CN101286006A - Radiation curable developing polyurethane and radiation curable developing light resistance composition - Google Patents
Radiation curable developing polyurethane and radiation curable developing light resistance composition Download PDFInfo
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- CN101286006A CN101286006A CNA2007100903817A CN200710090381A CN101286006A CN 101286006 A CN101286006 A CN 101286006A CN A2007100903817 A CNA2007100903817 A CN A2007100903817A CN 200710090381 A CN200710090381 A CN 200710090381A CN 101286006 A CN101286006 A CN 101286006A
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Abstract
The invention discloses a polyurethane which can be radiated, solidified and developed, and optical resistance composition which comprises the polyurethane and can be radiated, solidified and developed; the polyurethane consists of a main chain carboxylic group, a side chain acryloyl and repeated units (I), (II) and (III) as follows, which are arranged irregularly: R is C<1-12> direct chain or branched alkylidene, C<3-8> ring-shaped alkylidene, phenylene, biphenylene, naphthylene moiety, xylylene, xylidine, -Ph-A-Ph- group (wherein, A is CH2, -NH- or -O-); R' is dimethyl group; the repeated units (I), (II) and (III) can be provided with one or more OH substituents; furthermore R'' is C<1-6> alkyl of direct chain or branch chain provided with one or more OH substituents; the weight average molecular weight of the polyurethane measured by gel permeation chromatography is ranged from 3000 to 400,000 and the acid value thereof is ranged from 5 to 120 mgKOH/g.
Description
Technical field:
The light resistance composition that the present invention relates to a kind of Polyurethane of can develop by radiation curing and contain the radiation-curable development of this Polyurethane.
Background technology:
The colored filter of Thin Film Transistor-LCD (TFT LCD) is one of significant components in the general LCD, it is the colorize purposes that can be used for the shown image of liquid crystal indicator, main function is that white backlight is converted to redness (R), green (G), blue three primary colors such as (B), is formed full-colorization of display purpose.
The making of color filter patterns layer at present, it mostly is mode with rotary coating, evenly coat photoresist on the base material, and earlier via the prebake conditions mode with removal of solvents, again through light shield with the regioselectivity exposure of desire sclerosis, the processing procedure that makes it to harden with alkaline development and heating subsequently, so in regular turn three kinds of colors of RGB are etched on the base material behind the triplicate.
At present color liquid crystal display arrangement mainly is to use glass as substrate, but it has easily problem such as break, thick and heavy.And be head it off, just dropped into the research of certain degree on the developing material of flexible display, so that can reach lightweight, be difficult for broken, easy to carry and can roll up advantages such as flexible.In Japanese kokai publication hei 11-271736 communique etc., have the relevant research of using plastic base is discussed, but generally speaking, its plastic base has can't be in the problem of pyroprocessing; And in TOHKEMY 2000-214468 communique content, have and mention the hardening at subcritical temerature possibility of using plastic base.
Because the situation of above-mentioned technology, the inventor etc. carry out broad research to the can develop by radiation curing resin, and develop it and be applied to glass substrate and plastic base, in two kinds of high temperature process (glass substrate) or low temperature process (plastic base) all can colored filter can develop by radiation curing composition, thereby finish the present invention.
Summary of the invention;
Technical matters to be solved by this invention is: at above-mentioned the deficiencies in the prior art, and the light resistance composition that a kind of Polyurethane of can develop by radiation curing is provided and contains its radiation-curable development.
In order to solve the problems of the technologies described above; the technical solution adopted in the present invention is: a kind of Polyurethane of can develop by radiation curing; its main chain has the carboxylic acid group and has the side chain acryloyl group, and by following repetitive (I), (II) and (III) constituted with random arrangement:
Wherein:
R is C
1-12Straight chain or branch's alkylidene, C
3-8Cyclic alkylidene, phenylene, biphenylene, naphthylene, xylylene, methylene anilino-,-(wherein A is CH to the Ph-A-Ph-base
2,-NH-or-O-), these bases again can be according to circumstances through C
1-6Alkyl replaces;
R ' is the divalent aliphatic base, can have one or more OH substituting group on it again, this OH substituting group again can be according to circumstances and then and di-isocyanate reaction; And
R " be C with the substituent straight chain of one or more OH or branched chain
1-6Alkyl, this OH substituting group again can be according to circumstances and then and di-isocyanate reaction,
The weight average molecular weight that this Polyurethane is measured with GPC (gel permeation chromatography) is in 3,000～400,000 scope; And acid number is 5～120mgKOH/g.
