CN100506863C - Copolymer, resin composition, protection film and forming method thereof - Google Patents

Copolymer, resin composition, protection film and forming method thereof Download PDF

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CN100506863C
CN100506863C CNB2005101285381A CN200510128538A CN100506863C CN 100506863 C CN100506863 C CN 100506863C CN B2005101285381 A CNB2005101285381 A CN B2005101285381A CN 200510128538 A CN200510128538 A CN 200510128538A CN 100506863 C CN100506863 C CN 100506863C
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methyl
carbonatoms
alkyl
acrylate
ethyl
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CN1789296A (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
Technical field
The present invention relates to multipolymer, resin combination, form the method and the protective membrane of protective membrane with above-mentioned composition. more specifically relate to composition, use the formation method of protective membrane of above-mentioned composition and the protective membrane that uses above-mentioned composition to form, above-mentioned composition 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; with solvent, acid or alkaline solution etc. display element is carried out dip treating; when utilizing sputter to form the distribution electrode layer; the element surface part is exposed in the high temperature. therefore; in order to prevent that above-mentioned processing from making element generation deterioration or causing damage, the protective membrane that constitutes by the film that above-mentioned processing is had patience in the element surface setting.
Require said protection film to have following performance: the matrix or the lower floor that needs are formed 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 height; the process long period does not take place painted yet; xanthochromia; the albefaction iso-metamorphism; water tolerance; solvent resistance; acid resistance and alkali resistance are good etc. and as the material that is used to form the protective membrane that satisfies above-mentioned various characteristics, for example oneself knows the thermoset composition that contains the polymkeric substance with glycidyl (opening flat 5-78453 communique and the spy opens the 2001-91732 communique referring to the spy).
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 colour 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 TwistedNematic) 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 liquid crystal cells is sealed; but; therefore the heat and the pressure that apply the time; can be observed the phenomenon of the protective membrane depression of the part that has pearl, the problem of box gap disorder occurs.
When particularly preparing the color liquid crystal display device of STN mode, must guarantee the applying precision of colour filter and counter substrate extremely closely, claimed film has high jump planarization performance and heat-resisting withstand voltage properties.
In addition; in recent years; also in the following ways; promptly utilize sputter; on the protective membrane of colour filter, form distribution electrode (tin indium oxide: ITO or indium zinc oxide: IZO); with strong acid or highly basic etc.; form the pattern of ITO or IZO. therefore; color filter protecting layer surface when sputter is exposed in the high temperature by the part; or 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 composition self, operation is trouble very.That is, not only the coating performance of composition 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 usually as protective membrane, can form the protective membrane that satisfies above-mentioned various performances simply and as the storage stability excellent material of composition.
In addition, the spy opens and discloses thermoset composition that use, that contain potential carboxylated compound in coating, ink, tackiness agent, the molding in the flat 4-218561 communique, does not disclose the protective membrane of colour filter fully.
Summary of the invention
The present invention is based on the above fact and finish; its purpose is for providing a kind of composition, using formation method, and the protective membrane that forms with above-mentioned composition of the protective membrane of above-mentioned composition; even the matrix that the said composition surface is low also can form the high cured film of flatness on this matrix; it is and be applicable to the good light device of various patience protective membranes such as forming the transparency and surface hardness height, heat-resisting resistance to pressure, acid resistance, alkali resistance, anti-sputter, etching patience, and good as the storage stability of composition.
According to the present invention, above-mentioned purpose of the present invention at first can realize by 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 ニ Le base) and (a2) from the polymerized unit of the polymerizable unsaturated compound of the structure with following formula (01) expression.
Figure C200510128538D00061
Herein, R is that carbonatoms is the tertiary alkyl more than 5; By carbonatoms is that carbonatoms that 1~4 alkoxyl group replaces is the tertiary alkyl more than 4; (the ring carbon atom number O-) is the cycloalkyl 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 by realizing to contain the resin combination that above-mentioned multipolymer of the present invention (A-1) is a feature (hereinafter referred to as " resin combination (α 1) ").
According to the present invention, above-mentioned purpose of the present invention, the 3rd can realize by following resin combination (hereinafter referred to as " 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 by above-mentioned to contain (A-3) composition, and cationically polymerizable compound (B) be that the resin combination (hereinafter referred to as " resin combination (α 3) ") of feature is realized.
Above-mentioned purpose of the present invention, the 5th can realize by 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 by the protective membrane that uses the colour filter that above-mentioned resin combination forms.
Other purposes of the present invention and advantage can be determined by following explanation.
Embodiment
The following describes each composition of resin combination of the present invention.
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) beyond above-mentioned (a1) and 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 carbonatoms that 1~4 alkoxyl group replaces is the tertiary alkyl more than 4; (the ring carbon atom number O-) is the cycloalkyl 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 carbonatoms that 1~4 alkoxyl group replaces when being tertiary alkyl more than 4 by carbonatoms that formula (01) is represented with following formula (1).
Figure C200510128538D00071
Herein, R 1And R 2Represent that independently of one another carbonatoms is 1~8 alkyl or is that carbonatoms that 1~4 alkoxyl group replaces is 1~8 alkyl by carbonatoms, R 3For carbonatoms is 2~8 alkyl or is that carbonatoms that 1~4 alkoxyl group replaces is 1~8 alkyl by carbonatoms.
R is a ring carbon atom number when being cycloalkyl more than 3, and formula (01) is represented with following formula (2).
