CN100475902C - Cured resin compositions - Google Patents
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- CN100475902C CN100475902C CNB031438067A CN03143806A CN100475902C CN 100475902 C CN100475902 C CN 100475902C CN B031438067 A CNB031438067 A CN B031438067A CN 03143806 A CN03143806 A CN 03143806A CN 100475902 C CN100475902 C CN 100475902C
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Abstract
The invention discloses a cured resin compositions comprising a composition A, B and C, wherein composition A is a polymer obtained by separately polymerizing monomers containing epoxy radicals and double bonds or polymerizing together with other monomers having double bonds but no functional groups capable of reacting with the epoxy radicals through addition, B is carboxylic acid anhydride, and C is selected from at least one of (C1) group compounds and (C2) group compounds, wherein (C1) group compounds comprise tetra-aryl boric acid ester compounds, the (C2) group compounds comprise ureas.
Description
Technical field
The present invention relates to curable resin composition, in more detail, relate to be suitable for the curable resin composition of the protective membrane of colour filter.
Background technology
Insulation protective membrane as covering layer material in the liquid crystal display device color filter etc.; open in the flat 4-53879 communique the spy and to have reported; allocate the solution (イ) that is dissolved with the solution (ア) of poly (glycidyl methacrylate) and is dissolved with aromatic carboxylic acid acid anhydride and imidazoles at first respectively; then will (ア) and (イ) 2 kinds of solution mixing before the coating of applied thing, coating, thermofixation and the film that is protected.
The inventor etc. inquire into the protection film composition of being put down in writing in the above-mentioned communique, confirm 23 ℃ of preservations with above-mentioned (A) and (B) 2 kinds of solution obtain after mixing composition the time, soltion viscosity significantly increases, storage stability is abundant inadequately.
Understood fully the following fact in addition, that is, mixed above-mentioned (A) and (B) during 2 kinds of solution, involving in bubble sometimes, be involved in alveolate solution and the hole (hole) that can generation in the protective membrane that obtains generates because of bubble in directly coating, thermofixation.
Summary of the invention
The object of the present invention is to provide a kind of solidification compound; on applied thing the coating protective membrane use composition the time; there is no need to mix; and can be as a liquid type composition of excellent storage stability and utilize; and when solidifying this liquid type composition, can obtain the protective membrane of thermotolerance and resistance to chemical reagents excellence.
That is, the invention provides a kind of comprising of (A) composition, (B) composition and (C) curable resin composition of composition (below, be designated as this resin combination).
(A) composition: will contain epoxy group(ing) and two keys the independent polymerization of monomer or with its with contain two keys but do not contain the polymkeric substance that can obtain with other monomer addition polymerization of the functional group of epoxy reaction,
(B) composition: carboxylic acid anhydride,
(C) composition: be selected from following (C1) group compound and (C2) at least a in the compound of group,
(C1) group compound: four aryl boric acid ester cpds of amidine class,
(C2) group compound: urea class.
In addition, the invention provides a kind of coating this resin combination and thermofixation on applied thing and the protective membrane that obtains.
Embodiment
(A) composition in this resin combination, be to contain the independent addition polymerization of monomer of epoxy group(ing) and two keys and the polymkeric substance that obtains, or the monomer that will contain epoxy group(ing) and two keys does not contain other monomer addition polymerization of the functional group that can react with epoxy group(ing) and the polymkeric substance that obtains with having two keys.
As the monomeric desirable example that contains epoxy group(ing) and two keys, be monomer with following formula (1) expression as exemplifying
R-X-CH
2-E (1)
(in the formula: R represents that carbon number is 2～12 alkenyl, and X represents that carbonyl oxygen base or inferior methoxyl group, E represent to be selected from following
Epoxy group(ing)).
Monomer as with formula (1) expression for example can exemplify unsaturated glycidyl ethers such as glycidyl allyl ether, 2-methacrylic glycidyl ether, 4-hydroxybutyl (methyl) acrylate glycidyl ether; Unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, glycidyl itoconate; 3,4-epoxycyclohexyl methacrylic ester, 3, alicyclic epoxy (methyl) acrylate such as 4-epoxycyclohexyl methyl acrylate etc.
As monomer, can use the monomer more than 2 kinds with following formula (1) expression with formula (1) expression.
Monomer as with formula (1) expression it is desirable to unsaturated glycidyl ester and alicyclic epoxy (methyl) acrylate, and what especially be fit to is 3,4-epoxycyclohexyl methacrylic ester and glycidyl methacrylate.
(A) in the composition, as the unitary content of monomer structure that contains epoxy group(ing) and two keys, normally 5～100mol% it is desirable to 20～90mol%, and that even more ideal is 30～80mol%.
Polymkeric substance as (A) composition it is desirable to, and (methyl) acrylic monomer and/or styrene monomer can be carried out the polymkeric substance that addition polymerization obtains with other monomer of the functional group of epoxy reaction as having two keys and not containing.
As (methyl) acrylic monomer, as can the exemplified by acrylic methyl esters, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi etc. have (methyl) alkyl acrylate that carbon number is about 1～20 straight chain shape alkyl; Tert-butyl acrylate, methacrylic tert-butyl acrylate etc. have (methyl) alkyl acrylate that carbon number is about 3～20 branched-chain alkyl; Cyclohexyl acrylate, cyclohexyl methacrylate etc. have (methyl) alkyl acrylate that carbon number is about 5～20 saturated alicyclic alkyl; Benzyl acrylate, benzyl methacrylate etc. have aromatic nucleus (methyl) vinylformic acid aralkyl ester; Vinyl cyanide, methacrylonitrile etc. (methyl) vinyl cyanide etc.
As (methyl) acrylic monomer, can use (methyl) acrylic monomer more than 2 kinds.