Main chain of the present invention has the carboxylic acid group and has the side chain acryloyl group and by the preparation of repetitive (I), (II) and the Polyurethane that (III) constituted; system makes the compound that contains at least two hydroxyls and a carboxylic acid group functional group (better contain two hydroxyls and contain a carboxylic acid group functional group's compound); and the polyvalent alcohol of selecting for use (being preferably dibasic alcohol) elder generation and di-isocyanate reaction; obtain the Polyurethane that main chain has the carboxylic acid group functional group, carry out ring-opening reaction by its carboxylic-acid functional base and the acrylate monomer that contains an epoxy radicals again subsequently and make.This polyvalent alcohol of selecting for use is nonessential composition, uses as chain extender according to circumstances in the present invention.
Its reaction exemplary flow is as follows:
The reaction synoptic diagram
Wherein:
R is C
1-12Straight chain or branch's alkylidene, C
3-8Cyclic alkylidene, phenylene, biphenylene, naphthylene, xylylene, methylene anilino-,-(wherein A is CH to the Ph-A-Ph-base
2,-NH-or-O-), these bases again can be according to circumstances through C
1-6Alkyl replaces;
R ' is the divalent aliphatic base, can have one or more OH substituting group on it again, this OH substituting group again can be according to circumstances and then and di-isocyanate reaction; And
R " be the straight chain with one or more OH substituting group or the C of branched chain
1-6Alkyl, this OH substituting group again can be according to circumstances and then and di-isocyanate reaction,
Polyurethane of the present invention has the weight average molecular weight (hereinafter to be referred as Mw) measured with GPC (gel permeation chromatography) 3,000～400, and 000; Be preferably 6,000～80,000 scope; And acid number is 5～120mgKOH/g, is preferably 10～60mgKOH/g.
The present invention is the light resistance composition of relevant a kind of can develop by radiation curing again, and it comprises the Polyurethane of the present invention (A) that repetitive constituted, the acrylic monomers (B) shown in reaching (III) by formula (I), (II), reaches light initiator (C).
In the light resistance composition of the present invention, of the present invention by formula (I), (II) and the part by weight (A) of the Polyurethane of the present invention (A) that repetitive constituted (hereinafter claiming Polyurethane (A) sometimes) (III) and acrylic monomers (B): as to be 40～90: 10～60 (B).And the content of light initiator (C) with respect to Polyurethane (A) and acrylic monomers (B) gross weight, is 1～50% (weight).
Constituent of the present invention can comprise one or more in then auxiliary agent (D), colorant (E), spreading agent (F) and the solvent (G) again according to circumstances.The use amount of these compositions can change in wide scope as long as the purpose that the present invention desired to reach is had no adverse effects.
Embodiment:
Have the carboxylic acid group and have the side chain acryloyl group and in order to the preparation main chain among the present invention by repetitive (I); (II) reach in the Polyurethane that (III) is constituted; this diisocyanate means the compound that a part has two isocyanate functional groups; for example can use 1; 3-phenylene diisocyanate (MDI); 1; the 4-phenylene diisocyanate; 4; 4 '-biphenyl diisocyanate; 1; the 5-naphthalene diisocyanate; 4; 4 '-methyl diphenylene diisocyanate; 2; 4-or 2; 6-xylyl diisocyanate; the para-totuidine diisocyanate; 4; 4 '-diphenyl ether diisocyanate; 1; 3-or 1; the 4-Xylene Diisocyanate; 1; 3-cyclopentyl diisocyanate; 1; the 4-cyclohexane diisocyanate; 1; the 3-cyclohexane diisocyanate; 3-isocyanates ylmethyl-3; 5; 5-3-methyl cyclohexanol based isocyanate (isoflurane chalcone diisocyanate); methyl-2; the 4-cyclohexane diisocyanate; methyl-2; the 6-cyclohexane diisocyanate; trimethylene diisocyanate; tetramethylene diisocyanate; hexamethylene diisocyanate; pentamethylene diisocyanate; 1; the 2-trimethylene diisocyanate; 1; 2-butylidene diisocyanate; 2,3-butylidene diisocyanate; 1,3-butylidene diisocyanate; 2; 4; 4-or 2,2, the 4-trimethyl hexamethylene diisocyanate.
