CN1676549A - Thermosetting composition, solid photographic element anti-dizzy film and forming method thereof and solid photography element - Google Patents

Thermosetting composition, solid photographic element anti-dizzy film and forming method thereof and solid photography element Download PDF

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CN1676549A
CN1676549A CNA2005100595643A CN200510059564A CN1676549A CN 1676549 A CN1676549 A CN 1676549A CN A2005100595643 A CNA2005100595643 A CN A2005100595643A CN 200510059564 A CN200510059564 A CN 200510059564A CN 1676549 A CN1676549 A CN 1676549A
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methyl
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multipolymer
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carboxylic acid
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CN100500768C (en
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加藤嘉文
马场厚
梶田彻
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JSR Corp
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
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    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

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Abstract

The invention relates to a thermosetting composition containing a copolymer of a monomer mixture, the copolymer of a monomer mixture containing (a1) an epoxy group-containing unsaturated compound, (a2) a radiation-absorbing radically polymerizable compound and (a3) (a3-1) a polymerizable unsaturated carboxylic acid and/or a polymerizable unsaturated polycarboxylic acid anhydride or (a3-2) a polymerizable unsaturated compound having at least one structure chosen from an acetal ester structure of a carboxylic acid, a ketal ester structure of an carboxylic acid and a t-butyl ester structure of a carboxylic acid. The thermosetting composition of polymer with carboxylic acid acetal structure or thioacetal structure is obtained by adding vinyl ether compound or vinyl thioether compound to anhydride group of polymer containing (a1), (a2) and polymerizable unsaturated polycarboxylic acid anhydride. The a thermosetting composition is suitable for forming an antihalation film which can effectively inhibit diffused reflection from a base substrate and has high transmittance of visible light and a high heat resistance.

Description

Anti-halation film of thermoset composition, solid-state imager and forming method thereof and solid-state imager
Technical field
The present invention relates to the anti-halation film and forming method thereof and the solid-state imager of a kind of thermoset composition, solid-state imager.
Background technology
Solid-state imager comprises MOS (Metal Oxide Semiconductor, metal-oxide semiconductor (MOS)) type, CCD (Charge Coupled Device, inductive coupler) type etc., uses one dimension solid-state imager and two-dimensional solid imaging apparatus respectively.As the former concrete example, for example can enumerate facsimile recorder etc.In addition, as the latter's concrete example, can enumerate pick up camera etc.
In recent years, above-mentioned solid-state imager begins to digital development, for adapting to the user to quality requirements, further requires it to have high image quality.The means such as pixel count that increase pick up camera are one of them example.
Solid-state imager comprises black and white element and colored with two kinds of elements, and wherein, colour is made with solid-state imager forms 3 kinds of colors on the substrate of formation solid-state imager chromatic color filter.Solid-state imager can directly use, and also convex lens (microlens) can be installed on the surface corresponding to various solid-state imagers, improves light sensitivity (light gathering) (opening flat 3-223702 communique referring to the spy).
Form fine pattern in order chromatic color filter and/or microlens to be installed, to be adopted the photoetching technique of using photosensitive material on solid-state imager.
The following formation of microlens: form solid-state imager, as required, further on the substrate that has formed chromatic color filter, be coated with transparent resin again, behind flattening surface, the microlens material that coating is formed by photoresist, exposure lens pattern, develop, after the carrying out washing treatment, heat residual transparent resin caking, make its contraction after the micro melting, thereby make each caking form convex lens shape.
In the forming process of above-mentioned chromatic color filter or microlens, there is following problem, during promptly, with photosensitive material exposure, formation pattern, the bottom substrate produces diffuses to make and does not wish the part exposure that exposes, cause actual pattern dimension different, this phenomenon promptly so-called " halation " with target size.
Under the situation of using microlens, if above-mentioned phenomenon, then the shape of lens becomes irregular, and situations such as flash of light take place, and image quality is produced detrimentally affect.At present, along with the cell size of solid-state imager is dwindled, above-mentioned situation becomes more serious problem gradually.
At the problems referred to above, known have on the solid-state imager substrate form the antireflection film that is absorbed in the radioactive rays that use in the photolithography, with inhibitory reflex, prevent the method that halation takes place.In this example, can be principal constituent with the poly (glycidyl methacrylate), use trimellitic acid as the CCD of solidifying agent with complex dye (referring to No. 2956210 specification sheets of patent) in the protective membrane.But; there is following shortcoming in above-mentioned antireflection film; promptly, in the calcining process that carries out for the material crosslinking curing after making coating; the part of dyestuff distils from antireflection film; anti-halation effect is significantly reduced; or when using non-volatile dyestuff, dyestuff appears in one's mind on protective membrane, can't make the microlens that forms on the anti-halation film form desirable shape etc.
In addition, a kind of containing by unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, the multipolymer that forms with the free-radical polymerised compound that contains epoxy group(ing), with monoolefine and/or alkadiene unsaturated compound and the anti-halation film (opening flat 6-289201 communique referring to the spy) of radioactive rays absorbing compounds disclosed.Should anti-halation film be estimated as process below 150 ℃, the thermotolerance that surpasses under 150 ℃ the temperature do not verified in the temperature hysteresis after the formation.
But for the colour solid-state imager, owing to adopt the chromatic color filter material that uses existing dyestuff matrix, therefore, chromatic color filter may solidify under the lesser temps about 150 ℃.But, owing to along with in recent years high-precision requirement being begun to be extensive use of the pigment class material, therefore in this forming process, necessarily require more than 180 ℃ solidification value (referring to the spy open flat 11-211911 communique, the spy opens flat 11-258415 communique and the spy opens the 2000-111722 communique).Therefore, for the colour solid-state imager, the anti-halation film exposure that forms prior to chromatic color filter will be exposed to halation under the high temperature that is higher than existing temperature.
In addition, in recent years, begin to research and develop the CCD photographic camera is loaded in auxiliary technology of travelling on the automobile, but, because the CCD photographic camera that is used for this purposes is used to than under the harsher working conditions of existence conditions, therefore, need carry out pyritous forming process more, require to obtain to tolerate the anti-halation film of pyritous more than 230 ℃.
If known anti-halation film exposes under above-mentioned high temperature with material at present, with the function of forfeiture as anti-halation film.Infer the former of above-mentioned phenomenon to occur, overflow with the distillation of the radioactive rays absorption agent in the material, therefore the radioactive rays receptivity is significantly reduced owing to being engaged in anti-halation film because in surpassing 150 ℃ high-temperature area.
Summary of the invention
The present invention finishes in view of above situation, its purpose is to provide a kind of thermoset composition, use this thermoset composition to form the method for anti-halation film and anti-halation film that is formed by this method and the solid-state imager with this anti-halation film, above-mentioned thermoset composition is applicable in exposure process when formation can be suppressed at the chromatic color filter that forms in the solid-state imager or microlens effectively, by diffusing of producing of bottom substrate and have the anti-halation film of high heat resistance.
Other purposes of the present invention and advantage are as described below.
According to the present invention, first purpose of the present invention is for providing a kind of thermoset composition, it is characterized by, contain the polymkeric substance of at least a kind of structure in the thioacetal ester structure of the tert-butyl ester structure of ketone acetal ester structure that (1) epoxy group(ing), (2) radioactive rays absorbing group and (3) have the acetal ester structure that is selected from carboxyl, carboxylic acid, carboxylic acid, carboxylic acid and carboxylic acid.
In addition, second purpose of the present invention is characterized by described method and comprises following operation (1) and operation (2) for a kind of anti-halation film formation method of solid-state imager is provided:
(1) operation of filming of the above-mentioned thermoset composition of formation on substrate;
(2) this operation of filming of heat treated.
In addition, the 3rd purpose of the present invention is for providing a kind of anti-halation film of the solid-state imager that is formed by aforesaid method; And the 4th purpose of the present invention is for providing a kind of solid-state imager with above-mentioned anti-halation film.
Description of drawings
Fig. 1 is the mode declaration pattern specification figure of the shape of microlens pattern.
