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CN1320008C - Combination of acrylic ester containing ester group including partial radical of carboxyl group - Google Patents

Combination of acrylic ester containing ester group including partial radical of carboxyl group Download PDF

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Publication number
CN1320008C
CN1320008C CNB2005100245885A CN200510024588A CN1320008C CN 1320008 C CN1320008 C CN 1320008C CN B2005100245885 A CNB2005100245885 A CN B2005100245885A CN 200510024588 A CN200510024588 A CN 200510024588A CN 1320008 C CN1320008 C CN 1320008C
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acrylate
meth
monomer
cooh
acrylamide
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CN1687158A (en
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毛振民
詹晓平
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Shanghai Jiao Tong University
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Shanghai Jiao Tong University
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Abstract

本发明涉及一种包含酯基部分带羧基基团的丙烯酸酯的组合物，该组合物包括：(A)一种丙烯酸酯的酯基部分带有羧基基团；(B)一种丙烯酸酯或丙烯酰胺单体；(C)一种光引发剂，占组合物质量的0.1%～15%；组合物中单体A、B的比例可以任意调节。由此组合物制备得到的聚合物薄膜可用作经皮给药系统TDDs中的控释膜，通过调节组合物中单体A、B的种类和含量，可以微调薄膜物化性能，快速制备适用于不同药物的经皮给药系统中的控释膜。

The present invention relates to a composition comprising an acrylate having a carboxyl group in the ester group, the composition comprising: (A) an acrylate having a carboxyl group in the ester part; (B) an acrylate or Acrylamide monomer; (C) a photoinitiator, accounting for 0.1% to 15% of the mass of the composition; the ratio of monomers A and B in the composition can be adjusted arbitrarily. The polymer film prepared from this composition can be used as a controlled-release film in transdermal drug delivery system TDDs. By adjusting the type and content of monomers A and B in the composition, the physical and chemical properties of the film can be fine-tuned, and the rapid preparation is suitable for Controlled Release Membranes in Transdermal Delivery Systems for Different Drugs.