Have the carboxylic acid group in order to the preparation main chain among the present invention and have the side chain acryloyl group and by in repetitive (I), (II) and the Polyurethane that (III) constituted, the polyvalent alcohol that this is selected for use, can use mean molecular weight is 400～5,000 polyvalent alcohol, polyether glycol for example, as poly-(ethylene glycol), poly-(propylene glycol), poly-(butylene glycol) (PTMEG); Polyester polyol is as poly-(ethylene glycol adipate) glycol, poly-(decanedioic acid butanediol ester) glycol, poly-(hexane diacid hexanediol ester) glycol, poly-(hexane diacid 3-methyl isophthalic acid, the inferior pentadiol ester of 5-) glycol, poly-(decanedioic acid 3-methyl isophthalic acid, the inferior pentadiol ester of 5-) glycol, polycaprolactone glycol and poly-(Beta-methyl-δ-Wu Neizhi) glycol; Polycarbonate (being the master's) glycol is as poly-(hexa-methylene carbonic ester) glycol and poly-(3-methyl isophthalic acid, 5-pentylidene carbonic ester) glycol; The polyester-polycarbonate polyvalent alcohol; The hydrogenated products of the hydrogenated products of polyolefin polyhydric alcohol such as tygon polyvalent alcohol, polypropylene polyvalent alcohol, polybutylene polyvalent alcohol, polybutadiene polyol, polybutadiene polyol, polyisoprene polyvalent alcohol and polyisoprene polyvalent alcohol.
Have the carboxylic acid group in order to the preparation main chain among the present invention and have the side chain acryloyl group and by in repetitive (I), (II) and the Polyurethane that (III) constituted; the compound that has two or more hydroxyls and contain a carboxylic acid group functional group can be given an example as two (methylol) propionic acid (DMPA, Lancaster product), CAPA
HC1100 (polycaprolactone with pendant carboxylic acid functional group, SOLVAY company product), 2-ethylene glycol-2-methyl-2-glycolic acid.
Have the carboxylic acid group in order to the preparation main chain among the present invention and have the side chain acryloyl group and by in repetitive (I), (II) and the Polyurethane that (III) constituted; acryloyl monomer with epoxy radicals can be given an example as glycidyl methacrylate (GMA, Dow company product).
Main chain of the present invention has the carboxylic acid group and has the side chain acryloyl group and reach the Polyurethane that (III) is constituted by repetitive (I), (II); owing to have the amine ester group of higher molecular weight and more easy formation hydrogen bond and have acrylic for radiation curing and crosslinked, thus can improve solidified after-product rerum natura, follow property and thermotolerance.
The light resistance composition of the can develop by radiation curing that the present invention is relevant is to comprise that (A) main chain has the carboxylic acid group and has the side chain acryloyl group and by repetitive (I), (II) and the Polyurethane that (III) is constituted, (B) acrylic monomers, and (C) light initiator.
Used acrylic monomers (B) in the constituent of the present invention, can give an example as list, two-, three-or many-acrylic acid functional group monomer.Single acrylic acid functional group monomer can give an example as acrylic acid 2-phenoxy group ethyl ester, acrylic acid tetrahydrofuran base ester, isobornyl acrylate, isobornyl methacrylate, acrylic acid 2-(2-ethoxy ethoxy) ethyl ester, isodecyl acrylate, acrylic acid Lauryl Ester and methacrylic acid Lauryl Ester.Diacrylate functional group monomer can give an example as diacrylate tripropylene glycol ester, diacrylate 1,6-hexanediol ester, dimethacrylate 1,6-hexanediol ester, dipropylene glycol diacrylate, diethyleneglycol dimethacrylate, Ethylene glycol dimethacrylate, diacrylate triglycol ester, dimethacrylate triglycol ester, diacrylate TEG ester, dimethacrylate TEG ester.Three acrylic acid functional groups or many acrylic acid functional group monomer can give an example as three acrylic acid three (methylol) propyl ester, trimethyl acrylic acid three (methylol) propyl ester, tetrapropylene acid two (three (methylol) propyl ester), five acrylic acid dipentaerythritol ester and six acrylic acid dipentaerythritol ester etc.These acrylic monomers can use or mix two or more uses separately.Its use amount is for making the part by weight of Polyurethane (A) with main chain carboxylic acid group and side chain acryloyl structure and acrylic monomers (B) 40～90: 10～60 scope.
Light initiator (C) used in the constituent of the present invention is for being subjected under the radiant light irradiations such as visible light, ultraviolet light, extreme ultraviolet light, electron beam and X ray, cracking can take place and produce as free radical, kation or negative ion isoreactivity site in its molecular structure, and with have main chain carboxylic acid group and side chain acryloyl structure Polyurethane (A) and acrylic monomers (B) and carry out polyreaction.