Embodiment
Below, the present invention will be described.At first, describe each composition of thermoset composition of the present invention in detail.
Multipolymer (A)
The polymkeric substance that uses among the present invention has following structure, and described structure is for being selected from (1) epoxy group(ing), (2) radioactive rays absorbing group and (3) at least a kind of structure from the thioacetal ester structure of the tert-butyl ester structure of the ketone acetal ester structure of the acetal ester structure of carboxyl, carboxylic acid, carboxylic acid, carboxylic acid and carboxylic acid.
Above-mentioned polymkeric substance is preferably the multipolymer that (A) contain the monomer mixture of following compound (below be designated as " multipolymer (A) "), and described compound contains the unsaturated compound (below be designated as " compound (a1) ") of epoxy group(ing) for (a1), (a2) radioactive rays absorptivity free-radical polymerised compound (below be designated as " compound (a2) "), and (a3) (a3-1) polymerizable unsaturated carboxylic acids and/or the unsaturated polybasic acid anhydride of polymerizability, or (a3-2) has an acetal ester structure that is selected from carboxylic acid, the polymerizable unsaturated compound of at least a kind of structure in the ketone acetal ester structure of carboxylic acid and the tert-butyl ester structure of carboxylic acid (below be designated as " compound (a3) ")); Or (B) containing unsaturated compound that (a1) contain epoxy group(ing), (a2) radioactive rays absorptivity free-radical polymerised compound and (a3-1) in the anhydride group of the multipolymer of the monomer mixture of the unsaturated polybasic acid anhydride of polymerizability (A), the ethylidene ether structure that addition vinyl ether compound or vinyl sulfide compound obtain or the addition polymer of thioacetal structure (below be designated as " addition polymer (B) ") with carboxylic acid.
Be preferably 10～70 weight % by compound (a1) deutero-structural unit content in the multipolymer (A), be preferably 20～60 weight % especially.The multipolymer that contains quantity not sufficient 10 weight % of this structural unit has the tendency of the humidity resistance that reduces the anti-halation film that obtains.On the other hand, when content surpassed 70 weight %, the storage stability of solidification compound had the tendency of reduction.
Above-claimed cpd (a1) is for having the compound of epoxy group(ing) and polymerizability carbon-to-carbon double bond in a part, particularly, for example, can enumerate glycidyl acrylate, glycidyl methacrylate, methacrylic acid methyl glycidyl ester, the α-Yi Jibingxisuan glycidyl ester, α-n-propyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, vinylformic acid-3,4-oxyethyl group butyl ester, methacrylic acid-3,4-oxyethyl group butyl ester, vinylformic acid-6,7-oxyethyl group heptyl ester, methacrylic acid-6,7-oxyethyl group heptyl ester, α-Yi Jibingxisuan-6,7-oxyethyl group heptyl ester, adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether etc.
Wherein, consider from thermotolerance, the hardness aspect of the anti-halation film that improves copolyreaction and obtain, preferable methyl glycidyl acrylate, methacrylic acid methyl glycidyl ester, methacrylic acid-6,7-epoxy group(ing) heptyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether etc.The unsaturated compound that above-mentioned (a1) contains epoxy group(ing) may be used alone, can also be used in combination.
Content by compound (a2) deutero-structural unit in the multipolymer that uses among the present invention (A) is preferably 1～40 weight %, is preferably 3～30 weight % especially.During this structural unit less than 1 weight %, anti-corona sometimes image ability becomes insufficient.On the other hand, if this structural unit surpasses 40 weight %, the film-forming properties of then filming has the tendency of reduction.
As the radioactive rays absorbent structure that compound (a2) has, preferably can absorb the light of 400nm following wavelength, particularly 365nm wavelength and not absorb the structure of the light of visible region in fact.As this radioactive rays absorbent structure, more preferably for example benzotriazole structure, salicylate structure, benzophenone structure, substituted acrylonitrile structure, ton structure, tonka bean camphor structure, flavones structure, phenyl styryl ketone structure.Wherein, preferred especially benzotriazole structure.
As the skeleton with benzotriazole structure, particularly preferred example is as the skeleton by following formula (1) expression.
Figure A20051005956400081
As free-radical polymerised compound, for example can enumerate the compound of representing by following formula (2), (3) and (4) respectively with above-mentioned radioactive rays absorbent structure.
Figure A20051005956400082
Wherein, R 1And R 2Can be identical or different, expression hydrogen atom, carbonatoms are that 1～8 alkyl, carbonatoms are 1～8 alkoxyl group, cyano group, hydroxyl, halogen atom, carboxyl or alkoxy carbonyl, R 3The expression carbonatoms is 2～10 alkylidene group, R 4Expression hydrogen atom or methyl.
Wherein, R 4Definition same as described above, R 5Expression hydrogen atom or carbonatoms are 1～8 alkyl.
Figure A20051005956400091
Wherein, R 3, R 4And R 5Definition same as described above, R 6The carbonatoms that expression can be replaced by hydroxyl is 1～4 alkylidene group.
In the following formula (2), as R 1And R 2The carbonatoms of expression is 1～8 alkyl, for example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, tert-pentyl (amyl group), n-hexyl, uncle's hexyl, n-heptyl, uncle's heptyl, n-octyl, two uncle's octyl groups and so on carbonatoms is 1～8 straight or branched alkyl.Wherein, carbonatomss such as the preferable methyl or the tertiary butyl, tert-pentyl, uncle's heptyl, two uncle's octyl groups are 4～8 tertiary alkyl.
As R 1And R 2The carbonatoms of expression is 1～8 alkoxyl group, for example can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy, positive heptan oxygen base, n-octyloxy and so on carbonatoms and be 1～8 straight or branched alkoxyl group.
As R 1And R 2The halogen atom of expression for example, can be enumerated chlorine atom, bromine atoms, fluorine atom, iodine atom etc.Wherein, preferred chlorine atom.
As R 3The carbonatoms of expression is 2～10 alkylidene group, for example, can enumerate ethylidene, trimethylene, propylidene, tetramethylene, 1,1-dimethyl tetramethylene, butylidene, eight methylene radical, octylene, decamethylene, inferior decyl and so on carbonatoms is 1～10 straight or branched alkylidene group.Wherein, preferred ethylidene, propylidene etc.
In following formula (3) and (4), as R 5The carbonatoms of expression is 1～8 alkyl, can for following formula (2) in R 1And R 2The carbonatoms of expression is 1～8 the identical group of alkyl, and in addition, preferred group is also identical.
In the following formula (4), as R 6The carbonatoms that also can be replaced by hydroxyl of expression is 1～4 alkylidene group, for example can enumerate methylene radical, ethylidene, trimethylene, 2-hydroxyl trimethylene, 1-methyl ethylidene, tetramethylene, 1-methyl trimethylene, 1,1-dimethyl ethylidene and so on carbonatoms is the alkylidene group of 1～4 straight or branched and the above-mentioned group that is replaced by hydroxyl.Wherein, preferred ethylidene, trimethylene, 2-hydroxyl trimethylene and so on carbonatoms is 2～3 group.
Among the present invention, in the radioactive rays absorptivity free-radical polymerised compound of following formula (2)～(4) expression, especially preferably use the radioactive rays absorptivity free-radical polymerised compound of formula (2) expression.
And, in the radioactive rays absorptivity free-radical polymerised compound of formula (2) expression, preferred especially following radioactive rays absorptivity free-radical polymerised compound, i.e. R in the formula 1Be hydrogen atom or chlorine atom, under the situation for the chlorine atom, replace 5 of benzo triazole ring, R 2For hydrogen atom, methyl or carbonatoms are 4～8 tertiary alkyl, more preferably hydrogen atom, methyl or the tertiary butyl, R 3Be carbonatoms 2～10,2～3 alkylidene group more preferably, R 4Be hydrogen atom or methyl.As the concrete example of this radioactive rays absorptivity free-radical polymerised compound, for example can enumerate 2-(2 '-hydroxyl-5 '-acryloxy ethylphenyl)-2H-benzotriazole, 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-2H-benzotriazole, 2-(2 '-hydroxyl-5 '-methacryloxypropyl phenyl)-2H-benzotriazole, 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-5-chloro-2H-benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-methacryloxyethyl phenyl)-5-chloro-2H-benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-acryloxy ethylphenyl)-2H-benzotriazole, 2-(2 '-hydroxyl-5 '-methacryloxy hexyl phenyl)-2H-benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-methacryloxyethyl phenyl)-2H-benzotriazole etc.