As (methyl) acrylic monomer, it is desirable to (methyl) alkyl acrylate, especially it is desirable to, have straight chain shape or catenate carbon number and be about 1～4 alkyl (methyl) alkyl acrylate, have (methyl) alkyl acrylate of saturated alicyclic alkyl and have (methyl) vinylformic acid aralkyl ester of aromatic nucleus.
As styrene monomer, can use as vinylbenzene, alpha-methyl styrene, Vinylstyrene etc.As styrene monomer, can use the styrene monomer more than 2 kinds.
Optimization styrene in styrene monomer.
(A) in the composition, as have two keys and do not contain can with other monomer of the functional group of epoxy reaction, content as (methyl) acrylic monomer and/or styrene monomer structural unit, normally about 0～95mol%, it is desirable to it is desirable to about 20～70mol% especially about 10～80mol%.
(A) in the composition, as have two keys and do not contain can with other monomer of the functional group of epoxy reaction, can also exemplify chain acid vinyl esters such as vinyl butyrate, propionate, trimethylacetic acid vinyl acetate, vinyl laurate, different n-nonanoic acid vinyl acetate, tertiary ethylene carbonate; Halogen ethene such as vinylchlorid, bromine ethene; Protochloride vinyl such as vinylidene chloride class etc.
The monomer structure unitary 1～99mol%, particularly 5～95mol% that forms (A) composition is that thermotolerance improves easily, so desirable when having the monomer structure unit of the two keys of 1 replacement.As monomeric concrete example with the two keys of 1 replacement, can exemplify, not have substituent styrene monomer, chain acid vinyl ester class, ethylene halide class, glycidyl allyl ether, glycidyl acrylate etc. not having on substituent acryloyl class monomer, the α position on the interior α position of above-mentioned (methyl) Acrylic Acid Monomer.
As (A) composition, can use monomer more than 2 kinds, that will contain epoxy group(ing) and two keys addition polymerization and the polymkeric substance that obtains or make the monomer that contains epoxy group(ing) and two keys and have two keys and do not contain the polymkeric substance that can obtain individually with other monomer addition polymerization of the functional group of epoxy reaction.
As the epoxy equivalent (weight) of (A) composition, normally more than the 128g/ equivalent, it is desirable to about 150～4500g/ equivalent, even more ideal is about 150～1000g/ equivalent.
As the molecular weight of (A) composition, normally about 1000～1,000,000, it is desirable to about 2000～200,000, even more ideal is 5000～50, about 000.
As (A) composition, can use as BLEMER-CP-50M[glycidyl methacrylate alkylmethacrylate polymer, Japanese grease (strain) system], BLEMER-CP-50S[glycidyl methacrylate styrol copolymer, Japanese grease (strain) system] etc. commercially available product.
(A) there is no particular limitation for the manufacture method of composition.As exemplifying J.Polm.Sci., Polm.Chem. (1968), 6 (2), the described method of 257-267 is promptly mixed employed monomer and free radical generating agent in organic solvent, remix chain-transfer agent as required then, the method for about 60～300 ℃, carrying out solution polymerization; J.Polm.Sci., Polm.Chem. (1983), 21 (10), 2949-2960 is described, the undissolved solvent of use polymkeric substance carries out suspension polymerization or method of emulsion polymerization about 60～300 ℃; Put down in writing on the Te Kaiping 6-80735 communique 60～200 ℃ of methods of carrying out mass polymerization; Te Kaiping 10-195111 is put down in writing, supply with employed monomer to polymerizer continuously, and in same polymerizer, described polymkeric substance was heated 5～60 minutes the method for the continuous resultant of reaction that discharge obtains outside polymerizer etc. in the existence of polymerization starter or not at 180～300 ℃.
If when making above-mentioned (A) composition, use the organic solvent that uses as the solvent of this resin combination, then in the subsequent handling of allotment composition, can save the operation of dissolve polymer, therefore desirable.
Spendable organic solvent during as manufacturing above-mentioned (A) composition for example can exemplify methyl alcohol, ethanol, Virahol, 3-methoxyl group-1-butanols, 3-methyl-3-methoxyl group-alcohols such as 1-butanols; Ketones such as acetone, butanone, mibk, diisobutyl ketone, cyclopentanone, pimelinketone; Ethers such as glycol dimethyl ether, diglyme, glycol monoethyl ether, ethyl carbitol, ethylene glycol diethyl ether, diethyl carbitol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, glycol ether dibutyl ether, triglyme, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether; Ester classes such as vinyl acetic monomer, N-BUTYL ACETATE, pentyl acetate, ethyl lactate, n-Butyl lactate, 3-Methoxy acetic acid butyl ester, 3-methyl-3-methoxyl group-1-N-BUTYL ACETATE, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetic ester; Aromatic hydrocarbons such as toluene, dimethylbenzene etc.
As organic solvent, can use the organic solvent more than 2 kinds.
(B) composition that uses among the present invention is a carboxylic acid anhydride.
It is desirable to, (B) composition is for containing (B1) group compound and the mixture of (B2) organizing compound.
(B1) group compound: dicarboxylic anhydride
(B2) group compound: the compound that has the cyclic acid anhydride structure more than 2 in the molecule
As (B) group compound, can the illustration phthalate anhydride, aromatic dicarboxylic acid acid anhydride such as tetrabromophthalic anhydride; Tetrahydronaphthalic anhydride, hexahydro phthalic anhydride, methyltetrahydro Tetra hydro Phthalic anhydride, methyl hexahydro phthalic anhydride, 5-norbornane-2,3-dicarboxylic anhydride, 5-norbornylene-2,3-dicarboxylic anhydride, methyl norbornane-2,3-dicarboxylic anhydride, methyl norbornylene-2,3-dicarboxylic anhydride, maleic anhydride and C
10The reactant of diene (the system YH-306 of japanepoxy resin (strain) society etc.), 1,4,5,6,7,7-chlordene-5-norbornylene-2, the ester ring type dicarboxylic anhydride of 3-dicarboxylic anhydride etc.; Aliphatic dicarboxylic acid acid anhydrides such as dodecenyl succinic anhydride etc.