Light initiator (C) example can be given an example as imidazoles as 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-wantonly (4-methoxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-wantonly (4-phenyloxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-wantonly (4-methoxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-wantonly (4-phenyloxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-wantonly (4-methoxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-wantonly (4-phenyloxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-wantonly (4-methoxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-bromophenyls)-4,4 ', 5,5 '-wantonly (4-phenyloxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-wantonly (4-methoxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-wantonly (4-phenyloxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-wantonly (4-methoxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-wantonly (4-phenyloxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-cyano-phenyl)-4,4 ', 5,5 '-wantonly (4-methoxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-cyano-phenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-cyano-phenyls)-4,4 ', 5,5 '-wantonly (4-phenyloxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-wantonly (4-methoxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-aminomethyl phenyls)-4,4 ', 5,5 '-wantonly (4-phenyloxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-ethylphenyl)-4,4 ', 5,5 '-wantonly (4-methoxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-ethylphenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-ethylphenyls)-4,4 ', 5,5 '-wantonly (4-phenyloxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-phenyl)-4,4 ', 5,5 '-wantonly (4-methoxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-phenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-phenyl)-4,4 ', 5,5 '-wantonly (4-phenyloxycarbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2-cyano-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4-dicyano phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-tricyano phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-3,5-dimethylphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trimethylphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2-ethylphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4-diethyl phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-triethyl phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4-diphenyl phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-triphenyl phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole or the like with and like derivatives; Be preferably 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole and 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole.
Light initiator (C) can give an example again as benzoin (Benzoin) class light initiator for example benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether, methyl-2-benzoyl benzoic ether etc. with and like derivatives.
Light initiator (C) can be given an example as the acetophenones structure example again as 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 2, the 2-dimethoxy-acetophenone, 2, the 2-diethoxy acetophenone, 2-methyl-(4-methyl mercapto phenyl)-2-morpholinyl-1-third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) fourth-1-ketone, the 1-hydroxycyclohexylphenylketone, 2,2 '-dimethoxy-1,2-diphenyl second-1-ketone, 4-triazobenzene ethyl ketone, 4-azido benzylidene acetophenone etc. and like derivatives.
Light initiator (C) can be given an example again as benzophenone such as benzophenone, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylin) benzophenone, 3,3 '-dimethyl-4-methoxy benzophenone etc. and like derivatives thereof.
Light initiator (C) can be the light initiator with α-diketone structure again, for example diacetyl formic ether, dibenzoyl carbamate, toluyl carbamate etc. and like derivatives; Have the light initiator of multinuclear quinone structure such as anthraquinone, 2-EAQ, 2-tributyl anthraquinone, 1,4-naphthoquinones etc. and like derivatives; The light initiator of flavonoids (xanthone) structure such as flavones, sulfo-flavones, 2, the 4-diethyl sulfide is for flavones, 2-chlorine sulfo-flavones etc. and like derivatives; Have the light initiator of diazonium structure such as 4-diazonium diphenylamine, 4-diazonium-4 '-methoxyl diphenylamine, 4-azido-3-methoxyl diphenylamine etc. and like derivatives; Light initiator such as 2-(2 '-furyl ethylidene)-4 with triazine structure, two (the trichloromethyl)-s-triazines of 6-, 2-(3 ', 4 '-dimethoxy-styryl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4 '-methoxyl naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(2 '-bromo-4 '-aminomethyl phenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(2 '-thienyl ethylidene)-4, two (trichloromethyl)-s-triazines of 6-etc. and like derivatives.
Except above-mentioned cited light initiator; also can use 4-diazobenzene formaldehyde, azido pyrene, two (2; 6-dimethoxy benzoyl) 2,4,4-tri-methyl-amyl phosphorous oxides, N-phenyl sulfo-acridone, triphenyl pyrene perchlorate etc. and like derivatives.These light initiators can also use separately can mix two or more uses.Its use amount is 1～50% (weight) with respect to Polyurethane (A) and acrylic monomers (B) gross weight.
