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CN1320005C - Combination of acrylic ester containing ester group including paraffin base - Google Patents

Combination of acrylic ester containing ester group including paraffin base Download PDF

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CN1320005C
CN1320005C CNB200510024589XA CN200510024589A CN1320005C CN 1320005 C CN1320005 C CN 1320005C CN B200510024589X A CNB200510024589X A CN B200510024589XA CN 200510024589 A CN200510024589 A CN 200510024589A CN 1320005 C CN1320005 C CN 1320005C
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acrylate
meth
monomer
acrylamide
group
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CN1687155A (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烷烃基的丙烯酸酯的组合物,该组合物包括:(A)一种丙烯酸酯CR2R1=CR3COOR4的R4是烷烃基取代的基团;(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。

Figure 200510024589

The present invention relates to a composition comprising an acrylate with an alkane group in the ester group, the composition comprising: (A) an acrylate CR 2 R 1 =CR 3 COOR 4 where R 4 is a group substituted by an alkane group ; (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.

Figure 200510024589

Description

Comprise ester group partly with the composition of the acrylate of alkyl
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 alkyl.
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 acrylate CR 2R 1=CR 3COOR 4R 4It is the group that alkyl replaces; (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 acrylate monomer general formula CR of alkyl 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 alkyl, comprise-(CH 2) 3CH 3,-(CH 2) 11CH 3,-CH 2CH=CH 2The acrylate monomer that the ester group of using among the present invention is partly with alkyl is a vinylformic acid n-dodecane ester, but is not limited only to this monomer, all R 4The acrylate that is the group of alkyl can be as this monomer potential alternative.Be exemplified below: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecane ester, (methyl) vinylformic acid dodecane ester, (methyl) lauryl acrylate, (methyl) vinylformic acid octadecane ester, (methyl) stearyl acrylate base ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) vinylformic acid butoxy ethyl ester, (methyl) vinylformic acid ethoxydiglycol ester, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid phenoxy ethyl, methoxyl group ethylene glycol (methyl) acrylate, (methyl) vinylformic acid ethoxy ethyl ester, (methyl) vinylformic acid Dicyclopentadiene (DCPD) ester, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid two cyclopentenes oxygen base ethyl esters, (methyl) vinylformic acid three ring esters in the last of the ten Heavenly stems, (methyl) isobornyl acrylate, (methyl) vinylformic acid norbornene ester, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid 7-amino-3,7-dimethyl monooctyl ester, (methyl) acryloyl morpholine, 2-(methyl) acrylyl oxy-ethyl phthalic ester, 2-(methyl) acrylyl oxy-ethyl hexahydrophthalic acid ester, 2-(methyl) acryloyl-oxy propyl group phthalic ester, 2-(methyl) acryloyl-oxy propyl group tetrahydrophthalic acid ester, 2-(methyl) acryloyl-oxy propyl group hexahydrophthalic acid ester, 2-(methyl) acrylyl oxy-ethyl succinate, acryloyl morpholine or the like, but be not limited to above listed substituting group.
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 an alkyl, the same R of example 4The acrylate monomer that is alkyl is identical.