Figure C200510128538D00072
Herein, 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 hydrogen atom or carbonatoms be the end of 1~8 alkyl or alkyl or side chain 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, and 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.
Herein, 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 hydrogen atom or carbonatoms are that to have carbonatoms on the end of 1~8 alkyl or alkyl or the side chain 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 1=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 the end of 1~8 alkyl or alkyl or the side chain carbonatoms be that the carbonatoms of 1~4 alkoxyl group is 1~8 alkyl to carbonatoms. as carbonatoms 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 the end of 2~8 alkyl or alkyl or the side chain be that the carbonatoms of 1~4 alkoxyl group is 1~8 alkyl. as carbonatoms 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 cyclopropane, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane, cyclodecane .R 4~R 7Expression hydrogen atom or carbonatoms are that to have carbonatoms on the end of 1~8 alkyl or alkyl or the side chain be that the carbonatoms of 1~4 alkoxyl group is that 1~8 alkyl or carbonatoms are 1~4 alkoxyl group. the 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 hydrogen atom, or carbonatoms is that to have carbonatoms on the end of 1~8 alkyl or alkyl or the side chain be that the carbonatoms of 1~4 alkoxyl group is 1~8 alkyl, or carbonatoms is in 1~4 the alkoxyl group any. as carbonatoms 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-base, 2-methyl three ring [3.3.1.1 3,7] decane-2-base, 1-ethyl tricyclo [3.3.1.1 3,7] decane-1-base, 1-methyl three ring [3.3.1.1 3,7] decane-1-base, 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 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 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), as polymerizable unsaturated compound (a1), so long as epoxy ethyl or oxa-cyclobutyl and polymerizability unsaturated group get final product, be not particularly limited. for example, as the polymerizable unsaturated compound that contains epoxy ethyl, for example can enumerate glycidyl acrylate, glycidyl methacrylate, the α-Yi Jibingxisuan glycidyl ester, α-n-propyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, vinylformic acid-3,4-epoxy butyl ester, methacrylic acid-3,4-epoxy butyl ester, vinylformic acid-6,7-epoxy heptyl ester, methacrylic acid-6,7-epoxy heptyl ester, α-Yi Jibingxisuan-6,7-epoxy heptyl ester, adjacent vinyl benzyl glycidyl ether, between the 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 and protective membrane that obtains or insulating film; preferred glycidyl methacrylate, the methacrylic 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), as polymerizable unsaturated compound (a2), as long as have above-mentioned formula (1), (2) or the polymerizable unsaturated compound of the structure of (3) get final product, be not particularly limited. for example, as the polymerizability unsaturated polymer of structure, for example can enumerate 1-dimethyl (different) propyl group (methyl) acrylate with formula (1), 1-dimethyl (different) butyl (methyl) acrylate, 1-dimethyl (different) octyl group (methyl) acrylate, 1-methyl isophthalic acid-ethyl diethyldithiocarbamate (methyl) acrylate, 1-methyl isophthalic acid-ethyl (different) propyl group (methyl) acrylate, 1-methyl isophthalic acid-ethyl (different) butyl (methyl) acrylate, 1-methyl isophthalic acid-ethyl (different) octyl group acrylate, 1-diethyl (different) propyl group (methyl) acrylate, 1-diethyl (different) butyl (methyl) acrylate, 1-diethyl (different) octyl group (methyl) acrylate etc.
In addition, as the polymerizability unsaturated polymer of structure, for example can enumerate 1-methyl cyclopropane (methyl) acrylate with formula (2), 1-methyl cyclobutane (methyl) acrylate, 1-methylcyclopentyl (methyl) acrylate, 1-methylcyclohexyl (methyl) acrylate, 1-methyl suberane (methyl) acrylate, 1-methyl cyclooctane (methyl) acrylate, 1-methyl cyclononane (methyl) acrylate, 1-ethyl cyclodecane (methyl) acrylate, 1-ethyl cyclopropane (methyl) acrylate, 1-ethyl tetramethylene (methyl) acrylate, 1-ethyl cyclopentyl (methyl) acrylate, 1-ethyl cyclohexyl (methyl) acrylate, 1-ethyl cycloheptane (methyl) acrylate, 1-ethyl cyclooctane (methyl) acrylate, 1-ethyl cyclononane (methyl) acrylate, 1-methyl cyclodecane (methyl) acrylate, 1-(different) propyl group cyclopropane (methyl) acrylate, 1-(different) propyl group tetramethylene (methyl) acrylate, 1-(different) propyl group cyclopentyl (methyl) acrylate, 1-(different) propyl group cyclohexyl (methyl) acrylate, 1-(different) propyl group suberane (methyl) acrylate, 1-(different) propyl group cyclooctane (methyl) acrylate, 