Can contain then auxiliary agent (D) in the light resistance composition of the present invention again, the example comprises silanes with vinyl functional group such as vinyl trichloroethanes, vinyltrimethoxy silane, vinyltriethoxysilane; Contain the silanes of epoxide functional groups such as 2-(3,4-epoxy radicals cyclohexyl)-ethyl trimethoxy silane, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxypropyl triethoxysilane; The silanes that contains methacryloxy is 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane for example; The silanes such as the 3-acryloxy propyl trimethoxy silicane that contain acryloxy; Amino-contained functional group's silanes such as N-(2-amido ethyl)-3-aminocarbonyl propyl methyl dimethoxysilane, N-(2-amido ethyl)-3-aminocarbonyl propyl trimethoxy silane, N-(2-amido ethyl)-3-aminocarbonyl propyl triethoxysilane, 3-aminocarbonyl propyl trimethoxy silane, 3-aminocarbonyl propyl triethoxysilane, 3-triethoxysilicane alkyl-N-(1,3-dimethyl butylidene) propyl group amine, N-phenyl-3-aminocarbonyl propyl trimethoxy silane, N-(vinyl benzyl)-2-aminocarbonyl propyl trimethoxy silane hydrochloride; The silanes such as the 3-urea groups propyl-triethoxysilicane that contain the urea/ureido functional base; The silanes such as the 3-r-chloropropyl trimethoxyl silane that contain the chloropropyl functional group; Contain sulfhydryl functional group's silanes such as 3-sulfhydryl propyl group methyl dimethoxysilane, 3-sulfhydryl propyl trimethoxy silicane; Silanes such as two (tri-ethoxy silylpropyl) four thioethers of containing the thioether functional group; The silanes such as the different hydracid ester group of the 3-propyl-triethoxysilicane that contain the isocyanate group functional group.Then the use amount of auxiliary agent (D) with respect to Polyurethane (A) and acrylic monomers (B) gross weight, is about 0.1～5% (weight).
Can contain colorant (E) in the light resistance composition of the present invention again, it can use has stable on heating organic pigment, for example C.I. pigment yellow (Pigment Yellow) 83, C.I. pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150 and C.I. pigment yellow 155; C.I. pigment orange 71; C.I. pigment violet 19 and C.I. pigment Violet 23; C.I. pigment red 4 8:1, C.I. pigment red 4 8:2, C.I. pigment red 4 8:3, C.I. pigment red 4 8:4, C.I. pigment red 122, C.I. paratonere 177, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 209, C.I. paratonere 224 and C.I. paratonere 254; C.I. pigment blue 15: 3, C.I. pigment blue 15: 4 and the C.I. pigment blue 15: 6; C.I. pigment Green 7 and C.I. pigment green 36; C.I. pigment brown 23 and C.I. pigment brown 25; C.I. pigment black 1 and C.I. pigment black 7.(C.I is formulated announcement by The Society of Dyers and Colourists Co.).Above-mentioned colorant can use separately or two or more use capable of being combined, and its use amount, with respect to Polyurethane (A) and acrylic monomers (B) gross weight, is about 70～600% (weight).
Can contain spreading agent (F) in the light resistance composition of the present invention again, the example comprises the S32000 that Avecia company is for example produced, its acid amides that to be a kind of cationic poly (alkyl imines) form with the hydroxy stearic acid ester reaction with free carboxy.Add after abrasive machine grinds and to help the colorant stable dispersion.Its use amount with respect to Polyurethane (A) and acrylic monomers (B) gross weight, is about 3～15% (weight).
In the light resistance composition of the present invention, optionally also can comprise solvent (G), be in order to obtain the maintenance liquid state and to control constituent the being suitable for viscosity of spraying.Used solvent is so long as solubilized or disperse composition contained in the above-mentioned constituent, do not participate in reaction and have suitable volatility and get final product.
Spendable solvent for example as: (gathering) alkylene glycols monoalky lether such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl n-propyl ether, the glycol monomethyl n-butyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, DPGME, dihydroxypropane single-ethyl ether, the single n-propyl ether of dipropylene glycol, the single n-butyl ether of dipropylene glycol, tripropylene glycol monomethyl ether and tripropylene glycol list ethylether; (gathering) alkylene glycols monoalky lether acetate esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and propylene glycol list ethylether acetic acid esters; Other is as ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofurans; Ketone is methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone for example; Lactic acid alkane ester class such as 2 hydroxy propanoic acid methyl esters and 2 hydroxy propanoic acid ethyl ester; The ester class comprises 2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, acetate 3-methyl-3-methoxyl butyl ester, propionic acid 3-methyl-3-methoxyl butyl ester, ethyl acetate, n-butyl acetate, isobutyl acetate, isoamyl formate, isoamyl acetate, n-butyl propionate, isopropyl isobutyrate, ethyl butyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate and 2-ketobutyric acid ethyl ester; Aromatic series hydrocarbons such as toluene and dimethylbenzene; Amide-type such as N-Methyl pyrrolidone (NMP), N, dinethylformamide and N,N-dimethylacetamide etc.