In addition, using (B2) group compound also is ideal.Can illustration as above-mentioned (B2) group compound, pyromellitic acid dianhydride, 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-hydroxyl, two phthalic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-xenyl tetracarboxylic acid dicarboxylic anhydride, ethylene glycol bis trimellitate (new Japanese physics and chemistry (strain) system trade(brand)name TMEG), glycerol three trimellitates aromatic tetracarboxylic acid's dianhydrides such as (new Japanese physics and chemistry (strain) system trade(brand)name TMTA); 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl methyl), norbornane-2, ester ring type tetracarboxylic dianhydrides such as 3-dicarboxylic anhydride; The multipolymers of styrene-maleic anhydride etc. contain the polymer of monomers of cyclic acid anhydride structure and polymerizability unsaturated link(age) etc. at intramolecularly.
As above-mentioned (B) group compound, can use the compound more than 2 kinds.
As (B) composition, part or all is (B2) group compound to it is desirable to it.(B) in the carboxylic acid anhydride of composition, the special ideal content of described (B2) group compound is about 10～80 weight %.
As (B2) group compound, it is desirable to the ester ring type tetracarboxylic dianhydride.
In every 100g (B) composition, it is desirable to, convert with-COOH base and contain below the free carboxy acid 0.1mol, it is desirable to especially contain below the 0.05mol.If free carboxy acid's amount is below 0.05mol, then the storage stability of curable resin composition becomes good, so desirable especially.
For the content of (B) composition in this resin combination, among the every 1mol of total epoxy group(ing) that (A) contains in the composition, convert with anhydride group, normally contain about 0.3～1.2mol, it is desirable to contain about 0.6～1.0mol.
(C) composition in this resin combination is a curing catalyst, is to be selected from (C1) group compound and at least a kind that (C2) organizes compound.
(C1) group compound: four aryl boric acid ester cpds of amidine class
(C2) group compound: urea class
(C1) the amidine class in the group compound is the cationic that has in the molecule with the part-structure of following formula (2) expression.As this amidine class, it is desirable to have the cationic of part-structure with following formula (2 ') expression at intramolecularly, it is desirable to have cationic especially with the part-structure of following formula (2 ") expression at intramolecularly.
In this resin combination, described amidine class is to use with the salifiable form of four aryl-boric acid ester shapes.
(in the formula, the D of dotted portion represents to contain 5～8 element heterocycles of 1 nitrogen-atoms).
[in the formula, the D of dotted line part definition is same as described above.The E of dotted line part represents to contain 5～8 Yuans heterocycle of 2 nitrogen-atoms.]。
In described amidine class, ideal also has ring structure (2 ') at intramolecularly, and wherein 5 Yuans imidazoles is better.
As this imidazoles, for example can exemplify imidazoles such as imidazoles, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-ethyl imidazol(e), 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole; 4 grades of imidazoles that on the nitrogen-atoms of these imidazoles, further replace etc. with alkyl, aryl or aralkyl.
In addition, to have the amidine class (2 ") of 2 rings also be ideal to intramolecularly.Heterocycle amidine as such can exemplify 1,8-diaza-dicyclo-[5.4.0] 11-7-alkene, 1, and 5-diazabicyclo-[4.3.0] nine-5-alkene etc. has 3 grades of amidine classes of 2 rings; Further with the nitrogen-atoms of these amidine classes, be that 1～20 alkyl, carbon number are that 7～20 aralkyl or phenyl etc. carry out 4 grades and change 4 grades of amidine classes that obtain by carbon number.Wherein, it is desirable to 8-methyl isophthalic acid especially, 8-diaza-dicyclo-[5.4.0] 11-7-alkene, 8-benzyl-1,8-diaza-dicyclo-[5.4.0] 11-7-alkene etc. as 4 grades of amidines.
Four aryl-boric acid esters as in (C1) group compound can exemplify the material with following formula (3) expression.
[in the formula, Ar
1～Ar
4Respectively independently expression can be selected from carbon number be that 1～10 alkyl, carbon number are 1～10 alkoxyl group and the aryl that more than one substituting group replaced in the halogen.]
Concrete example as four aryl-boric acid esters of formula (3) can exemplify tetraphenyl boric acid ester, tetramethyl benzoyl boric acid ester etc.
As (C2) group compound, have in the molecule with following formula (4) as exemplifying
N-CO-N (4)
The compound of the part-structure of expression.
Urea class as above-mentioned it is desirable to, and has the usefulness following formula (4 ') more than 1 in the molecule
-NH-CO-N＜(4’)
The tri-substituted ureas structure of expression or represent with formula (4 ")
＞N-CO-N＜(4”)
The compound of four substituted ureas structures.
As the compound that has the four substituted ureas structures of representing with the tri-substituted ureas structure of following formula (4 ') expression or with formula (4 ") more than 1 in the molecule; can exemplify tributyl urea, 1, the aliphatics urea class of 1-dimethyl-3-cyclohexyl urea, thricyclohexyl urea, Fourth Ring hexyl urea etc.; 3-(4-chloro-phenyl-)-1,1-dimethyl urea, 3-(3, the 4-dichlorophenyl)-1, the aromatic series urea class of 1-dimethyl urea, 3-(3, the 4-dichlorophenyl)-1-methoxyl group-1-methyl urea etc.
It is desirable to especially, in molecule, have the tri-substituted ureas structure of usefulness formula (the 4 ') expression more than 2 or the compound of the four substituted ureas structures represented with formula (4 ").As the tri-substituted ureas structure that in molecule, has usefulness formula (the 4 ') expression more than 2 or with the compound of four substituted ureas structures of formula (4 ") expression, can exemplify toluene pair dimethyl urea, methylene bis aromatic series urea classes such as (phenyl dimethyl ureas); The ester ring type urea class of the two dimethyl urea of isophorone etc. etc.
