CN101328298B - Copolymer, resin composition, overcoating film and process for forming the same - Google Patents

Copolymer, resin composition, overcoating film and process for forming the same Download PDF

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CN101328298B
CN101328298B CN2008101283407A CN200810128340A CN101328298B CN 101328298 B CN101328298 B CN 101328298B CN 2008101283407 A CN2008101283407 A CN 2008101283407A CN 200810128340 A CN200810128340 A CN 200810128340A CN 101328298 B CN101328298 B CN 101328298B
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acrylate
methacrylate
methyl
ethyl
delta
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CN101328298A (en
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吉泽纯司
梶田彻
加藤嘉文
山内英树
上田二朗
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JSR Corp
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Abstract

To provide a resin composition which can form highly flat cured films, is suitably be used for forming optical device-protecting films having high transparency, surface hardness and various kinds of excellent resistance such as heat and pressure resistance, acid resistance, alkali resistance, spattering resistance, and etching resistance, and has excellent storage stability, to provide a method for forming a protecting film from the composition, and to provide a protecting film formed from the composition. This composition comprises a copolymer comprising (a1) polymerization units originated from a polymerizable unsaturated compound having an oxiranyl group or oxetanyl group, (a2) polymerization units originated from a polymerizable unsaturated compound having a specific structure and represented by 1-diethylpropyl methacrylate, and (a3) polymerization units different from the polymerization units (a1) and (a2). The protecting film is formed from the composition.

Description

The formation method of multipolymer, resin combination, protective membrane and protective membrane
The application is that application number is 2005101285381, the applying date is on November 28th, 2005, denomination of invention Branch for the application for a patent for invention of " the formation method of multipolymer, resin combination, protective membrane and protective membrane " The case application.
Technical field
The present invention relates to multipolymer, resin combination, form the method and the protective membrane of protective membrane with above-mentioned compsn.More specifically relate to compsn, use formation method and the protective membrane that uses above-mentioned compsn to form of the protective membrane of above-mentioned compsn, above-mentioned compsn is preferably used as and forms liquid crystal display device (LCD) with colour filter and charge coupled cell (CCD) material with the protective membrane that uses in the colour filter.
Background technology
LCD or CCD isoradial equipment in its preparation section, carry out dip treating with solvent, acid or alkaline solution etc. to display element, and when utilizing sputter to form the distribution electrode layer, the element surface part is exposed in the high temperature.Therefore, make element generation deterioration or cause damage, the protective membrane that constitutes by the film that above-mentioned processing is had patience in the element surface setting in order to prevent above-mentioned processing.
Require said protection film to have following performance: needs are formed matrix or the lower floor of this protective membrane even the layer that is formed on the protective membrane has high adaptation; Film itself is level and smooth, tough; Has the transparency; Thermotolerance and photostabilization are high, painted, xanthochromia, albefaction iso-metamorphism do not take place yet through the long period, and water tolerance, solvent resistance, acid resistance and alkali resistance are good etc.As the material that is used to form the protective membrane that satisfies above-mentioned various characteristics, the for example known thermoset composition that contains polymkeric substance (opening flat 5-78453 communique and the spy opens the 2001-91732 communique) referring to the spy with glycidyl.
In addition, with said protection film during as the protective membrane of the colour filter of color liquid crystal display arrangement or charge coupled cell, the requirement jump planarization that will produce by the filter that is formed on the bottom substrate usually.
And in the color liquid crystal display device of color liquid crystal display arrangement, for example STN (supertwist is to row Super Twisted Nematic) mode or TFT (thin film transistor Thin Film Transister) mode; In order to keep the box gap of liquid crystal layer equably; On protective membrane, scatter pearl spacer (spacer), the panel of fitting then.Then, sealing material is implemented thermo-compressed, thus with the liquid crystal cells sealing, still, thus the time heat and the pressure that apply, can be observed the phenomenon of the protective membrane depression of the part that has pearl, the disorderly problem in box gap appears.
When particularly preparing the color liquid crystal display device of STN mode, must guarantee the applying precision of colour filter and counter substrate extremely tightly, require protective membrane to have high jump planarization performance and heat-resisting withstand voltage properties.
In addition, in recent years, also adopt following mode, promptly utilize sputter, on the protective membrane of colour filter, form distribution electrode (tin indium oxide: ITO or indium zinc oxide: IZO),, form the pattern of ITO or IZO with strong acid or highly basic etc.Therefore, color filter protecting layer is exposed in the high temperature by the part on the surface when sputter, or has implemented all ingredients processing.Therefore, require it can tolerate above-mentioned processing, and have the adaptation with the distribution electrode, so that ITO or IZO can not peel off from protective membrane when agent treated.
In order to form said protection film; It is convenient suitable that use has the thermoset composition that adopts simple method can form the advantage of the good protective membrane of hardness; The protective membrane resin combination that is used to show above-mentioned various characteristics has the strong crosslinked reactive good crosslinking group or the catalyzer of formation; Therefore have the very short problem of quality guaranteed period of compsn self, operation is trouble very.That is, not only the coating performance of compsn itself take place through the time worsen, and must safeguard continually, wash coating machine etc., also very loaded down with trivial details in the operation.
Still unknownly satisfy performance that the transparency etc. requires as protective membrane usually, can form the protective membrane that satisfies above-mentioned various performances simply and as the storage stability excellent material of compsn.
In addition, the spy opens in the flat 4-218561 communique and discloses thermoset composition that use, that contain potential carboxylated compound in coating, ink, tackiness agent, the molding, does not disclose the protective membrane of colour filter fully.
Summary of the invention
The present invention is based on the above fact and accomplish; Its purpose is formation method, and the protective membrane that forms with above-mentioned compsn that a kind of compsn is provided, uses the protective membrane of above-mentioned compsn; Even the matrix that the said composition surface is low also can form the high cured film of flatness on this matrix; And it is be applicable to that the good light devices of various patience such as forming the transparency and surface hardness height, heat-resisting resistance to pressure, acid resistance, alkali resistance, anti-sputter property, etching patience uses protective membrane, and good as the storage stability of compsn.
According to the present invention; Above-mentioned purpose of the present invention at first can realize through following (A-1) multipolymer; It is characterized by, above-mentioned multipolymer contains (a1) by from the polymerized unit of the polymerizable unsaturated compound with epoxy ethyl (オ キ シ ラ ニ Le base) or oxa-cyclobutyl (オ キ セ タ ニ Le base) and (a2) from the polymerized unit of the polymerizable unsaturated compound of the structure with following formula (01) expression.
Figure S2008101283407D00031
Here, R is that carbonatoms is the tertiary alkyl more than 5; By carbonatoms is that 1～4 the substituted carbonatoms of alkoxyl group is the tertiary alkyl more than 4; (the ring carbon atom number 0-) is the naphthenic base more than 3 to be bonded in the Sauerstoffatom of R bonding with tertiary carbon atom in the above-mentioned formula; Or in the above-mentioned formula with tertiary carbon atom be bonded in the Sauerstoffatom of R bonding (lactonic ring or lactam nucleus that 4 yuan of rings O-) are above,
According to the present invention, above-mentioned purpose of the present invention, second can be through realizing to contain the resin combination that above-mentioned multipolymer of the present invention (A-1) is a characteristic (below be called " resin combination (α 1) ").
According to the present invention; Above-mentioned purpose of the present invention, the 3rd can realize through following resin combination (below be called " resin combination (α 2) "), and being characterized as of this resin combination contains multipolymer, and the multipolymer of (A-3) above-mentioned polymerizable unsaturated compound (a2) and polymerizable unsaturated compound (a3) of (A-2) above-mentioned polymerizable unsaturated compound (a1) and polymerizable unsaturated compound (a3).
Above-mentioned purpose of the present invention, the 4th can through above-mentioned to contain (A-3) composition, and cationically polymerizable compound (B) be that the resin combination (below be called " resin combination (α 3) ") of characteristic is realized.
Above-mentioned purpose of the present invention, the 5th can realize through the protective membrane formation method of colour filter, it is characterized by, and uses above-mentioned each resin combination (α 1), resin combination (α 2), resin combination (α 3) to form and film, and carries out heat treated then.
Above-mentioned purpose of the present invention, the 6th can realize through the protective membrane that uses the colour filter that above-mentioned resin combination forms.
Other purposes of the present invention and advantage can be confirmed by following explanation.
Embodiment
Each composition of resin combination of the present invention is described below.
Multipolymer (A-1)
Multipolymer of the present invention (A-1) contain (a1) from the polymerized unit of polymerizable unsaturated compound, (a2) with epoxy ethyl or oxa-cyclobutyl from the polymerized unit of the polymerizable unsaturated compound of structure with above-mentioned formula (01) expression and (a3) above-mentioned (a1) and beyond the polymerized unit (a2), from the polymerized unit of polymerizable unsaturated compound.
R in the formula (01) is that carbonatoms is the tertiary alkyl more than 5; By carbonatoms is that 1～4 the substituted carbonatoms of alkoxyl group is the tertiary alkyl more than 4; (the ring carbon atom number O-) is the naphthenic base more than 3 to be bonded in Sauerstoffatom with the R bonding with tertiary carbon atom in the above-mentioned formula (01); Or be bonded in and the Sauerstoffatom of R bonding (lactonic ring or lactam nucleus that 4 yuan of rings O-) are above with tertiary carbon atom in the above-mentioned formula (01).
R is that carbonatoms is the tertiary alkyl more than 5 or is 1～4 the substituted carbonatoms of alkoxyl group when being the tertiary alkyl more than 4 by carbonatoms that formula (01) is represented with following formula (1).
Here, R 1And R 2Represent that independently of one another carbonatoms is 1～8 alkyl or is that 1～4 the substituted carbonatoms of alkoxyl group is 1～8 alkyl by carbonatoms, R 3For carbonatoms is 2～8 alkyl or is that 1～4 the substituted carbonatoms of alkoxyl group is 1～8 alkyl by carbonatoms.
R is a ring carbon atom number when being the naphthenic base more than 3, and formula (01) is represented with following formula (2).
Figure S2008101283407D00051
Here, R 1Definition identical with above-mentioned formula (1), n is 1～8 integer, R 4, R 5, R 6And R 7Represent independently of one another Wasserstoffatoms or carbonatoms be end or the side chain of 1～8 alkyl or alkyl to have carbonatoms be that the carbonatoms of 1～4 alkoxyl group is that 1～8 alkyl or carbonatoms are 1～4 alkoxyl group, or R 4, R 5, R 6And R 7Also can at least 2 bondings, carbon atom of their bondings and R 1The carbon atom of bonding together constitutes ring carbon atom and adds up to 7～16 bicyclic alkane or three naphthenic hydrocarbon structures.Wherein, n=2～8 o'clock, a plurality of R 6Reach R each other 7Can be the same or different each other.
In addition, when R was above lactonic ring of 4 yuan of rings or lactam nucleus, above-mentioned formula (01) was the structure with following formula (3) expression.
Figure S2008101283407D00052
Here, R 1Definition identical with above-mentioned formula (1), l is 0,1 or 2, m is 1～4 integer, X is Sauerstoffatom or nitrogen-atoms, R 8, R 9, R 10And R 11Represent that independently of one another Wasserstoffatoms or carbonatoms are that to have carbonatoms on end or the side chain of 1～8 alkyl or alkyl be that the carbonatoms of 1～4 alkoxyl group is that 1～8 alkyl or carbonatoms are 1～4 alkoxyl group, wherein, 2 R during l=2 8And 2 R 9, and a plurality of Rs of m when being 2～4 integer 10And a plurality of R 11Can be identical, also can be different.
R in formula (1), (2) or (3) 1, and formula (1) in R 2Be that to represent to have on end or the side chain of 1～8 alkyl or alkyl carbonatoms be that the carbonatoms of 1～4 alkoxyl group is 1～8 alkyl to carbonatoms.As carbonatoms is 1～8 alkyl, for example can enumerate methyl, ethyl, (different) propyl group, (different) butyl, (different) amyl group, (different) hexyl, (different) heptyl, (different) octyl group.As carbonatoms is 1～4 alkoxyl group, for example can enumerate methoxyl group, oxyethyl group, (different) propoxy-, (different) butoxy etc.
R 3Be that carbonatoms is that to have carbonatoms on end or the side chain of 2～8 alkyl or alkyl be that the carbonatoms of 1～4 alkoxyl group is 1～8 alkyl.As carbonatoms is 2～8 alkyl, for example can enumerate ethyl, (different) propyl group, (different) butyl, (different) amyl group, (different) hexyl, (different) heptyl, (different) octyl group.As carbonatoms is 1～4 alkoxyl group, can enumerate methoxyl group, oxyethyl group, (different) propoxy-, (different) butoxy etc.
Ring texture in the formula (2) is represented the naphthenic hydrocarbon structure of n=1～8.As naphthenic hydrocarbon, can enumerate Trimetylene, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane, cyclodecane.R 4～R 7Expression Wasserstoffatoms or carbonatoms are that to have carbonatoms on end or the side chain of 1～8 alkyl or alkyl be that the carbonatoms of 1～4 alkoxyl group is that 1～8 alkyl or carbonatoms are 1～4 alkoxyl group.R on the cyclic alkane 6And R 7Under the situation more than the n=2; Though have a plurality of; But needn't be identical, can be that to have carbonatoms on end or the side chain of 1～8 alkyl or alkyl be that the carbonatoms of 1～4 alkoxyl group is that 1～8 alkyl or carbonatoms are any in 1～4 the alkoxyl group for Wasserstoffatoms or carbonatoms.As carbonatoms is 1～8 alkyl, for example can enumerate methyl, ethyl, (different) propyl group, (different) butyl, (different) amyl group, (different) hexyl, (different) heptyl, (different) octyl group etc.As carbonatoms is 1～4 alkoxyl group, for example can enumerate methoxyl group, oxyethyl group, (different) propoxy-, (different) butoxy etc.
In addition, R 4～R 7In at least 2 bondings, with the carbon atom and the R of its bonding 1The carbon atom of bonding together forms ring carbon atom and adds up to 7～16 bicyclic alkane or three naphthenic hydrocarbon structures.As above-mentioned bicyclic alkane or three naphthenic hydrocarbon, for example can enumerate 2-ethyl tricyclo [3.3.1.1 3,7] decane-2-is basic, 2-methyl three ring [3.3.1.1 3,7] decane-2-is basic, 1-ethyl tricyclo [3.3.1.1 3,7] decane-1-is basic, 1-methyl three ring [3.3.1.1 3,7] decane-1-is basic, 3-hydroxyl three ring [3.3.1.1 3,7] decane-1-base.
As the R in the formula (3) 8～R 11, can enumerate and R 4～R 7The identical group of listed above-mentioned group.