Above-mentioned solvent can use or make up two or more uses separately.There is no particular restriction for the addition of solvent, as long as can reach required viscosity, but general better accounting for respect to Polyurethane (A) and acrylic monomers (B) gross weight is about 200～2500% (weight).
The present invention will be with the following example further specifying the present invention, only these embodiment only in order to explanation the present invention not in order to limit the scope of the invention.
In the following example, used MDI (-phenylene vulcabond) be available from BASF AG; Wherein dibasic alcohol PPG-1000 (poly-(propylene glycol)-1000) is that molecular weight is 1000 gram/moles available from steady good high polymer chemistry industry (thigh) company; Dibasic alcohol CAPA
2101A (polycaprolactone glycol) is available from SOLVAY company, and molecular weight is about 1000 gram/moles, and the hydroxyl valency is 112 milligrams of KOH/ grams; Dibasic alcohol PC-diol PCDL) be the product available from company of Japanese Asahi Chemical Industry, molecular weight is about 1000 gram/moles, and the hydroxyl valency is 100～120 milligrams of KOH/ grams; Dibasic alcohol PTMEG (poly-(butylene glycol)) is a Mitsubishi KCC product, and molecular weight is about 1000 gram/moles; The Compound D MPA (two (methylol) propionic acid) that has dibasic alcohol and contain a carboxylic acid group functional group is available from the Lancaster product, has dibasic alcohol and contains a carboxylic acid group functional group's Compound C APA
HC1100 is a SOLVAY company product, and molecular weight is about 1000 gram/moles, and the hydroxyl valency is 110 milligrams of KOH/ grams, and the carboxylic acid valency is less than 60 milligrams of KOH/ grams; For the GMA (glycidyl methacrylate) of the acrylate monomer that contains an epoxy radicals is a Dow CHEMICAL company product, molecular weight is 142 gram/moles; Used solvent PMA (propylene glycol monomethyl ether) then is the product of DOWCHEMICAL company; Solvent NMP (N-methylpyrrole pyridine ketone) then is the product of BASF AG.
Embodiment 1;
31.9 gram MDI (-phenylene vulcabond) and 80 gram PMA (propylene glycol monomethyl ether) are placed the detachable reaction bulb of four necks of 500mL, make temperature be warming up to 60 ℃ and stir with mechanical stirrer and to dissolve fully until MDI.Subsequently, beginning to splash into the 16.2 gram DMPA (two (methylol) propionic acid) and 13.6 gram PPG-1000 (poly-(propylene glycol)-1000) molecular weight that are mixed in 50 gram NMP (N-methylpyrrole pyridine ketone) in advance fully is 1000), and wait to drip off the back and judge whether complete reaction of NCO (isocyanate functional groups) with FTIR (fourier transform infrared spectrometer).After reacting completely, be warming up at last 100 ℃ and add 8.3 the gram GMA (glycidyl methacrylate), when holding temperature reaches about 18mgKOH/g until the solution acid value, promptly finish synthetic.Obtain the Polyurethane 1 with can develop by radiation curing of the present invention, it is made of with random arrangement following repetitive, and the weight average molecular weight of being measured with GPC (gel permeation chromatography) (being designated hereinafter simply as Mw) is 15,000～35,000.
Embodiment 2:
31.9 gram MDI and 80 gram PMA are placed the detachable reaction bulb of four necks of 500mL, make temperature be warming up to 60 ℃ and stir with mechanical stirrer and to dissolve fully until MDI.Subsequently, begin to splash into 16.2 gram DMPA and the 13.6 gram CAPA that are mixed in 50 gram NMP in advance fully
2101A (polycaprolactone glycol) (molecular weight is 1000), and wait to drip off the back and judge whether complete reaction of NCO with FTIR.After reacting completely, be warming up at last 100 ℃ and add 8.3 the gram GMA, when holding temperature reaches about 18mgKOH/g until the solution acid value, promptly finish synthetic.Obtain the Polyurethane 2 with can develop by radiation curing of the present invention, and be 15,000～35,000 with GPC (gel permeation chromatography) Mw that measured.
Embodiment 3:
31.9 gram MDI and 80 gram PMA are placed the detachable reaction bulb of four necks of 500mL, make temperature be warming up to 60 ℃ and stir with mechanical stirrer and to dissolve fully until MDI.Subsequently, begin to splash into the 16.2 gram DMPA and the 13.6 gram PC-diol (molecular weight is 1000) that are mixed in 50 gram NMP in advance fully, and wait to drip off the back and judge whether complete reaction of NCO with FTIR.After reacting completely, be warming up at last 100 ℃ and add 8.3 the gram GMA, when holding temperature reaches about 18mgKOH/g until the solution acid value, promptly finish synthetic.Obtain the Polyurethane 3 with can develop by radiation curing of the present invention, and be 15,000～35,000 with GPC (gel permeation chromatography) Mw that measured.