1-(different) propyl group cyclononane (methyl) acrylate, 1-(different) propyl group cyclodecane (methyl) acrylate, 1-(different) butyl cyclopropane (methyl) acrylate, 1-(different) butyl tetramethylene (methyl) acrylate, 1-(different) butyl cyclopentyl (methyl) acrylate, 1-(different) butyl cyclohexyl (methyl) acrylate, 1-(different) butyl suberane (methyl) acrylate, 1-(different) butyl cyclooctane (methyl) acrylate, 1-(different)-butyl cyclononane (methyl) acrylate, 1-(different) butyl ring decyl (methyl) acrylate, 1-(different) amyl group cyclopropyl (methyl) acrylate, 1-(different) amyl group cyclobutyl (methyl) acrylate, 1-(different) amyl group cyclopentyl (methyl) acrylate, 1-(different) amyl group cyclohexyl (methyl) acrylate, 1-(different) amyl group suberyl (methyl) acrylate, 1-(different) amyl group ring octyl group (methyl) acrylate, 1-(different) amyl group ring nonyl (methyl) acrylate, 1-(different) amyl group ring decyl (methyl) acrylate;
1-(different) hexyl cyclopropyl (methyl) acrylate, 1-(different) hexyl cyclobutyl (methyl) acrylate, 1-(different) hexyl cyclohexyl (methyl) acrylate, 1-(different) hexyl suberyl (methyl) acrylate, 1-(different) hexyl ring octyl group (methyl) acrylate, 1-(different) hexyl ring nonyl (methyl) acrylate, 1-(different) hexyl ring decyl (methyl) acrylate,
1-(different) heptyl cyclopropyl (methyl) acrylate, 1-(different) heptyl cyclobutyl (methyl) acrylate, 1-(different) heptyl suberyl (methyl) acrylate, 1-(different) heptyl cyclohexyl (methyl) acrylate, 1-(different) heptyl suberyl (methyl) acrylate, 1-(different) heptyl ring octyl group (methyl) acrylate, 1-(different) heptyl ring nonyl (methyl) acrylate, 1-(different) heptyl ring decyl (methyl) acrylate,
1-(different) octyl group cyclopropyl (methyl) acrylate, 1-(different) octyl group cyclobutyl (methyl) acrylate, 1-(different) octyl group ring octyl group (methyl) acrylate, 1-(different) octyl group cyclohexyl (methyl) acrylate, 1-(different) octyl group suberyl (methyl) acrylate, 1-(different) octyl group ring octyl group (methyl) acrylate, 1-(different) octyl group ring nonyl (methyl) acrylate, 1-(different) octyl group ring decyl (methyl) acrylate,
2-ethyl tricyclo [3.3.1.1 3,7] decane-2-base-(methyl) acrylate, 2-methyl three ring [3.3.1.1 3,7] decane-2-base-(methyl) acrylate, 1-ethyl tricyclo [3.3.1.1 3,7] decane-1-base-(methyl) acrylate, 1-methyl three ring [3.3.1.1 3,7] decane-1-base-(methyl) acrylate, 3-hydroxyl three ring [3.3.1.1 3,7] decane-1-base-(methyl) acrylate etc.
Wherein, preferred 1-diethyl propyl group (methyl) acrylate that uses; 1-ethyl cyclopentyl (methyl) acrylate; 1-ethyl cyclohexyl (methyl) acrylate; 1-(different) propyl group cyclopentyl (methyl) acrylate; 1-(different) propyl group cyclohexyl (methyl) acrylate; 1-(different) butyl cyclopentyl (methyl) acrylate; 1-(different) butyl cyclohexyl (methyl) acrylate; more preferably 1-diethyl propyl group (methyl) acrylate; 1-ethyl cyclopentyl (methyl) acrylate; 1-ethyl cyclohexyl (methyl) acrylate; preferred especially 1-ethyl cyclopentyl (methyl) acrylate; 1-ethyl cyclohexyl (methyl) acrylate. from improving the thermotolerance of copolyreaction and protective membrane that obtains or insulating film; the surface hardness aspect is considered, is preferably used above-claimed cpd.
In addition, polymerizable unsaturated compound as structure with formula (3), for example can enumerate 2-ethyl-gamma-butyrolactone-2-base-(methyl) acrylate, 2-methyl-gamma-butyrolactone-2-base-(methyl) acrylate, 2-ethyl-gamma-butyrolactone-3-base-(methyl) acrylate, 2-methyl-gamma-butyrolactone-3-base-(methyl) acrylate, 2-ethyl-gamma-butyrolactone-4-base-(methyl) acrylate, 2-methyl-gamma-butyrolactone-4-base-(methyl) acrylate, 2-ethyl-δ-Wu Neizhi-2-base-(methyl) acrylate, 2-methyl-δ-Wu Neizhi-2-base-(methyl) acrylate, 2-ethyl-δ-Wu Neizhi-3-base-(methyl) acrylate, 2-methyl-δ-Wu Neizhi-3-base-(methyl) acrylate, 2-ethyl-δ-Wu Neizhi-4-base-(methyl) acrylate, 2-methyl-δ-Wu Neizhi-4-base-(methyl) acrylate, 2-ethyl-δ-Wu Neizhi-5-base-(methyl) acrylate, 2-methyl-δ-Wu Neizhi-5-base-lactones such as (methyl) acrylate
2-ethyl-butyrolactam-2-base-(methyl) acrylate, 2-methyl-butyrolactam-2-base-(methyl) acrylate, 2-ethyl-butyrolactam-3-base-(methyl) acrylate, 2-methyl-butyrolactam-3-base-(methyl) acrylate, 2-ethyl-butyrolactam-4-base-(methyl) acrylate, 2-methyl-butyrolactam-4-base-(methyl) acrylate, 2-ethyl-δ-Valerolactim-2-base-(methyl) acrylate, 2-methyl-δ-Valerolactim-2-base-(methyl) acrylate, 2-ethyl-δ-Valerolactim-3-base-(methyl) acrylate, 2-methyl-δ-Valerolactim-3-base-(methyl) acrylate, 2-ethyl-δ-Valerolactim-4-base-(methyl) acrylate, 2-methyl-δ-Valerolactim-4-base-(methyl) acrylate, 2-ethyl-δ-Valerolactim-5-base-(methyl) acrylate, 2-methyl-δ-Valerolactim-5-base-lactan such as (methyl) acrylate.