As X is the lactonic ring in the Sauerstoffatom up-to-date style (3), for example can enumerate 2-ethyl-gamma-butyrolactone-2-base, 2-methyl-gamma-butyrolactone-2-base, 2-ethyl-gamma-butyrolactone-3-base, 2-methyl-gamma-butyrolactone-3-base, 2-ethyl-gamma-butyrolactone-4-base, 2-methyl-gamma-butyrolactone-4-base, 2-ethyl-δ-Wu Neizhi-2-base, 2-ethyl-δ-Wu Neizhi-2-base, 2-ethyl-δ-Wu Neizhi-3-base, 2-methyl-δ-Wu Neizhi-3-base, 2-ethyl-δ-Wu Neizhi-4-base, 2-methyl-δ-Wu Neizhi-4-base, 2-ethyl-δ-Wu Neizhi-5-base and 2-methyl-δ-Wu Neizhi-5-base etc.
In addition; As X is the lactam nucleus in the nitrogen-atoms up-to-date style (3), for example can enumerate 2-ethyl-butyrolactam-2-base, 2-methyl-butyrolactam-2-base, 2-ethyl-butyrolactam-3-base, 2-methyl-butyrolactam-3-base, 2-ethyl-butyrolactam-4-base, 2-methyl-butyrolactam-4-base, 2-ethyl-δ-Valerolactim-2-base, 2-methyl-δ-Valerolactim-2-base, 2-ethyl-δ-Valerolactim-3-base and 2-methyl-δ-Valerolactim-3-base, 2-ethyl-δ-Valerolactim-4-base, 2-methyl-δ-Valerolactim-4-base, 2-ethyl-δ-Valerolactim-5-base and 2-methyl-δ-Valerolactim-5-base etc.
In the multipolymer (A-1),,, do not have special qualification so long as epoxy ethyl or oxa-cyclobutyl and polymerizability unsaturated group get final product as polymerizable unsaturated compound (a1).For example; As the polymerizable unsaturated compound that contains epoxy ethyl; For example can enumerate glycidyl acrylate, SY-Monomer G, α-Yi Jibingxisuan glycidyl ester, α-n-propyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, vinylformic acid-3; 4-epoxy butyl ester, methylacrylic acid-3,4-epoxy butyl ester, vinylformic acid-6,7-epoxy heptyl ester, methylacrylic acid-6; 7-epoxy heptyl ester, α-Yi Jibingxisuan-6,7-epoxy heptyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether etc.
As the polymerizable unsaturated compound that contains the oxa-cyclobutyl, for example can enumerate 3-methyl-3-(methyl) acryloyl-oxy ylmethyl trimethylene oxide, 3-ethyl-3-(methyl) acryloyl-oxy ylmethyl trimethylene oxide etc.
Wherein, Consider from the thermotolerance, the surface hardness aspect that improve copolyreaction property and protective membrane that obtains or insulating film; Preferred SY-Monomer G, the methylacrylic acid-6 of using, 7-epoxy heptyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to the vinyl benzyl glycidyl ether etc.
In the multipolymer (A-1),,, do not have special qualification as long as have the polymerizable unsaturated compound of the structure of above-mentioned formula (1), (2) or (3) as polymerizable unsaturated compound (a2).For example; As the polymerizability unsaturated polymer of structure, for example can enumerate 1-dimethyl-(different) propyl group (methyl) propenoate, 1-dimethyl-(different) butyl (methyl) propenoate, 1-dimethyl-(different) octyl group (methyl) propenoate, 1-methyl isophthalic acid-ethyl diethyldithiocarbamate (methyl) propenoate, 1-methyl isophthalic acid-ethyl (different) propyl group (methyl) propenoate, 1-methyl isophthalic acid-ethyl (different) butyl (methyl) propenoate, 1-methyl isophthalic acid-ethyl (different) octyl group propenoate, 1-diethylammonium (different) propyl group (methyl) propenoate, 1-diethylammonium (different) butyl (methyl) propenoate, 1-diethylammonium (different) octyl group (methyl) propenoate etc. with formula (1).
In addition; As the polymerizability unsaturated polymer of structure with formula (2), for example can enumerate 1-methyl cyclopropane (methyl) propenoate, 1-methyl cyclobutane (methyl) propenoate, 1-methylcyclopentyl (methyl) propenoate, 1-methylcyclohexyl (methyl) propenoate, 1-methyl suberane (methyl) propenoate, 1-methyl cyclooctane (methyl) propenoate, 1-methyl cyclononane (methyl) propenoate, 1-ethyl cyclodecane (methyl) propenoate, 1-ethyl Trimetylene (methyl) propenoate, 1-ethyl tetramethylene (methyl) propenoate, 1-ethyl cyclopentyl (methyl) propenoate, 1-ethyl cyclohexyl (methyl) propenoate, 1-ethyl cycloheptane (methyl) propenoate, 1-ethyl cyclooctane (methyl) propenoate, 1-ethyl cyclononane (methyl) propenoate, 1-methyl cyclodecane (methyl) propenoate, 1-(different) propyl group Trimetylene (methyl) propenoate, 1-(different) propyl group tetramethylene (methyl) propenoate, 1-(different) propyl group cyclopentyl (methyl) propenoate, 1-(different) propyl group cyclohexyl (methyl) propenoate, 1-(different) propyl group suberane (methyl) propenoate, 1-(different) propyl group cyclooctane (methyl) propenoate, 1-(different) propyl group cyclononane (methyl) propenoate, 1-(different) propyl group cyclodecane (methyl) propenoate, 1-(different) butyl Trimetylene (methyl) propenoate, 1-(different) butyl tetramethylene (methyl) propenoate, 1-(different) butyl cyclopentyl (methyl) propenoate, 1-(different) butyl cyclohexyl (methyl) propenoate, 1-(different) butyl suberane (methyl) propenoate, 1-(different) butyl cyclooctane (methyl) propenoate, 1-(different)-butyl cyclononane (methyl) propenoate, 1-(different) butyl ring decyl (methyl) propenoate, 1-(different) amyl group cyclopropyl (methyl) propenoate, 1-(different) amyl group cyclobutyl (methyl) propenoate, 1-(different) amyl group cyclopentyl (methyl) propenoate, 1-(different) amyl group cyclohexyl (methyl) propenoate, 1-(different) amyl group suberyl (methyl) propenoate, 1-(different) amyl group ring octyl group (methyl) propenoate, 1-(different) amyl group ring nonyl (methyl) propenoate, 1-(different) amyl group ring decyl (methyl) propenoate,
1-(different) hexyl cyclopropyl (methyl) propenoate, 1-(different) hexyl cyclobutyl (methyl) propenoate, 1-(different) hexyl cyclohexyl (methyl) propenoate, 1-(different) hexyl suberyl (methyl) propenoate, 1-(different) hexyl ring octyl group (methyl) propenoate, 1-(different) hexyl ring nonyl (methyl) propenoate, 1-(different) hexyl ring decyl (methyl) propenoate,
1-(different) heptyl cyclopropyl (methyl) propenoate, 1-(different) heptyl cyclobutyl (methyl) propenoate, 1-(different) heptyl suberyl (methyl) propenoate, 1-(different) heptyl cyclohexyl (methyl) propenoate, 1-(different) heptyl suberyl (methyl) propenoate, 1-(different) heptyl ring octyl group (methyl) propenoate, 1-(different) heptyl ring nonyl (methyl) propenoate, 1-(different) heptyl ring decyl (methyl) propenoate,
1-(different) octyl group cyclopropyl (methyl) propenoate, 1-(different) octyl group cyclobutyl (methyl) propenoate, 1-(different) octyl group ring octyl group (methyl) propenoate, 1-(different) octyl group cyclohexyl (methyl) propenoate, 1-(different) octyl group suberyl (methyl) propenoate, 1-(different) octyl group ring octyl group (methyl) propenoate, 1-(different) octyl group ring nonyl (methyl) propenoate, 1-(different) octyl group ring decyl (methyl) propenoate,
2-ethyl tricyclo [3.3.1.1 3,7] decane-2-base-(methyl) propenoate, 2-methyl three ring [3.3.1.1 3,7] decane-2-base-(methyl) propenoate, 1-ethyl tricyclo [3.3.1.1 3,7] decane-1-base-(methyl) propenoate, 1-methyl three ring [3.3.1.1 3,7] decane-1-base-(methyl) propenoate, 3-hydroxyl three ring [3.3.1.1 3,7] decane-1-base-(methyl) propenoate etc.
Wherein, Preferred 1-diethylammonium propyl group (methyl) propenoate, 1-ethyl cyclopentyl (methyl) propenoate, 1-ethyl cyclohexyl (methyl) propenoate, 1-(different) propyl group cyclopentyl (methyl) propenoate, 1-(different) propyl group cyclohexyl (methyl) propenoate, 1-(different) butyl cyclopentyl (methyl) propenoate, 1-(different) butyl cyclohexyl (methyl) propenoate of using; More preferably 1-diethylammonium propyl group (methyl) propenoate, 1-ethyl cyclopentyl (methyl) propenoate, 1-ethyl cyclohexyl (methyl) propenoate, preferred especially 1-ethyl cyclopentyl (methyl) propenoate, 1-ethyl cyclohexyl (methyl) propenoate.Consider from the thermotolerance, the surface hardness aspect that improve copolyreaction property and protective membrane that obtains or insulating film, preferably use above-claimed cpd.
In addition; Polymerizable unsaturated compound as structure with formula (3); For example can enumerate 2-ethyl-gamma-butyrolactone-2-base-(methyl) propenoate; 2-methyl-gamma-butyrolactone-2-base-(methyl) propenoate; 2-ethyl-gamma-butyrolactone-3-base-(methyl) propenoate; 2-methyl-gamma-butyrolactone-3-base-(methyl) propenoate; 2-ethyl-gamma-butyrolactone-4-base-(methyl) propenoate; 2-methyl-gamma-butyrolactone-4-base-(methyl) propenoate; 2-ethyl-δ-Wu Neizhi-2-base-(methyl) propenoate; 2-methyl-δ-Wu Neizhi-2-base-(methyl) propenoate; 2-ethyl-δ-Wu Neizhi-3-base-(methyl) propenoate; 2-methyl-δ-Wu Neizhi-3-base-(methyl) propenoate; 2-ethyl-δ-Wu Neizhi-4-base-(methyl) propenoate; 2-methyl-δ-Wu Neizhi-4-base-(methyl) propenoate; 2-ethyl-δ-Wu Neizhi-5-base-(methyl) propenoate; 2-methyl-δ-Wu Neizhi-5-base-lactones such as (methyl) propenoate
2-ethyl-butyrolactam-2-base-(methyl) propenoate; 2-methyl-butyrolactam-2-base-(methyl) propenoate; 2-ethyl-butyrolactam-3-base-(methyl) propenoate; 2-methyl-butyrolactam-3-base-(methyl) propenoate; 2-ethyl-butyrolactam-4-base-(methyl) propenoate; 2-methyl-butyrolactam-4-base-(methyl) propenoate; 2-ethyl-δ-Valerolactim-2-base-(methyl) propenoate; 2-methyl-δ-Valerolactim-2-base-(methyl) propenoate; 2-ethyl-δ-Valerolactim-3-base-(methyl) propenoate; 2-methyl-δ-Valerolactim-3-base-(methyl) propenoate; 2-ethyl-δ-Valerolactim-4-base-(methyl) propenoate; 2-methyl-δ-Valerolactim-4-base-(methyl) propenoate; 2-ethyl-δ-Valerolactim-5-base-(methyl) propenoate; 2-methyl-δ-Valerolactim-5-base-lactan such as (methyl) propenoate.
Multipolymer (A-1) can contain (a1) and (a2) in addition, also contains (a1) and (a2) in addition the polymerized unit of polymerizable unsaturated compound from (a3).As polymerizable unsaturated compound (a3), for example can enumerate (methyl) alkyl acrylate, (methyl) vinylformic acid cyclic alkyl ester, aryl methacrylate, vinylformic acid aryl ester, unsaturated dicarboxylic acid diester, two ring unsaturated compounds, maleimide compound, unsaturated aromatics, conjugated diene compound, unsaturated monocarboxylic, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid acid anhydride, other unsaturated compounds.
As its concrete example; For example; As alkyl methacrylate; Can enumerate methylacrylic acid hydroxyl methyl esters, 2-hydroxyethyl methacrylate, methylacrylic acid 3-hydroxy propyl ester, methylacrylic acid 4-hydroxyl butyl ester, Diethylene Glycol monomethacrylates, methylacrylic acid 2,3-dihydroxyl propyl ester, 2-methacryloxyethyl glucosides, methylacrylic acid 4-hydroxylphenyl ester, TEB 3K, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methylacrylic acid, methylacrylic acid 2-ethylhexyl, methylacrylic acid isodecyl ester, methylacrylic acid dodecyl ester, methylacrylic acid three decyl ester, methylacrylic acid Octadecane base ester etc.;
As alkyl acrylate, can enumerate methyl acrylate, isopropyl acrylate etc.;
As methylacrylic acid cyclic alkyl ester, can enumerate cyclohexyl methacrylate, methylacrylic acid 2-methylcyclohexyl ester, three ring [5.2.1.0 2,6] decane-8-ylmethyl propenoate, three the ring [5.2.1.0 2,6] decane-8-base oxygen ethyl-methyl propenoate, isobornyl methacrylate etc.;
As vinylformic acid cyclic alkyl ester, can enumerate cyclohexyl acrylate, vinylformic acid 2-methyl cyclohexane ester, three ring [5.2.1.0 2,6] decane-8-base propenoate, three ring [5.2.1.0 2,6] decane-8-base oxygen ethyl propylene acid esters, IBOA etc.;
As aryl methacrylate, can enumerate phenyl methacrylate, benzyl methacrylate etc.;
As the vinylformic acid aryl ester, can enumerate phenyl acrylate, benzyl acrylate etc.;
As the unsaturated dicarboxylic acid diester, can enumerate ethyl maleate, DEF, diethyl itaconate etc.;
As two ring unsaturated compounds; Can enumerate two ring [2.2.1] hept-2-ene"s, 5-methyl bicyclic [2.2.1] hept-2-ene", 5-ethyl two ring [2.2.1] hept-2-ene"s, 5-methoxyl group two ring [2.2.1] hept-2-ene"s, 5-oxyethyl group two ring [2.2.1] hept-2-ene"s, 5; 6-dimethoxy two ring [2.2.1] hept-2-ene"s, 5; 6-diethoxy two ring [2.2.1] hept-2-ene"s, 5-(2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s, 5; 6-dihydroxyl two ring [2.2.1] hept-2-ene"s, 5; 6-two (hydroxymethyl) two ring [2.2.1] hept-2-ene"s, 5,6-two (2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s, 5-hydroxy-5-methyl base two ring [2.2.1] hept-2-ene"s, 5-hydroxyl-5-ethyl two ring [2.2.1] hept-2-ene"s, 5-hydroxymethyl-5-methyl bicyclic [2.2.1] hept-2-ene" etc.;
As maleimide compound, can enumerate phenyl maleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridyl) maleimide etc.;
As unsaturated aromatics, can enumerate vinylbenzene, alpha-methyl styrene, a vinyl toluene, p-methylstyrene, Vinyl toluene, to methoxy styrene etc.;
As conjugated diene compound, can enumerate 1,3-butadiene, isoprene, 2,3-dimethyl--1,3-butadiene etc.;
As unsaturated monocarboxylic, can enumerate vinylformic acid, methylacrylic acid, butenoic acid etc.; As unsaturated dicarboxylic acid, can enumerate toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid etc.;
As the unsaturated dicarboxylic acid acid anhydride, can enumerate the acid anhydrides of above-mentioned unsaturated dicarboxylic acid;
As other unsaturated compounds, can enumerate vinyl cyanide, methacrylonitrile, vinylchlorid, vinylidene chloride, acrylic amide, USAF RH-1, vinyl-acetic ester etc.