Description

Comprise ester group partly with the composition of the acrylate of carboxylic group
Technical field
The present invention relates to a kind of photocurable monomer composition, be specifically related to a kind of ester group that comprises, can be used as the release-controlled film in the preparation transdermal delivery system partly with the composition of the acrylate of carboxylic group.
Background technology
Transdermal delivery system is meant that medicine discharges from the device of particular design, by complete skin absorption, enters the controlled release drug administration formulation of systemic blood system.Transdermal delivery system can be divided into two big class, i.e. membrane controlled release type and skeleton dispersion patterns basically.The membrane controlled release type transdermal delivery system is that medicine or transdermal absorption accelerator are rolled into the storage storehouse by release-controlled film or other controlled-release materials, by the character control release rate of drugs of release-controlled film or controlled-release material.Scopolamine (trade(brand)name Transderm-Scop), clonidine (trade(brand)name CatapresTTS) are film controlling types in the at present commercially available patch, and controlling diaphragm is a microporous polypropylene membrane; Pannonit (trade(brand)name Transderm-Nitro), fentanyl (trade(brand)name Duragesic), estradiol (trade(brand)name Estraderm), testosterone (trade(brand)name Androderm) are film controlling types, and release-controlled film is a polyethylene vinyl acetate; Nicotine (trade(brand)name trade(brand)name NicoDerm CQ) is a film controlling type, and controlling diaphragm is a polyethylene film.
At European patent No.46069, U.S. Patent No. 3,797 is described in 494 and utilizes microporous membrane control rate of releasing drug.The hole of film from 0.1 to 0.85, the curvature of film from 1 to 10, from 10 to 100 microns of film thicknesses, the film of usefulness has polypropylene, tetrafluoroethylene, polycarbonate, polyvinyl chloride, cellulose acetate, nitrocellulose, polyacrylonitrile etc. for example.Their shortcoming is that the kind of the microporous membrane that can Gong select for use is few, does not satisfy the formulation that more medicine is made percutaneous dosing.
In U.S. Patent No. 6,537, the Scopolamine Patch that is described among the 571B1, U.S. Patent No. 4,681, the Deponit TTS that is described in 584, used release-controlled film all is the multipolymer of ethene-vinyl acetate.Shortcoming is an organic solvent residue problem in the ethylene-vinyl acetate copolymer, and needs constantly to regulate the content of vinyl acetate between to for plastic to regulate the permeability of medicine.
At European patent No.1103260A2, in the clonidine patch that is described among the U.S. Patent No. 2004/0028726A1, utilize vinylformic acid-(2-ethyl) own ester, methyl methacrylate, vinylformic acid and vinyl acetate, Raolical polymerizable takes place, and the multipolymer that obtains can be controlled the release of medicine simultaneously as pressure-sensitive adhesive layer and bin-storing layer in the patch.Shortcoming is that Raolical polymerizable is influenced by several factors, factors such as the time that responds, temperature of reaction, raw material initial concentration, solvent, and also there is the residue problem of organic solvent in patch.
The film of in transdermal delivery system, using, generally speaking the release-controlled film kind lacks, and alternative little, this brings very big obstruction for the exploitation of percutaneous drug administration preparation.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of excellent curing performance that has is provided, can produce the monomer composition of the polymkeric substance that can be used for the release-controlled film in the transdermal delivery system.
For the shortcoming that the kind that solves release-controlled film in the existing transdermal delivery system lacks, the present invention finds that on extensive and deep research basis it is abundant to adopt a kind of special photo curable monomer composition just can obtain kind, the release-controlled film of excellent performance.Said composition comprises: (A) a kind of ester group of acrylate is partly with carboxylic group; (B) a kind of acrylate or acrylamide monomer; (C) a kind of light trigger accounts for 0.1%～15% of composition quality; The ratio of monomer A, B can be regulated arbitrarily in the composition.