Wherein, especially preferably use 2-(2 '-hydroxyl-5 '-methacryloxyethyl the phenyl)-2H-benzotriazole (below be designated as monomer (a2-1)) of following formula (5) expression and 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-methacryloxyethyl the phenyl)-2H-benzotriazole of following formula (6) expression (below be designated as monomer (a2-2)).Among the present invention, radioactive rays absorptivity free-radical polymerised compound can use a kind separately, also can use mixing more than 2 kinds or 2 kinds.
Figure A20051005956400111
Content by compound (a3) deutero-structural unit in the multipolymer that uses among the present invention (A) is preferably 5～60 weight %, is preferably 10～50 weight % especially.The humidity resistance of the anti-halation film that is obtained by the multipolymer of this structural unit less than 5 weight % has the tendency of reduction.On the other hand, when surpassing 60 weight %, the storage stability of solidification compound has the tendency of reduction.
Above-claimed cpd (a3) for (a3-1) polymerizable unsaturated carboxylic acids or the unsaturated polybasic acid anhydride of polymerizability or (a3-2) contains the polymerizable unsaturated compound of at least a structure of the tert-butyl ester structure of the ketone acetal ester structure of the acetal ester structure that is selected from carboxylic acid, carboxylic acid and carboxylic acid.
As (a3-1), for example can enumerate (methyl) vinylformic acid, butenoic acid, α-Yi Jibingxisuan, α-n-propyl vinylformic acid, α-normal-butyl vinylformic acid, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid and so on unsaturated carboxylic acid; Maleic anhydride, itaconic anhydride, citraconic anhydride, suitable-1,2,3, the unsaturated polybasic acid anhydride of 4-tetrahydroxy Tetra hydro Phthalic anhydride and so on; (methyl) vinylformic acid 2-carboxyl ethyl ester, (methyl) vinylformic acid 3-carboxyl propyl ester and so on contain the esters of unsaturated carboxylic acids of carboxyl etc.
In above-mentioned (a3-1), as unsaturated carboxylic acid, preferred especially vinylformic acid, methacrylic acid; As unsaturated polybasic acid anhydride, preferred especially maleic anhydride.The copolyreaction height of above-mentioned preferred unsaturated carboxylic acid, unsaturated polybasic acid anhydride can improve the thermotolerance or the surface hardness of the protective membrane that obtains in addition effectively.
Above-mentioned substance may be used alone, can also be 2 or more kinds in combination.
As polymerizable unsaturated compound (a3-2), for example, can enumerate (methyl) acrylic compound, the tertiary butyl (methyl) acrylate of norbornene compound, acetal or ketone acetal ester structure of the ketone acetal ester structure of acetal ester structure with carboxylic acid or carboxylic acid with carboxylic acid.
Concrete example as norbornene compound with above-mentioned acetal ester structure or ketone acetal ester structure, for example can enumerate 2,3-two-tetrahydropyrans-2-base oxygen base carbonyl-5-norbornylene, 2,3-two-TMS oxygen base carbonyl-5-norbornylene, 2,3-two-triethyl silyl oxygen base carbonyl-5-norbornylene, 2,3-two-tertiary butyl dimethylsilyl oxygen base carbonyl-5-norbornylene, 2,3-two-trimethylammonium germyl oxygen base carbonyl-5-norbornylene, 2,3-two-triethyl germyl oxygen base carbonyl-5-norbornylene, 2,3-two-tertiary butyl dimethyl germyl oxygen base carbonyl-5-norbornylene, 2,3-two-tertiary butyl oxygen base carbonyl-5-norbornylene, 2,3-two-benzyl oxygen base carbonyl-5-norbornylene, 2,3-two-tetrahydrofuran (THF)-2-base oxygen base carbonyl-5-norbornylene, 2,3-two-tetrahydropyrans-2-base oxygen base carbonyl-5-norbornylene, 2,3-two-cyclobutyl oxygen base carbonyl-5-norbornylene, 2,3-two-cyclopentyloxy carbonyl-5-norbornylene, 2,3-two-cyclohexyl oxygen base carbonyl-5-norbornylene, 2,3-two-suberyl oxygen base carbonyl-5-norbornylene, 2,3-two-1-methoxy ethoxy carbonyl-5-norbornylene, 2,3-two-1-tert.-butoxy ethoxy carbonyl-5-norbornylene, 2,3-two-1-benzyl oxygen base oxethyl carbonyl-5-norbornylene, 2,3-two-(cyclohexyl) (oxyethyl group) methoxycarbonyl-5-norbornylene, 2,3-two-1-methyl isophthalic acid-methoxy ethoxy carbonyl-5-norbornylene, 2,3-two-1-methyl isophthalic acid-isobutoxy ethoxy carbonyl-5-norbornylene, 2,3-two-(benzyl) (oxyethyl group) methoxycarbonyl-5-norbornylene etc.
Concrete example as (methyl) acrylic compound with above-mentioned acetal ester structure or ketone acetal ester structure, for example can enumerate 1-ethoxyethyl group (methyl) acrylate, tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate, 1-(cyclohexyl oxygen base) ethyl (methyl) acrylate, 1-(2-methyl propoxy-) ethyl (methyl) acrylate, 1-(1,1-dimethyl-oxyethyl group) ethyl (methyl) acrylate, 1-(cyclohexyl oxygen base) ethyl (methyl) acrylate etc.
Wherein, preferably have the acetal ester structure of carboxylic acid or (methyl) acrylic compound and the tertiary butyl (methyl) acrylate of ketone acetal ester structure, preferred especially 1-ethoxyethyl group methacrylic ester, tetrahydrochysene-2H-pyrans-2-ylmethyl acrylate, 1-(cyclohexyl oxygen base) ethyl-methyl acrylate, 1-(2-methyl propoxy-) ethyl-methyl acrylate, 1-(1,1-dimethyl-oxyethyl group) ethyl-methyl acrylate, 1-(cyclohexyl oxygen base) ethyl-methyl acrylate, tertiary butyl methacrylic ester.
Above-mentioned substance may be used alone, can also be used in combination.
As mentioned above, the multipolymer that uses among the present invention (A) is to serve as the multipolymer of the monomer mixture of essential composition with compound (a1), compound (a2) and compound (a3), as required, this monomer mixture can also contain except that (a1), (a2) and (a4) olefines unsaturated compound (a3) (below be designated as " compound (a4) ").
By this compound (a4) and compound (a1), compound (a2) and compound (a3) are together used the advantages such as thermotolerance of the anti-halation film of the storage stability of the thermoset composition that can be improved and gained as copolymer composition.
Be preferably below the 50 weight %, more preferably below the 40 weight % by compound (a4) deutero-structural unit content in the multipolymer of the present invention (A).
If this structural unit surpasses 50 weight %, the anti-halation function of the anti-halation film that then obtains or reagent resistance may be insufficient.
The olefines unsaturated compound of above-mentioned (a4) is not for having epoxy group(ing) and radioactive rays absorbing group and having the compound of polymerizability carbon-to-carbon double bond, as its concrete example, can enumerate alkyl methacrylate, alkyl acrylate, methacrylic acid cycloalkyl ester, vinylformic acid cycloalkyl ester, aryl methacrylate, vinylformic acid aryl ester, dicarboxylic diester, indene derivative, dicarbapentaborane imide derivative, hydroxyalkyl acrylate, aromatic series unsaturated compound, conjugated diolefine, other unsaturated compounds.