Wherein, consider optimization styrene, three ring [5.2.1.0 from aspects such as copolyreaction property, thermotolerances 2,6] decane-8-ylmethyl propenoate, to methoxy styrene, 2-methylcyclohexyl propenoate, 1,3-butadiene, two ring [2.2.1] hept-2-ene"s, N-cyclohexyl maleimide etc.
Said mixture can use separately, also can make up use.
Be preferably (a1) 5～95 weight %, (a2) 5～95 weight %, reach (a3) 0～90 weight % from the monomeric structural unit content of polymerizable unsaturated compound in the multipolymer (A-1); More preferably (a1) 20～80 weight %, (a2) 20～80 weight %, and (a3) 0～60 weight % most preferably are (a1) 30～60 weight %, (a2) 30～60 weight %, and (a3) 10～40 weight %.In above-mentioned content range, can realize good planarization performance and thermotolerance.
As the preferred concrete example of multipolymer (A-1), for example, can enumerate styrene/methacrylic acid 1-diethylammonium propyl ester/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-diethylammonium propyl ester/N-phenylmaleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-diethylammonium propyl ester/N-cyclohexyl maleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-ethyl cyclohexyl/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-ethyl cyclohexyl/N-phenylmaleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-ethyl cyclohexyl/N-cyclohexyl maleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-ethyl ring pentyl ester/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-ethyl ring pentyl ester/N-phenylmaleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-ethyl ring pentyl ester/N-cyclohexyl maleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-diethylammonium propyl ester/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base/SY-Monomer G/Sipacril 2739OF, styrene/methacrylic acid 1-diethylammonium propyl ester/N-phenylmaleimide/SY-Monomer G/Sipacril 2739OF, styrene/methacrylic acid 1-diethylammonium propyl ester/N-cyclohexyl maleimide/SY-Monomer G/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl cyclohexyl/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base/SY-Monomer G/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl cyclohexyl/N-phenylmaleimide/SY-Monomer G/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl cyclohexyl/N-cyclohexyl maleimide/SY-Monomer G/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl ring pentyl ester/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base/SY-Monomer G/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl ring pentyl ester/N-phenylmaleimide/SY-Monomer G/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl ring pentyl ester/N-cyclohexyl maleimide/SY-Monomer G/Sipacril 2739OF etc.
(being total to) polymkeric substance (A-2)
(being total to) polymkeric substance (A-2) makes the composition polymerization that contains above-mentioned polymerizable unsaturated compound (a1) obtain (being total to) polymkeric substance (except the above-mentioned multipolymer (A-1)).
(being total to) polymkeric substance (A-2) can also be the multipolymer that forms with above-mentioned polymerizable unsaturated compound (a3) except that polymerizable unsaturated compound (a1).
Be preferably (a1) 5～100 weight %, reach (a3) 0～95 weight % from the monomeric structural unit content of polymerizable unsaturated compound in (being total to) polymkeric substance (A-2); More preferably (a1) 20～100 weight %, and (a3) 0～80 weight % most preferably are (a1) 30～90 weight %, and (a3) 10～70 weight %.In above-mentioned content range, can realize good planarization performance and thermotolerance.
As the preferred concrete example of multipolymer (A-2), for example can enumerate styrene/methacrylic acid 1-diethylammonium propyl ester/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base/Sipacril 2739OF, styrene/methacrylic acid 1-diethylammonium propyl ester/N-phenylmaleimide/Sipacril 2739OF, styrene/methacrylic acid 1-diethylammonium propyl ester/N-cyclohexyl maleimide/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl cyclohexyl/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl cyclohexyl/N-phenylmaleimide/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl cyclohexyl/N-cyclohexyl maleimide/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl ring pentyl ester/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl ring pentyl ester/N-phenylmaleimide/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl ring pentyl ester/N-cyclohexyl maleimide/Sipacril 2739OF etc.
(being total to) polymkeric substance (A-3)
(being total to) polymkeric substance (except the above-mentioned multipolymer (A-1)) that (being total to) polymkeric substance (A-3) obtains for the composition polymerization that contains above-mentioned polymerizable unsaturated compound (a2).
(being total to) polymkeric substance (A-3) can also be the multipolymer that forms with above-mentioned polymerizable unsaturated compound (a3) except polymerizable unsaturated compound (a2).
Content from the monomeric structural unit of polymerizable unsaturated compound in (being total to) polymkeric substance (A-3) is preferably (a2) 5～100 weight %, reaches (a3) 0～95 weight %; More preferably (a2) 20～100 weight %, and (a3) 0～80 weight % most preferably are (a2) 30～90 weight %, and (a3) 10～70 weight %.In above-mentioned content range, can realize good planarization performance and thermotolerance.
As the preferred concrete example of multipolymer (A-3), for example can enumerate styrene/methacrylic acid 1-diethylammonium propyl ester/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base co-polymer, styrene/methacrylic acid 1-diethylammonium propyl ester/N-phenylmaleimide multipolymer, styrene/methacrylic acid 1-diethylammonium propyl ester/N-cyclohexyl maleimide copolymer, styrene/methacrylic acid 1-ethyl cyclohexyl/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base co-polymer, styrene/methacrylic acid 1-ethyl cyclohexyl/N-phenylmaleimide multipolymer, styrene/methacrylic acid 1-ethyl cyclohexyl/N-cyclohexyl maleimide copolymer, styrene/methacrylic acid 1-ethyl ring pentyl ester/methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base co-polymer, styrene/methacrylic acid 1-ethyl ring pentyl ester/N-phenylmaleimide multipolymer, styrene/methacrylic acid 1-ethyl ring pentyl ester/N-cyclohexyl maleimide copolymer etc.
(the stripping solvent: THF) the polystyrene conversion weight-average molecular weight of mensuration (below be called " Mw ") is preferably 1,000～100,000 with GPC for multipolymer (A-1), (A-2) and (A-3); More preferably 2,000～50,000; Be preferably 3,000～40,000 especially.At this moment, if Mw less than 1,000, then the coating of compsn is insufficient sometimes, or the thermotolerance of the protective membrane that forms is not enough; If Mw surpasses 100,000 in addition, then planarization performance becomes insufficient sometimes.
And the MWD (Mw/Mn) of multipolymer (A-1), (A-2) and (A-3) is preferably below 5.0, more preferably below 3.0.
For above-mentioned multipolymer; Multipolymer (A-1) can make above-mentioned polymerizable unsaturated compound (a1), and (a2), polymkeric substance (A-2) can make above-mentioned polymerizable unsaturated compound (a1), polymkeric substance (A-3) can make above-mentioned polymerizable unsaturated compound (a2) in the presence of appropriate solvent and suitable polymerization starter, utilize known method, for example radical polymerization and synthesize.
Cationically polymerizable compound (B)
The cationically polymerizable compound (B) that uses among the present invention has the compound (wherein, except the above-mentioned multipolymer (A-1) (A-2)) of 2 above epoxy ethyls or oxa-cyclobutyl as intramolecularly.As the compound that above-mentioned intramolecularly has 2 above epoxy ethyls or oxa-cyclobutyl, for example can enumerate intramolecularly and have the compound of 2 above epoxy group(ing) or have 3, the compound of 4-epoxycyclohexyl.
The compound that has 2 above epoxy group(ing) as above-mentioned intramolecularly; For example, can enumerate the diglycidylether of bisphenol cpds such as bisphenol A diglycidyl ether, Bisphenol F diglycidylether, bisphenol-S diglycidyl ether, Hydrogenated Bisphenol A 99 diglycidylether, A Hydrogenated Bisphenol A F diglycidylether, Hydrogenated Bisphenol A 99 D diglycidylether, brominated bisphenol A diglycidylether, brominated bisphenol F diglycidylether, brominated bisphenol S diglycidylether;
1,4-butanediol diglycidyl ether, 1, the polyglycidyl ether of polyvalent alcohols such as 6-hexanediol diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether;
The polyglycidyl ether of the addition polyether polyvalent alcohol that ethylene oxide obtains more than a kind or 2 kinds on the aliphatic polyols such as terepthaloyl moietie, Ucar 35, glycerine; Novolac epoxy resin; Line style line style cresols epoxy resin; The polyphenol epoxy resin; The diglycidyl ester of aliphatic long-chain dichloro acid; The glycidyl ester of higher fatty acid; Epoxidised soybean oil, epoxy linseed oil etc.
The commercially available article that have the compound of 2 above epoxy group(ing) as above-mentioned intramolecularly; For example; As bisphenol A type epoxy resin, can enumerate EPICOAT 1001, EPICOAT 1002, EPICOAT1003, EPICOAT 1004, EPICOAT 1007, EPICOAT 1009, EPICOAT 1010, EPICOAT 828 (the above Japanese EPOXY RESIN (strain) of being system) etc.;
As bisphenol f type epoxy resin, can enumerate EPICOAT 807 (Japanese EPOXY RESIN (strain) system) etc.;
As novolac epoxy resin, can enumerate EPICOAT 152, EPICOAT 154, EPICOAT 157S65 (the above Japanese EPOXY RESIN (strain) of being system), EPPN201, EPPN202 (above is Japanese chemical drug (strain) system) etc.;
As line style cresols epoxy resin, can enumerate EOCN102, EOCN103S, EOCN104S, 1020,1025,1027 (above is Japanese chemical drug (strain) system), EPICOAT 180S75 (Japanese EPOXY RESIN (strain) system) etc.;
As polyphenol type epoxy resin, can enumerate EPICOAT 1032H60, EPICOATXY-4000 (the above Japanese EPOXY RESIN (strain) of being system) etc.;
As cyclic aliphatic epoxy resin, can enumerate CY-175, CY-177, CY-179, ARALDIT CY-182, ARALDIT 192,184 (the above CIBA SPECIALITYCHEMICALS (strain) of being makes), ERL-4234,4299,4221,4206 (above is the U.C.C corporate system), SHOWDYNE 509 (clear and electrician's (strain) makes), EPICLON 200, EPICLON400 (above is that big Japanese ink (strain) is made), EPICOAT 871, EPICOAT 872 (the above Japanese EPOXY RESIN (strain) of being makes), ED-5661, ED-5662 (the above CELANESECOATING (strain) of being makes) etc.;
As the aliphatic poly glycidyl ether, can enumerate out EPORITE 100MF (common prosperity society chemistry (strain) system), EPIOLE TMP (Japanese grease (strain) system) etc.
Have more than 23 as above-mentioned intramolecularly, the compound of 4-epoxycyclohexyl, for example; Can enumerate 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 2-(3; 4-epoxycyclohexyl-5,5-spiral shell-3,4-epoxy) hexanaphthene-methyl-Jian dioxs (metadioxane), two (3; 4-epoxycyclohexyl methyl) adipic acid ester, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester, 3,4-epoxy-6-methylcyclohexyl-3 '; 4 '-epoxy-6 '-methylcyclohexanecarboxylic acid ester, methylene-bis (3, the 4-epoxy cyclohexane), Dicyclopentadiene (DCPD) diepoxide, two (3,4-epoxycyclohexyl methyl) ether of terepthaloyl moietie, ethylenebis (3; The 4-epoxycyclohexane carboxylate), lactone sex change 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate etc.
In the above-mentioned cationically polymerizable compound (B), preferred novolac epoxy resin and polyphenol type epoxy resin.
The usage quantity of cationically polymerizable compound (B) is with respect to total amount 100 weight parts of polymkeric substance (A-1), (A-2) and (A-3) in the resin combination of the present invention; Be preferably 3～200 weight parts; More preferably 5～100 weight parts are preferably 10～50 weight parts especially.Cationically polymerizable compound (B) if usage quantity greater than 200 weight parts, then the coating of compsn goes wrong sometimes; In addition, if less than 3 weight parts, the hardness of the protective membrane that then obtains is not enough sometimes.
Thermo-sensitivity acid-producing agent (C)
As the thermo-sensitivity acid-producing agent, can enumerate sulfonium salt class, benzothiazole salt, ammonium salt class, microcosmic salt class etc., wherein, preferably use sulfonium salt class, benzothiazole salt.
As the concrete example of above-mentioned sulfonium salt class, can enumerate 4-acetyl phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, dimethyl--4-(benzyloxy carbonyl oxygen base) phenyl sulfonium hexafluoro antimonate, dimethyl--4-(benzoyloxy) phenyl sulfonium hexafluoro antimonate, dimethyl--4-(benzoyloxy) phenyl sulfonium hexafluoro arsenate, dimethyl--alkyl sulfonium salts such as 3-chloro-4-acetoxyl group phenyl sulfonium hexafluoro antimonate;
Benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, benzyl-4-anisole ylmethyl sulfonium hexafluoro antimonate, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro arsenate, 4-methoxy-benzyl-benzyl sulfonium salts such as 4-hydroxy phenyl methyl sulfonium hexafluorophosphate;
Dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro antimonate, dibenzyl-4-p-methoxy-phenyl sulfonium hexafluoro antimonate, dibenzyl-3-chloro-4-hydroxy phenyl sulfonium hexafluoro arsenate, dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium hexafluoro antimonate, benzyl-4-methoxy-benzyl-dibenzyl sulfonium salts such as 4-hydroxy phenyl sulfonium hexafluorophosphate;
P-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, to nitrobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 3,5-dichloro benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, o-chlorobenzyl-substituted benzyl sulfonium salts such as 3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate etc.
Wherein, preferably use 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl sulfonium hexafluoro antimonate etc.
As above-mentioned benzothiazole salt, can enumerate 3-benzyl benzothiazole hexafluoro antimonate, 3-benzyl benzothiazole hexafluorophosphate, 3-benzyl benzothiazole a tetrafluoro borate, 3-(to methoxy-benzyl) benzothiazole hexafluoro antimonate, 3-benzyl-2-methyl-thio-benzothiazole hexafluoro antimonate, 3-benzyl-benzyl benzothiazolium salts such as 5-chloro benzothiazole hexafluoro antimonate.