The ester group of using among the present invention is partly with the acrylic ester monomer general formula CR of carboxylic group 2R 1=CR 3COOR 4Expression, wherein R 1, R 2, R 3Be any substituting group, comprise-H ,-CH 3,-C 6H 5,-CH=CH 2,-OH ,-COOH ,-OCH 3,-SO 3H ,-NH 2,-N (CH 3) 3Cl, R 4Be the substituting group that has carboxyl, comprise-CH 2OOH ,-(CH 2) 2COOH ,-(CH 2) 3COOH ,-(CH 2) 4COOH ,-(CH 2) 5COOH ,-(CH 2) 6COOH.The example of using among the present invention is the 2-carboxy ethyl acrylate, but is not limited only to this monomer, and all ester groups are partly with the acrylate of carboxylic group can be as this monomer potential alternative.Be exemplified below: (methyl) vinylformic acid-2-carboxyl ethyl ester, (methyl) vinylformic acid-3-carboxyl propyl ester, (methyl) vinylformic acid-2-carboxyl propyl ester, (methyl) vinylformic acid-positive butyl ester of 4-carboxyl, (methyl) vinylformic acid-positive butyl ester of 3-carboxyl, (methyl) vinylformic acid-positive butyl ester of 2-carboxyl, (methyl) vinylformic acid-2-carboxyl isobutyl ester, the just own ester of (methyl) vinylformic acid-6-carboxyl, the just own ester of (methyl) vinylformic acid-5-carboxyl, the just own ester of (methyl) vinylformic acid-4-carboxyl, the just own ester of (methyl) vinylformic acid-3-carboxyl, (methyl) vinylformic acid-just own ester of 2-carboxyl or the like, but be not limited to above listed monomer.
The acrylic ester monomer of using among the present invention can be used general formula CR 2R 1=CR 3COOR 4Expression, wherein R 1, R 2, R 3Can be any substituting group, such as-H ,-CH 3,-C 6H 5,-CH=CH 2,-OH ,-COOH ,-OCH 3,-SO 3H ,-NH 2,-N (CH 3) 3Cl or the like, but be not limited to above listed substituting group.R 4Substituting group can be the group of carboxyl substituted, and example is identical with the acrylate monomer that ester group is partly with carboxyl substituent.
R in the described acrylic ester monomer general formula 4Substituting group can be an alkyl also, and the example of using among the present invention is a vinylformic acid n-dodecane ester, but is not limited only to this monomer, all R 4Substituting group is that the acrylate of alkyl can be as this monomer potential alternative.Be exemplified below :-CH 3,-C 2H 5,-C 3H 7,-(CH 2) 3CH 3,-(CH 2) 4CH 3,-(CH 2) 5CH 3,-(CH 2) 7CH 3,-(CH 2) 11CH 3,-CH 2CH=CH 2Or the like, but be not limited to above listed substituting group.
R in the described acrylic ester monomer general formula 4Substituting group can be the group that ester group replaces, and the example of using among the present invention is 1, the 6-hexanediol dimethacrylate, but be not limited only to this monomer, all R 4Substituting group is that the acrylate of the group of ester group replacement can be as this monomer potential alternative.Be exemplified below :-CH 2OOCCH=CH 2,-(CH 2) 2OOCCH=CH 2,-(CH 2) 3OOCCH=CH 2,-(CH 2) 4OOCCH=CH 2,-(CH 2) 5OOCCH=CH 2,-(CH 2) 6OOCCH=CH 2,-(CH 2) 8OOCCH=CH 2,-(CH 2) 2OOCC (CH 3)=CH 2,-(CH 2) 3OOCC (CH 3)=CH 2,-(CH 2) 4OOCC (CH 3)=CH 2,-(CH 2) 5OOCC (CH 3)=CH 2,-(CH 2) 6OOCC (CH 3)=CH 2,-(CH 2) 8OOCC (CH 3)=CH 2Or the like, but be not limited to above listed substituting group.
R in the described acrylic ester monomer general formula 4Substituting group can be the group that hydroxyl replaces, and the example of using among the present invention is 2-hydroxyl-3-phenoxy group propyl acrylate, but is not limited only to this monomer, all R 4Substituting group is that the acrylate of the group of hydroxyl replacement can be as these two monomer potential alternatives.Be exemplified below :-CH 2OH ,-(CH 2) 2OH ,-(CH 2) 3OH ,-(CH 2) 4OH ,-(CH 2) 5OH ,-CH 2CH (OH) CH 3,-CH 2CH (OH) C 2H 5,-CH 2CH (OH) C 3H 7,-CH 2CH (OH) CH 2OC 6H 5,-C 2H 5CH (OH) CH 3,-C 2H 5CH (OH) C 2H 5,-C 3H 6CH (OH) CH 3,-C 3H 6CH (OH) C 2H 5,-C 3H 6(OH) CH 2OC 6H 5Or the like, but be not limited to above listed substituting group.
R in the described acrylic ester monomer general formula 4Substituting group can also be the group that alkoxyl group replaces, and the example of using among the present invention is a 2-butoxy ethyl propenoate, but is not limited only to this monomer, all R 4Substituting group is that the acrylate of alkoxyl group can be as this monomer potential alternative.Be exemplified below :-CH 2OCH 2CH 3,-CH 2O (CH 2) 2CH 3,-CH 2O (CH 2) 3CH 3,-CH 2O (CH 2) 4CH 3,-CH 2O (CH 2) 6CH 3,-CH 2O (CH 2) 8CH 3,-(CH 2) 2OCH 2,-(CH 2) 2OCH 2CH 3,-(CH 2) 2O (CH 2) 2CH 3,-(CH 2) 3O (CH 2) 2CH 3,-(CH 2) 2O (CH 2) 4CH 3Or the like, but be not limited to above listed substituting group.
