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 PDF

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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
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WO
WIPO (PCT)
Prior art keywords
formula
adhesive
salt
polymer
compounds
Prior art date
Application number
PCT/GB1996/000782
Other languages
English (en)
Inventor
Hazel Ann King
John Kenneth Hicks
Original Assignee
Smith & Nephew Plc
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 Smith & Nephew Plc filed Critical Smith & Nephew Plc
Priority to AU51574/96A priority Critical patent/AU5157496A/en
Publication of WO1996030429A1 publication Critical patent/WO1996030429A1/fr

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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)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Hematology (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials For Medical Uses (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne des composés qui sont utilisés comme agents tensio-actifs polymérisables pour des adhésifs, notamment des adhésifs médicaux. Ces composés comportent des résidus d'alcools ou d'acides à chaînes longues et des anhydrides d'acide dibasique. Ces agents tensio-actifs sont copolymérisables avec des monomères acryliques afin de former des adhésifs utilisables pour enduire des substrats flexibles tels que des films sur du tissu afin de former des pansements adhésifs médicaux et chirurgicaux.
PCT/GB1996/000782 1995-03-30 1996-04-01 Agents tensio-actifs, adhesifs et pansements formes a partir de ceux-ci WO1996030429A1 (fr)

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
GBGB9506495.2A GB9506495D0 (en) 1995-03-30 1995-03-30 Surfactants
GB9506495.2 1995-03-30

Publications (1)

Publication Number Publication Date
WO1996030429A1 true WO1996030429A1 (fr) 1996-10-03

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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)

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AU (1) AU5157496A (fr)
GB (1) GB9506495D0 (fr)
WO (1) WO1996030429A1 (fr)
ZA (1) ZA962586B (fr)

Citations (6)

* Cited by examiner, † Cited by third party
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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
AU5157496A (en) 1996-10-16
ZA962586B (en) 1996-07-30

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