Wherein, preferably use 3-benzyl benzothiazole hexafluoro antimonate etc.
The commercially available article of the acid-producing agent that preferably uses as the thermo-sensitivity acid-producing agent can be enumerated rising sun electrochemical industry (strain) the system trade(brand)name as the alkyl sulfonium salt: ADEKA OPTON CP-66, CP-77.
In addition, then the benzyl sulfonium salt can be enumerated three new chemical industry (strain) system trade(brand)name: SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L.
Wherein, because the protective membrane that obtains has high surface hardness, therefore preferred SI-80, SI-100, SI-110.
When resin combination of the present invention contained (C) thermo-sensitivity acid-producing agent, its usage quantity was with respect to total amount 100 weight parts of polymkeric substance (A-1), (A-2) and (A-3), was preferably 0.05～20 weight part, 0.1～10 weight part more preferably.Adopt the usage quantity of above-mentioned scope, can obtain having the protective membrane of enough hardness.
In addition, can change (C) thermo-sensitivity acid-producing agent into the radioactivity-sensitive acid-producing agent.
The radioactivity-sensitive acid-producing agent is can be through irradiation visible light, ultraviolet ray, far ultraviolet rays yue, electron rays, X ray isoradial and acidic compound.
As above-mentioned radioactivity-sensitive acid-producing agent, can enumerate diaryl group iodized salt class, triaryl matte salt, diaryl microcosmic salt class, preferably use above-claimed cpd.
As above-mentioned diaryl group iodized salt class, for example can enumerate phenylbenzene iodine a tetrafluoro borate, phenylbenzene iodine hexafluoro phosphonate, phenylbenzene iodine hexafluoro arsenate, phenylbenzene iodine fluoroform sulphonate, phenylbenzene iodine trifluoroacetate, phenylbenzene iodine tosilate, 4-p-methoxy-phenyl phenyl-iodide a tetrafluoro borate, 4-p-methoxy-phenyl phenyl-iodide hexafluoro phosphonate, 4-p-methoxy-phenyl phenyl-iodide hexafluoro arsenate, 4-p-methoxy-phenyl phenyl-iodide fluoroform sulphonate, 4-p-methoxy-phenyl phenyl-iodide trifluoroacetate, 4-p-methoxy-phenyl phenyl-iodide tosilate, two (4-tert-butyl-phenyl) iodine a tetrafluoro borate, two (4-tert-butyl-phenyl) iodine hexafluoro arsenate, two (4-tert-butyl-phenyl) iodine fluoroform sulphonate, two (4-tert-butyl-phenyl) iodine trifluoroacetate, two (4-tert-butyl-phenyl) iodine tosilate etc.Wherein, preferably use phenylbenzene iodine hexafluoro phosphonate.
As above-mentioned triaryl matte salt, for example can enumerate triphenylsulfonium a tetrafluoro borate, triphenylsulfonium hexafluoro phosphonate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium fluoroform sulphonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium tosilate, 4-p-methoxy-phenyl phenylbenzene sulfonium a tetrafluoro borate, 4-p-methoxy-phenyl phenylbenzene sulfonium hexafluoro phosphonate, 4-p-methoxy-phenyl phenylbenzene sulfonium hexafluoro arsenate, 4-p-methoxy-phenyl phenylbenzene sulfonium fluoroform sulphonate, 4-p-methoxy-phenyl phenylbenzene sulfonium trifluoroacetate, 4-p-methoxy-phenyl phenylbenzene sulfonium tosilate, 4-phenyl thio-phenyl phenylbenzene a tetrafluoro borate, 4-phenyl thio-phenyl phenylbenzene hexafluoro phosphonate, 4-phenyl thio-phenyl phenylbenzene hexafluoro arsenate, 4-phenyl thio-phenyl phenylbenzene fluoroform sulphonate, 4-phenyl thio-phenyl phenylbenzene trifluoroacetate, 4-phenyl thio-phenyl phenylbenzene tosilate etc.Wherein, preferably use the triphenylsulfonium fluoroform sulphonate.
As above-mentioned diaryl microcosmic salt class, can enumerate (1-6-η-cumene) (η-cyclopentadienyl moiety) iron hexafluoro phosphonate etc.
As the radioactivity-sensitive acid-producing agent, the commercially available article of the preferred acid-producing agent that uses have the UNION CARBIDE corporate system trade(brand)name as the diaryl group iodized salt class: UVI-6950, UVI-6970, UVI-6974, UVI-6990, greening (strain) system trade(brand)name: MPI-103, BBI-103 etc.
In addition; As the triaryl matte salt, can enumerate rising sun electrochemical industry (strain) system trade(brand)name: ADEKA Optomer SP-150, SP-151, SP-170, SP-171, Japanese Cao Da (strain) system trade(brand)name: CI-2481, CI-2624, CI-2639, CI-2064, greening (strain) system trade(brand)name: DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, Sartomer corporate system trade(brand)name: CD-1010, CD-1011, CD-1012 etc.
In addition, as diaryl microcosmic salt class, can enumerate CIBA SPECIALITYCHEMICALS (strain) system trade(brand)name: Irgakur 261, Japanese chemical drug (strain) system trade(brand)name: PCI-061T, PCI-062T, PCI-020T, PCI-022T etc.
Wherein, Because the protective membrane that obtains has high surface hardness, therefore preferred UNION CARBIDE corporate system trade(brand)name: UVI-6970, UVI-6974, UVI-6990, rising sun electrochemical industry (strain) system trade(brand)name: (strain) system trade(brand)name: MPI-103 is learned in ADEKA Optomer SP-170, SP-171, Sartomer corporate system trade(brand)name: CD-1012, greening.
When resin combination of the present invention contains the radioactivity-sensitive acid-producing agent, its usage quantity with respect to total amount 100 weight parts of polymkeric substance (A-1), (A-2) and (A-3), be preferably 0.05～20 weight part, 0.1～10 weight part more preferably.Through adopting the usage quantity of above-mentioned scope, the protective membrane that can obtain having enough hardness.
(D) bonding agent
For the protective membrane that improves formation and the adaptation of substrate, can add above-mentioned (D) bonding agent.
As above-mentioned (D) bonding agent, for example can use functional silanes coupling agent with reactive substituents.As above-mentioned reactive substituents, for example can enumerate carboxyl, methacryloyl, NCO, epoxy group(ing) etc.
Concrete example as (D) bonding agent; For example can enumerate trimethoxysilyl phenylformic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanic ester propyl-triethoxysilicane, γ-glycidyl oxygen base propyl trimethoxy silicane, γ-glycidyl oxygen base propyl-triethoxysilicane, β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan etc.
The usage quantity of above-mentioned (D) bonding agent is preferably below 30 weight parts, more preferably below 25 weight parts with respect to total amount 100 weight parts of multipolymer (A-1), (A-2) and (A-3).If the amount of bonding agent surpasses 30 weight parts, it is insufficient that the thermotolerance of the protective membrane that then obtains becomes sometimes (D).
(E) tensio-active agent
In order to improve the coating performance of resin combination of the present invention, can add above-mentioned tensio-active agent.
As above-mentioned tensio-active agent, for example can enumerate fluorine class tensio-active agent, silicone based tensio-active agent, nonionic class tensio-active agent, other tensio-active agents.
As above-mentioned fluorine class tensio-active agent; For example, can enumerate BM CHIMIE corporate system trade(brand)name: BM-1000, BM-1100, big Japanese ink chemical industry (strain) corporate system trade(brand)name: MegafacF142D, Megafac F172, Megafac F173, Megafac F183, Sumitomo 3M (strain) corporate system trade(brand)name: Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, FluoradFC-431, Asahi Glass (strain) society system trade(brand)name: commercially available article such as Surfron S-112, Surfron S-113, SurfronS-131, Surfron S-141, Surfron S-145, Surfron S-382, Surfron SC-101, SurfronSC-102, Surfron SC-103, Surfron SC-104, Surfron SC-105, Surfron SC-106.
As above-mentioned silicone based tensio-active agent, for example can enumerate eastern beautiful DowcorningSilicone (strain) corporate system trade(brand)name: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190, SHIN-ETSU HANTOTAI's chemical industry (strain) corporate system trade(brand)name: KP341, new autumn fields changes into (strain) corporate system trade(brand)name: commercially available article such as F-TOP EF301, F-TOP EF303, F-TOP EF352.
As above-mentioned nonionic class tensio-active agent, for example, can enumerate polyethylene oxide alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl etc.
As above-mentioned polyethylene oxide alkyl ethers; For example, can enumerate polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oleyl ether etc., as the polyoxyethylene aryl ethers; For example; Polyoxyethylene octylphenyl ether, polyoxyethylene nonylplenyl ether be can enumerate,, polyoxyethylene dilauryl ester, polyoxyethylene SUNSOFT Q-182S etc. for example can be enumerated as the polyoxyethylene dialkyl.
As above-mentioned other tensio-active agents, can enumerate chemistry (strain) society of common prosperity society system trade(brand)name: (methyl) acrylic copolymer POLYFLOW No.57, POLYFLOWNo.90 etc.
The addition of above-mentioned (E) tensio-active agent is preferably below 5 weight parts, more preferably below 2 weight parts with respect to total amount 100 weight parts of polymkeric substance (A-1), (A-2) and (A-3).When amount of surfactant surpassed 5 weight parts, the film of filming easily in the painting process was coarse.
The embodiment of resin combination
As the preferred implementation of resin combination of the present invention, can enumerate following (1)～(3).
(1) contains: multipolymer (A-1), and the resin combination of the cationic polymerizable compound (B) that contains as required, thermo-sensitivity acid-producing agent (C).
(2) contain: multipolymer (A-2) and multipolymer (A-3), and the resin combination of the cationic polymerizable compound (B) that contains as required, thermo-sensitivity acid-producing agent (C).In the compsn (2), the usage quantity of multipolymer (A-3) is with respect to total amount 100 weight parts of multipolymer (A-2), (A-3), is 10～90 weight parts, is preferably 20～80 weight parts.During quantity not sufficient 10 weight parts of multipolymer (A-3), take place to solidify not enough sometimes, when surpassing 90 weight parts, thermotolerance worsens sometimes.
(3) contain: multipolymer (A-3) and cationic polymerizable compound (B), and the resin combination of the thermo-sensitivity acid-producing agent (C) that contains as required.
Resin combination of the present invention preferably prepares through above-mentioned each composition is dissolved equably or is dispersed in the appropriate solvent.As employed solvent, preferred use can dissolve or each composition of dispersive composition and not with the solvent of each composition reaction.
As above-mentioned solvent, can enumerate alcohol, ether, glycol ether, terepthaloyl moietie alkyl oxide acetic ester, Diethylene Glycol monoalky lether, diethylene glycol dialkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, aromatic hydrocarbons, ketone, ester etc.
As the concrete example of above-mentioned solvent, for example,, can enumerate methyl alcohol, ethanol, benzyl alcohol etc. as alcohol;
As ether, can enumerate THF etc.;
As glycol ethers, can enumerate glycol monomethyl methyl ether, ethylene glycol monomethyl ether etc.;
As terepthaloyl moietie alkyl oxide acetic ester, can enumerate methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetic ester, TC acetic ester etc.;
As the Diethylene Glycol monoalky lether, can enumerate diethylene glycol monomethyl ether, TC etc.;
As diethylene glycol dialkyl ether, can enumerate diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol ethyl-methyl ether etc.;
As propylene-glycol monoalky lether, can enumerate methyl proxitol, Ucar 35 ethyl ether, Ucar 35 propyl ether, propylene glycol butyl ether etc.;
As propylene glycol alkyl ether acetic acid ester, can enumerate methyl proxitol acetate, Ucar 35 ethyl ether acetic ester, Ucar 35 propyl ether acetic ester, propylene glycol butyl ether acetic ester etc.;
As propylene glycol alkyl ether propionic ester, can enumerate methyl proxitol propionic ester, Ucar 35 ethyl ether propionic ester, Ucar 35 propyl ether propionic ester, propylene glycol butyl ether propionic ester etc.;
As aromatic hydrocarbons, can enumerate toluene, YLENE etc.;
As ketone, can enumerate methyl ethyl ketone, pimelinketone, 4-hydroxy-4-methyl-2-heptanone, methyl isoamyl ketone etc.;
As ester, can enumerate methyl acetate, ETHYLE ACETATE, propyl acetate, butylacetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, oxyacetic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy-propionic acid ethyl ester, 3-hydroxy-propionic acid propyl ester, 3-hydroxy-propionic acid butyl ester, 2-hydroxy-3-methyl methyl-butyrate, methoxy menthyl acetate, NSC 7300 ethyl ester, NSC 7300 propyl ester, NSC 7300 butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxy-methyl acetate, propoxy-ETHYLE ACETATE, propoxy-propyl acetate, propoxy-butylacetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxy-methyl propionate, 3-propoxy-ethyl propionate, 3-propoxy-propyl propionate, 3-propoxy-butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, 3-butoxy butyl propionate etc.
Wherein, Alcohols, Diethylene Glycol, propylene glycol alkyl acetic ester, terepthaloyl moietie alkyl oxide acetic ester, diethylene glycol dialkyl ether, preferred especially benzyl alcohol, Diethylene Glycol ethyl-methyl ether, methyl proxitol acetate, Ucar 35 ethyl ether acetic ester, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetic ester, TC acetic ester, diethylene glycol diethyl ether.
As the usage quantity of solvent, whole solid in the present composition forms the amounts that divide (from the total composition that comprises solvent, deducting the amount that quantity of solvent obtains) and is preferably 1～50 weight %, 5～40 weight % more preferably.
Can with above-mentioned solvent together and use high boiling solvent.As here can and the high boiling solvent of usefulness; For example can enumerate N-NMF, N; Dinethylformamide, N-methyl formylphenyl aniline, N-methylacetamide, DMAC N,N, N-Methyl pyrrolidone, methyl-sulphoxide, benzyl ethyl ether, hexyl ether, acetonyl-acetone, different Buddhist diketone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, jasmal, ethyl benzoate, oxalic acid diethyl ester, ethyl maleate, gamma-butyrolactone, ethylene carbonate, Texacar PC, phenyl cellosolve acetic ester etc.
As and usage quantity during with high boiling solvent, with respect to the total solvent amount, be preferably 90 weight % following, more preferably below the 80 weight %.
The compsn of preparation can be in that to use the aperture be 0.2～3.0 μ m, be preferably and use after millipore filter about 0.2～0.5 μ m of aperture etc. leaches as described above.
The formation of the protective membrane of colour filter
Explanation uses compsn of the present invention to form the method for the protective membrane of colour filter below.