Acrylamide monomer of the present invention can be used general formula CR 2R 1=CR 3CONR 4Expression, wherein R 1, R 2, R 3, R 4Define identical with acrylate monomer.The acrylamide monomers of using among the present invention is N-(1,1-dimethyl-3-oxo butyl)-acrylamide, but is not limited only to this monomer, and all acrylamide monomers can be as this monomer potential alternative.The acrylamide monomers example is exemplified below: (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-(butoxymethyl) (methyl) acrylamide, N-(methylol) (methyl) acrylamide, N-[(trishydroxymethyl) methyl] (methyl) acrylamide, N-[3-(dimethylamino) propyl group] (methyl) acrylamide or the like, but be not limited to above listed monomer.
Among the present invention can with light trigger comprise the initiator of the ultraviolet light polymerization that is useful on, as diphenyl peroxide ketone, 1-hydroxycyclohexylphenylketone, bitter almond oil camphor propyl ether, but not only be confined to these light triggers, all are for the UV-light sensitivity, and the light trigger that can trigger monomer be cured reaction is all unrestricted.
The polymeric film that preparation of compositions among the present invention obtains can be used as the release-controlled film in the transdermal delivery system (TDDs), by regulating kind and the content of monomer A, B in the composition, can finely tune the film physical and chemical performance, prepare the release-controlled film in the transdermal delivery system that is applicable to different pharmaceutical fast.Can in mixing solutions, add softening agent when adopting preparation of compositions release-controlled film of the present invention, comprise Citrate trianion, phthalate, sebacate etc., can further improve the physicals of release-controlled film.The present invention has widened the material category of the release-controlled film in the preparation transdermal delivery system, has enlarged the material range of choice.
Description of drawings
Fig. 1 is the 2-carboxy ethyl acrylate and get 30ul, the permeability experiment of the release-controlled film that ultraviolet light polymerization obtains after vinylformic acid n-dodecane ester mixes by quality at 5: 5.
Embodiment
Following examples are to the further specifying of technical solution of the present invention, and are not construed as limiting the invention.
Embodiment 1
The 2-carboxy ethyl acrylate is mixed by mass ratio with vinylformic acid n-dodecane ester at 5: 5, add the diphenyl peroxide ketone of 5% (w/w) again, dissolving, filter, get mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.
The cured film that obtains places the Franz diffusion cell of improvement, is wintergreen oil solution in the supply pool, and accepting in the pond is the phosphate buffered saline buffer of pH7.4.Utilize the rate of release of efficient liquid phase chromatographic analysis wintergreen oil.See Fig. 1: wintergreen oil is to the permeability experiment (correlation coefficient r=0.9874) of cured film, and cured film has linear controlled-release function to medicine as can be seen from Figure.
Embodiment 2
With 2-carboxy ethyl acrylate and 1, the 6-hexanediol dimethacrylate is pressed mass ratio mixing in 2: 8 by quality, adds the diphenyl peroxide ketone of 8% (w/w) again, dissolving is filtered, and gets mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.
Embodiment 3
The 2-carboxy ethyl acrylate is mixed by mass ratio with vinylformic acid-4-hydroxyl butyl ester at 2: 8, add the diphenyl peroxide ketone of 5% (w/w) again, dissolving, filter, get mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.
Embodiment 4
The 2-carboxy ethyl acrylate is mixed by mass ratio with 2-butoxy ethyl propenoate at 7: 3, add the 1-hydroxycyclohexylphenylketone of 0.1% (w/w) again, get mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.
Embodiment 5
With 2-carboxy ethyl acrylate and N-(1,1-dimethyl-3-oxo butyl)-acrylamide press mass ratio 1: 9 mixing by quality, the bitter almond oil camphor propyl ether that adds 15% (w/w) again, dissolving, filter, get mixing solutions 30ul, be placed on the carrier substrates, coating is paved, and places ultraviolet light polymerization instrument completion of cure.