(C) content of composition is generally about 0.05～30 weight part with respect to per 100 weight parts (A) composition, it is desirable to about 0.5～10 weight part.
This resin combination uses with the state that is dissolved in the organic solvent usually.As organic solvent, it is desirable to not contain the material of the functional group that free carboxy or amino etc. can react with epoxy group(ing) and anhydride group, can exemplify above-mentioned organic solvent.
As organic solvent, can use the organic solvent more than 2 kinds.
In this resin combination, can contain antioxidant (below, be designated as (D) composition) in addition.
As (D) composition, it is desirable to be selected from least a in one group of the phenol antioxidant, Phosphorus antioxidant, sulphur class antioxidant, even more ideal is phenol antioxidant.As the content of (D) composition in this resin combination, contain usually about 0.001～10 weight part in (A) composition of per 100 weight parts, it is desirable to contain about 0.01～1 weight part.
As phenol antioxidant; as exemplifying 2; 6-two-tertiary butyl-4-methylphenol; 2; 6-di-t-butyl-4-ethylphenol; 2; 6-dicyclohexyl-4-methylphenol; 2; 6-two tert-pentyls-4-methylphenol; 2; 6-two uncles octyl group-4-n-propyl phenol; 2; 6-dicyclohexyl-4-n-octyl phenol; 2-sec.-propyl-4-methyl-6-tert butyl phenol; the 2-tertiary butyl-2-ethyl-6-tert-octyl phenol; 2-isobutyl--4-ethyl-uncle's 6-hexylphenol; 2-cyclohexyl-4-normal-butyl-6-isopropyl-phenol; the d1-alpha-tocopherol; Tert. Butyl Hydroquinone; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol); 4; 4 '-butylidene-bis(3-methyl-6-t-butyl phenol); 4; 4 '-sulfenyl two (3 methy 6 tert butyl phenol); 2; 2 '-sulfenyl two (4-methyl-6-tert butyl phenol); 4; 4 '-methylene-bis (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis [6-(1-methylcyclohexyl)-p-cresol]; 2; 2 '-ethylenebis (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-butylidene (the 2-tertiary butyl-4-methylphenol); the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate; 2-[1-(2-hydroxyl-3; 5-tert-pentyl phenyl) ethyl]-4; 6-two-tert-pentyl phenyl acrylate; 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; triglycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester]; 1; the 6-hexylene glycol is two, and [3-(3; 5-two-tertiary butyl-4-hydroxyphenyl) propionic ester]; 2; 2-sulfenyl dimethylene is two, and [3-(3; 5-two-tert-butyl-hydroxy phenyl) propionic ester]; N; N-six ethylenes two (3; 5-two-tertiary butyl-4-hydroxy-hydrocinnamamide); 3; 5-two-tertiary butyl-4-hydroxy benzylphosphonic acid ester diethyl ester; three (2; 6-dimethyl-3-hydroxyl-4-tertiary butyl benzyl) isocyanuric acid ester; three (3; 5-two-tertiary butyl-4-hydroxy benzyl) isocyanuric acid ester; three [(3; 5-two-tert-butyl-hydroxy phenyl) propionyloxy ethyl] isocyanuric acid ester; three (the 4-tertiary butyls-2; 6-dimethyl-3-hydroxybenzyl) isocyanuric acid ester; 2; two (positive hot sulfenyl)-6-(the 4-hydroxyls-3 of 4-; 5-two-tert.-butylbenzene amido) 1; 3; the 5-triazine; four [methylene radical-3-(3; 5-two-tertiary butyl-4-hydroxyphenyl) propionic ester] methane; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol) terephthalate; 1; 3; 5-trimethylammonium-2; 4; 6-three (3; 5-two-tertiary butyl-4-acrinyl) benzene; 3; 9-two [1; 1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy } ethyl]-2; 4; 8; 10-four oxaspiros [5; 5] undecane; 2; 2-is two, and [(2-(3 for 4-; 5-two-tertiary butyl-4-hydroxy hydrocinnamoyl oxygen)) ethoxyl phenenyl] propane; β-(3,5-two-tert-butyl-hydroxy phenyl) propionic acid stearyl ester etc.
Wherein, it is desirable to β-(3,5-two-tert-butyl-hydroxy phenyl) propionic acid stearyl ester, four [methylene radical-3-(3,5-two-tertiary butyl-4-hydroxyphenyl) propionic ester] methane, three (3,5-two-tertiary butyl-4-hydroxy benzyl) isocyanuric acid ester, 1,3,5-trimethylammonium-2,4,6-three (3,5-two-tertiary butyl-4-acrinyl) benzene, the d1-alpha-tocopherol, three (2,6-dimethyl-3-hydroxyl-4-tertiary butyl benzyl) isocyanuric acid ester, three [(3,5-two-tert-butyl-hydroxy phenyl) propionyloxy ethyl] isocyanuric acid ester, 3,9-pair [1,1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy } ethyl]-2,4,8,10-four oxaspiros [5,5] undecane.
As phenol antioxidant, can use commercially available phenol antioxidant, for example (Irganox 1010 for Irganox1010, チ バ specialtychemicals system), (Irganox 1076 for Irganox1076, チ バ specialtychemicals system), (Irganox 1330 for Irganox1330, チ バ specialtychemicals system), Irganox3114 (Irganox3114, チ バ specialtychemicals system), Irganox3125 (Irganox3125, チ バ specialtychemicals system), Sumilizer-BHT (Sumilizer BHT, Sumitomo Chemical system), (Cyanox 1790 for Cyanox1790, the scitech system), Sumilizer-GA-80 (Sumilizer GA-80, Sumitomo Chemical system), vitamin-E (エ ザ イ system) etc.
As phenol antioxidant, can use the phenol antioxidant more than 2 kinds.