Resin combination solution coat of the present invention at substrate surface, is carried out prebake, remove and desolvate, after formation is filmed, carry out heat treated, form the protective membrane of purpose colour filter thus.
As can be used as the material that aforesaid substrate uses, for example can use substrates such as glass, quartz, silicon, resin.As resin, for example can enumerate resins such as polyethyleneterephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, the ring-opening polymerization polymer that reaches cyclic olefin and hydrogenate thereof.
As coating process, for example can adopt spraying method, rolling method, spin-coating method, rod to be coated with proper method such as method, ink jet method, especially preferably use spinner, spreader, slit mould are coated with the coating that device carries out without spin.
Above-mentioned prebake condition is because of the kind of each composition or cooperation ratio etc. are different, adopts usually under 70～90 ℃, about 1～15 minute condition.As the thickness of filming, be preferably 0.15～8.5 μ m, more preferably 0.15～6.5 μ m, most preferably be 0.15～4.5 μ m.In addition, the coating thickness here is to be understood that to removing the thickness after desolvating.
The heat treated of filming after forming can be implemented with suitable heating unit such as hot-plate or dustless baking oven.As treatment temp, be preferably about 150～250 ℃, be 5～30 minutes heat-up time when adopting hot-plate, when using baking oven, adopts 30～90 minutes treatment time.
In addition, when in resin combination, using the radioactivity-sensitive acid-producing agent, this resin combination is coated on substrate surface,, removes and desolvate through prebake, process film after, implement radiation exposure and handle (exposure-processed), form thus as the protection of goal film.Also can after exposure-processed, carry out heat treated more as required.
Operable radioactive rays in the radiation treatment as above-mentioned radioactive rays can be enumerated visible light, ultraviolet ray, far ultraviolet rays yue, electron rays, X ray etc., preferably contain the ultraviolet ray of light of the wavelength of 190～450nm.
As exposure, be generally 100～20,000J/m 2, be preferably 150～10,000J/m 2
Also can behind the irradiation radioactive rays, carry out heat treated more arbitrarily.As the Heating temperature of this moment, preferred about 150～250 ℃,, for example can use suitable device such as hot-plate, dustless baking oven as heating unit.Be 5～30 minutes heat-up time when using hot-plate, when using baking oven, can adopt 30～90 minutes treatment time.
The protective membrane of colour filter
The thickness of the protective membrane that is formed as described above be preferably 0.1～8 μ m, more preferably 0.1～6 μ m, be preferably 0.1～4 μ m again.In addition, when protective membrane of the present invention was formed on the substrate that colour filter has jump, above-mentioned thickness was to be understood that the thickness of starting at for from the topmost of colour filter.
Can know by following embodiment; Protective membrane of the present invention satisfies adaptation, surface hardness, the transparency, thermotolerance, photostabilization, solvent resistance etc.; Under the influence of executing the loading under the heating condition, do not cave in simultaneously yet; In addition, the light device of excellent property that is applicable to the jump planarization of the colour filter that is formed on the bottom substrate is used protective membrane.
Protective membrane particularly of the present invention is exposed in the panel preparation section and surpasses under 250 ℃ the heating condition, therefore also has the thermotolerance that is enough to tolerate this moment, and this point is to be able to guarantee through under 270 ℃, having enough dimensional stabilitys.
According to the present invention; A kind of resin combination can be provided, use formation method, and the protective membrane that forms by above-mentioned compsn of the protective membrane of this resin combination; Even the low matrix of above-mentioned resin combination surface; Also can on this matrix, form the high cured film of flatness; And, be applicable to that the good light devices of various patience such as forming the transparency and surface hardness height, heat-resisting resistance to pressure, acid resistance, alkali resistance, anti-sputter property, etching patience use protective membrane, and good as the storage stability of compsn.
Embodiment
Provide synthetic example, embodiment below, the present invention more specifically is described, the present invention does not limit and following embodiment.
The preparation of (being total to) polymkeric substance
Synthetic example 1
In the flask that possesses prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, propylene glycol monomethyl ether 200 weight parts.Next, put into SY-Monomer G 50 weight parts, methylacrylic acid 1-ethyl ring pentyl ester 50 weight parts, carry out stirring lentamente after nitrogen replaces.Solution temperature is risen to 70 ℃, this temperature was kept 5 hours, obtain comprising the polymers soln of multipolymer (A1-1).The solid formation branch concentration of the polymers soln that obtains is 32.9%.
Synthetic example 2
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, propylene glycol monomethyl ether 200 weight parts.Next put into SY-Monomer G 40 weight parts, methylacrylic acid 1-diethylammonium propyl ester 40 weight parts, vinylbenzene 10 weight parts, reach methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base 10 weight parts, to carry out after nitrogen replaces, beginning is stirred lentamente.The temperature of solution is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (A1-2).The solid formation branch concentration of the polymers soln that obtains is 33.0%.
Synthetic example 3
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, propylene glycol monomethyl ether 200 weight parts.Next put into SY-Monomer G 40 weight parts, methylacrylic acid 1-ethyl cyclohexyl 40 weight parts, vinylbenzene 10 weight parts, and cyclohexyl maleimide 10 weight parts, carry out after nitrogen replaces, beginning is stirred lentamente.Solution temperature is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (A1-3).The solid formation branch concentration of the polymers soln that obtains is 33.0%.
Synthetic example 4
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, propylene glycol monomethyl ether 200 weight parts.Next put into SY-Monomer G 40 weight parts, methylacrylic acid 1-ethyl ring pentyl ester 40 weight parts, vinylbenzene 10 weight parts, and N-cyclohexyl maleimide 10 weight parts, carry out after nitrogen replaces, beginning is stirred lentamente.Solution temperature is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (A1-4).The solid formation branch concentration of the polymers soln that obtains is 32.7%.
Synthetic example 5
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, Diethylene Glycol ethyl-methyl ether 200 weight parts.Next put into SY-Monomer G 40 weight parts, methylacrylic acid 1-ethyl ring pentyl ester 40 weight parts, methylacrylic acid 10 weight parts, vinylbenzene 5 weight parts, reach N-cyclohexyl maleimide 5 weight parts; After carrying out the nitrogen replacement, beginning is stirred lentamente.Solution temperature is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (A1-5).The solid formation branch concentration of the polymers soln that obtains is 32.8%.
Synthetic example 6
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, Diethylene Glycol ethyl-methyl ether 200 weight parts.Next put into SY-Monomer G 40 weight parts, 2-methyl-gamma lactone-4-base-methacrylic ester 40 weight parts, vinylbenzene 10 weight parts, and N-cyclohexyl maleimide 10 weight parts, carry out after nitrogen replaces, beginning is stirred lentamente.Solution temperature is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (A1-6).The solid formation branch concentration of the polymers soln that obtains is 31.9%.
Synthetic example 7
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, propylene glycol monomethyl ether 200 weight parts.Next put into SY-Monomer G 100 weight parts, carry out after nitrogen replaces, beginning is stirred lentamente.Solution temperature is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (A2-1).The solid formation branch concentration of the polymers soln that obtains is 33.2%.
Synthetic example 8
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, propylene glycol monomethyl ether 200 weight parts.Next put into SY-Monomer G 80 weight parts, vinylbenzene 20 weight parts, carry out after nitrogen replaces, beginning is stirred lentamente.Solution temperature is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (A2-2).The solid formation branch concentration of the polymers soln that obtains is 33.3%.
Synthetic example 9
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, propylene glycol monomethyl ether 200 weight parts.Next put into methylacrylic acid 1-ethyl cyclohexyl 100 weight parts, carry out after nitrogen replaces, beginning is stirred lentamente.Solution temperature is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (A3-1).The solid formation branch concentration of the polymers soln that obtains is 33.0%.
Synthetic example 10
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, propylene glycol monomethyl ether 200 weight parts.Next put into methylacrylic acid 1-ethyl cyclohexyl 80 weight parts, vinylbenzene 10 weight parts, reach methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base 10 weight parts, to carry out after nitrogen replaces, beginning is stirred lentamente.Solution temperature is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (A3-2).The solid formation branch concentration of the polymers soln that obtains is 33.3%.
Relatively more synthetic example 1
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, Diethylene Glycol ethyl-methyl ether 200 weight parts.Next put into vinylbenzene 25 weight parts, methylacrylic acid 20 weight parts, SY-Monomer G 45 weight parts and methylacrylic acid three ring [5.2.1.0 2,6] decane-8-base 10 weight parts, to carry out after nitrogen replaces, beginning is stirred lentamente.The temperature of solution is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (a-1).The solid formation branch concentration of the polymers soln that obtains is 33.0%.
Relatively more synthetic example 2
In the flask of having equipped prolong, stirrer, put into 2, two (2, the 4-methyl pentane nitrile) 5 weight parts of 2 '-azo, propylene glycol monomethyl ether 200 weight parts.Next put into SY-Monomer G 40 weight parts, vinylbenzene 10 weight parts, methylacrylic acid tertiary butyl ester 40 weight parts, and cyclohexyl maleimide 10 weight parts, carry out after nitrogen replaces, beginning is stirred lentamente.Solution temperature is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of multipolymer (a-2).The solid formation branch concentration of the polymers soln that obtains is 33.0%.
The preparation of resin combination and evaluation
Embodiment 1
Entering contains the solution (amount that is equivalent to multipolymer (A1-1) 100 weight parts (Gu form divide)) of the multipolymer (A1-1) that obtains in above-mentioned synthetic routine 1 and (E) as SH-28PA (eastern beautiful DowcorningSilicone (strain) system) 0.1 weight part of tensio-active agent; Add propylene glycol monomethyl ether again; After making solid formation branch concentration be 20%; The use aperture is that the millipore filter of 0.5 μ m filters, the preparation resin combination.
Use spinner, above-mentioned compsn is applied to SiO 2After on the dipping glass substrate, on hot-plate, carry out prebake in 5 minutes in 80 ℃, formation is filmed, and in baking oven, carries out 60 minutes heat treated in 230 ℃ again, forms the protective membrane of thickness 2.0 μ m.
The evaluation of protective membrane
(1) evaluation of the transparency
For the substrate that is formed as described above, use spectrophotometer (150-20 type twin-beam (Hitachi (strain) system)) to measure the transmittance of 400～800nm with protective membrane.The minimum value of the transmittance of 400～800nm is shown in table 1.This value is 95% when above, thinks that the transparency of protective membrane is for good.
(2) evaluation of heat-resisting dimensional stability
The substrate with protective membrane that is formed as described above is heated under 250 ℃, 1 hour condition in baking oven, measure the thickness of heating front and back.The heat-resisting dimensional stability of calculating by following formula is shown in table 1.This value is 95% when above, thinks that its heat-resisting dimensional stability is good.
Heat-resisting dimensional stability=(thickness after the heating)/(thickness before the heating) * 100 (%)
(3) evaluation of heat-resisting discolouration
With the substrate that is formed as described above with protective membrane in baking oven, 250 ℃ of down heating 1 hour, likewise measures the transparency of heating front and back with above-mentioned (1).The heat-resisting discolouration of calculating by following formula is shown in table 1.This value is 5% when following, thinks that heat-resisting discolouration is good.
Transmittance (%) after transmittance-heating before heat-resisting discolouration=heating
(4) mensuration of surface hardness
For the substrate that is formed as described above, utilize the surface hardness of the 8.4.1 pencil stretching test measurement protective membrane of JIS K-5400-1990 with protective membrane.This value is shown in table 1.This value thinks that for 4H or when harder its surface hardness is good.
(5) mensuration of dynamic small hardness
For the substrate that is formed as described above with protective membrane; Use the dynamic micro-hardness tester DUH-201 in Tianjin, island ((strain) Shimadzu Seisakusho Ltd. system); Utilizing the indentation test of 115 ° of triangle pressure heads of corner angle (Herchovitch type), is the dynamic small hardness of measuring protective membrane under the condition determination of 23 ℃ and 140 ℃ in loading: 0.1gf, speed: 0.0145gf/sec., hold-time: 5sec., temperature.The result is shown in table 1.
(6) evaluation of adaptation
After carrying out pressure kettle test (120 ℃, humidity 100%, 4 hour) for the substrate with protective membrane that is formed as described above, utilize the 8.5.3 tack mesh tape test method of JIS K-5400-1990, the adaptation of estimating protective membrane is (to SiO 2Adaptation).In 100 in the mesh, remaining mesh count is shown in table 2.
In addition, as evaluation, use the Cr substrate to replace SiO to the adaptation of Cr 2In addition the dipping glass substrate, with the above-mentioned protective membrane that likewise forms thickness 2.0 μ m, adopts above-mentioned mesh tape test method likewise to estimate.The result is shown in table 1.
(7) evaluation of ITO etching patience
For the substrate with protective membrane that is formed as described above, in Japanese vacuum technique corporate system High rate Sputtering device SH-550-C12, (the ITO filling ratio is more than 95%, In to use the ITO target 2O 3/ SnO 2=90/10 weight ratio), implement the ITO sputter down at 60 ℃.The atmosphere of this moment is decompression degree 1.0 * 10 -5Pa, Ar airshed 3.12 * 10 -3m 3/ h, O 2Airshed 1.2 * 10 -5m 3/ h.Substrate after the sputter at 240 ℃ * 60min of above-mentioned dustless baking oven internal heating, is implemented annealing.Then, substrate is fixed in the spinner, JSR (strain) system G line is dropped on the substrate with positive photoresist PFR3650-21cp, be coated with 3500rpm * 30sec.Substrate with 90 ℃ * 2min of hot-plate heating, is removed and desolvates.Then,, use exposure machine Canon PLA501F (Canon (strain) system), ghi line (strength ratio of wavelength 436nm, 405nm, 365nm=2.7: 2.5: 4.8) is converted with the i line, according to degree 23mW/m via the pattern mask of 10 μ m/10 μ m 2, 25mJ/m 2Exposure shine, used 2.4%TMAH aqueous solution dipping under the room temperature 60 seconds, develop, rinsing was carried out air-dry after 60 seconds in ultrapure water.Then, 150 ℃ * 60min of back roasting in dustless baking oven.Nitric acid/hydrochloric acid is mixed as etching reagent with 1/3 weight ratio.Substrate is immersed in the etching reagent, every at a distance from 10 seconds taking-up substrates, the just etching time of the ITO line of decision formation 10 μ m, the ITO live width during with 1.2 times of optical microscope measuring just etching time, the result is as shown in table 1.The conservation rate of the ITO line of 10 μ m is high more, and ITO etching patience is good more.