For its concrete example,, for example can enumerate methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, methacrylic tert-butyl acrylate etc. as alkyl methacrylate; As alkyl acrylate, for example can enumerate methyl acrylate, isopropyl acrylate etc.; As the methacrylic acid cycloalkyl ester, for example can enumerate methacrylic acid cyclohexyl ester, 2-methylcyclohexyl methacrylic ester, methacrylic acid cyclohexyl ester, methacrylic acid three ring [5.2.1.0 2,6] ten-8-base ester (the methacrylic acid two pentamethylene base esters that are called commonly used this area in), methacrylic acid two pentamethylene base oxygen base ethyl esters, the different boryl ester of methacrylic acid etc.; As the vinylformic acid cycloalkyl ester, for example can enumerate vinylformic acid cyclohexyl ester, 2-methylcyclohexyl acrylate, vinylformic acid cyclohexyl ester, vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester (the vinylformic acid two pentamethylene base esters that are called commonly used this area in), vinylformic acid two pentamethylene base oxygen base ethyl esters, the different boryl ester of methacrylic acid etc.; As aryl methacrylate, for example, can enumerate phenyl methacrylate, methacrylic acid benzyl ester etc.; As the vinylformic acid aryl ester, for example can enumerate phenyl acrylate, vinylformic acid benzyl ester etc.; As dicarboxylic diester, for example, can enumerate ethyl maleate, DEF, diethyl itaconate etc.; As indene derivative, for example, can enumerate indenes, 1-methyl indenes etc.; As the dicarbapentaborane imide derivative, for example, can enumerate phenyl maleimide, benzyl maleimide, N-cyclohexyl maleimide, N-succinimido-3-maleimide phenyl ester, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridyl) maleimide etc.; As hydroxyalkyl acrylate, for example can enumerate 2-hydroxyethyl methacrylic ester, 2-hydroxy propyl methacrylate etc.; As the aromatic series unsaturated compound, for example, can enumerate vinylbenzene, alpha-methyl styrene, a vinyl toluene, p-methylstyrene, Vinyl toluene, to methoxy styrene etc.; As conjugated diolefine, for example, can enumerate 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.; As other unsaturated compounds, for example, can enumerate vinyl cyanide, methacrylonitrile, vinylchlorid, Ethylene Dichloride, acrylamide, Methacrylamide, vinyl-acetic ester etc.
Wherein, preferably use alkyl methacrylate, methacrylic acid cycloalkyl ester, vinylformic acid cycloalkyl ester, aromatic series unsaturated compound, conjugated diolefine, dicarbapentaborane imide derivative.Wherein, consider from the thermotolerance aspect of copolyreaction and the anti-halation film that obtains, especially preferably use vinylbenzene, methacrylic tert-butyl acrylate, methacrylic acid two cyclopentyl esters, to methoxy styrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, phenyl maleimide, N-cyclohexyl maleimide.
Above-claimed cpd (a4) may be used alone, can also be used in combination.
The multipolymer that uses among the present invention (A) preferably will contain above-claimed cpd (a1), compound (a2) and compound (a3), and the monomer mixture of the compound (a4) that adds as required, in solvent and polymerization starter in the presence of carry out radical polymerization and synthesize.
As the solvent that uses in multipolymer (A) manufacturing, for example, can enumerate alcohol, ether, glycol ether, ethylene glycol alkyl oxide acetic ester, diglycol monotertiary alkyl oxide, glycol ether dialkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, aromatic hydrocarbons, ketone, ester etc.
For its concrete example,, for example, can enumerate methyl alcohol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propyl alcohol etc. as alcohol; As ether, for example, can enumerate tetrahydrofuran (THF) etc.; As glycol ether, for example, can enumerate glycol monomethyl methyl ether, ethylene glycol monomethyl ether etc.; As ethylene glycol alkyl oxide acetic ester, for example, can enumerate acetic acid methyl cellosolve, acetate ethyl cellosolve, ethylene glycol monobutyl ether acetic ester, diethylene glycol monoethyl ether acetate etc.; As the diglycol monotertiary alkyl oxide, for example, can enumerate diglycol monotertiary methyl ether, carbiphene etc.; As the glycol ether dialkyl ether, for example, can enumerate diethylene glycol dimethyl ether, diethylene glycol diethyl ether, glycol ether ethyl-methyl ether etc.; As propylene-glycol monoalky lether, for example, 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, for example, 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, for example, 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, for example, can enumerate toluene, dimethylbenzene etc.; As ketone, for example, can enumerate methyl ethyl ketone, pimelinketone, 4-hydroxy-4-methyl-2 pentanone, methyl isoamyl ketone etc.; As ester, for example, 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, ketones such as 3-butoxy butyl propionate.
Wherein, preferred alcohols, ethylene glycol alkyl oxide acetic ester, glycol ether dialkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester; Preferred especially benzyl alcohol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, glycol ether ethyl-methyl ether, methyl proxitol, methyl proxitol acetate, propylene glycol ethyl ether acetic ester, ethylene glycol monobutyl ether acetic ester, diethylene glycol monoethyl ether acetate.
The polymerization starter that uses in the manufacturing of multipolymer (A) can use known radical polymerization initiator.For example, can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-azo-compounds such as (4-methoxyl group-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, tertiary butyl pivalate superoxide, 1,1 '-two-organo-peroxides such as (tert-butyl hydroperoxide) hexanaphthene; And hydrogen peroxide.Using under the situation of superoxide as radical polymerization initiator, also superoxide and reductive agent together can be used as the oxidation-reduction type initiator.
In the manufacturing of multipolymer (A),, can use molecular weight regulator in order to adjust molecular weight.As its concrete example, can enumerate halohydrocarbon such as chloroform, tetracol phenixin; N-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, Thiovanic acid, and so on mercaptan; Sulfuration dimethyl yellow ortho ester, dithiodiisopropyl xanthate and so on xanthate; Terpinolene, α-Jia Jibenyixierjuwu etc.
As the preferred concrete example of the multipolymer that uses among the present invention (A), for example, can enumerate vinylbenzene/(methyl) vinylformic acid/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/(methyl) vinylformic acid/phenyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/(methyl) vinylformic acid/cyclohexyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/(methyl) vinylformic acid/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) vinylformic acid-6,7-oxyethyl group heptyl ester/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/(methyl) vinylformic acid/maleic anhydride/(methyl) vinylformic acid-6,7-oxyethyl group heptyl ester/(monomer a2-1 or monomer a2-2) multipolymer, the tertiary butyl (methyl) acrylate/(methyl) vinylformic acid/maleic anhydride/(methyl) vinylformic acid-6,7-oxyethyl group heptyl ester/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/(methyl) vinylformic acid/(methyl) methyl acrylate/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, to methoxy styrene/(methyl) vinylformic acid/cyclohexyl (methyl) acrylate/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/1-(cyclohexyl oxygen base) ethyl (methyl) acrylate/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate/phenyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/2,3-two-tetrahydropyrans-2-base oxygen base carbonyl-5-norbornylene/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/1-(cyclohexyl oxygen base) ethyl (methyl) acrylate/cyclohexyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate/cyclohexyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/2,3-two-tetrahydropyrans-2-base oxygen base carbonyl-5-norbornylene/cyclohexyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, Butadiene/1-(cyclohexyl oxygen base) ethyl (methyl) acrylate/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, divinyl/tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, the tertiary butyl (methyl) acrylate/tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate/maleic anhydride/(methyl) vinylformic acid-6,7-oxyethyl group heptyl ester/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate/(methyl) methyl acrylate/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, to methoxy styrene/tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate/cyclohexyl (methyl) acrylate/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer etc., the tertiary butyl (methyl) acrylate/vinylbenzene/(methyl) glycidyl acrylate/cyclohexyl maleimide/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/tertiary butyl (methyl) acrylate/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) vinylformic acid-6,7-oxyethyl group heptyl ester/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/tertiary butyl (methyl) acrylate/maleic anhydride/(methyl) vinylformic acid-6,7-oxyethyl group heptyl ester/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/tertiary butyl (methyl) acrylate/phenyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer etc.