Embodiment 4:
31.9 gram MDI and 80 gram PMA are placed the detachable reaction bulb of four necks of 500mL, make temperature be warming up to 60 ℃ and stir with mechanical stirrer and to dissolve fully until MDI.Subsequently, begin to splash into the 16.2 gram DMPA and the 13.6 gram PTMEG (molecular weight is 1000) that are mixed in 50 gram NMP in advance fully, and wait to drip off the back and judge whether complete reaction of NCO with FTIR.After reacting completely, be warming up at last 100 ℃ and add 8.3 the gram GMA, when holding temperature reaches about 18mgKOH/g until the solution acid value, promptly finish synthetic.Obtain the Polyurethane 4 with can develop by radiation curing of the present invention, and be 15,000～35,000 with GPC (gel permeation chromatography) Mw that measured.
Embodiment 5:
16.79 gram MDI and 112.5 gram PMA are placed the detachable reaction bulb of four necks of 500mL, make temperature be warming up to 60 ℃ and stir with mechanical stirrer and to dissolve fully until MDI.Subsequently, begin to splash into the 70.71 gram CAPA that are mixed in 50 gram NMP in advance fully
HC1100 (molecular weight is 1000), and wait to drip off the back and judge whether complete reaction of NCO with FTIR.After reacting completely, be warming up at last 100 ℃ and add 8.3 the gram GMA, when holding temperature reaches about 12mgKOH/g until the solution acid value, promptly finish synthetic.Obtain the Polyurethane 5 with can develop by radiation curing of the present invention, and be 15,000～45,000 with GPC (gel permeation chromatography) Mw that measured.
Embodiment 6 to 9:
With in the foregoing description 1,2,3,4 prepared comprise main chain have the carboxylic acid group and have the amount shown in Polyurethane 1,2,3,4 following tables 1 of repetitive (I) of side chain acryloyl group (the amount system shown in it in composition (A) and (B) adds up to 100 weight %) and composition (the amount system of these all the other compositions is with respect to (A) and (B) total restatement) after abundant mixing; be aided with suitable spreading agent through the abrasive machine grinding size distribution is controlled at below the 200nm, obtain light resistance composition 1,2,3,4.
Table 1
Annotate:
(C), (D), (E), (F), (G) weight % all are the general assembly (TW)s (i.e. the ratio during as benchmark with (A)+(B) composition) with respect to (A)+(B) composition.
TPGDA: tripropylene glycol diacrylate, Xinlimei Science and Technology Co Ltd's product.
KBM503:3-methacryloxypropyl triethoxysilane, Japan XINYUE's product.
Igacure 907:2-methyl-(4-methylthiophene base)-2-morpholinyl-third-1-ketone, Ciba company product.
S32000: spreading agent is Avecia company product
PMA: propylene glycol monomethyl ether.
Test example-endurance test, thermotolerance test and yellowing resistance test
The light resistance composition 1,2,3,4 of above-mentioned gained is coated on the glass sheet with thickness 1～3 μ m, through 70～110 ℃ of prebake conditions 100～300 seconds, through 50～200mJ/cm
2Exposure, through the NaOH developing liquid developing after 20～150 seconds, again through 200～250 ℃ carry out after the baking 20～40 minutes, and will contain through the glass sheet of coating and be immersed in all kinds of solvents (80 ℃ of water, propylene glycol monomethyl ether (PM), N-Methyl pyrrolidone (NMP), tetramethylammonium hydroxide (TMAH) 2.38%) and last 5～20 minutes (being the endurance test) or be exposed under the various environment (in the air 170 ℃, 10 hours, be the thermotolerance test), test its yellowing resistance (Δ E*ab), it the results are shown in following table 2.
Table 2
| Light resistance composition 1 | Light resistance composition 2 | Light resistance composition 3 | Light resistance composition 4 | |
| In 80 ℃ of water | 2.13 | 1.53 | 1.71 | 2.04 |
| PM | 1.86 | 1.03 | 1.30 | 1.76 |
| NMP | 2.31 | 1.02 | 1.86 | 2.15 |
| TMAH 2.38％ | 1.97 | 0.94 | 1.03 | 1.67 |
| In the air 170 ℃ | 1.25 | 0.62 | 0.86 | 0.95 |
Annotate: the Δ E*ab value of above-mentioned yellowing resistance is Yi Da Peng electronics system spectrophotometer endurance that MCPD-3000 is measured and the thermotolerance dichroism of testing front and back (represented be aberration Δ E*ab value) by L*a*b*.