As Phosphorus antioxidant; can exemplify the trioctylphosphine phosphoric acid ester; three Tryfac 5573s; three decyl phosphoric acid ester; (octyl group) diphenyl phosphoester; three (2; 4-two-tert-butyl-phenyl) phosphoric acid ester; triphenyl; three (butoxyethyl group) phosphoric acid ester; three (nonyl phenyl) phosphoric acid ester; distearyl acyl group pentaerythritol diphosphate; four (tridecyl)-1; 1; 3-three (2-methyl-5-tert-butyl-hydroxy phenyl) butane bisphosphate; four (C12～C15 mixed alkyl)-4; 4 '-isopropylidene phenylbenzene bisphosphate; four (tridecyl)-4; 4 '-butylidene-bis(3-methyl-6-t-butyl phenol) bisphosphate; three (3; 5-two-tert-butyl-hydroxy phenyl) phosphoric acid ester; three (single two mix the nonyl phenyl) phosphoric acid ester; hydrogenation-4; 4 '-isopropylidene biphenol poly phosphate; two (octyl phenyl) two [4; 4 '-butylidene-bis(3-methyl-6-t-butyl phenol)]-1; 6-hexylene glycol bisphosphate; phenyl (4; 4 '-isopropylidene phenylbenzene) pentaerythritol diphosphate; two hard acyl group pentaerythritol diphosphate; three [4; 4 '-isopropylidene two (2-tert.-butyl phenol)] phosphoric acid ester; two (isodecyl) phenyl phosphate ester; 4; 4 '-isopropylidene two (2-tert.-butyl phenol)] two (nonyl phenyl) phosphoric acid ester; 9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound; two (2; 4-two-tertiary butyl-6-aminomethyl phenyl) ethyl phosphonic acid ester; 2-[{2; 4; 8; 10-four-tert-butyl diphenyl [d; f] [1; 3; 2]-and the dioxaphosphepin-6-yl } oxygen]-N; two [the 2-[{2 of N-; 4; 8; 10-four-tert-butyl diphenyl [d; f] [1.3.2]-dioxaphosphepin-6-yl } oxygen] ethyl] ethamine; 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-]-2; 4; 8; 10-four-tert-butyl diphenyl [d, f] [1.3.2.]-dioxaphosphepin etc.
In addition, as two (dialkyl phenyl organic) pentaerythritol diphosphate, can exemplify with following general formula (10)
The spiral type of (in the formula, R1, R2, R3 represent independently that respectively hydrogen atom or carbon number are about 1～9 alkyl etc.) expression or with following general formula (11)
The material of the cage modle of (in the formula, R4, R5, R6 represent independently that respectively hydrogen atom or carbon number are about 1～9 alkyl etc.) expression.
As such phosphoric acid ester, use the mixture of general formula (10) and (11) usually.
Wherein, be under the situation of alkyl as R1～R6, preferably have the alkyl of side chain, particularly preferably be the tertiary butyl.
The position of substitution of R1～R6 in the phenyl, preferred 2,4,6.
As the concrete example of phosphoric acid ester, can exemplify two (2,4-two-tert-butyl-phenyl) pentaerythritol diphosphate, two (2,6-two-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphate, two (nonyl phenyl) pentaerythritol diphosphate etc.In addition, as the phosphonic acid ester with the direct bonded structure of carbon and phosphorus, can exemplify four (2,4-two-trimethylphenylmethane base)-4,4 '-biphenyl is embraced compounds such as bisphosphonates.
As Phosphorus antioxidant, commercially available product can be used, for example Irgafos168 (Irgafos168 can be exemplified, チ バ specialtychemicals system), (Irgafos 12 for Irgafos12, チ バ specialtychemicals system), Irgafos38 (Irgafos38, チ バ specialtychemicals system), ADK STAB 329K (ADK STAB 329K, rising sun electrification system), ADK STAB PET36 (ADK STAB PET36, rising sun electrification system), ADK STAB PET-8 (ADK STAB PET-8, rising sun electrification system), Sandstab P-EPQ (Network ラ リ ア Application ト system), (Weston 618 for Weston618, the GE system), Weston619G (Weston 619G, the GE system), (Ultranox 626 for Ultranox626, the GE system), Sumilizer-GP (Sumilizer GP, Sumitomo Chemical system) etc.
As Phosphorus antioxidant, can use the Phosphorus antioxidant more than 2 kinds.
In the Phosphorus antioxidant; it is desirable to; three (2; 4-two-tert-butyl-phenyl) phosphoric acid ester; four (2; 4-two-tert-butyl-phenyl)-4; 4 '-biphenyl is embraced bisphosphonates; two hard acyl group pentaerythritol diphosphate; two (2,4-two-tert-butyl-phenyl) pentaerythritol diphosphate; 2-[{2,4; 8; 10-four-tert-butyl diphenyl [d, f] [1.3.2]-dioxaphosphepin-6-yl } oxygen]-N, the two [2-[{2 of N-; 4; 8,10-four-tert-butyl diphenyl [d, f] [1.3.2]-dioxaphosphepin-6-yl } oxygen] ethyl] ethamine; 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-]-2; 4; 8,10-four-tert-butyl diphenyl [d, f] [1.3.2.]-dioxaphosphepin.
As Sulfur class antioxidant, can exemplify the ester (for example tetramethylolmethane four-3-lauryl thiohydracrylic acid ester) etc. of the polyvalent alcohol (for example glycerol, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, trihydroxy-ethyl isocyanuric acid ester) of alkylthio propionic acid such as the dialkyl group thiodipropionate of dilauryl, myristyl, distearyl acyl group etc. and butyl, octyl group, lauryl, stearyl-.
More specifically, can exemplify dilauryl thiodipropionate, myristyl thiodipropionate, distearyl thiodipropionate, the hard ester group thiodipropionate of lauryl, distearyl acyl group sulfo-dibutyrate etc.Wherein, it is desirable to tetramethylolmethane four-3-lauryl thiopropionate.