Multipolymer (A-1) can contain (a1) and reach (a2) in addition, also contain (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, the vinylformic acid aryl ester, the unsaturated dicarboxylic acid diester, two ring unsaturated compounds, maleimide compound, unsaturated aromatics, conjugated diene compound, unsaturated monocarboxylic, unsaturated dicarboxylic acid, unsaturated two number acid anhydrides, other unsaturated compounds.
As its concrete example, for example, as alkyl methacrylate, can enumerate methacrylic acid hydroxyl methyl esters, 2-hydroxyethyl methacrylate, methacrylic acid 3-hydroxy propyl ester, methacrylic acid 4-hydroxyl butyl ester, the Diethylene Glycol monomethacrylates, methacrylic acid 2,3-dihydroxyl propyl ester, 2-methacryloxyethyl glucosides, methacrylic acid 4-hydroxylphenyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, methacrylic acid 2-ethylhexyl, methacrylic acid isodecyl ester, methacrylic acid dodecyl ester, methacrylic acid three decyl ester, methacrylic acid Octadecane base ester etc.;
As alkyl acrylate, can enumerate methyl acrylate, isopropyl acrylate etc.;
As methacrylic acid cyclic alkyl ester, can enumerate cyclohexyl methacrylate, methacrylic acid 2-methylcyclohexyl ester, three ring [5.2.1.0 2,6] decane-8-ylmethyl acrylate, three the ring [5.2.1.0 2,6] decane-8-base oxygen ethyl-methyl acrylate, 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 acrylate, three ring [5.2.1.0 2,6] decane-8-base oxygen ethyl propylene acid esters, isobornyl acrylate 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 unsaturated two number acid diesters, 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, methacrylic 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, acrylamide, Methacrylamide, vinyl-acetic ester etc.
Wherein, consider optimization styrene, three ring [5.2.1.0 from aspects such as copolyreaction, thermotolerances 2,6] decane-8-ylmethyl acrylate, to methoxy styrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, two ring [2.2.1] hept-2-ene"s, N-cyclohexyl maleimide etc.
Said mixture may be used alone, can also be used in combination.
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 be (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-diethyl propyl ester/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-diethyl propyl ester/N-phenylmaleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-diethyl propyl ester/N-cyclohexyl maleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid 1-ethyl cyclohexyl/methacrylic 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/methacrylic 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-diethyl propyl ester/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base/glycidyl methacrylate/Sipacril 2739OF, styrene/methacrylic acid 1-diethyl propyl ester/N-phenylmaleimide/glycidyl methacrylate/Sipacril 2739OF, styrene/methacrylic acid 1-diethyl propyl ester/N-cyclohexyl maleimide/glycidyl methacrylate/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl cyclohexyl/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base/glycidyl methacrylate/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl cyclohexyl/N-phenylmaleimide/glycidyl methacrylate/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl cyclohexyl/N-cyclohexyl maleimide/glycidyl methacrylate/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl ring pentyl ester/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base/glycidyl methacrylate/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl ring pentyl ester/N-phenylmaleimide/glycidyl methacrylate/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl ring pentyl ester/N-cyclohexyl maleimide/glycidyl methacrylate/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-diethyl propyl ester/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base/Sipacril 2739OF, styrene/methacrylic acid 1-diethyl propyl ester/N-phenylmaleimide/Sipacril 2739OF, styrene/methacrylic acid 1-diethyl propyl ester/N-cyclohexyl maleimide/Sipacril 2739OF, styrene/methacrylic acid 1-ethyl cyclohexyl/methacrylic 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/methacrylic 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 be (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-diethyl propyl ester/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base co-polymer, styrene/methacrylic acid 1-diethyl propyl ester/N-phenylmaleimide multipolymer, styrene/methacrylic acid 1-diethyl propyl ester/N-cyclohexyl maleimide copolymer, styrene/methacrylic acid 1-ethyl cyclohexyl/methacrylic 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/methacrylic 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.
Multipolymer (A-1), (A-2) reach (A-3), and (the stripping solvent: tetrahydrofuran (THF)) the polystyrene conversion weight-average molecular weight of Ce Dinging (hereinafter referred to as " Mw ") is preferably 1 with gel permeation chromatography, 000~100,000, more preferably 2,000~50,000, be preferably 3 especially, 000~40,000.At this moment, if Mw less than 1,000, then the coating of composition is insufficient sometimes, or the thermotolerance deficiency of the protective membrane that forms; If Mw surpasses 100,000 in addition, then planarization performance becomes insufficient sometimes.