By above-mentioned test as can be known, though with the about 10wt% that general assembly (TW) is only arranged of light resistance composition 1 its ratio that embodiment 1 gained Polyurethane 1 is allocated, a plurality of amine ester groups (hydrogen bond is provided) that had in 1 body structure of Polyurethane and acrylic acid functional group can provide splendid thermotolerance and endurance (being Δ E*ab≤3).In addition, in total system, all be single phase, show that constituent of the present invention has very highly compatible.
According to Polyurethane of the present invention is the highly cross-linked resin of radiation-hardenable, uses the principal ingredient of this resin as photoresistance liquid, can be firmly on glass substrate with pigment, can promote endurance and thermotolerance after the film forming.
In addition, if similarly that radiation-hardenable of the present invention is highly cross-linked polyurethane resin is as the principal ingredient of photoresistance liquid and cooperate suitable spreading agent and auxiliary agent again, behind low temperature (＜150 ℃) maturation sclerosis processing procedure, promptly earlier at 100～300 seconds → 50～200mJ/cm of 70～100 ℃ of prebake conditions
2Exposure → NaOH developing liquid developing is after 20～150 seconds → again through 50～200mJ/cm
2Exposure → carried out back baking 20～60 minutes with 150 ℃ at last, but have after its photoresistance composition solidifies flexible character also film forming on plastic base (as polyimide (PI), polyethersulfone (PES) film, polycarbonate (PC) film etc.).
Claims (8)
1, a kind of Polyurethane of can develop by radiation curing is characterized in that: its main chain has the carboxylic acid group and has the side chain acryloyl group, and by following repetitive (I), (II) and (III) constituted with random arrangement:
Wherein:
R is C
1-12Straight chain or branch's alkylidene, C
3-8Cyclic alkylidene, phenylene, biphenylene, naphthylene, xylylene, methylene anilino-,-the Ph-A-Ph-base, wherein A is CH
2,-NH-or-O-, these bases again can be according to circumstances through C
1-6Alkyl replaces;
R ' is the divalent aliphatic base, can have one or more OH substituting group on it again, this OH substituting group again can be according to circumstances and then and di-isocyanate reaction; And
R " be C with the substituent straight chain of one or more OH or branched chain
1-6Alkyl, this OH substituting group again can be according to circumstances and then and di-isocyanate reaction,
The weight average molecular weight that this Polyurethane is measured with gel permeation chromatography is 3,000～400,000 scope; And acid number is 5～120mg KOH/g.
2, Polyurethane according to claim 1 is characterized in that: the weight average molecular weight of described Polyurethane is 6,000～80,000 scope.
3, Polyurethane according to claim 1 is characterized in that: the acid number of described Polyurethane is 10～60mg KOH/g.
4, a kind of light resistance composition of can develop by radiation curing, it is characterized in that: it comprises following effective ingredient: the described main chain of claim 1 has the carboxylic acid group and has the side chain acryloyl group, and reaches Polyurethane (A), acrylic monomers (B) and the light initiator (C) that (III) is constituted by repetitive (I), (II); The part by weight (A) of Polyurethane (A) and acrylic monomers (B) wherein: be 40～90: 10～60 (B), and the content of light initiator (C) is 1～50% (weight) of Polyurethane (A) and acrylic monomers (B) gross weight.
5, light resistance composition according to claim 4 is characterized in that: further comprise then auxiliary agent (D), its use amount is 0.1～5% (weight) with respect to Polyurethane (A) and acrylic monomers (B) gross weight.
6, light resistance composition according to claim 4 is characterized in that: further comprise colorant (E), its use amount is 5～40% (weight) with respect to Polyurethane (A) and acrylic monomers (B) gross weight.
7, light resistance composition according to claim 4 is characterized in that: further comprise spreading agent (F), its use amount is 3～15% (weight) with respect to Polyurethane (A) and acrylic monomers (B) gross weight.
8, light resistance composition according to claim 4 is characterized in that: further comprise solvent (G).
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| CN102190763A (en) * | 2010-01-26 | 2011-09-21 | 日立电线株式会社 | Ultraviolet curable resin composition, wire cable using the composition and method for fabricating the same. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102190763A (en) * | 2010-01-26 | 2011-09-21 | 日立电线株式会社 | Ultraviolet curable resin composition, wire cable using the composition and method for fabricating the same. |
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