R in the described acrylic ester monomer general formula 4Substituting group also 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 alkyl 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 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 of carboxyl substituted, and the example of using among the present invention is the 2-carboxy ethyl acrylate, but is not limited only to this monomer, all R 4Substituting group is that the acrylate of the group of carboxyl substituted can be as this monomer potential alternative.Be exemplified below :-CH 2COOH ,-(CH 2) 2COOH ,-(CH 2) 3COOH ,-(CH 2) 4COOH ,-(CH 2) 5COOH ,-(CH 2) 6COOH ,-(CH 2) 8COOH ,-(CH 2) 12COOH or 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 a vinylformic acid n-dodecane ester and get 30ul, the permeability experiment of the cured film that ultraviolet light polymerization obtains and the comparison of zoodermic transdermal test in vitro experiment after vinylformic acid-4-hydroxyl butyl ester mixes by mass ratio at 2: 8.
Fig. 2 is a vinylformic acid n-dodecane ester and get 30ul, the permeability experiment of the cured film that ultraviolet light polymerization obtains and the comparison of zoodermic transdermal test in vitro experiment after 2-hydroxyl-3-phenoxy group propyl acrylate mixes by mass ratio at 2: 8.
Embodiment
The following example of the present invention proposes for illustration purpose, and is not construed as limiting the invention.
Embodiment 1
Vinylformic acid n-dodecane ester 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.
The cured film that obtains places the Valia-Chien diffusion cell, is the Tenso-Timelets aqueous solution of 1mg/ml in the supply pool, and accepting in the pond is physiological saline.Utilize the rate of release of efficient liquid phase chromatographic analysis Tenso-Timelets.
Animal skin is relatively got fresh Kunming kind small white mouse skin of abdomen and is placed the Valia-Chien diffusion cell, is the Tenso-Timelets aqueous solution of 1mg/ml in the supply pool, and accepting in the pond is physiological saline.Utilize the rate of release of efficient liquid phase chromatographic analysis Tenso-Timelets.See Fig. 1: curve 1 is the transdermal test in vitro experiment (correlation coefficient r=0.9938) of Tenso-Timelets to cured film, and curve 2 is that Tenso-Timelets is tested zoodermic permeability, and cured film has linear controlled-release function to medicine as can be seen from Figure.
Embodiment 2
Vinylformic acid n-dodecane ester is mixed by mass ratio with 2-hydroxyl-3-phenoxy group propyl acrylate 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.
The cured film that obtains places the Valia-Chien diffusion cell, is wintergreen oil solution in the supply pool, and accepting in the pond is physiological saline.Utilize the rate of release of efficient liquid phase chromatographic analysis wintergreen oil.
Animal skin is relatively got fresh Kunming kind small white mouse skin of abdomen and is placed the Valia-Chien diffusion cell, is wintergreen oil solution in the supply pool, and accepting in the pond is physiological saline.Utilize the rate of release of efficient liquid phase chromatographic analysis wintergreen oil.See Fig. 1: curve 1 is the transdermal test in vitro experiment (correlation coefficient r=0.9873) of wintergreen oil to cured film, and curve 2 is that wintergreen oil is tested zoodermic permeability, and cured film has linear controlled-release function to medicine as can be seen from Figure.
Embodiment 3
With vinylformic acid n-dodecane ester and 1, the 6-hexanediol dimethacrylate is pressed mass ratio mixing in 2: 8, adds the diphenyl peroxide ketone of 15% (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 4
Vinylformic acid n-dodecane ester is mixed by mass ratio with the 2-carboxy ethyl acrylate at 5: 5, add the 1-hydroxycyclohexylphenylketone of 8% (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
Vinylformic acid n-dodecane ester is mixed by mass ratio with 2-butoxy ethyl propenoate at 6: 4, add the diphenyl peroxide ketone of 5% (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 6
Vinylformic acid n-dodecane ester and N-(1,1-dimethyl-3-oxo butyl)-acrylamide are pressed mass ratio mixing in 8: 2, add the bitter almond oil camphor propyl ether 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.