And the molecular weight distribution (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 diglycidylether, A Hydrogenated Bisphenol A F diglycidylether, Hydrogenated Bisphenol A 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 ethylene glycol, propylene glycol, glycerine; Novolac epoxy resin; Line style line style cresols Resins, epoxy; 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 product that has 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, EPICOAT 1003, 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 EPOXYRESIN (strain) system) etc.;
As novolac epoxy resin, can enumerate EPICOAT 152, EPICOAT154, EPICOAT 157S65 (the above Japanese EPOXY RESIN (strain) of being system), EPPN201, EPPN 202 (above is Japanese chemical drug (strain) system) etc.;
As line style cresols Resins, epoxy, can enumerate EOCN102, EOCN103S, EOCN104S, 1020,1025,1027 (above is Japanese chemical drug (strain) system), EPICOAT180S75 (Japanese EPOXY RESIN (strain) system) etc.;
As polyphenol type Resins, epoxy, can enumerate EPICOAT 1032H60, EPICOATXY-4000 (the above Japanese EPOXYRESIN (strain) of being system) etc.;
As cyclic aliphatic epoxy resin, can enumerate CY-175, CY-177, CY-179, ARALDIT CY-182, ARALDIT 192,184 (above is CIBA SPECIALITYCHEMICALS (strain) system), ERL-4234,4299,4221,4206 (above is the U.C.C corporate system), SHOWDYNE 509 (clear and electrician's (strain) system), EPICLON200, EPICLON 400 (above is big Japanese ink (strain) system), EPICOAT 871, EPICOAT 872 (above is Japanese EPOXY RESIN (strain) system), ED-5661, ED-5662 (above is CELANESE COATING (strain) system) etc.;
As the aliphatic poly glycidyl ether, can list 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 '-epoxy cyclohexane is counted acid esters, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3, the 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), the Dicyclopentadiene (DCPD) diepoxide, two (3 of ethylene glycol, 4-epoxycyclohexyl methyl) ether, ethylenebis (3, the 4-epoxycyclohexane carboxylate), lactone sex change 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxy cyclohexane is counted acid esters etc.
In the above-mentioned cationically polymerizable compound (B), preferred novolac epoxy resin and polyphenol type Resins, epoxy.
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, 5~100 weight parts more preferably, be preferably 10~50 weight parts especially. cationically polymerizable compound (B) if usage quantity greater than 200 weight parts, then the coating of composition goes wrong sometimes; In addition, if less than 3 weight parts, the hardness of the protective membrane that then obtains is not enough sometimes.
Thermonasty acid-producing agent (C)
As the thermonasty 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 product of the acid-producing agent that preferably uses as the thermonasty 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 contains (C) thermonasty acid-producing agent; its usage quantity is 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. adopt the usage quantity of above-mentioned scope, can obtain having the protective membrane of enough hardness.
In addition, can change (C) thermonasty acid-producing agent into the radioactivity-sensitive acid-producing agent.
The radioactivity-sensitive acid-producing agent is can be by 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 hexafluorophosphate, 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 the triphenylsulfonium a tetrafluoro borate, triphenylsulfonium hexafluoro phosphonate, the triphenylsulfonium hexafluoro arsenate, the triphenylsulfonium fluoroform sulphonate, the triphenylsulfonium trifluoroacetate, the 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) iron hexafluoro phosphonate etc.
As the radioactivity-sensitive acid-producing agent, the commercially available product of the preferred acid-producing agent that uses has 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 UNIONCARBIDE 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. by 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, isocyanate group, 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, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.
The usage quantity of above-mentioned (D) bonding agent is with respect to total amount 100 weight parts of multipolymer (A-1), (A-2) and (A-3); be preferably below 30 weight parts, more preferably below 25 weight parts. 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: Megafac F142D, Megafac F172, Megafac F173, Megafac F183, Sumitomo 3M (strain) corporate system trade(brand)name: Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, system trade(brand)name: the SurfronS-112 of Asahi Glass (strain) society, Surfron S-113, Surfron S-131, Surfron S-141, Surfron S-145, Surfron S-382, Surfron SC-101, Surfron SC-102, Surfron SC-103, Surfron SC-104, Surfron SC-105, commercially available products such as 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, SH193, SZ-6032, SF-8428, DC-57, DC-190, SHIN-ETSU HANTOTAI's chemical industry (strain) corporate system trade(brand)name: KP341, new autumn fields change into (strain) corporate system trade(brand)name: commercially available products such as F-TOPEF301, 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 society of common prosperity society chemistry (strain) system trade(brand)name: (methyl) acrylic copolymer POLYFLOW No.57, POLYFLOWNo.90 etc.
The addition of above-mentioned (E) tensio-active agent is with respect to total amount 100 weight parts of polymkeric substance (A-1), (A-2) and (A-3), be preferably below 5 weight parts, more preferably below 2 weight parts. 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, thermonasty 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, thermonasty acid-producing agent (C). in the composition (2), the usage quantity of multipolymer (A-3) is with respect to total amount 100 weight parts of multipolymer (A-2), (A-3), be 10~90 weight parts, be preferably 20~80 weight parts. during quantity not sufficient 10 weight parts of multipolymer (A3), sometimes take place to solidify not enough, when surpassing 90 weight parts, thermotolerance worsens sometimes.
(3) contain: multipolymer (A-3) and cationic polymerizable compound (B), and the resin combination of the thermonasty acid-producing agent (C) that contains as required.