Claims (5)

1、一种包含酯基部分带羧基基团的丙烯酸酯的组合物，其特征在于该组合物包括：(A)一种丙烯酸酯的酯基部分带有羧基的单体；(B)一种丙烯酸酯或丙烯酰胺单体；和(C)一种用于紫外光固化的光引发剂，占组合物质量的O.1％～15％；组合物中单体A、B的比例可以任意调节；1. A composition comprising an acrylate with a carboxyl group in the ester group, characterized in that the composition includes: (A) a monomer with a carboxyl group in the ester group of an acrylate; (B) a Acrylate or acrylamide monomer; and (C) a photoinitiator for ultraviolet light curing, accounting for 0.1% to 15% of the mass of the composition; the ratio of monomers A and B in the composition can be adjusted arbitrarily ; 所述丙烯酸酯的酯基部分带有羧基的单体用通式CR2R1＝CR3COOR4表示，其中R1、R2、R3是任意取代基，R4是带有羧基的取代基；所述丙烯酸酯单体用通式CR2′R1′＝CR3′COOR4′表示，所述的丙烯酰胺单体用通式CR2′R1′＝CR3′CONR4′表示，其中R1’、R2’、R3’是任意取代基，R4’选自羧基、烷烃基、酯基、羟基或烷氧基。The monomer with carboxyl group in the ester part of the acrylate is represented by the general formula CR 2 R 1 =CR 3 COOR 4 , wherein R 1 , R 2 , R 3 are any substituents, and R 4 is a substituted carboxyl group. group; the acrylate monomer is represented by the general formula CR 2 ′R 1 ′=CR 3 ′COOR 4 ′, and the acrylamide monomer is represented by the general formula CR 2 ′R 1 ′=CR 3 ′CONR 4 ′ , wherein R 1 ', R 2 ', R 3 ' are any substituents, and R 4 ' is selected from carboxyl, alkane, ester, hydroxyl or alkoxy. 2、根据权利要求1的组合物，其特征在于所述丙烯酸酯的酯基部分带有羧基的单体、丙烯酸酯单体和丙烯酰胺单体通式中的R1、R2、R3、R1’、R2’、R3’各自独立地选自-H、-CH3、-C6H5、-CH＝CH2、-OH、-COOH、-OCH3、-SO3H、-NH2或-N(CH3)3Cl。2. The composition according to claim 1, characterized in that R 1 , R 2 , R 3 , R 1 ′, R 2 ′, and R 3 ′ are each independently selected from the group consisting of -H, -CH 3 , -C 6 H 5 , -CH═CH 2 , -OH, -COOH, -OCH 3 , -SO 3 H, -NH 2 or -N(CH 3 ) 3 Cl. 3、根据权利要求1的组合物，其特征在于所述丙烯酸酯的酯基部分带有羧基的单体通式中的R4选自-CH2COOH、-(CH2)2COOH、-(CH2)3COOH、-(CH2)4COOH、-(CH2)5COOH或-(CH2)6COOH。3. The composition according to claim 1, characterized in that R 4 in the general formula of the monomer having a carboxyl group in the ester group of the acrylate is selected from -CH 2 COOH, -(CH 2 ) 2 COOH, -( CH 2 ) 3 COOH, -(CH 2 ) 4 COOH, -(CH 2 ) 5 COOH or -(CH 2 ) 6 COOH. 4、根据权利要求1的组合物，其特征在于所述丙烯酸酯单体和丙烯酰胺单体通式中的R4’选自-CH3、-C2H5、-C3H7、-(CH2)3CH3、-(CH2)4CH3、-(CH2)5CH3、-(CH2)7CH3、-(CH2)11CH3、-CH2CH＝CH2、-CH2OH、-(CH2)2OH、-(CH2)3OH、-(CH2)4OH、-(CH2)5OH、-CH2CH(OH)CH3、-CH2CH(OH)C2H5、-CH2CH(OH)C3H7、-CH2CH(OH)CH2OC6H5、-C2H5CH(OH)CH3、-C2H5CH(OH)C2H5、-C3H6CH(OH)CH3、-C3H6CH(OH)C2H5、-C3H6(OH)CH2OC6H5、-CH2OOCCH＝CH2、-(CH2)2OOCCH＝CH2、-(CH2)3OOCCH＝CH2、-(CH2)4OOCCH＝CH2、-(CH2)5OOCCH＝CH2、-(CH2)6OOCCH＝CH2、-(CH2)8OOCCH＝CH2、-(CH2)2OOCC(CH3)＝CH2、-(CH2)3OOCC(CH3)＝CH2、-(CH2)4OOCC(CH3)＝CH2、-(CH2)5OOCC(CH3)＝CH2、-(CH2)6OOCC(CH3)＝CH2、-(CH2)8OOCC(CH3)＝CH2、-CH2COOH、-(CH2)2COOH、-(CH2)3COOH、-(CH2)4COOH、-(CH2)5COOH、-(CH2)6COOH、-CH2OCH2CH3、-CH2O(CH2)2CH3、-CH2O(CH2)3CH3、-CH2O(CH2)4CH3、-CH2O(CH2)6CH3、-CH2O(CH2)8CH3、-(CH2)2OCH2、-(CH2)2OCH2CH3、-(CH2)2O(CH2)2CH3、-(CH2)3O(CH2)2CH3或-(CH2)2O(CH2)4CH3。