Wherein, optimization styrene/(methyl) vinylformic acid/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/(methyl) vinylformic acid/phenyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/(methyl) vinylformic acid/cyclohexyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate/phenyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/2,3-two-tetrahydropyrans-2-base oxygen base carbonyl-5-norbornylene/(methyl) vinylformic acid three ring [5.2.1.0 2,6] ten-8-base ester/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/1-(cyclohexyl oxygen base) ethyl (methyl) acrylate/cyclohexyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/tetrahydrochysene-2H-pyrans-2-base (methyl) acrylate/cyclohexyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, vinylbenzene/2,3-two-tetrahydropyrans-2-base oxygen base carbonyl-5-norbornylene/cyclohexyl maleimide/(methyl) glycidyl acrylate/(monomer a2-1 or monomer a2-2) multipolymer, tertiary butyl methacrylic ester/vinylbenzene/(methyl) glycidyl acrylate/cyclohexyl maleimide/(monomer a2-1 or monomer a2-2) multipolymer.
Addition polymer (B)
In addition, in the present invention, the Equivalent of the following addition polymer of making (B) as above-mentioned multipolymer (A) can be used, promptly under the condition that does not have acid catalyst, under the temperature about room temperature～100 ℃, addition vinyl ether compound or vinyl sulfide compound obtain addition polymer (B) in the anhydride group in the multipolymer (A) that unsaturated polybasic acid anhydride copolymerization forms.
As vinyl ether compound, for example, can enumerate methylvinylether, ethyl vinyl ether, isopropyl-ethylene base ether, n-propyl vinyl ether, n-butyl vinyl ether, IVE, tert-Butyl vinyl ether, the n-pentyl vinyl ether, 2-amyl group vinyl ether, 3-amyl group vinyl ether, the isopentyl vinyl ether, the neo-pentyl vinyl ether, 3,4-dihydro-2H-pyrans, 3,4-dihydro-2-methoxyl group-2H-pyrans etc., preferred ethyl vinyl ether, isopropyl-ethylene base ether, n-propyl vinyl ether, n-butyl vinyl ether, IVE, tert-Butyl vinyl ether, 3,4-dihydro-2H-pyrans etc.
As the vinyl sulfide compound, for example can enumerate the methyl ethylene thioether, the ethyl vinyl thioether, isopropyl-ethylene base thioether, the n-propyl vinyl thioether, normal-butyl vinyl thioether, the isobutyl vinyl ether-glycidyl thioether, tert butyl vinyl sulfide ether, n-pentyl vinyl thioether, 2-amyl group vinyl thioether, 3-amyl group vinyl thioether, isopentyl vinyl thioether, neo-pentyl vinyl thioether, 3,4-dihydro-2H-sulfo-pyrans, 3,4-dihydro-2-methoxyl group-2H-sulfo-pyrans etc., preferred ethyl vinyl thioether, isopropyl-ethylene base thioether, the n-propyl vinyl thioether, normal-butyl vinyl thioether, the isobutyl vinyl ether-glycidyl thioether, tert butyl vinyl sulfide ether, 3,4-dihydro-2H-sulfo-pyrans etc.
As the vinyl ether that adds or the ratio of vinyl thioether, be 1.8 times more than the mole 2.5 times below the mole with respect to anhydride group, be preferably above 2.4 times below the mole of 1.9 times of moles, be preferably above 2.4 times below the mole of 2.0 times of moles especially.If 1.8 times of moles of the quantity not sufficient of vinyl ether or vinyl thioether, then storage stability variation; In addition, if surpass 2.5 times of moles, the hardness step-down of the composition that then obtains.
Because this addition polymer (B) has the ethylidene ether structure or the thioacetal structure of carboxylic acid, therefore do not have the free carboxyl or both just had seldom yet, for example, the anhydride group in the above-mentioned multipolymer (A) is preferably 20 moles below the %.
As this addition polymer (B), for example, can enumerate the multipolymer that in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer 2 times of moles of addition obtain in the ethyl vinyl ether of anhydride group, the multipolymer that 2 times of moles of addition obtain in the n-propyl vinyl ether of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that 2 times of moles of addition obtain in the isopropyl-ethylene base ether of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that 2 times of moles of addition obtain in the n-butyl vinyl ether of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that 2 times of moles of addition obtain in the IVE of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that 2 times of moles of addition obtain in the tert-Butyl vinyl ether of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, 2 times of moles of addition are in 3 of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that the 4-dihydro-the 2H-pyrans obtains, the multipolymer that 2 times of moles of addition obtain in the ethyl vinyl ether of anhydride group in (methyl) glycidyl acrylate/itaconic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that 2 times of moles of addition obtain in the isopropyl-ethylene base ether of anhydride group in (methyl) glycidyl acrylate/itaconic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, 2 times of moles of addition are in 3 of anhydride group in (methyl) glycidyl acrylate/itaconic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that the 4-dihydro-the 2H-pyrans obtains, the multipolymer that 2 times of moles of addition obtain in the ethyl vinyl ether of anhydride group in (methyl) glycidyl acrylate/citraconic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that 2 times of moles of addition obtain in the isopropyl-ethylene base ether of anhydride group in (methyl) glycidyl acrylate/citraconic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, 2 times of moles of addition are in 3 of anhydride group in (methyl) glycidyl acrylate/citraconic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that the 4-dihydro-the 2H-pyrans obtains, in (methyl) glycidyl acrylate/suitable-1,2,3, the multipolymer that 2 times of moles of addition obtain in the ethyl vinyl ether of anhydride group in 4-tetrahydroxy Tetra hydro Phthalic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, in (methyl) glycidyl acrylate/suitable-1,2,3, the multipolymer that 2 times of moles of addition obtain in the isopropyl-ethylene base ether of anhydride group in 4-tetrahydroxy Tetra hydro Phthalic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, in (methyl) glycidyl acrylate/suitable-1,2,3,2 moles of additions are doubly to 3 of anhydride group in 4-tetrahydroxy Tetra hydro Phthalic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that the 4-dihydro-the 2H-pyrans obtains, or each vinyl ether in the above-mentioned multipolymer replaced with the multipolymer that corresponding thioether obtains respectively;
In the above-mentioned addition polymer (B), the more preferably multipolymer that 2 times of moles of addition obtain in the ethyl vinyl ether of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that 2 times of moles of addition obtain in the n-propyl vinyl ether of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that 2 times of moles of addition obtain in the isopropyl-ethylene base ether of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that 2 times of moles of addition obtain in the n-butyl vinyl ether of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, 2 moles of additions are doubly to 3 of anhydride group in (methyl) glycidyl acrylate/maleic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that the 4-dihydro-the 2H-pyrans obtains, the multipolymer that 2 times of moles of addition obtain in the ethyl vinyl ether of anhydride group in (methyl) glycidyl acrylate/itaconic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that 2 times of moles of addition obtain in the isopropyl-ethylene base ether of anhydride group in (methyl) glycidyl acrylate/itaconic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, 2 times of moles of addition are in 3 of anhydride group in (methyl) glycidyl acrylate/itaconic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that the 4-dihydro-the 2H-pyrans obtains, 2 times of moles of addition are in 3 of anhydride group in (methyl) glycidyl acrylate/citraconic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, the multipolymer that the 4-dihydro-the 2H-pyrans obtains, in (methyl) glycidyl acrylate/suitable-1,2,3, the multipolymer that 2 times of moles of addition obtain in the ethyl vinyl ether of anhydride group in 4-tetrahydroxy Tetra hydro Phthalic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer, in (methyl) glycidyl acrylate/suitable-1,2,3, multipolymer that 2 times of moles of addition obtain in the isopropyl-ethylene base ether of anhydride group in 4-tetrahydroxy Tetra hydro Phthalic anhydride/N-cyclohexyl maleimide/vinylbenzene/(monomer a2-1 or monomer a2-2) multipolymer etc.
The multipolymer that uses among the present invention (A) and (B) be preferably 2 * 10 by the weight-average molecular weight of polystyrene conversion (below be designated as " Mw ") 3～5 * 10 5, more preferably 5 * 10 3～1 * 10 5If Mw less than 2 * 10 3, the thermotolerance of the anti-halation film that then obtains, surface hardness may be not enough.And if surpass 5 * 10 5, then the flatness on film surface may be not enough.