Resin combination of the present invention preferably prepares by 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, ethylene glycol 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 tetrahydrofuran (THF) etc.;
As glycol ethers, can enumerate glycol monomethyl methyl ether, ethylene glycol monomethyl ether etc.;
As ethylene glycol 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, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether etc.;
As propylene glycol alkyl ether acetic acid ester, can enumerate methyl proxitol acetate, propylene glycol ethyl ether acetic ester, propylene glycol propyl ether acetic ester, propylene glycol butyl ether acetic ester etc.;
As propylene glycol alkyl ether propionic ester, can enumerate methyl proxitol propionic ester, propylene glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester etc.;
As aromatic hydrocarbons, can enumerate toluene, dimethylbenzene 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, ethyl acetate, propyl acetate, butylacetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the oxyacetic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, the 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, the methoxyacetic acid ethyl ester, the methoxyacetic acid propyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid propyl ester, the ethoxyacetic acid butyl ester, the propoxy-methyl acetate, the propoxy-ethyl acetate, the propoxy-propyl acetate, the propoxy-butylacetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the 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, the 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, the 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, preferred alcohols, Diethylene Glycol, propylene glycol alkyl acetic ester, ethylene glycol alkyl oxide acetic ester, diethylene glycol dialkyl ether, preferred especially benzyl alcohol, Diethylene Glycol ethyl-methyl ether, methyl proxitol acetate, propylene glycol 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 (deducting the amount that quantity of solvent obtains from the total composition that comprises solvent) and is preferably 1~50 weight %, 5~40 weight %. more preferably
Can with above-mentioned solvent together and use high boiling solvent. as herein can and the high boiling solvent of usefulness, for example can enumerate the N-methylformamide, N, dinethylformamide, N-methyl formylphenyl aniline, the N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide, benzyl ethyl ether, hexyl ether, acetonyl-acetone, different Buddhist diketone, caproic acid, sad, the 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 when the high boiling solvent, with respect to the total solvent amount, be preferably 90 weight % following, more preferably below the 80 weight %.
Zhi Bei composition 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
The following describes the method for using composition of the present invention to form the protective membrane of colour filter.
Resin combination solution coat of the present invention at substrate surface, is carried out prebake, removes 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 polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, the ring-opening polymerization polymer that reaches cyclic olefin and hydride 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 different because of the kind of each composition or cooperation ratio etc., usually under adopting 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, coating thickness herein should be understood to remove 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, adopts 30~90 minutes treatment time when using baking oven.
In addition; when in resin combination, using the radioactivity-sensitive acid-producing agent; this resin combination is coated on substrate surface; through prebake, remove and to desolvate, make 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 be behind the irradiation radioactive rays, carry out heat treated more arbitrarily. as the Heating temperature of this moment, preferred about 150~250 ℃, as heating unit, for example can use suitable device such as hot-plate, dustless baking oven. be 5~30 minutes heat-up time when using hot-plate, can adopt 30~90 minutes treatment time when using baking oven.
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. in addition again; when protective membrane of the present invention was formed on the substrate that colour filter has jump, above-mentioned thickness should be understood to the thickness of starting at from the topmost of colour filter.
By following embodiment as can be known; 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, be applicable to the light device protective membrane of excellent property of the jump planarization of the colour filter that is formed on the bottom substrate.
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 guaranteed by have enough dimensional stabilitys under 270 ℃.
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 composition 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 the good light device of various patience protective membranes such as the formation transparency and surface hardness height, heat-resisting resistance to pressure, acid resistance, alkali resistance, anti-sputter, etching patience, and good as the storage stability of composition.
Embodiment
Provide synthesis example, embodiment below, be described more specifically the present invention, the present invention does not limit and following embodiment.
The preparation of (being total to) polymkeric substance
Synthesis example 1
In the flask that possesses prolong, stirrer, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 5 weight parts, propylene glycol monomethyl ether 200 weight parts. next, put into glycidyl methacrylate 50 weight parts, methacrylic acid 1-ethyl ring pentyl ester 50 weight parts, carry out stirring lentamente after nitrogen replaces. solution temperature is risen to 70 ℃, this temperature being 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%.
Synthesis 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 glycidyl methacrylate 40 weight parts, methacrylic acid 1-diethyl propyl ester 40 weight parts, vinylbenzene 10 weight parts, reach methacrylic acid three ring [5.2.1.0 2,6] decane-8-base 10 weight parts, after carrying out the nitrogen replacement, beginning is stirred lentamente. and 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%.
Synthesis example 3
Equipping prolong, put into 2 in the flask of stirrer, 2 '-azo two (2, the 4-methyl pentane nitrile) 5 weight parts, propylene glycol monomethyl ether 200 weight parts. next put into glycidyl methacrylate 40 weight parts, methacrylic acid 1-ethyl cyclohexyl 40 weight parts, vinylbenzene 10 weight parts, and cyclohexyl maleimide 10 weight parts, after carrying out the nitrogen replacement, beginning is stirred lentamente. solution temperature is risen to 70 ℃, this temperature being 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%.
Synthesis 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 glycidyl methacrylate 40 weight parts, methacrylic acid 1-ethyl ring pentyl ester 40 weight parts, vinylbenzene 10 weight parts, reach N-cyclohexyl maleimide 10 weight parts, after carrying out the nitrogen replacement, beginning is stirred lentamente. solution temperature is risen to 70 ℃, this temperature being 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%.
Synthesis example 5
In the flask of having equipped prolong, stirrer, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 5 weight parts, Diethylene Glycol ethyl-methyl ether 200 weight parts. next put into glycidyl methacrylate 40 weight parts, methacrylic acid 1-ethyl ring pentyl ester 40 weight parts, methacrylic 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%.