As Sulfur class antioxidant, can exemplify Sumilizer-TPS (Sumilizer TPS, Sumitomo Chemical system), Sumilizer-TPL-R (Sumilizer TPL-R, Sumitomo Chemical system), Sumilizer-TPM (Sumilizer TPM, Sumitomo Chemical system), Sumilizer-TP-D (Sumilizer TP-D, Sumitomo Chemical system) etc.
As Sulfur class antioxidant, can use the Sulfur class antioxidant more than 2 kinds.
In addition, be recommended at least a tensio-active agent that contains in this resin combination in one group in the silicone tensio-active agent that is selected from silicone tensio-active agent, fluorine class tensio-active agent and has fluorine atom.
As the silicone tensio-active agent, can exemplify ト one レ silicone DC3PA, ト one レ silicone SH7PA, ト one レ silicone DC11PA, ト one レ silicone SH21PA, ト one レ silicone SH28PA, ト one レ silicone 29SHPA, ト one レ silicone SH30PA, polyether modified silicone oil SH8400 (trade(brand)name: ト one レ silicone (strain) system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's silicone system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (ジ-イ one Toshiba's silicone (strain) system) etc.
As fluorine class tensio-active agent, can exemplify Off ロ リ Na one ト (registered trademark) FC430, Off ロ リ Na one ト (registered trademark) FC431 (Sumitomo ス リ one エ system (strain) system), メ ガ Off ア Star Network (registered trademark) F142D, メ ガ Off ア Star Network (registered trademark) F171, メ ガ Off ア Star Network (registered trademark) F172, メ ガ Off ア Star Network (registered trademark) F173, メ ガ Off ア Star Network (registered trademark) F177, メ ガ Off ア Star Network (registered trademark) F183, メ ガ Off ア Star Network (registered trademark) R30 (big Japanese ink chemical industry (strain) system), エ Off ト Star プ (registered trademark) EF301, エ Off ト Star プ (registered trademark) EF303, エ Off ト Star プ (registered trademark) EF351, エ Off ト Star プ (registered trademark) EF352 (new autumn fields changes into (strain) system), サ one Off ロ Application (registered trademark) S381, サ one Off ロ Application (registered trademark) S382, サ one Off ロ Application (registered trademark) SC101, サ one Off ロ Application (registered trademark) SC105 (Asahi Glass (strain) system), E5844 ((strain) ダ イ キ Application Off ア イ Application ケ ミ power Le institute system), BM-1000, BM-1100 (is trade(brand)name: BM Chemie society system) etc.As silicone tensio-active agent, can exemplify メ ガ Off ア Star Network (registered trademark) R08, メ ガ Off ア Star Network (registered trademark) BL20, メ ガ Off ア Star Network (registered trademark) F475, メ ガ Off ア Star Network (registered trademark) F477, メ ガ Off ア Star Network (registered trademark) F443 (big Japanese ink chemical industry (strain) system) etc. with fluorine atom.
These tensio-active agents can separately or make up more than 2 kinds and use.Contain under the situation of these tensio-active agents, its content is with respect to (A) composition, and normally 0.0001～1 weight % it is desirable to 0.001～0.1 weight %.
At the storage stability that does not damage this resin combination or use under the prerequisite of thermotolerance, resistance to chemical reagents of the protective membrane that this resin combination obtains; can contain be different from will contain epoxy group(ing) and two keys monomer individually addition polymerization and the polymkeric substance that obtains or will contain epoxy group(ing) and the monomer of two keys with have two keys but do not contain the Resins, epoxy (below, be sometimes referred to as other Resins, epoxy) of the polymkeric substance that can obtain with other monomer addition polymerization of the functional group of epoxy reaction.
As other such Resins, epoxy, for example can exemplify aromatic epoxy resin, contain heterocyclic Resins, epoxy, hydrogenation type aromatic epoxy resin, aliphatic epoxy resin, the glycidyl ester of carboxylic acid, the Resins, epoxy that contains volution, alicyclic epoxy resin etc.
Described resistance to chemical reagents; be meant protective membrane of the present invention about the tens of branches of dipping soaking of surface is not taken place respectively yet in acidic aqueous solution, alkaline aqueous solution or proton-inert polar solvent; be meant that specifically protective membrane can not absorb medicine and swelling, and then is dispersed into the granulous state.
As aromatic epoxy resin, can exemplify bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, biphenyl type epoxy resin etc.
As containing heterocyclic Resins, epoxy, for example can exemplify hydantoin type Resins, epoxy, isocyanuric acid three-glycidyl ester etc.
As the hydrogenation type aromatic epoxy resin, for example can exemplify hydrogenation bisphenol A type epoxy resin, hydrogenation bisphenol f type epoxy resin, hydrogenation phenol novolak type epoxy resin, hydrogenation cresols phenolic resin varnish type epoxy resin hydrogenation biphenyl type epoxy resin etc.
As aliphatic epoxy resin, for example can exemplify butylglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, cyclohexanedimethanol diglycidylether, poly-dipropylene glycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether etc.
As the glycidyl ester of carboxylic acid, for example can exemplify neodecanoic acid glycidyl ester, hexahydro-phthalic acid 2-glycidyl ester etc.
As alicyclic epoxy resin, can exemplify 3,4-epoxycyclohexyl methyl-3,4-oxirane carboxylicesters, 6-caprolactone sex change 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate, two (3, the 4-epoxycyclohexyl) adipic acid ester, 1,2:8,9-diepoxy limonene etc.
The content of other Resins, epoxy normally below the identical weight, it is desirable to about 0～20% with respect to (A) composition.
In the scope of the resistance to chemical reagents of storage stability that does not damage this resin combination and protective membrane of the present invention; except organic solvent, tensio-active agent, can also contain various additives such as organosilane coupler, defoamer, thixotropy imparting agent, dyestuff, antioxidant, UV light absorber in this resin combination.