(8) evaluation of smooth voltinism
At SiO 2With the colored resist of spinner coating pigment class (trade(brand)name " JCRRED 689 ", " JCR GREEN 706 ", " CR 8200B ", above be that JSR (strain) makes), on hot-plate, carry out prebake in 150 seconds in 90 ℃ on the dipping glass substrate, formation is filmed.Then,, use exposure machine Canon PLA501F (Canon (strain) system), ghi line (strength ratio of wavelength 436nm, 405nm, 365nm=2.7: 2.5: 4.8) is pressed the i line convert via the pattern mask of regulation, with 2,000J/m 2Exposure shine, use 0.05% potassium hydroxide aqueous solution, develop, in the ultrapure water rinsing after 60 seconds, again in baking oven,, form 3 red, green and blue or green stripe shape colour filters (the wide 100 μ m of striped) in 230 ℃ of heat treated 30 minutes.
(trade(brand)name: when the Tencor corporate system) measuring the substrate surface formed colour filter concavo-convex, the result is 1.0 μ m with surfaceness meter " α-STEP ".Condition determination is: measured length 2,000 μ m, 2,000 μ m are square for measurement range, measure the n=5 that counts.That is, measure direction and be 2 directions of streak line long axis direction of streak line short-axis direction and red, green, the blue and green same color of red, green, blue or green direction, on all directions, measure (n adds up to 10) with n=5.
Form with behind the compsn with spinner coating said protection film above that, on hot-plate, carry out prebake in 5 minutes in 90 ℃, formation is filmed, and in baking oven, carries out 60 minutes heat treated in 230 ℃ again, and the thickness that forms above colour filter is the protective membrane of 2.0 μ m.Alleged here thickness is meant that distance is formed on the uppermost thickness of colour filter on the substrate.
Measure the concave-convex surface that has the substrate protection film of protective membrane on the colour filter that is formed as described above with contact determining film thickness device α-STEP (Tencor Japan (strain) system).Condition determination is: measured length 2,000 μ m, 2,000 μ m are square for measurement range, measure the n=5 that counts.Promptly, measure 2 directions of the streak line long axis direction of streak line short-axis direction that direction is red, green, blue or green direction and red, green, blue and green same color, all directions are measured (n adds up to 10) by n=5.The highest 10 MVs with the difference of height (nm) of bottommost were shown in table 1 during each was measured.This value is 300nm when following, thinks that smooth voltinism is good.
(9) evaluation of storage stability
Use the protective membrane of preparation among Tokyo gauge (strain) the system ELD type viscometer determining embodiment 1 to form viscosity with resin combination.Then, said composition is left standstill the soltion viscosity when measuring 25 ℃ every day simultaneously under 25 ℃.Viscosity to prepare after the firm completion is benchmark, and obtaining viscosity increases by 5% required number of days, and this number of days is as shown in table 1.This number of days is more than 20 days the time, thinks that storage stability is good.
Embodiment 2～28 and comparative example 1,2
The kind of each composition of compsn and amount are used the solvent of record in table 1 and the table 2 shown in table 1 and table 2, make it meet the solid formation branch concentration of table 1 and table 2 record, in addition, likewise prepare resin combination with embodiment 1.
Use the protective membrane formation of preparation as described above to use resin combination, likewise form protective membrane, estimate with embodiment 1.The result is shown in table 1 and table 2.
Embodiment 29～32
The kind of each composition of compsn and measure is as shown in table 2ly used the solvent of table 2 record, makes it meet the solid formation branch concentration of table 2 record, in addition likewise prepares resin combination with embodiment 1.
Replace spinner, use the slit mould to be coated with device and be coated with, in addition likewise prepare resin combination, form protective membrane, estimate with embodiment 1.The result is shown in table 2.
Figure S2008101283407D00331
Figure S2008101283407D00341
Figure S2008101283407D00351
Figure S2008101283407D00361
Figure S2008101283407D00371
Figure S2008101283407D00381
Figure S2008101283407D00391
Figure S2008101283407D00401
In addition, in table 1 and the table 2, the abbreviation of cationically polymerizable compound (B), thermo-sensitivity acid-producing agent (C), bonding agent (D) and solvent (S) is as follows respectively.
B-1: (Japanese EPOXY RESIN (strain) makes trade(brand)name to the dihydroxyphenyl propane linear phenolic epoxy resin: EPICOAT 157S65)
C-1: triphenylsulfonium fluoroform sulphonate
D-1: γ-glycidyl oxygen base propyl trimethoxy silicane
D-2: γ-glycidyl oxygen base propyl-triethoxysilicane
E-1: (eastern beautiful DowcorningSilicone (strain) makes trade(brand)name to silicone based tensio-active agent: SH-28PA)
S-1: propylene glycol monomethyl ether
S-2: diethylene glycol dimethyl ether

Claims (10)

1.一种树脂组合物，其特征在于含有共聚物〔A-2〕和〔A-3〕，其中，〔A-2〕是含有5至小于100重量％的来自(a1)聚合性不饱和化合物的聚合单元和大于0至95重量％的来自(a3)聚合性不饱和化合物的聚合单元的共聚物，该共聚物用凝胶渗透色谱法测定的聚苯乙烯换算重均分子量Mw为1,000～100,000，且分子量分布Mw/Mn为5.0以下；1. A resin composition characterized by containing copolymers [A-2] and [A-3], wherein [A-2] contains 5 to less than 100% by weight of the polymerizable unsaturated compound derived from (a1) A copolymer of a polymerized unit of a compound and more than 0 to 95% by weight of a polymerized unit derived from (a3) a polymerizable unsaturated compound, the copolymer having a polystyrene-equivalent weight average molecular weight Mw of 1,000 to 1,000 as measured by gel permeation chromatography 100,000, and the molecular weight distribution Mw/Mn is 5.0 or less; 〔A-3〕是含有5至小于100重量％的来自(a2)聚合性不饱和化合物的聚合单元和大于0至95重量％的来自(a3)聚合性不饱和化合物的聚合单元的共聚物，该共聚物用凝胶渗透色谱法测定的聚苯乙烯换算重均分子量Mw为1,000～100,000，且分子量分布Mw/Mn为5.0以下，[A-3] is a copolymer containing 5 to less than 100% by weight of polymerized units derived from (a2) a polymerizable unsaturated compound and more than 0 to 95% by weight of polymerized units derived from (a3) a polymerizable unsaturated compound, The copolymer has a polystyrene-equivalent weight average molecular weight Mw of 1,000 to 100,000 as measured by gel permeation chromatography, and a molecular weight distribution Mw/Mn of 5.0 or less, 所述(a1)聚合性不饱和化合物选自丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、α-乙基丙烯酸缩水甘油酯、α-正丙基丙烯酸缩水甘油酯、α-正丁基丙烯酸缩水甘油酯、丙烯酸-3，4-环氧丁酯、甲基丙烯酸-3，4-环氧丁酯、丙烯酸-6，7-环氧庚酯、甲基丙烯酸-6，7-环氧庚酯、α-乙基丙烯酸-6，7-环氧庚酯、邻乙烯基苄基缩水甘油醚、间乙烯基苄基缩水甘油醚、对乙烯基苄基缩水甘油醚、3-甲基-3-(甲基)丙烯酰氧基甲基氧杂环丁烷和3-乙基-3-(甲基)丙烯酰氧基甲基氧杂环丁烷，The (a1) polymerizable unsaturated compound is selected from glycidyl acrylate, glycidyl methacrylate, α-glycidyl ethacrylate, α-n-propyl glycidyl acrylate, α-n-butyl acrylate glycidyl Glycerides, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate , α-ethacrylic acid-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-methyl-3- (Meth)acryloyloxymethyloxetane and 3-ethyl-3-(meth)acryloyloxymethyloxetane, 所述(a2)聚合性不饱和化合物选自1-二甲基丙基丙烯酸酯、1-二甲基异丙基丙烯酸酯、1-二甲基丙基甲基丙烯酸酯、1-二甲基异丙基甲基丙烯酸酯、1-二甲基丁基丙烯酸酯、1-二甲基异丁基丙烯酸酯、1-二甲基丁基甲基丙烯酸酯、1-二甲基异丁基甲基丙烯酸酯、1-二甲基辛基丙烯酸酯、1-二甲基异辛基丙烯酸酯、1-二甲基辛基甲基丙烯酸酯、1-二甲基异辛基甲基丙烯酸酯、1-甲基-1-乙基乙基丙烯酸酯、1-甲基-1-乙基乙基甲基丙烯酸酯、1-甲基-1-乙基丙基丙烯酸酯、1-甲基-1-乙基异丙基丙烯酸酯、1-甲基-1-乙基丙基甲基丙烯酸酯、1-甲基-1-乙基异丙基甲基丙烯酸酯、1-甲基-1-乙基丁基丙烯酸酯、1-甲基-1-乙基异丁基丙烯酸酯、1-甲基-1-乙基丁基甲基丙烯酸酯、1-甲基-1-乙基异丁基甲基丙烯酸酯、1-甲基-1-乙基辛基丙烯酸酯、1-甲基-1-乙基异辛基丙烯酸酯、1-二乙基丙基丙烯酸酯、1-二乙基异丙基丙烯酸酯、1-二乙基丙基甲基丙烯酸酯、1-二乙基异丙基甲基丙烯酸酯、1-二乙基丁基丙烯酸酯、1-二乙基异丁基丙烯酸酯、1-二乙基丁基甲基丙烯酸酯、1-二乙基异丁基甲基丙烯酸酯、1-二乙基辛基丙烯酸酯、1-二乙基异辛基丙烯酸酯、1-二乙基辛基甲基丙烯酸酯、1-二乙基异辛基甲基丙烯酸酯、1-甲基环丙烷丙烯酸酯、1-甲基环丙烷甲基丙烯酸酯、1-甲基环丁烷丙烯酸酯、1-甲基环丁烷甲基丙烯酸酯、1-甲基环戊基丙烯酸酯、1-甲基环戊基甲基丙烯酸酯、1-甲基环己基丙烯酸酯、1-甲基环己基甲基丙烯酸酯、1-甲基环庚烷丙烯酸酯、1-甲基环庚烷甲基丙烯酸酯、1-甲基环辛烷丙烯酸酯、1-甲基环辛烷甲基丙烯酸酯、1-甲基环壬烷丙烯酸酯、1-甲基环壬烷甲基丙烯酸酯、1-乙基环癸烷丙烯酸酯、1-乙基环癸烷甲基丙烯酸酯、1-乙基环丙烷丙烯酸酯、1-乙基环丙烷甲基丙烯酸酯、1-乙基环丁烷丙烯酸酯、1-乙基环丁烷甲基丙烯酸酯、1-乙基环戊基丙烯酸酯、1-乙基环戊基甲基丙烯酸酯、1-乙基环己基丙烯酸酯、1-乙基环己基甲基丙烯酸酯、1-乙基环庚烷丙烯酸酯、1-乙基环庚烷甲基丙烯酸酯、1-乙基环辛烷丙烯酸酯、1-乙基环辛烷甲基丙烯酸酯、1-乙基环壬烷丙烯酸酯、1-乙基环壬烷甲基丙烯酸酯、1-甲基环癸烷丙烯酸酯、1-甲基环癸烷甲基丙烯酸酯、1-丙基环丙烷丙烯酸酯、1-异丙基环丙烷丙烯酸酯、1-丙基环丙烷甲基丙烯酸酯、1-异丙基环丙烷甲基丙烯酸酯、1-丙基环丁烷丙烯酸酯、1-异丙基环丁烷丙烯酸酯、1-丙基环丁烷甲基丙烯酸酯、1-异丙基环丁烷甲基丙烯酸酯、1-丙基环戊基丙烯酸酯、1-异丙基环戊基丙烯酸酯、1-丙基环戊基甲基丙烯酸酯、1-异丙基环戊基甲基丙烯酸酯、1-丙基环己基丙烯酸酯、1-异丙基环己基丙烯酸酯、1-丙基环己基甲基丙烯酸酯、1-异丙基环己基甲基丙烯酸酯、1-丙基环庚烷丙烯酸酯、1-异丙基环庚烷丙烯酸酯、1-丙基环庚烷甲基丙烯酸酯、1-异丙基环庚烷甲基丙烯酸酯、1-丙基环辛烷丙烯酸酯、1-异丙基环辛烷丙烯酸酯、1-丙基环辛烷甲基丙烯酸酯、1-异丙基环辛烷甲基丙烯酸酯、1-丙基环壬烷丙烯酸酯、1-异丙基环壬烷丙烯酸酯、1-丙基环壬烷甲基丙烯酸酯、1-异丙基环壬烷甲基丙烯酸酯、1-丙基环癸烷丙烯酸酯、1-异丙基环癸烷丙烯酸酯、1-丙基环癸烷甲基丙烯酸酯、1-异丙基环癸烷甲基丙烯酸酯、1-丁基环丙