Synthesis example 6
Equipping prolong, put into 2 in the flask of stirrer, 2 '-azo two (2, the 4-methyl pentane nitrile) 5 weight parts, Diethylene Glycol ethyl-methyl ether 200 weight parts. next put into glycidyl methacrylate 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, after carrying out the nitrogen replacement, beginning is stirred lentamente. solution temperature is risen to 70 ℃, this temperature being 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%.
Synthesis example 7
In the flask of having equipped prolong, stirrer, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 5 weight parts, propylene glycol monomethyl ether 200 weight parts. next put into glycidyl methacrylate 100 weight parts, after carrying out the nitrogen replacement, beginning is stirred lentamente. solution temperature is risen to 70 ℃, this temperature being 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%.
Synthesis example 8
In the flask of having equipped prolong, stirrer, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 5 weight parts, propylene glycol monomethyl ether 200 weight parts. next put into glycidyl methacrylate 80 weight parts, vinylbenzene 20 weight parts, after carrying out the nitrogen replacement, beginning is stirred lentamente. and 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%.
Synthesis example 9
In the flask of having equipped prolong, stirrer, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 5 weight parts, propylene glycol monomethyl ether 200 weight parts. next put into methacrylic acid 1-ethyl cyclohexyl 100 weight parts, after carrying out the nitrogen replacement, beginning is stirred lentamente. and 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%.
Synthesis 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 methacrylic acid 1-ethyl cyclohexyl 80 weight parts, vinylbenzene 10 weight parts, reach methacrylic 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 being 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%.
Compare synthesis 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, methacrylic acid 20 weight parts, glycidyl methacrylate 45 weight parts and methacrylic 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. and 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%.
Compare synthesis example 2
In the flask of having equipped prolong, stirrer, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 5 weight parts, propylene glycol monomethyl ether 200 weight parts. next put into glycidyl methacrylate 40 weight parts, vinylbenzene 10 weight parts, methacrylic acid tertiary butyl ester 40 weight parts, reach cyclohexyl maleimide 10 weight parts, after carrying out the nitrogen replacement, beginning is stirred lentamente. and 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 system of resin combination respectively reaches evaluation
Embodiment 1
Enter the solution that contains the multipolymer (A1-1) that obtains in the above-mentioned synthesis example 1 (being equivalent to multipolymer (A1-1) the 100 weight parts amount of (dividing)) and (E) as SH-28PA (eastern beautiful DowcorningSilicone (strain) system) 0.1 weight part of tensio-active agent Gu form, add propylene glycol monomethyl ether again, after making solid formation branch concentration be 20%, with the aperture is that the millipore filter of 0.5 μ m filters, the preparation resin combination.
Use spinner, above-mentioned composition 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 carries out 60 minutes heat treated in 230 ℃ again in baking oven, forms the protective membrane of thickness 2.0 μ m.
The evaluation of protective membrane
(1) Tou Mingxing evaluation
For the substrate that is formed as described above with protective membrane; it is 95% when above that the minimum value of transmittance of using spectrophotometer (150-20 type twin-beam (Hitachi (strain) system)) to measure transmittance .400~800nm of 400~800nm is shown in this value of table 1., thinks that the transparency of protective membrane is for well.
(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.It is 95% when above that the heat-resisting dimensional stability of calculating by following formula is shown in this value of table 1., 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 heating 1 hour down; similarly measure the transparency before and after the heating with above-mentioned (1). it is 5% when following that the heat-resisting discolouration of calculating by following formula is shown in this value of table 1., 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., and this is worth for 4H or when harder, thinks that 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 results are 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 similarly forms thickness 2.0 μ m, adopts above-mentioned mesh tape test method similarly to estimate. the results are 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 3The substrate of/h. after with sputter is at 240 ℃ * 60min of above-mentioned dustless baking oven internal heating, implement 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 is heated 90 ℃ * 2min with hot-plate, remove and desolvate. then, pattern mask via 10 μ m/10 μ m, use exposure machine Canon PLA501F (Canon (strain) system), with ghi line (wavelength 436nm, 405nm, the strength ratio of 365nm=2.7:2.5:4.8) convert with the i line is according to degree 23mW/m 2, 25mJ/m 2Exposure shine, used 2.4%TMAH aqueous solution dipping under the room temperature 60 seconds, develop, rinsing is after 60 seconds in ultrapure water, carry out air-dry. then, roasting 150 ℃ * 60min. in back mixes nitric acid/hydrochloric acid as etching reagent with 1/3 weight ratio in dustless baking oven. substrate is immersed in the etching reagent, every 10 seconds taking-up substrates, decision forms the just etching time of the ITO line of 10 μ m, ITO live width during with 1.2 times of optical microscope measuring just etching time, the conservation rate of the ITO line of result .10 μ as shown in table 1 m is high more, and ITO etching patience is good more.
(8) evaluation of smooth voltinism
At SiO 2On the dipping glass substrate with the colored resist of spinner coating pigment class (trade(brand)name " JCR RED 689 ", " JCR GREEN 706 ", " CR 8200B ", above be that JSR (strain) makes), on hot-plate, carry out prebake in 150 seconds in 90 ℃, formation is filmed. then, via the pattern mask of regulation, use exposure machine Canon PLA501F (Canon (strain) system), with the ghi line (strength ratio of wavelength 436nm, 405nm, 365nm=2.7:2.5:4.8) press the i line to convert, 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 look striated colour filters (the wide 100 μ m of striped) in 230 ℃ of heat treated 30 minutes.