As the manufacture method of this resin combination, as can exemplifying, in organic solvent, make and add (B) composition and (C) composition, the method for also suitably adding other composition as required behind (A) composition; In organic solvent, make and remove organic solvent behind (A) composition and obtain polymkeric substance, then will (A) composition, (B) composition and (C) composition, and also other composition is dissolved in method in the organic solvent as required.
After the curable resin composition that obtains like this being coated on the applied things such as glass substrate or colour filtering chip basic board, can obtain protective membrane of the present invention by heating.
As coating process, can exemplify the method for using spin coater, slit coater, rod to be coated with machine, spraying machine, coating roller, flexographic printing or offset printing etc.; With slit and spin coater or rod is coated with the method etc. of the coating process combination more than 2 kinds such as machine and spraying machine.
As above-mentioned heating means, can exemplify and use hot plate, purify stove (clean oven), infrared heating device etc., usually more than 150 ℃, it is desirable to 190～260 ℃, even more ideal be at 220～250 ℃, heat 10～120 minutes method etc.
If Heating temperature is more than 150 ℃, thermotolerance improves easily, so be ideal.
If Heating temperature is below 260 ℃, then cured article is difficult for being colored, so desirable.
In room temperature～150 ℃, it is desirable to the temperature about 50～120 ℃, normal pressure or decompression heating 0.5～5 minute is down removed after the organic solvent, and the method for carrying out above-mentioned heating also is an ideal.
The thickness of protective membrane of the present invention is generally about 0.07～20 μ m, if in this scope, and the tendency that then exists the rerum natura of protective membrane, particularly planarization and surface strength to improve.
This resin combination coated the polyolefins films such as film that for example constitute, acetyl cellulose film by 4 methyl 1 pentene copolymer, with contacted of the layer that constitutes by hot curing resin composition on be coated with applied things such as the release paper of silicone releasing agent or fluorine class releasing agent and demoulding polyethylene terephthalate (PET) film after; remove organic solvent; make film with cementability; then it is fitted in and carries out thermofixation on the matrix that needs protection, also can obtain protective membrane of the present invention.
Applied things such as above-mentioned releasing agent, release paper, demoulding PET film can be peeled off after thermofixation or before thermofixation on the matrix.
In addition, as required, can be on protective membrane of the present invention stacked other resin or matrix.
Below, according to embodiment etc. the present invention is described in further detail, but the present invention is not limited to these embodiment.If not special explanation, [portion] expression [weight portion] among the embodiment.
Embodiment 1
With 50 ones of 100 ones of (A) compositions, (B1) compositions of following expression and (C) 2 ones of compositions, be dissolved in 450 ones the propylene glycol monomethyl ether acetic ester (below, be called PGMEA), obtained curable resin composition.
(A) composition:
BLEMER CP-50M (glycidyl methacrylate-methylmethacrylate copolymer, Mw=10,000, epoxy equivalent (weight)=310g/ equivalent, Japanese grease (strain) system)
(B1) composition
HN-5500[methyl hexahydro phthalic anhydride, Hitachi change into (strain) system]
(C) composition
U-CAT 5002[1,8-diazabicyclo [5.4.0]-7-undecylene class tetraphenyl borate salts, サ Application ア プ ロ (strain) system]
[storage stability test]
Use eastern machine industry system TV-30L type viscometer (No.1 rotor), measured above-mentioned curable resin composition 23 ℃ viscosity (below, be called initial stage viscosity).
Then, in 23 ℃ insulation can,, and measure the initial stage method of viscosity and measure viscosity (below, be called and preserve viscosity) in the same manner the airtight preservation of said composition 10 days.
To be designated as zero at the storage stability below ± 5% according to the viscosity velocity of variation (%) that try to achieve following formula (5), velocity of variation greater than ± 5% storage stability be designated as *, consequently zero.
In table 2, express the result.
(viscosity velocity of variation)=100 * [(preservation viscosity)-(initial stage viscosity)]/(initial stage viscosity) (5)
[Production Example of protective membrane]
Composition before slide glass (alkali glass) is spin-coated on the preservation that obtains in the Production Example of curable resin composition; and after baking 2 minutes and remove is desolvated in 85 ℃ the stove that is heating and curing; heating is 40 minutes in 230 ℃ the stove that is heating and curing, and has obtained 3 protective membranes.The thickness of this protective membrane is 1.5 μ m (measuring according to the contact film thickness gauge).
[thermal test]
Heated 1 hour in 250 ℃ of baking ovens by the protective membrane that will in above-mentioned Production Example, obtain, and measure the thickness of heating front and back, estimated thermotolerance.
For thermotolerance, be evaluated as [◎] with the heat-resisting residual film ratio of following formula (6) expression greater than 95% o'clock, be evaluated as [zero] greater than 90% o'clock property, be evaluated as in 80～90% o'clock [△], less than being evaluated as [*] at 80% o'clock.
The thermotolerance of the protective membrane of embodiment 1 is [zero].In table 2, express the result.
(heat-resisting residual film ratio)=100 * (thickness after the heating)/(thickness before the heating) (6)
[resistance to chemical reagents test]
3 protective membranes that will obtain in above-mentioned Production Example (thickness 1.5 μ m) flood the time that table 1 is put down in writing respectively in the steeping fluid shown in the table 1.Measure the thickness of each protective membrane after flooding, estimate acid resistance, alkali resistance and anti-NMP.That is, will be evaluated as zero at the protective membrane below ± 10% with the variation of the drug-resistant residual film ratio of following formula (7) expression, the variation of residual film ratio greater than ± 10% protective membrane be evaluated as *.The acid resistance of the protective membrane of embodiment 1, alkali resistance and anti-NMP are zero.In table 2, express the result.