烷丙烯酸酯、1-异丁基环丙烷丙烯酸酯、1-丁基环丙烷甲基丙烯酸酯、1-异丁基环丙烷甲基丙烯酸酯、1-丁基环丁烷丙烯酸酯、1-异丁基环丁烷丙烯酸酯、1-丁基环丁烷甲基丙烯酸酯、1-异丁基环丁烷甲基丙烯酸酯、1-丁基环戊基丙烯酸酯、1-异丁基环戊基丙烯酸酯、1-丁基环戊基甲基丙烯酸酯、1-异丁基环戊基甲基丙烯酸酯、1-丁基环己基丙烯酸酯、1-异丁基环己基丙烯酸酯、1-丁基环己基甲基丙烯酸酯、1-异丁基环己基甲基丙烯酸酯、1-丁基环庚烷丙烯酸酯、1-异丁基环庚烷丙烯酸酯、1-丁基环庚烷甲基丙烯酸酯、1-异丁基环庚烷甲基丙烯酸酯、1-丁基环辛烷丙烯酸酯、1-异丁基环辛烷丙烯酸酯、1-丁基环辛烷甲基丙烯酸酯、1-异丁基环辛烷甲基丙烯酸酯、1-丁基环壬烷丙烯酸酯、1-异丁基环壬烷丙烯酸酯、1-丁基环壬烷甲基丙烯酸酯、1-异丁基环壬烷甲基丙烯酸酯、1-丁基环癸基丙烯酸酯、1-异丁基环癸基丙烯酸酯、1-丁基环癸基甲基丙烯酸酯、1-异丁基环癸基甲基丙烯酸酯、1-戊基环丙基丙烯酸酯、1-异戊基环丙基丙烯酸酯、1-戊基环丙基甲基丙烯酸酯、1-异戊基环丙基甲基丙烯酸酯、1-戊基环丁基丙烯酸酯、1-异戊基环丁基丙烯酸酯、1-戊基环丁基甲基丙烯酸酯、1-异戊基环丁基甲基丙烯酸酯、1-戊基环戊基丙烯酸酯、1-异戊基环戊基丙烯酸酯、1-戊基环戊基甲基丙烯酸酯、1-异戊基环戊基甲基丙烯酸酯、1-戊基环己基丙烯酸酯、1-异戊基环己基丙烯酸酯、1-戊基环己基甲基丙烯酸酯、1-异戊基环己基甲基丙烯酸酯、1-戊基环庚基丙烯酸酯、1-异戊基环庚基丙烯酸酯、1-戊基环庚基甲基丙烯酸酯、1-异戊基环庚基甲基丙烯酸酯、1-戊基环辛基丙烯酸酯、1-异戊基环辛基丙烯酸酯、1-戊基环辛基甲基丙烯酸酯、1-异戊基环辛基甲基丙烯酸酯、1-戊基环壬基丙烯酸酯、1-异戊基环壬基丙烯酸酯、1-戊基环壬基甲基丙烯酸酯、1-异戊基环壬基甲基丙烯酸酯、1-戊基环癸基丙烯酸酯、1-异戊基环癸基丙烯酸酯、1-戊基环癸基甲基丙烯酸酯、1-异戊基环癸基甲基丙烯酸酯、1-己基环丙基丙烯酸酯、1-异己基环丙基丙烯酸酯、1-己基环丙基甲基丙烯酸酯、1-异己基环丙基甲基丙烯酸酯、1-己基环丁基丙烯酸酯、1-异己基环丁基丙烯酸酯、1-己基环丁基甲基丙烯酸酯、1-异己基环丁基甲基丙烯酸酯、1-己基环己基丙烯酸酯、1-异己基环己基丙烯酸酯、1-己基环己基甲基丙烯酸酯、1-异己基环己基甲基丙烯酸酯、1-己基环庚基丙烯酸酯、1-异己基环庚基丙烯酸酯、1-己基环庚基甲基丙烯酸酯、1-异己基环庚基甲基丙烯酸酯、1-己基环辛基丙烯酸酯、1-异己基环辛基丙烯酸酯、1-己基环辛基甲基丙烯酸酯、1-异己基环辛基甲基丙烯酸酯、1-己基环壬基丙烯酸酯、1-异己基环壬基丙烯酸酯、1-己基环壬基甲基丙烯酸酯、1-异己基环壬基甲基丙烯酸酯、1-己基环癸基丙烯酸酯、1-异己基环癸基丙烯酸酯、1-己基环癸基甲基丙烯酸酯、1-异己基环癸基甲基丙烯酸酯、1-庚基环丙基丙烯酸酯、1-异庚基环丙基丙烯酸酯、1-庚基环丙基甲基丙烯酸酯、1-异庚基环丙基甲基丙烯酸酯、1-庚基环丁基丙烯酸酯、1-异庚基环丁基丙烯酸酯、1-庚基环丁基甲基丙烯酸酯、1-异庚基环丁基甲基丙烯酸酯、1-庚基环己基丙烯酸酯、1-异庚基环己基丙烯酸酯、1-庚基环己基甲基丙烯酸酯、1-异庚基环己基甲基丙烯酸酯、1-庚基环庚基丙烯酸酯、1-异庚基环庚基丙烯酸酯、1-庚基环庚基甲基丙烯酸酯、1-异庚基环庚基甲基丙烯酸酯、1-庚基环辛基丙烯酸酯、1-异庚基环辛基丙烯酸酯、1-庚基环辛基甲基丙烯酸酯、1-异庚基环辛基甲基丙烯酸酯、1-庚基环壬基丙烯酸酯、1-异庚基环壬基丙烯酸酯、1-庚基环壬基甲基丙烯酸酯、1-异庚基环壬基甲基丙烯酸酯、1-庚基环癸基丙烯酸酯、1-异庚基环癸基丙烯酸酯、1-庚基环癸基甲基丙烯酸酯、1-异庚基环癸基甲基丙烯酸酯、1-辛基环丙基丙烯酸酯、1-异辛基环丙基丙烯酸酯、1-辛基环丙基甲基丙烯酸酯、1-异辛基环丙基甲基丙烯酸酯、1-辛基环丁基丙烯酸酯、1-异辛基环丁基丙烯酸酯、1-辛基环丁基甲基丙烯酸酯、1-异辛基环丁基甲基丙烯酸酯、1-辛基环己基丙烯酸酯、1-异辛基环己基丙烯酸酯、1-辛基环己基甲基丙烯酸酯、1-异辛基环己基甲基丙烯酸酯、1-辛基环庚基丙烯酸酯、1-异辛基环庚基丙烯酸酯、1-辛基环庚基甲基丙烯酸酯、1-异辛基环庚基甲基丙烯酸酯、1-辛基环辛基丙烯酸酯、1-异辛基环辛基丙烯酸酯、1-辛基环辛基甲基丙烯酸酯、1-异辛基环辛基甲基丙烯酸酯、1-辛基环壬基丙烯酸酯、1-异辛基环壬基丙烯酸酯、1-辛基环壬基甲基丙烯酸酯、1-异辛基环壬基甲基丙烯酸酯、1-辛基环癸基丙烯酸酯、1-异辛基环癸基丙烯酸酯、1-辛基环癸基甲基丙烯酸酯、1-异辛基环癸基甲基丙烯酸酯、2-乙基三环[3.3.1.13，7]癸烷-2-基-丙烯酸酯、2-乙基三环[3.3.1.13，7]癸烷-2-基-甲基丙烯酸酯、2-甲基三环[3.3.1.13，7]癸烷-2-基-丙烯酸酯、2-甲基三环[3.3.1.13，7]癸烷-2-基-甲基丙烯酸酯、1-乙基三环[3.3.1.13，7]癸烷-1-基-丙烯酸酯、1-乙基三环[3.3.1.13，7]癸烷-1-基-甲基丙烯酸酯、1-甲基三环[3.3.1.13，7]癸烷-1-基-丙烯酸酯、1-甲基三环[3.3.1.13，7]癸烷-1-基-甲基丙烯酸酯、3-羟基三环[3.3.1.13，7]癸烷-1-基-丙烯酸酯、3-羟基三环[3.3.1.13，7]癸烷-1-基-甲基丙烯酸酯、2-乙基-γ-丁内酯-2-基-丙烯酸酯、2-乙基-γ-丁内酯-2-基-甲基丙烯酸酯、2-甲基-γ-丁内酯-2-基-丙烯酸酯、2-甲基-γ-丁内酯-2-基-甲基丙烯酸酯、2-乙基-γ-丁内酯-3-基-丙烯酸酯、2-乙基-γ-丁内酯-3-基-甲基丙烯酸酯、2-甲基-γ-丁内酯-3-基-丙烯酸酯、2-甲基-γ-丁内酯-3-基-甲基丙烯酸酯、2-乙基-γ-丁内酯-4-基-丙烯酸酯、2-乙基-γ-丁内酯-4-基-甲基丙烯酸酯、2-甲基-γ-丁内酯-4-基-丙烯酸酯、2-甲基-γ-丁内酯-4-基-甲基丙烯酸酯、2-乙基-δ-戊内酯-2-基-丙烯酸酯、2-乙基-δ-戊内酯-2-基-甲基丙烯酸酯、2-甲基-δ-戊内酯-2-基-丙烯酸酯、2-甲基-δ-戊内酯-2-基-甲基丙烯酸酯、2-乙基-δ-戊内酯-3-基-丙烯酸酯、2-乙基-δ-戊内酯-3-基-甲基丙烯酸酯、2-甲基-δ-戊内酯-3-基-丙烯酸酯、2-甲基-δ-戊内酯-3-基-甲基丙烯酸酯、2-乙基-δ-戊内酯-4-基-丙烯酸酯、2-乙基-δ-戊内酯-4-基-甲基丙烯酸酯、2-甲基-δ-戊内酯-4-基-丙烯酸酯、2-甲基-δ-戊内酯-4-基-甲基丙烯酸酯、2-乙基-δ-戊内酯-5-基-丙烯酸酯、2-乙基-δ-戊内酯-5-基-甲基丙烯酸酯、2-甲基-δ-戊内酯-5-基-丙烯酸酯、2-甲基-δ-戊内酯-5-基-甲基丙烯酸酯、2-乙基-γ-丁内酰胺-2-基-丙烯酸酯、2-乙基-γ-丁内酰胺-2-基-甲基丙烯酸酯、2-甲基-γ-丁内酰胺-2-基-丙烯酸酯、2-甲基-γ-丁内酰胺-2-基-甲基丙烯酸酯、2-乙基-γ-丁内酰胺-3-基-丙烯酸酯、2-乙基-γ-丁内酰胺-3-基-甲基丙烯酸酯、2-甲基-γ-丁内酰胺-3-基-丙烯酸酯、2-甲基-γ-丁内酰胺-3-基-甲基丙烯酸酯、2-乙基-γ-丁内酰胺-4-基-丙烯酸酯、2-乙基-γ-丁内酰胺-4-基-甲基丙烯酸酯、2-甲基-γ-丁内酰胺-4-基-丙烯酸酯、2-甲基-γ-丁内酰胺-4-基-甲基丙烯酸酯、2-乙基-δ-戊内酰胺-2-基-丙烯酸酯、2-乙基-δ-戊内酰胺-2-基-甲基丙烯酸酯、2-甲基-δ-戊内酰胺-2-基-丙烯酸酯、2-甲基-δ-戊内酰胺-2-基-甲基丙烯酸酯、2-乙基-δ-戊内酰胺-3-基-丙烯酸酯、2-乙基-δ-戊内酰胺-3-基-甲基丙烯酸酯、2-甲基-δ-戊内酰胺-3-基-丙烯酸酯、2-甲基-δ-戊内酰胺-3-基-甲基丙烯酸酯、2-乙基-δ-戊内酰胺-4-基-丙烯酸酯、2-乙基-δ-戊内酰胺-4-基-甲基丙烯酸酯、2-甲基-δ-戊内酰胺-4-基-丙烯酸酯、2-甲基-δ-戊内酰胺-4-基-甲基丙烯酸酯、2-乙基-δ-戊内酰胺-5-基-丙烯酸酯、2-乙基-δ-戊内酰胺-5-基-甲基丙烯酸酯、2-甲基-δ-戊内酰胺-5-基-丙烯酸酯、2-甲基-δ-戊内酰胺-5-基-甲基丙烯酸酯，The (a2) polymerizable unsaturated compound is selected from 1-dimethyl propyl acrylate, 1-dimethyl isopropyl acrylate, 1-dimethyl propyl methacrylate, 1-dimethyl Isopropyl methacrylate, 1-dimethyl butyl acrylate, 1-dimethyl isobutyl acrylate, 1-dimethyl butyl methacrylate, 1-dimethyl isobutyl methacrylate, 1-dimethyloctyl acrylate, 1-dimethylisooctyl acrylate, 1-dimethyloctyl methacrylate, 1-dimethylisooctyl methacrylate, 1-methyl -1-ethyl ethyl acrylate, 1-methyl-1-ethyl ethyl methacrylate, 1-methyl-1-ethyl propyl acrylate, 1-methyl-1-ethyl iso Propyl acrylate, 1-methyl-1-ethylpropyl methacrylate, 1-methyl-1-ethylisopropyl methacrylate, 1-methyl-1-ethylbutyl acrylate ester, 1-methyl-1-ethylisobutyl acrylate, 1-methyl-1-ethylbutyl methacrylate, 1-methyl-1-ethylisobutyl methacrylate, 1-methyl -1-Ethyloctylacrylate, 1-methyl-1-ethylisooctylacrylate, 1-diethylpropylacrylate, 1-diethylisopropylacrylate, 1-diethyl Propyl methacrylate, 1-diethyl isopropyl methacrylate, 1-diethyl butyl acrylate, 1-diethyl isobutyl acrylate, 1-diethyl butyl methacrylate ester, 1-diethylisobutylmethacrylate, 1-diethyloctylacrylate, 1-diethylisooctylacrylate, 1-diethyloctylmethacrylate, 1-diethyloctylacrylate Isooctyl methacrylate, 1-methylcyclopropane methacrylate, 1-methylcyclopropane methacrylate, 1-methylcyclobutane acrylate, 1-methylcyclobutane methacrylate , 1-methylcyclopentyl acrylate, 1-methylcyclopentyl methacrylate, 1-methylcyclohexyl acrylate, 1-methylcyclohexyl methacrylate, 1-methylcycloheptane Acrylates, 1-methylcycloheptane methacrylate, 1-methylcyclooctane acrylate, 1-methylcyclooctane methacrylate, 1-methylcyclononane acrylate, 1-methano Cyclononane methacrylate, 1-ethylcyclodecane methacrylate, 1-ethylcyclodecane methacrylate, 1-ethylcyclopropane acrylate, 1-ethylcyclopropane methacrylate , 1-ethylcyclobutane acrylate, 1-ethylcyclobutane methacrylate, 1-ethylcyclopentyl acrylate, 1-ethylcyclopentyl methacrylate, 1-ethylcyclobutane Hexyl acrylate, 1-ethylcyclohexyl methacrylate, 1-ethylcycloheptane acrylate, 1-ethylcycloheptane methacrylate, 1-ethylcyclooctane acrylate, 1-ethyl Cyclooctyl methacrylate, 1-ethylcyclononane acrylate, 1-ethylcyclononane methacrylate, 1-methylcyclodecane acrylate, 1-methylcyclodecane methyl Acrylates, 1-propylcyclopropane acrylate, 1-isopropylcyclopropane acrylate, 1-propylcyclopropane methacrylate Ester, 1-isopropylcyclopropane methacrylate, 1-propylcyclobutane acrylate, 1-isopropylcyclobutane acrylate, 1-propylcyclobutane methacrylate, 1- Isopropyl cyclobutane methacrylate, 1-propyl cyclopentyl acrylate, 1-isopropyl cyclopentyl acrylate, 1-propyl cyclopentyl methacrylate, 1-isopropyl cyclopentyl acrylate Pentyl methacrylate, 1-propylcyclohexyl acrylate, 1-isopropylcyclohexyl acrylate, 1-propylcyclohexyl methacrylate, 1-isopropylcyclohexyl methacrylate, 1 -Propylcycloheptane acrylate, 1-isopropylcycloheptane acrylate, 1-propylcycloheptane methacrylate, 1-isopropylcycloheptane methacrylate, 1-propylcycloheptane Octane Acrylate, 1-Isopropyl Cyclooctane Acrylate, 1-Propyl Cyclooctane Methacrylate, 1-Isopropyl Cyclooctane Methacrylate, 1-Propyl Cyclononane Acrylate , 1-isopropylcyclononane acrylate, 1-propylcyclononane methacrylate, 1-isopropylcyclononane methacrylate, 1-propylcyclodecane acrylate, 1-iso Propylcyclodecane acrylate, 1-propylcyclodecane methacrylate, 1-isopropylcyclodecane methacrylate, 1-butylcyclopropane acrylate, 1-isobutylcyclopropane acrylate, 1- Butylcyclopropane methacrylate, 1-isobutylcyclopropane methacrylate, 1-butylcyclobutane acrylate, 1-isobutylcyclobutane acrylate, 1-butylcyclobutane methacrylate, 1-isobutylcyclobutane Methacrylate, 1-butylcyclopentyl acrylate, 1-isobutylcyclopentyl acrylate, 1-butylcyclopentyl methacrylate, 1-isobutylcyclopentyl methacrylate, 1-butylcyclohexyl acrylate, 1-isobutylcyclohexyl acrylate, 1-butylcyclohexyl methacrylate, 1-isobutylcyclohexyl methacrylate, 1-butylcyclohexyl acrylate, 1-isobutylcyclohexyl acrylate, 1-butylcyclohexyl methyl Acrylate, 1-isobutylcycloheptane methacrylate, 1-butylcyclooctane acrylate, 1-isobutylcyclooctane acrylate, 1-butylcyclooctane methacrylate, 1-isobutylcyclooctane methyl Acrylate, 1-butylcyclononane acrylate, 1-isobutylcyclononane acrylate, 1-butylcyclononane methacrylate, 1-isobutylcyclononane methacrylate, 1-butylcyclodecyl acrylate, 1 - Isobutyl cyclodecyl acrylate, 1-butyl cyclodecyl methacrylate, 1-isobutyl cyclodecyl methacrylate, 1-pentyl cyclopropyl acrylate, 1-isopentyl cyclopropyl acrylate, 1-Pentylcyclopropylmethacrylate, 1-Isopentylcyclopropylmethacrylate, 1-Pentylcyclobutylacrylate, 1-Isopentylcyclobutylacrylate, 1-Pentyl Cyclobutyl methacrylate, 1-Isopentyl cyclobutyl methacrylate, 1-Pentyl cyclopentyl acrylate, 1-Isopentyl cyclopentyl acrylate, 1-Pentyl cyclopentyl methacrylate, 1-Isopentyl cyclopentyl methacrylate, 1-pentyl cyclohexyl acrylic acid ester, 1-isopentylcyclohexyl acrylate, 1-pentylcyclohexyl methacrylate, 1-isopentylcyclohexyl methacrylate, 1-pentylcyclohexyl acrylate, 1-isopentyl Cycloheptyl Acrylate, 1-Pentyl Cycloheptyl