With surfaceness meter " α-STEP " (trade(brand)name: when the Tencor corporate system) measuring the substrate surface formed colour filter concavo-convex, the result is that 1.0 μ m. condition determinations are: measured length 2,000 μ m, measurement range 2,000 μ m is square, mensuration is counted n=5. promptly, measures direction and be 2 directions of the streak line long axis direction of the streak line short-axis direction of red, green, blue or green direction and red, green, blue and green same color, measures (n adds up to 10) with n=5 on all directions.
Form with behind the composition with spinner coating said protection film thereon; on hot-plate; carry out prebake in 5 minutes in 90 ℃; formation is filmed; carry out 60 minutes heat treated in 230 ℃ again in baking oven, the thickness that forms above colour filter is the protective membrane of 2.0 μ m. alleged herein 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 mean values 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 the viscosity of using resin combination. then, said composition is left standstill the soltion viscosity when measuring 25 ℃ every day simultaneously under 25 ℃.With the viscosity for preparing after just finishing 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 composition 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, prepare resin combination similarly to Example 1.
Use the protective membrane formation of preparation as described above to use resin combination, form protective membrane similarly to Example 1, estimate. the results are shown in table 1 and table 2.
Embodiment 29~32
The kind of each composition of composition 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 prepares resin combination similarly to Example 1.
Replace spinner, use the slit mould to be coated with device and be coated with, in addition prepare resin combination similarly to Example 1, form protective membrane, estimate. the results are shown in table 2.
Figure C200510128538D00341
Figure C200510128538D00351
Figure C200510128538D00361
Figure C200510128538D00371
Figure C200510128538D00391
Figure C200510128538D00401
Figure C200510128538D00411
In addition, in table 1 and the table 2, the abbreviation of cationically polymerizable compound (B), thermonasty 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 (8)

1. multipolymer, it is characterized by, this multipolymer (A-1) contains following polymerized unit: from (a1) have the polymerizable unsaturated compound of epoxy ethyl or oxa-cyclobutyl polymerized unit, and have the polymerized unit of (methyl) acrylate of structure shown in the following formula (01) from (a2)
Figure C200510128538C00021
Herein, R is: carbonatoms is the tertiary alkyl more than 5; The carbonatoms that is replaced by the alkoxyl group of carbonatoms 1~4 is the tertiary alkyl more than 4; The ring carbon atom number is the cycloalkyl more than 3, and this cycloalkyl is with R was connected in tertiary carbon atom and the above-mentioned formula Sauerstoffatom-O-bonding; Perhaps above lactonic ring or lactam nucleus of 4 yuan of rings, this lactonic ring or lactam nucleus are with R was connected in tertiary carbon atom and the above-mentioned formula Sauerstoffatom-O-bonding;
And the polystyrene conversion molecular weight weight-average molecular weight of this multipolymer is 1,000~100,000.
2. multipolymer as claimed in claim 1, wherein, structure shown in the above-mentioned formula (01) is the structure of following formula (1) expression,
Figure C200510128538C00022
Herein, R 1And R 2Represent that independently of one another carbonatoms is 1~8 alkyl or is 1~8 alkyl by the carbonatoms that the alkoxyl group of carbonatoms 1~4 replaces, R 3Be that carbonatoms is 2~8 alkyl or is 1~8 alkyl by the carbonatoms that the alkoxyl group of carbonatoms 1~4 replaces;
Or the structure of following formula (2) expression,
Herein, R 1Definition identical with above-mentioned formula (1), n is 1~8 integer, R 4, R 5, R 6And R 7Represent that independently of one another hydrogen atom or carbonatoms are that the carbonatoms that has the alkoxyl group of carbonatoms 1~4 on the end of 1~8 alkyl or alkyl or the side chain is that 1~8 alkyl or carbonatoms are 1~4 alkoxyl group, perhaps R 4, R 5, R 6And R 7In at least 2 combinations, and the carbon atom and the R that are connected with them 1The carbon atom that is connected forms ring carbon atom together and adds up to 7~16 bicyclic alkane or three naphthenic hydrocarbon structures; Wherein, n=2~8 o'clock, a plurality of R 6Each other and R 7Identical each other or different;
Or be the structure of following formula (3) expression,
Figure C200510128538C00031
Herein, R 1Definition identical with above-mentioned formula (1), 1 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 hydrogen atom or carbonatoms are that the carbonatoms that has the alkoxyl group of carbonatoms 1~4 on the end of 1~8 alkyl or alkyl or the side chain is that 1~8 alkyl or carbonatoms are 1~4 alkoxyl group, wherein, 2 R during 1=2 8With 2 R 9And m is a plurality of R of integer 2~4 o'clock 10With a plurality of R 11Identical or different.
3. a resin combination is characterized by and contains the described multipolymer of claim 1 (A-1).
4. resin combination as claimed in claim 3 wherein, also contains (B) cationically polymerizable compound.
5. as claim 3 or 4 described resin combinations, wherein, also contain (C) thermo-sensitivity acid-producing agent.
6. as claim 3 or 4 described resin combinations, wherein, said composition is used to form the protective membrane of colour filter.
7. the formation method of a color filter protecting layer is characterized by, and forms filming of the described resin combination of claim 5 on substrate, carries out heat treated then.
8. the protective membrane of a colour filter, it is formed by the described resin combination of claim 6.
CNB2005101285381A 2004-11-26 2005-11-28 Copolymer, resin composition, protection film and forming method thereof Expired - Fee Related CN100506863C (en)

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