4. The composition according to claim 1, characterized in that R 4 ' in the general formula of the acrylate monomer and acrylamide monomer is selected from -CH 3 , -C 2 H 5 , -C 3 H 7 , - (CH 2 ) 3 CH 3 , -(CH 2 ) 4 CH 3 , -(CH 2 ) 5 CH 3 , -(CH 2 ) 7 CH 3 , -(CH 2 ) 11 CH 3 , -CH 2 CH═CH 2 , -CH 2 OH, -(CH 2 ) 2 OH, -(CH 2 ) 3 OH, -(CH 2 ) 4 OH, -(CH 2 ) 5 OH, -CH 2 CH(OH)CH 3 , - CH 2 CH(OH)C 2 H 5 , -CH 2 CH(OH)C 3 H 7 , -CH 2 CH(OH)CH 2 OC 6 H 5 , -C 2 H 5 CH(OH)CH 3 , - C 2 H 5 CH(OH)C 2 H 5 , -C 3 H 6 CH(OH)CH 3 , -C 3 H 6 CH(OH)C 2 H 5 , -C 3 H 6 (OH)CH 2 OC 6 H 5 , -CH 2 OOCCH=CH 2 , -(CH 2 ) 2 OOCCH=CH 2 , -(CH 2 ) 3 OOCCH=CH 2 , -(CH 2 ) 4 OOCCH=CH 2 , -(CH 2 ) 5 OOCCH=CH 2 , -(CH 2 ) 6 OOCCH=CH 2 , -(CH 2 ) 8 OOCCH=CH 2 , -(CH 2 ) 2 OOCC(CH 3 )=CH 2 , -(CH 2 ) 3 OOCC (CH 3 )=CH 2 , -(CH 2 ) 4 OOCC(CH 3 )=CH 2 , -(CH 2 ) 5 OOCC(CH 3 )=CH 2 , -(CH 2 ) 6 OOCC(CH 3 )= CH 2 , -(CH 2 ) 8 OOCC(CH 3 )=CH 2 , -CH 2 COOH, -(CH 2 ) 2 COOH, -(CH 2 ) 3 COOH, -(CH 2 ) 4 COOH, -(CH 2 ) 5 COOH, -(CH 2 ) 6 COOH, -CH 2 OCH 2 CH 3 , -CH 2 O(CH 2 ) 2 CH 3 , -CH 2 O(CH 2 ) 3 CH 3 , -CH 2 O( CH 2 ) 4 CH 3 , -CH 2 O(CH 2 ) 6 CH 3 , -CH 2 O(CH 2 ) 8 CH 3 , -(CH 2 ) 2 OCH 2 , -(CH 2 ) 2 OCH 2 CH 3 , -(CH 2 ) 2 O(CH 2 ) 2 CH 3 , -(CH 2 ) 3 O(CH 2 ) 2 CH 3 , or -(CH 2 ) 2 O(CH 2 ) 4 CH 3 . 5、根据权利要求1的组合物，其特征在于所述的丙烯酸酯的酯基部分带有羧基的单体选自2-羧基丙烯酸乙酯、(甲基)丙烯酸-2-羧基乙酯、(甲基)丙烯酸-3-羧基丙酯、(甲基)丙烯酸-2-羧基丙酯、(甲基)丙烯酸-4-羧基正丁酯、(甲基)丙烯酸-3-羧基正丁酯、(甲基)丙烯酸-2-羧基正丁酯、(甲基)丙烯酸-2-羧基异丁酯、(甲基)丙烯酸-6-羧基正己酯、(甲基)丙烯酸-5-羧基正己酯、(甲基)丙烯酸-4-羧基正己酯、(甲基)丙烯酸-3-羧基正己酯或(甲基)丙烯酸-2-羧基正己酯；所述的丙烯酸酯单体选自丙烯酸正十二烷酯、1，6-己二醇二甲基丙烯酸酯、2-羟基-3-苯氧基丙烯酸丙酯或2-丁氧基丙烯酸乙酯；所述的丙烯酰胺单体选自N-(1，1-二甲基-3-氧代丁基)-丙烯酰胺、(甲基)丙烯酰胺、N，N-二甲基(甲基)丙烯酰胺、N-异丙基(甲基)丙烯酰胺、N-(丁氧基甲基)(甲基)丙烯酰胺、N-(羟甲基)(甲基)丙烯酰胺、N-[(三羟甲基)甲基](甲基)丙烯酰胺或N-[3-(二甲基氨基)丙基](甲基)丙烯酰胺。5. The composition according to claim 1, characterized in that the monomer having a carboxyl group in the ester group of the acrylate is selected from the group consisting of 2-carboxyethyl acrylate, (meth)acrylate-2-carboxyethyl, ( Meth) acrylate-3-carboxypropyl, (meth)acrylate-2-carboxypropyl, (meth)acrylate-4-carboxy n-butyl, (meth)acrylate-3-carboxy n-butyl, ( 2-carboxy n-butyl methacrylate, 2-carboxy isobutyl (meth) acrylate, 6-carboxy n-hexyl (meth) acrylate, 5-carboxy n-hexyl (meth) acrylate, ( Meth) acrylate-4-carboxy n-hexyl, (meth) acrylate-3-carboxy n-hexyl or (meth) acrylate-2-carboxy n-hexyl; the acrylate monomer is selected from n-dodecyl acrylate , 1,6-hexanediol dimethacrylate, 2-hydroxyl-3-phenoxypropyl acrylate or 2-butoxy ethyl acrylate; the acrylamide monomer is selected from N-(1, 1-dimethyl-3-oxobutyl)-acrylamide, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-(butoxymethyl)(meth)acrylamide, N-(hydroxymethyl)(meth)acrylamide, N-[(trimethylol)methyl](meth)acrylamide or N -[3-(Dimethylamino)propyl](meth)acrylamide.
CNB2005100245885A 2005-03-24 2005-03-24 Combination of acrylic ester containing ester group including partial radical of carboxyl group Expired - Fee Related CN1320008C (en)