＜other compositions 〉
Solidification compound of the present invention is essential composition with above-mentioned multipolymer (A) or addition polymer (B), can contain other compositions as required.As other compositions, for example can enumerate bonding agent, curing catalyst, tensio-active agent, UV light absorber etc.
Bonding agent
For the anti-halation film that improves formation and the adaptation of substrate, can add bonding agent.
As this bonding agent, preferred use for example contains carboxyl, methacryloyl, isocyanate group, the substituent functional silanes coupler of epoxy group(ing) isoreactivity.Particularly, can enumerate trimethoxysilyl phenylformic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrimewasxysilane, β-(3,4-oxyethyl group cyclohexyl) ethyl trimethoxy silane etc.
The usage ratio of bonding agent is preferably below 30 weight parts with respect to 100 weight part multipolymers (A) or addition polymer (B), and more preferably 0.1～25 weight part is preferably 1～20 weight part especially.If the usage ratio of bonding agent surpasses 100 weight parts, the thermotolerance of the anti-halation film that then obtains may become insufficient.
Curing catalyst
In order to promote the reaction of multipolymer (A) or addition polymer (B), can add curing catalyst.As this curing catalyst, for example, can enumerate compound with the heterocycle structure that contains secondary nitrogen-atoms or tertiary N atom.
As the concrete example of this compound, can enumerate the derivative of pyrroles, imidazoles, pyrazoles, pyridine, pyrazine, pyrimidine, indoles, indazole, benzoglyoxaline or isocyanic acid or above-mentioned substance etc.Wherein, preferred glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-heptadecyl imidazoles, 4-methyl-2-phenylimidazole, 1 benzyl 2 methyl imidazole, 2-ethyl-4-methyl isophthalic acid-(2 '-cyano ethyl) imidazoles, 2-ethyl-4-methyl isophthalic acid-[2 '-(3 "; 5 "-diamino three azine groups) ethyl] imdazole derivatives such as imidazoles, benzoglyoxaline, most preferably 2-ethyl-4-methylimidazole, 4-methyl-2-phenylimidazole, 1 benzyl 2 methyl imidazole etc.
Above-claimed cpd can be used as curing catalyst separately or with combination more than 2 kinds.
The usage quantity of curing catalyst is preferably below 5 weight parts with respect to 100 weight part multipolymers (A) or addition polymer (B), more preferably below 1 weight part.
Tensio-active agent
In order to improve the coating of composition, can add tensio-active agent.
As this tensio-active agent, for example, can enumerate fluorine class tensio-active agent, silicon class tensio-active agent, nonionic surfactant etc.
As above-mentioned nonionic surfactant, for example, can enumerate Voranol EP 2001, polyoxyethylene aryl ethers, polyoxyethylene dialkyl ether etc.
As its concrete example, for example,, can enumerate polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether etc. as Voranol EP 2001; As the polyoxyethylene aryl ethers, can enumerate polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether; As the polyoxyethylene dialkyl ether, can enumerate polyoxyethylene dilaurate, polyoxyethylene SUNSOFT Q-182S etc.
Commercially available product as this tensio-active agent, as fluorine class tensio-active agent, can enumerate system trade(brand)name: the BM-1000 of BM CHIMIE society, BM-1100, big Japanese ink chemical industry (strain) society system trade(brand)name: MEGAFACE F142D, same F172, same F173, same F183, Sumitomo 3M (strain) society system trade(brand)name: FRORARD FC-135, same FC-170C, same FC-430, same FC-431, FC4430, FC4432, Asahi Glass (strain) society system trade(brand)name: SARFRON S-112, same S-113, same S-131, same S-141, same S-145, same S-382, same SC-101, same SC-102, same SC-103, same SC-104, same SC-105, with SC-106 etc., system trade(brand)name: the FTX-216D of (strain) NEOS society, FTX-218, FTX-20D etc.
As silicon class tensio-active agent, can enumerate TORAYDOW CORNINGSILICONE (strain) society 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) society system trade(brand)name: KP341, new autumn fields changes into (strain) society system trade(brand)name: F-TOP EF301, same EF303, with EF352 etc.
As nonionic surfactant, can enumerate society of common prosperity society chemistry (strain) system trade(brand)name: (methyl) acrylic copolymer POLYFLOW No.57, same No.90, with No.95 etc.
Above-mentioned tensio-active agent may be used alone, or two or more kinds may be used in combination.
The usage ratio of tensio-active agent according to its kind constitute each composition kind of solidification compound or ratio etc. different and different, be preferably below 5 weight parts with respect to multipolymer (A) or addition polymer (B) 100 weight parts, more preferably 0.0001～2 weight part, the more preferably scope of 0.001～0.5 weight part.
The preparation of thermoset composition
Use under the solution state that thermoset composition of the present invention can form in being dissolved in appropriate solvent.For example, multipolymer (A) or addition polymer (B) and other compositions of adding are as required mixed to scale, can prepare the thermoset composition of solution state.
Thermoset composition of the present invention is preferably by with each composition uniform dissolution or be dispersed in the appropriate solvent and prepare.As the solvent that uses, can use can dissolve or each composition of dispersive composition but not with the solvent of each composition reaction.
As above-mentioned solvent, can use the solvent that uses when making above-mentioned multipolymer (A) and the solvent of enumerating.The usage quantity of solvent for the content that can make all solids composition in the thermoset composition of the present invention (total amounts of multipolymer (A) and other compositions of adding as required) be preferably 1～50 weight part, more preferably in the scope of 5～40 weight parts.
In addition, can and use high boiling solvent and above-mentioned solvent.Can and the high boiling solvent of usefulness, for example, can enumerate N-methylformamide, N, dinethylformamide, N-methyl formyl aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide, benzyl ethyl ether, hexyl ether, acetonyl-acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, acetate benzyl ester, ethyl benzoate, diethyl oxalate, ethyl maleate, gamma-butyrolactone, ethylene carbonate, Texacar PC, phenylacetic acid cellosolve etc.
As and usage quantity when the high boiling solvent, be preferably below 90 weight parts with respect to the total solvent amount, more preferably below 80 weight parts.
The solution of Zhi Bei thermoset composition for example uses that the aperture is 0.2～3.0 μ m, uses after being preferably the filtrations such as millipore filter about 0.2～0.5 μ m of aperture as described above.
The formation method of the anti-halation film of solid-state imager
Below, the method for using thermoset composition of the present invention to form the anti-halation film of solid-state imager of the present invention is described.
The anti-halation film formation method of solid-state imager of the present invention comprises following operation (1) and (2) at least.
(1) operation of filming of the above-mentioned thermoset composition of formation on substrate.
(2) this operation of filming of heat treated.
Describe successively below.
(1) operation of filming of the above-mentioned thermoset composition of formation on substrate
For the formation method of the anti-halation film of solid-state imager of the present invention, at first carry out on substrate, forming the operation of filming of thermoset composition of the present invention.By coating thermoset composition of the present invention on substrate, on substrate, form thus and film
Among the present invention,, for example, can use substrates such as glass, quartz, silicon, resin as substrate.As resin, for example, can enumerate resins such as the ring-opening polymerization polymer of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide and cyclic olefin and hydride thereof.
As coating process, for example, can adopt spraying method, rolling method, method of spin coating (spin-coating method), slit die coating method, rod to be coated with proper methods such as method, ink jet method, preferred especially spin-coating method, slit die coating method.
Then, remove and desolvate, film thereby on substrate, form.Among the present invention, needn't solvent be set separately and remove operation, in the operation, solvent can be nature evaporable state, also solvent can be removed operation and subsequently " operation that (2) heat treated is filmed " merging.In addition, also can adopt other solvent to remove operation.When implementing solvent in addition and removing operation, can under the temperature about room temperature～150 ℃, keep reasonable time to remove and desolvate.
