to 75° to 95°C, under an inert atmosphere, such as nitrogen or carbon dioxide.
- free-radical catalyst for example ammonium persulphate
- polymerisation effected by heating, typically to 75° to 95°C, under an inert atmosphere, such as nitrogen or carbon dioxide.
- the monomer emulsion may be added to the catalyst solution over a period of time during the polymerisation reaction.
- the monomer emulsion may be purged with nitrogen before use.
- the polyacrylate adhesive emulsions of the invention may contain thickeners, fillers and medicaments such as anti-microbial agents including anti fungal and anti bacterial agents.
- the adhesive can be coated onto a suitable substrate by a direct or transfer coating process using conventional coating techniques.
- polyacrylate adhesives of the invention containing residues of an ammonium salt of the compound of the invention when heated lose ammonia and the salt is converted to the acid form.
- Surgical or medical dressings coated with such polyacrylate adhesives have been found to have good adhesion to skin and are not sensitive to water.
- Cetostearic acid ethoxylate (100 EO) (41.8g 8.9 mmol) was heated to 90°C and itaconic anhydride (1.00g. 8.9 mmol) was added. The temperature was maintained for 60 mins then the product was discharged. After cooling the product was recrystallised from acetone.
- Aqueous ammonium salt surfactant (equivalent to 3.5g solids) from Example 2 was added to deionised water (143. Og). Premixed n-butyl acrylate (154g), 2-ethylhexyl acrylate (175g), 2-hydroxyethyl methacrylate (3.5g) and n-butyl methacrylate (17.5g) were added whilst the solution was stirred with a high shear mixer to form a monomer emulsion.
- the monomer emulsion was purged with nitrogen then fed dropwise using a peristaltic pump over a period of 3 hours to a solution of ammonium persulphate (0.91g) in water (186.8g) in a reaction flask fitted with an agitator and a condenser and maintained at a constant temperature in the range of 80 to 90°C by a constant temperature water bath.
- the polymerisation reaction was allowed to continue for a further hour to give a total reaction time of 4 hours.
- Example 3 The procedure of Example 3 was repeated for the sodium salt surfactant from Example 2, except that the monomer feed was carried out over 2 hours at a temperature of 75 to 80°C, with the reaction being allowed to continue for a further 2 hours at a temperature of 80 to 90°C.
- the polyacrylate adhesive emulsion of Example 4 thickened by the addition of an acrylic thickening solution (Primal ASE 60, available from Rohm and Haas) was coated onto a siiicone coated release paper by means of a blade over flat bed coater, and dried in an air circulating oven at a temperature of 55°C to give a dried pressure sensitive adhesive coating with a weight per unit area of 35g/m 2 .
- the adhesive coating was transferred to a polyurethane- containing film, and cut into 1.5cm wide surgical tapes. The resulting tapes showed good adherence to glass and polypropylene surfaces, and should adhere well to human skin under both dry and wet conditions.
- Example 5 The procedure of Example 5 was repeated on a cloth substrate wherein the coating weight of the adhesive was 150g/m 2 .
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Hematology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Materials For Medical Uses (AREA)
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU51574/96A AU5157496A (en) | 1995-03-30 | 1996-04-01 | Surfactants, adhesives and dressings formed therefrom |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9506495.2 | 1995-03-30 | ||
GBGB9506495.2A GB9506495D0 (en) | 1995-03-30 | 1995-03-30 | Surfactants |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996030429A1 true WO1996030429A1 (fr) | 1996-10-03 |
Family
ID=10772145
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1996/000782 WO1996030429A1 (fr) | 1995-03-30 | 1996-04-01 | Agents tensio-actifs, adhesifs et pansements formes a partir de ceux-ci |
Country Status (4)
Country | Link |
---|---|
AU (1) | AU5157496A (fr) |
GB (1) | GB9506495D0 (fr) |
WO (1) | WO1996030429A1 (fr) |
ZA (1) | ZA962586B (fr) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2214747A1 (fr) * | 1973-01-19 | 1974-08-19 | Kao Corp | |
GB2148910A (en) * | 1983-10-28 | 1985-06-05 | Chevron Res | Stable emulsifier for substituted succinic anhydride compositions |
WO1993002717A1 (fr) * | 1991-08-09 | 1993-02-18 | Smith & Nephew Plc | Produits adhesifs |
JPH05214289A (ja) * | 1991-12-10 | 1993-08-24 | Arakawa Chem Ind Co Ltd | プラスチックフィルム用被覆剤 |
EP0565825A1 (fr) * | 1992-04-16 | 1993-10-20 | Hüls Aktiengesellschaft | Procédé de préparation de dispersions aqueuses de polymères |
JPH0748550A (ja) * | 1993-08-06 | 1995-02-21 | Sekisui Chem Co Ltd | 粘着テープ又はシート |
-
1995
- 1995-03-30 GB GBGB9506495.2A patent/GB9506495D0/en active Pending
-
1996
- 1996-04-01 ZA ZA962586A patent/ZA962586B/xx unknown
- 1996-04-01 AU AU51574/96A patent/AU5157496A/en not_active Abandoned
- 1996-04-01 WO PCT/GB1996/000782 patent/WO1996030429A1/fr active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2214747A1 (fr) * | 1973-01-19 | 1974-08-19 | Kao Corp | |
GB2148910A (en) * | 1983-10-28 | 1985-06-05 | Chevron Res | Stable emulsifier for substituted succinic anhydride compositions |
WO1993002717A1 (fr) * | 1991-08-09 | 1993-02-18 | Smith & Nephew Plc | Produits adhesifs |
JPH05214289A (ja) * | 1991-12-10 | 1993-08-24 | Arakawa Chem Ind Co Ltd | プラスチックフィルム用被覆剤 |
EP0565825A1 (fr) * | 1992-04-16 | 1993-10-20 | Hüls Aktiengesellschaft | Procédé de préparation de dispersions aqueuses de polymères |
JPH0748550A (ja) * | 1993-08-06 | 1995-02-21 | Sekisui Chem Co Ltd | 粘着テープ又はシート |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Derwent World Patents Index; AN 93-299826(38), XP002007626 * |
DATABASE WPI Derwent World Patents Index; AN 95-126288(17), XP002007625 * |
Also Published As
Publication number | Publication date |
---|---|
GB9506495D0 (en) | 1995-05-17 |
ZA962586B (en) | 1996-07-30 |
AU5157496A (en) | 1996-10-16 |
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