Claims (5)

1、一种包含酯基部分带烷烃基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烷烃基的单体;(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0.1%~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 an alkane group in the ester group, characterized in that the composition includes: (A) a monomer with an alkane group in the ester group of an acrylate; (B) a Acrylate or acrylamide monomer; and (C) a photoinitiator for UV 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烷烃基的单体用通式CR2R1=CR3COOR4表示,其中R1、R2、R3是任意取代基,R4是带有烷烃基的取代基;所述丙烯酸酯单体用通式CR2′R1′=CR3′COOR4′表示,所述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’选自烷烃基、羟基、酯基、羧基或烷氧基。The monomer with alkane 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 , and R 3 are any substituents, and R 4 is a monomer with alkane group. substituent; 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 ′ Represents, wherein R 1 ', R 2 ', R 3 ' are any substituents, and R 4 ' is selected from alkane group, hydroxyl group, ester group, carboxyl group or alkoxy group. 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烷烃基的单体、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 , and R 3 in the general formula of the monomer having an alkane group in the ester group of the acrylate, the acrylate monomer and the acrylamide monomer , R 1 ', R 2 ', R 3 ' are each independently selected from -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烷烃基的单体通式中的R4选自-(CH2)3CH3、-(CH2)11CH3或-CH2CH=CH23. The composition according to claim 1, characterized in that R 4 in the general formula of the monomer having an alkane group in the ester part of the acrylate is selected from -(CH 2 ) 3 CH 3 , -(CH 2 ) 11 CH 3 or -CH 2 CH=CH 2 . 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-(CH2)3CH3、-(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、-(CH2)8COOH、-(CH2)12COOH、-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)4CH34. 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 2 ) 3 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 ) 8 COOH, -(CH 2 ) 12 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烷烃基的单体选自丙烯酸正十二烷酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸十一烷酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十八烷酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸乙氧基二甘醇酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苯氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸二环戊二烯酯、(甲基)丙烯酸二环戊烯酯、(甲基)丙烯酸二环戊烯氧基乙酯、(甲基)丙烯酸三环癸酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸冰片酯、(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二乙基氨基乙酯、(甲基)丙烯酸7-氨基-3,7-二甲基辛酯、(甲基)丙烯酰吗啉、2-(甲基)丙烯酰氧乙基邻苯二甲酸酯、2-(甲基)丙烯酰氧乙基六氢邻苯二甲酸酯、2-(甲基)丙烯酰氧丙基邻苯二甲酸酯、2-(甲基)丙烯酰氧丙基四氢邻苯二甲酸酯、2-(甲基)丙烯酰氧丙基六氢邻苯二甲酸酯、2-(甲基)丙烯酰氧乙基琥珀酸酯或丙烯酰吗啉;所述的丙烯酸酯单体选自2-羟基-3-苯氧基丙烯酸丙酯、1,6-己二醇二甲基丙烯酸酯、2-羧基丙烯酸乙酯或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 an alkane group in the ester part of the acrylate is selected from the group consisting of n-dodecyl acrylate, methyl (meth)acrylate, (meth) Ethyl acrylate, Propyl (meth)acrylate, Isopropyl (meth)acrylate, Butyl (meth)acrylate, Amyl (meth)acrylate, Isobutyl (meth)acrylate, (Meth) tert-butyl acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate ) 2-ethylhexyl acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, deca(meth)acrylate Dialkyl, lauryl (meth)acrylate, octadecyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyl (meth)acrylate Ethyl ester, Ethoxydiethylene glycol (meth)acrylate, Benzyl (meth)acrylate, Cyclohexyl (meth)acrylate, Phenoxyethyl (meth)acrylate, Methoxyethylene glycol (Meth)acrylate, Ethoxyethyl (meth)acrylate, Dicyclopentadienyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, Dicyclopentene (meth)acrylate Oxyethyl ester, Tricyclodecanyl (meth)acrylate, Isobornyl (meth)acrylate, Bornyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, Dimethyl (meth)acrylate Ethylaminoethyl ester, 7-amino-3,7-dimethyloctyl (meth)acrylate, (meth)acryloylmorpholine, 2-(meth)acryloyloxyethylphthalic acid Esters, 2-(meth)acryloyloxyethylhexahydrophthalate, 2-(meth)acryloyloxypropylphthalate, 2-(meth)acryloyloxypropyl 2-(meth)acryloyloxypropylhexahydrophthalate, 2-(meth)acryloyloxyethylsuccinate or acryloylmorpholine; The acrylate monomer is selected from 2-hydroxy-3-phenoxypropyl acrylate, 1,6-hexanediol dimethacrylate, 2-carboxy ethyl acrylate or 2-butoxy ethyl acrylate ; The acrylamide monomer is selected from N-(1,1-dimethyl-3-oxobutyl)-acrylamide, (meth)acrylamide, N,N-dimethyl (methyl) Acrylamide, N-isopropyl(meth)acrylamide, N-(butoxymethyl)(meth)acrylamide, N-(hydroxymethyl)(meth)acrylamide, N-[(tri Hydroxymethyl)methyl](meth)acrylamide or N-[3-(dimethylamino)propyl](meth)acrylamide.
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US20040131826A1 (en) * 2003-01-06 2004-07-08 General Electric Company Radiation curable microstructure-bearing articles
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