At this moment, the thickness of filming is preferably 0.1～5 μ m, more preferably 0.3～3 μ m.In addition, this value should be understood to remove the thickness after desolvating.
(2) the heat treated operation of filming
Filming of forming on substrate thus implemented following heating treatment step, thereby can form the anti-halation film of solid-state imager of the present invention.
As Heating temperature, be preferably 150～250 ℃.Can carry out suitable setting heat-up time according to differences such as employed heating machine kinds, for example when using the electric heating metal plate as heating machine, heated about 3～15 minutes; When using dustless formula baking box, heated about 15～30 minutes.
This heating treatment step can be 1 step operation, also can make up above operation of 2 steps and carry out.
The anti-halation film of solid-state imager
The anti-halation film of the solid component of the present invention of Xing Chenging thus can be suppressed at effectively in the exposure process when forming chromatic color filter or microlens on this anti-halation film by diffusing that the bottom substrate produces, and have high heat resistance.Therefore, chromatic color filter or the microlens that is formed on the anti-halation film of solid-state imager of the present invention can be made desirable shape, size.
In addition, the thickness of the anti-halation film of solid-state imager is preferably 0.1～5 μ m, more preferably 0.3～3 μ m.
During this value less than 0.1 μ m, suppress the DeGrain that diffuses that the bottom substrate produces; And thickness is not increased to necessity more than the 5 μ m.
Solid-state imager
Solid-state imager of the present invention has above-mentioned anti-halation film.
Be formed on shape, size that chromatic color filter on this anti-halation film or microlens have regulation, therefore solid-state imager of the present invention is credible good.
Embodiment
Below, by synthesis example, embodiment, be described more specifically the present invention, but the present invention is not limited to following examples.
Synthesis example 1
In the flask that prolong and stirrer have been installed, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 6 weight parts and glycol ether ethyl-methyl ether 200 weight parts.Then, add vinylbenzene 13 weight parts, tetrahydrochysene-2H-pyrans-2-ylmethyl acrylate 20 weight parts, glycidyl methacrylate 40 weight parts and cyclohexyl maleimide 22 weight parts, monomer (a2-1) (big chemistry (strain) system, trade(brand)name " RUVA-93 ") 5 weight parts, after carrying out the nitrogen replacement, beginning is slowly stirred.Solution temperature is risen to 70 ℃, under this temperature, kept 5 hours, obtain containing the polymers soln of multipolymer (A-1).The solid component concentration of the polymers soln that obtains is 33.0 weight %.In addition, the weight-average molecular weight (Mw) of multipolymer (A-1) is 6000.
Synthesis example 2
In the flask that prolong and stirrer have been installed, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 3 weight parts and glycol ether ethyl-methyl ether 200 weight parts, then, add glycidyl methacrylate 45 weight parts, maleic anhydride 15 weight parts, N-cyclohexyl maleimide 15 weight parts and vinylbenzene 15 weight parts, monomer (a2-1) (big chemistry (strain) system, trade(brand)name " RUVA-93 ") 10 weight parts, after carrying out the nitrogen replacement, slowly stir, the reaction soln temperature is risen to 70 ℃, under this temperature, keep carrying out in 5 hours polymerization.Then, drip isopropyl-ethylene base ether 30 weight parts, continue to stir, reacted 2 hours, obtain containing the polymers soln of multipolymer (A-2).The solid component concentration of the polymers soln that obtains is 33.2 weight %.In addition, the weight-average molecular weight (Mw) of multipolymer (A-2) is 15000.
Synthesis example 3
In the flask that prolong and stirrer have been installed, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 8 weight parts and glycol ether ethyl-methyl ether 200 weight parts, then, add methyl propenoic acid glycidyl base methyl esters 45 weight parts, methacrylic acid 15 weight parts, N-cyclohexyl maleimide 15 weight parts and vinylbenzene 15 weight parts, monomer (a2-2) 10 weight parts, after carrying out the nitrogen replacement, slowly stir, the reaction soln temperature is risen to 70 ℃, under this temperature, kept 5 hours, carry out polymerization, obtain containing the polymers soln of multipolymer (A-3).The solid component concentration of the polymers soln that obtains is 33.2 weight %.In addition, the weight-average molecular weight (Mw) of multipolymer (A-3) is 4000.
Synthesis example 4
In the flask that prolong and stirrer have been installed, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 4 weight parts and glycol ether ethyl-methyl ether 200 weight parts, then, add methacrylic acid methyl glycidyl ester 45 weight parts, maleic anhydride 15 weight parts, N-cyclohexyl maleimide 12.5 weight parts and vinylbenzene 12.5 weight parts, monomer (a2-2) 15 weight parts, carry out slowly stirring after nitrogen replaces, the reaction soln temperature is risen to 70 ℃, under this temperature, kept 5 hours.Then, drip isopropyl-ethylene base ether 30 weight parts, continue to stir, reacted 2 hours, obtain containing the polymers soln of multipolymer (A-4).The solid component concentration of the polymers soln that obtains is 33.1 weight %.In addition, the weight-average molecular weight (Mw) of multipolymer (A-4) is 10000.
Compare synthesis example 1
In the flask that prolong and stirrer have been installed, put into 2,2 '-azo two (2, the 4-methyl pentane nitrile) 6 weight parts and glycol ether ethyl-methyl ether 200 weight parts, then, add glycidyl methacrylate 45 weight parts, vinylformic acid 15 weight parts, N-cyclohexyl maleimide 15 weight parts and vinylbenzene 25 weight parts, after carrying out the nitrogen replacement, slowly stir, the reaction soln temperature is risen to 70 ℃, under this temperature, kept 5 hours, carry out polymerization, obtain containing the polymers soln of multipolymer (R-1).The solid component concentration of the polymers soln that obtains is 33.2 weight %.In addition, the weight-average molecular weight (Mw) of multipolymer (R-1) is 6000.
Embodiment 1
To be equivalent to contain the amount of multipolymer (A-1) 100 weight parts (solids component) in the polymers soln of synthetic multipolymer (A-1) in the above-mentioned synthesis example 1, after the dilution of glycol ether ethyl-methyl ether 100 weight parts, interpolation is as γ-glycidoxypropyl Ethoxysilane 5 weight parts of bonding agent, and as SH28PA (the silicon class tensio-active agent of tensio-active agent, TORAYDOW CORNINGSILICONE (strain) system) 0.075 weight part obtains thermoset composition (S-1) through fully stirring.
The formation of anti-halation film
Use spinner that the thermoset composition (S-1) of above preparation is coated on the glass substrate, use the electric heating metal plate, carry out 6 minutes heat treated under 230 ℃, forming thickness is the anti-halation film of 1.6 μ m.
The evaluation of anti-halation film
(1) transmittance
Use 150-20 type dual beam spectrophotometer (Hitachi (strain) system), mensuration has the transmittance of the substrate of the anti-halation film that as above forms at 365nm and 400nm place.Then, use the electric heating metal plate,, similarly measure the transmittance at 365nm and 400nm place appending heating under 180 ℃, 230 ℃ and 250 ℃ after 20 minutes.Its value is shown in table 1.The transmittance at 365nm place is 70% when following, and anti-halation performance, promptly to be suppressed at the effect of the diffuse light that is produced by the bottom substrate in the exposure process when forming chromatic color filter or microlens good.In addition, the transmittance at 400nm place is 95% when above, and the transmittance of visible rays is good.
For the anti-halation film that forms among the embodiment 1, append before the heating and after appending heating and all have good anti-halation performance and visible rays transmittance.
(2) pattern of microlens material forms
Use spinner, behind the coating microlens material (JSR (strain) system, trade(brand)name " MFR-380 "), under 100 ℃, prebake is 90 seconds on the electric heating metal plate on the substrate with the anti-halation film that forms thus, and forming thickness is filming of 2.5 μ m.Via pattern mask with 4.0 μ m points, 2.0 μ m space patterns, obtain film on, (NA=0.50, λ=365nm) are with 2200J/m with NIKON (strain) system NSR1755i7A reduced projection exposure machine 2Exposure expose, with the tetramethylammonium hydroxide aqueous solution of 1 weight %, under 23 ℃, shake the dipping 1 minute, with its development.Then, carry out 30 second flow water rinses with ultrapure water under 23 ℃, drying forms pattern on the anti-halation film on the substrate.