(drug-resistant residual film ratio)=100 * (thickness behind the dipping)/(thickness before the dipping) (7)
Table 1
| Steeping fluid | Temperature | Dipping time | |
| Acid resistance | HCl/39％FeCl 3The aqueous solution/H 2O (weight ratio 1.3: 1.0: 0.3) | 45℃ | 15 minutes |
| Alkali resistance | 5% sodium hydroxide solution | 30℃ | 30 minutes |
| Anti-NMP | N-N-methyl-2-2-pyrrolidone N-(NMP) | 40℃ | 40 minutes |
Embodiment 2, comparative example 1 and comparative example 2
(B) composition of being put down in writing except use table 2, (C) composition and (D) the composition are allocated curable resin composition and protective membrane similarly to Example 1, and have been implemented identical test.
Table 2
Embodiment 3～5
Except (B) composition of using table 2 record, (C) composition and (D) composition and use conning (strain) the system #1737, allocate curable resin composition and protective membrane similarly to Example 1, and implemented identical test as base plate glass.The result is illustrated in the table 3.
Comparative example 3
With the composition of the good comparative example 1 of storage stability, similarly allocate protective membrane with embodiment 3～7, test.The result is illustrated in the table 3.
Table 3
(A) composition:
A1:BLEMER CP-50M (glycidyl methacrylate-methylmethacrylate copolymer, Mw=10,000, epoxy equivalent (weight)=310g/ equivalent, Japanese grease (strain) system)
A2:BLEMER CP-50S (glycidyl methacrylate-styrol copolymer, Mw=16,800, epoxy equivalent (weight)=297g/ equivalent, Japanese grease (strain) system)
(B) composition
B1:HN-5500[methyl hexahydro phthalic anhydride, Hitachi change into (strain) system]
B2:5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, Tokyo change into (strain) system
(C) composition
C1:1,8-diazabicyclo [5,4,0]-7-undecylene class tetraphenyl borate salts, U-CAT5002, サ Application ア プ ロ (strain) system
C2:2, the two dimethyl urea (オ ミ キ ユ ア 24, CVCspecialtychemicals system) of 4-toluene
C3:2-ethyl-4-methylimidazole (キ ユ ア ゾ one Le 2E4MZ, four countries change into industry (strain) system)
Curable resin composition of the present invention can be used as and needn't handle by blended one liquid type composition, even and preserve as liquid, also have excellent stability.The protective membrane that the said composition thermofixation is obtained, its excellent heat resistance and also demonstrate excellent resistance to chemical reagents for acid, alkali and proton-inert polar solvent etc.
In addition, because the excellent storage stability of curable resin composition of the present invention, so carry out at needs also can under the prerequisite of not damaging operability, being coated with under the occasion of large-scale coating.
Because of protective membrane of the present invention has described excellent specific property, so can be first-class as liquid-crystal display aptly with the electronic components such as planarization film, protective membrane, antireflection film, insulating material or solder protective film in element, solid photographic element and the colour filter.In addition, protective membrane of the present invention also is used in coating or the caking agent etc.
Claims (9)
1, a kind of curable resin composition comprises (A) composition, (B) composition and (C) composition,
(A) composition: will contain epoxy group(ing) and two keys the independent polymerization of monomer or with contain two keys but do not contain the polymkeric substance that can obtain with other monomer addition polymerization of the functional group of epoxy reaction,
(B) composition: carboxylic acid anhydride,
(C) composition: four aryl boric acid ester cpds of amidine class.
2, curable resin composition according to claim 1, wherein the monomer that contains epoxy group(ing) and two keys in (A) composition is the monomer with general formula (1) expression,
R-X-CH
2-E (1)
In the formula, R represents that carbon number is 2～12 alkenyl, and X represents carbonyl oxygen base or inferior methoxyl group, and E represents to be selected from following
Epoxy group(ing).
3, curable resin composition according to claim 1 and 2 wherein, except (A) composition, (B) composition, (C) composition, also contains (D) composition,
(D) composition: antioxidant.
4, curable resin composition according to claim 1 and 2, wherein, (B) composition is to contain following (B1) group compound and (B2) organize compound compositions,
(B1) group compound: dicarboxylic anhydride,
(B2) group compound: the compound that has the cyclic acid anhydride structure more than 2 in the molecule.
5, curable resin composition according to claim 1 and 2, wherein, (A) composition is to have the polymkeric substance that the monomer of epoxy group(ing) and two keys and (methyl) acrylic monomer and/or styrene monomer addition polymerization obtain.
6, curable resin composition according to claim 1 and 2, wherein, the 1～99mol% that comes from the monomeric structural unit of formation (A) composition comes from the monomeric structural unit with the two keys of 1 replacement.
7, curable resin composition according to claim 1 and 2 wherein, in every 100g (B) composition, converts with-COOH base and to contain below the free carboxy acid 0.1mol.
8, curable resin composition according to claim 1 and 2, wherein, the C composition is four aryl boric acid ester cpds with class of heterocyclic radical.
9, a kind of protective membrane, on applied thing any described resin combination of coating claim 1～8, and carry out that thermofixation forms.
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| CN200710102535A CN100584907C (en) | 2003-07-25 | 2003-07-25 | Cured resin composition |
| CNB031438067A CN100475902C (en) | 2003-07-25 | 2003-07-25 | Cured resin compositions |
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| CNB031438067A CN100475902C (en) | 2003-07-25 | 2003-07-25 | Cured resin compositions |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164245A (en) * | 1994-10-21 | 1997-11-05 | 陶氏化学公司 | Curable epoxy resin accelerated by boric acid and its analogs |
| JP3040459B2 (en) * | 1990-11-30 | 2000-05-15 | ヤマハ発動機株式会社 | Support structure for brake for front wheel of motorcycle |
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2003
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3040459B2 (en) * | 1990-11-30 | 2000-05-15 | ヤマハ発動機株式会社 | Support structure for brake for front wheel of motorcycle |
| CN1164245A (en) * | 1994-10-21 | 1997-11-05 | 陶氏化学公司 | Curable epoxy resin accelerated by boric acid and its analogs |
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