Methacrylate, 1-Isopentyl Cycloheptyl Methacrylate, 1-Pentyl Cyclooctyl Acrylate, 1-Isopentyl Cyclooctyl Acrylate Esters, 1-pentyl cyclooctyl methacrylate, 1-isopentyl cyclooctyl methacrylate, 1-pentyl cyclononyl acrylate, 1-isopentyl cyclononyl acrylate, 1- Pentyl cyclononyl methacrylate, 1-isopentyl cyclononyl methacrylate, 1-pentyl cyclodecyl acrylate, 1-isopentyl cyclodecyl acrylate, 1-pentyl cyclodecyl acrylate methacrylate, 1-isopentylcyclodecyl methacrylate, 1-hexylcyclopropyl acrylate, 1-isohexylcyclopropyl acrylate, 1-hexylcyclopropyl methacrylate, 1 -Isohexylcyclopropyl methacrylate, 1-hexylcyclobutyl acrylate, 1-isohexylcyclobutyl acrylate, 1-hexylcyclobutyl methacrylate, 1-isohexylcyclobutyl methacrylate, 1 -Hexylcyclohexyl acrylate, 1-isohexylcyclohexyl acrylate, 1-hexylcyclohexyl methacrylate, 1-isohexylcyclohexyl methacrylate, 1-hexylcyclohexyl acrylate, 1-isohexyl Cycloheptyl acrylate, 1-hexyl cycloheptyl methacrylate, 1-isohexyl cycloheptyl methacrylate, 1-hexyl cyclooctyl acrylate, 1-isohexyl cyclooctyl acrylate, 1- Hexyl cyclooctyl methacrylate, 1-isohexyl cyclooctyl methacrylate, 1-hexyl cyclononyl acrylate, 1-isohexyl cyclononyl acrylate, 1-hexyl cyclononyl methacrylate , 1-isohexylcyclononylmethacrylate, 1-hexylcyclodecanylacrylate, 1-isohexylcyclodecanylacrylate, 1-hexylcyclodecanylmethacrylate, 1-isohexylcyclodecanylacrylate Methacrylate, 1-heptylcyclopropylacrylate, 1-isoheptylcyclopropylacrylate, 1-heptylcyclopropylmethacrylate, 1-isoheptylcyclopropylmethacrylate , 1-heptylcyclobutyl acrylate, 1-isoheptylcyclobutyl acrylate, 1-heptylcyclobutyl methacrylate, 1-isoheptylcyclobutyl methacrylate, 1-heptylcyclohexyl acrylate ester, 1-isoheptylcyclohexyl acrylate, 1-heptylcyclohexyl methacrylate, 1-isoheptylcyclohexyl methacrylate, 1-heptylcyclohexyl acrylate, 1-isoheptyl Cycloheptyl acrylate, 1-heptyl cycloheptyl methacrylate, 1-isoheptyl cycloheptyl methacrylate, 1-heptyl cyclooctyl acrylate, 1-isoheptyl cyclooctyl acrylate Esters, 1-heptyl cyclooctyl methacrylate, 1-isoheptyl cyclooctyl methacrylate, 1-heptyl cyclononyl acrylate, 1-isoheptyl cyclononyl acrylate, 1- Heptyl cyclononyl methacrylate, 1-isoheptyl cyclononyl methacrylate, 1-heptyl cyclodecyl acrylate, 1-isoheptyl cyclodecyl acrylate, 1-heptyl cyclodecyl methacrylate , 1-isoheptylcyclodecanyl methacrylate, 1-octylcyclopropyl acrylate, 1-isooctylcyclopropyl acrylate, 1-octylcyclopropyl methacrylate, 1-iso Octylcyclopropyl methacrylate, 1-octylcyclobutyl acrylate, 1-isooctylcyclobutyl acrylate, 1-octylcyclobutyl methacrylate, 1-isooctylcyclobutyl methacrylate ester, 1-octylcyclohexyl acrylate, 1-isooctylcyclohexyl acrylate, 1-octylcyclohexyl methacrylate, 1-isooctylcyclohexyl methacrylate, 1-octylcyclohexyl Acrylate, 1-isooctyl cycloheptyl acrylate, 1-octyl cycloheptyl methacrylate, 1-isooctyl cycloheptyl methacrylate, 1-octyl cyclooctyl acrylate, 1-isooctyl cyclooctyl acrylate, 1-octyl cyclooctyl methacrylate, 1-isooctyl cyclooctyl methacrylate, 1-octyl cyclononyl acrylate, 1-isooctyl Cyclononyl Acrylate, 1-Octyl Cyclononyl Methacrylate, 1-Isooctyl Cyclononyl Methacrylate, 1-Octyl Cyclodecyl Acrylate, 1-Isooctyl Cyclodecyl Acrylates, 1-octylcyclodecanylmethacrylate, 1-isooctylcyclodecanylmethacrylate, 2-ethyltricyclo[ 3.3.1.13,7 ]decane-2-yl-acrylic acid Esters, 2-ethyltricyclo[ 3.3.1.13,7 ]decane-2-yl-methacrylate, 2-methyltricyclo[3.3.1.13,7]decane-2- yl -acrylic acid Esters, 2-methyltricyclo[ 3.3.1.13,7 ]decane-2-yl-methacrylate, 1-ethyltricyclo[ 3.3.1.13,7 ]decane-1-yl-acrylic acid Esters, 1-ethyltricyclo[ 3.3.1.13,7 ]decane-1-yl-methacrylate, 1-methyltricyclo[ 3.3.1.13,7 ]decane-1-yl-acrylic acid Esters, 1-methyltricyclo[3.3.1.13,7]decane-1-yl-methacrylate , 3-hydroxytricyclo[ 3.3.1.13,7 ]decane-1-yl-acrylate , 3-Hydroxytricyclo[3.3.1.1 3,7 ]decane-1-yl-methacrylate, 2-ethyl-γ-butyrolactone-2-yl-acrylate, 2-ethyl-γ -butyrolactone-2-yl-methacrylate, 2-methyl-γ-butyrolactone-2-yl-acrylate, 2-methyl-γ-butyrolactone-2-yl-methacrylic acid Esters, 2-Ethyl-γ-butyrolactone-3-yl-acrylate, 2-Ethyl-γ-butyrolactone-3-yl-methacrylate, 2-Methyl-γ-butyrolactone -3-yl-acrylate, 2-methyl-γ-butyrolactone-3-yl-methacrylate, 2-ethyl-γ-butyrolactone-4-yl-acrylate, 2-ethyl -γ-butyrolactone-4-yl-methacrylate, 2-methyl-γ-butyrolactone-4-yl-acrylate, 2-methyl-γ-butyrolactone-4-yl-methacrylate Acrylate, 2-ethyl-δ-valerolacton-2-yl-acrylate, 2-ethyl -δ-valerolactone-2-yl-methacrylate, 2-methyl-δ-valerolactone-2-yl-acrylate, 2-methyl-δ-valerolactone-2-yl-methacrylate 2-ethyl acrylate, 2-ethyl-δ-valerolactone-3-yl-acrylate, 2-ethyl-δ-valerolactone-3-yl-methacrylate, 2-methyl-δ-pentyl acrylate Lactone-3-yl-acrylate, 2-methyl-δ-valerolactone-3-yl-methacrylate, 2-ethyl-δ-valerolactone-4-yl-acrylate, 2- Ethyl-delta-valerolacton-4-yl-methacrylate, 2-methyl-delta-valerolacton-4-yl-acrylate, 2-methyl-delta-valerolacton-4-yl -methacrylate, 2-ethyl-delta-valerolactone-5-yl-acrylate, 2-ethyl-delta-valerolactone-5-yl-methacrylate, 2-methyl-delta -valerolactone-5-yl-acrylate, 2-methyl-δ-valerolactone-5-yl-methacrylate, 2-ethyl-γ-butyrolactam-2-yl-acrylate, 2-Ethyl-γ-butyrolactam-2-yl-methacrylate, 2-methyl-γ-butyrolactam-2-yl-acrylate, 2-methyl-γ-butyrolactam-2 -yl-methacrylate, 2-ethyl-γ-butyrolactam-3-yl-acrylate, 2-ethyl-γ-butyrolactam-3-yl-methacrylate, 2-methyl -γ-butyrolactam-3-yl-acrylate, 2-methyl-γ-butyrolactam-3-yl-methacrylate, 2-ethyl-γ-butyrolactam-4-yl-acrylic acid Esters, 2-Ethyl-γ-butyrolactam-4-yl-methacrylate, 2-Methyl-γ-butyrolactam-4-yl-acrylate, 2-Methyl-γ-butyrolactam -4-yl-methacrylate, 2-ethyl-δ-valerolactam-2-yl-acrylate, 2-ethyl-δ-valerolactam-2-yl-methacrylate, 2- Methyl-delta-valerolactam-2-yl-acrylate, 2-methyl-delta-valerolactam-2-yl-methacrylate, 2-ethyl-delta-valerolactam-3-yl - Acrylate, 2-Ethyl-delta-valerolactam-3-yl-methacrylate, 2-Methyl-delta-valerolactam-3-yl-acrylate, 2-methyl-delta-pentalactam-3-yl-acrylate Lactam-3-yl-methacrylate, 2-ethyl-delta-valerolactam-4-yl-acrylate, 2-ethyl-delta-valerolactam-4-yl-methacrylate, 2-Methyl-delta-valerolactam-4-yl-acrylate, 2-methyl-delta-valerolactam-4-yl-methacrylate, 2-ethyl-delta-valerolactam-5 -yl-acrylate, 2-ethyl-delta-valerolactam-5-yl-methacrylate, 2-methyl-delta-valerolactam-5-yl-acrylate, 2-methyl-delta -valerolactam-5-yl-methacrylate, 所述(a3)聚合性不饱和化合物是(a1)和(a2)以外的聚合性不饱和化合物，其选自丙烯酸烷基酯、甲基丙烯酸烷基酯、丙烯酸环状烷基酯、甲基丙烯酸环状烷基酯、不饱和二羧酸二酯、二环不饱和化合物、马来酰亚胺化合物、不饱和芳香族化合物、共轭二烯类化合物、不饱和单羧酸、不饱和二羧酸、不饱和二羧酸酐、丙烯腈、甲基丙烯腈、氯乙烯、偏氯乙烯、丙烯酰胺、甲基丙烯酰胺和乙酸乙烯酯。The (a3) polymerizable unsaturated compound is a polymerizable unsaturated compound other than (a1) and (a2), which is selected from the group consisting of alkyl acrylate, alkyl methacrylate, cyclic alkyl acrylate, methyl Cyclic alkyl acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated di Carboxylic acids, unsaturated dicarboxylic anhydrides, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate. 2.如权利要求1所述的树脂组合物，其中还含有〔B〕阳离子聚合性化合物。2. The resin composition according to claim 1, further comprising [B] a cationically polymerizable compound. 3.如权利要求1所述的树脂组合物，其中所述(a3)聚合性不饱和化合物选自甲基丙烯酸芳基酯和丙烯酸芳基酯。3. The resin composition according to claim 1, wherein the (a3) polymerizable unsaturated compound is selected from aryl methacrylate and aryl acrylate. 4.一种树脂组合物，其特征在于：含有权利要求1所述的〔A-3〕成分和权利要求2所述的〔B〕成分。4. A resin composition comprising the component [A-3] according to claim 1 and the component [B] according to claim 2. 5.如权利要求1～4任一项所述的树脂组合物，其中，还含有〔C〕热敏性酸发生剂。5. The resin composition according to any one of claims 1 to 4, further comprising [C] a heat-sensitive acid generator. 6.如权利要求1～4任一项所述的树脂组合物，其中，该组合物用于形成滤色器的保护膜。6. The resin composition according to any one of claims 1 to 4, which is used for forming a protective film of a color filter. 7.如权利要求5所述的树脂组合物，其中，该组合物用于形成滤色器的保护膜。7. The resin composition according to claim 5, wherein the composition is used to form a protective film of a color filter. 8.一种滤色器保护膜的形成方法，其特征在于：在基板上形成权利要求5所述的树脂组合物的涂膜，然后进行加热处理。8. A method for forming a protective film for a color filter, comprising forming a coating film of the resin composition according to claim 5 on a substrate, followed by heat treatment. 9.一种滤色器的保护膜，其是由权利要求6所述的树脂组合物形成的。The protective film of a color filter formed from the resin composition of Claim 6. 10.一种滤色器的保护膜，其是由权利要求7所述的树脂组合物形成的。The protective film of a color filter formed from the resin composition of Claim 7.
CN2008101283407A 2004-11-26 2005-11-28 Copolymer, resin composition, overcoating film and process for forming the same Expired - Fee Related CN101328298B (en)

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