Use scanning electron microscope (the tester Service of (strain) Hitachi system, model " S-4200 ") to observe the microlens pattern that forms herein.The shape of pattern is as shown in table 1.At this moment, if fully, then shown in the mode declaration pattern specification figure of Fig. 1 (a), the pattern side is formed on the plane the anti-halation performance of anti-halation film (suppressing the function that diffuses that the bottom substrate produces).But if anti-halation performance is insufficient, under the influence of the standing wave that halation produces, the pattern side forms the waveform shown in Fig. 1 (b) when then exposing.
In addition, the substrate that will have an anti-halation film that is formed as described above appending heating after 20 minutes under with 230 ℃ on the electric heating metal plate, is appending through this on anti-halation film of heat treated, with the above-mentioned microlens pattern that similarly forms again.Similarly use the electron microscope observation pattern form, observations is shown in table 1.
Embodiment 2～4
As multipolymer (A), interpolation is scaled the solution of the multipolymer that contains table 1 record of 100 weight parts to replace containing among the embodiment 1 solution of multipolymer (A-1) by solids component, SH28PA (silicon class tensio-active agent as tensio-active agent, TORAYDOWCORNINGSILICONE (strain) system) and as shown in table 1 respectively as the addition of the γ-glycidoxypropyl Ethoxysilane of bonding agent, in addition, implement similarly to Example 1 to handle.
In addition, the thickness of the anti-halation film that forms among each embodiment is as shown in table 1.
Evaluation result is as shown in table 1.
Comparative example 1
Interpolation is scaled the solution of synthetic multipolymer (R-1) in the above-mentioned relatively synthesis example 1 of containing of 100 weight parts to replace containing among the embodiment 1 solution of multipolymer (A-1) by solids component, in addition, interpolation is as TINUVIN234 (Ciba-Geigy (strain) system) 10 weight parts of radioactive rays absorption agent, in addition, implement similarly to Example 1 to handle.In addition, the thickness of the anti-halation film that herein forms is 1.6 μ m.
Evaluation result is as shown in table 1.
The anti-halation of the anti-halation film of comparative example 1 before appending heating is functional, and the anti-halation performance after appending heating significantly reduces, as can be known the thermotolerance deterioration.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 1
The multipolymer kind ????A-1 ????A-2 ????A-3 ????A-4 ???R-1
Bonding agent (weight part) ????5 ????5 ????5 ????6 ???5
Tensio-active agent (weight part) ????0.075 ????0.075 ????0.075 ????0.076 ???0.076
Other compositions Do not have Do not have Do not have Do not have ???TINUVIN234(10)
Antihalation thickness (μ m) ????1.62 ????0.5 ????0.7 ????1.6 ???1.6
Light penetration (%) ?365nm Before appending heating ????60 ????65 ????58 ????60 ???56
180 ℃ append heating after ????60 ????66 ????58 ????50 ???78
230 ℃ append heating after ????70 ????73 ????62 ????55 ???96
250 ℃ append heating after ????95 ????93 ????67 ????62 ???99
?400nm Before appending heating ????97 ????98 ????98 ????98 ???98
180 ℃ append heating after ????98 ????98 ????98 ????98 ???98
230 ℃ append heating after ????98 ????98 ????98 ????98 ???99
250 ℃ append heating after ????98 ????98 ????98 ????98 ???99
The microlens pattern form Before appending heating ????(a) ????(a) ????(a) ????(a) ???(a)
230 ℃ append heating after ????(a) ????(a) ????(a) ????(a) ???(b)
As mentioned above, according to the present invention, a kind of thermoset composition can be provided, use this thermoset composition to form the method for anti-halation film and anti-halation film that is formed by this method and the solid-state imager with this anti-halation film, this thermoset composition is suitable for forming in the exposure process in the time of can being suppressed at the chromatic color filter that forms on the solid-state imager or microlens effectively by diffusing of producing of bottom substrate, other visible rays transmittance height and has the anti-halation film of high heat resistance.
In exposure process when anti-halation film of the present invention forms chromatic color filter or microlens on this anti-halation film, can suppress diffusing of bottom substrate generation effectively, and have high heat resistance.Therefore, chromatic color filter or the microlens that is formed on the anti-halation film of solid-state imager of the present invention can have desirable shape, size.
And because solid-state imager of the present invention has above-mentioned anti-halation film, the chromatic color filter or the microlens that are formed on this anti-halation film have desirable shape, size, and therefore solid-state imager of the present invention has good credibility.

Claims (9)

1. thermoset composition, it is characterized by and contain the polymkeric substance with following structure, described structure is at least a kind of structure in the thioacetal ester structure of the tert-butyl ester structure of ketone acetal ester structure, carboxylic acid of (1) epoxy group(ing), (2) radioactive rays absorbing group and (3) the acetal ester structure that is selected from carboxyl, carboxylic acid, carboxylic acid and carboxylic acid.
2. thermoset composition as claimed in claim 1, wherein, polymkeric substance is the multipolymer that contains the monomer mixture of following compound, described compound for (a1) contain the unsaturated compound, (a2) radioactive rays absorptivity free-radical polymerised compound of epoxy group(ing) and (a3) (a3-1) polymerizable unsaturated carboxylic acids and/or the unsaturated polybasic acid anhydride of polymerizability or (a3-2) have the ketone acetal ester structure of the acetal ester structure that is selected from carboxylic acid, carboxylic acid and the tert-butyl ester structure of carboxylic acid in the polymerizable unsaturated compound of at least a kind of structure.
3. thermoset composition as claimed in claim 1, wherein, polymkeric substance is a kind of addition polymer, this addition polymer contains unsaturated compound that (a1) contain epoxy group(ing), (a2) radioactive rays absorptivity free-radical polymerised compound and (a3-1) on the anhydride group of the multipolymer (A) of the monomer mixture that contains the unsaturated polybasic acid anhydride of polymerizability, ethylidene ether structure with carboxylic acid that addition vinyl ether compound or vinyl sulfide compound obtain or thioacetal structure.
4. as claim 2 or 3 described thermoset compositions, wherein, (a2) radioactive rays absorptivity free-radical polymerised compound has the radioactive rays absorbent structure of following formula (1) expression,
Figure A2005100595640002C1
5. as claim 2 or 3 described thermoset compositions, wherein, (a2) radioactive rays absorptivity free-radical polymerised compound is for being selected from following formula (2). and (3) reach at least a kind in the compound of (4) representing respectively,
Figure A2005100595640002C2
Wherein, R 1And R 2Can be identical or different, expression hydrogen atom, carbonatoms are that 1～8 alkyl, carbonatoms are 1～8 alkoxyl group, cyano group, hydroxyl, halogen atom, carboxyl or alkoxy carbonyl, R 3The expression carbonatoms is 2～10 alkylidene group, R 4Expression hydrogen atom or methyl;
Wherein, R 4Definition same as described above, R 5Expression hydrogen atom or carbonatoms are 1～8 alkyl;
Wherein, R 3, R 4And R 5Definition same as described above, R 6The carbonatoms that expression can be replaced by hydroxyl is 1～4 alkylidene group.
6. as each described thermoset composition of claim 1～5, it is used to form the anti-halation film of solid-state imager.
7. the anti-halation film formation method of a solid-state imager is characterized by and comprises following operation (1) and operation (2) at least:
(1) operation of filming of the described thermoset composition of formation claim 6 on substrate;
(2) this operation of filming of heat treated.
8. anti-halation film that adopts the solid-state imager that the described method of claim 7 forms.
9. solid-state imager with the described anti-halation film of claim 8.
CNB2005100595643A 2004-03-29 2005-03-29 Thermosetting composition, solid photographic element anti-dizzy film and forming method thereof and solid photography element Expired - Fee Related CN100500768C (en)

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