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CNB2005100245885A CN1320008C (en) 2005-03-24 2005-03-24 Combination of acrylic ester containing ester group including partial radical of carboxyl group
PCT/CN2006/000509 WO2006099818A1 (en) 2005-03-24 2006-03-24 Light curable monomer compostion and use thereof

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CNB2005100245885A CN1320008C (en) 2005-03-24 2005-03-24 Combination of acrylic ester containing ester group including partial radical of carboxyl group

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EP3210945B1 (en) * 2016-02-29 2019-04-10 Agfa-Gevaert Method of manufacturing an etched glass article

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045355A (en) * 1988-12-22 1990-09-19 Lts洛曼医疗系统公司 A kind ofly be used to produce to contain the method for calabar bean alkali as the Transcutaneous Therapeutic System of active component
CN1097635A (en) * 1993-07-22 1995-01-25 计威康 Medicine pressure-sensitive adhesive electrode
EP0913445A1 (en) * 1997-10-28 1999-05-06 National Starch and Chemical Investment Holding Corporation Enhancer tolerant pressure sensitive adhesives for transdermal drug delivery
WO2003101433A1 (en) * 2002-05-28 2003-12-11 LABTEC Gesellschaft für technologische Forschung und Entwicklung mbH Plaster containing fentanyl
US20040131826A1 (en) * 2003-01-06 2004-07-08 General Electric Company Radiation curable microstructure-bearing articles
CN1545408A (en) * 2001-08-24 2004-11-10 LTS��������ϵͳ�ɷݹ�˾ Transdermal therapeutic system based on polyacrylate adhesive patches without functional groups

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045355A (en) * 1988-12-22 1990-09-19 Lts洛曼医疗系统公司 A kind ofly be used to produce to contain the method for calabar bean alkali as the Transcutaneous Therapeutic System of active component
CN1097635A (en) * 1993-07-22 1995-01-25 计威康 Medicine pressure-sensitive adhesive electrode
EP0913445A1 (en) * 1997-10-28 1999-05-06 National Starch and Chemical Investment Holding Corporation Enhancer tolerant pressure sensitive adhesives for transdermal drug delivery
CN1545408A (en) * 2001-08-24 2004-11-10 LTS��������ϵͳ�ɷݹ�˾ Transdermal therapeutic system based on polyacrylate adhesive patches without functional groups
WO2003101433A1 (en) * 2002-05-28 2003-12-11 LABTEC Gesellschaft für technologische Forschung und Entwicklung mbH Plaster containing fentanyl
US20040131826A1 (en) * 2003-01-06 2004-07-08 General Electric Company Radiation curable microstructure-bearing articles

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