JP5529370B2 - Photosensitive resin composition for black resist containing polyfunctional thiol compound, black matrix for color filter using the same, and color filter - Google Patents

Description

  The present invention is a photosensitive resin composition for a black resist containing a polyfunctional thiol compound having a plurality of mercapto groups in the same molecule, and has high sensitivity and a line width retention property of a fine line pattern during alkali development. The present invention relates to an excellent photosensitive resin composition for black resist.

  In recent years, photosensitive compositions have been used in all fields of color liquid crystal display devices (liquid crystal televisions, liquid crystal monitors, color liquid crystal mobile phones, etc.). A color liquid crystal display device includes a liquid crystal unit that controls the amount of light transmitted or reflected and a color filter as components. The manufacturing method of the color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic sheet, and then sequentially colors different colors of red, green and blue in stripes or mosaics. A pattern forming method is used. The pattern size varies depending on the use of the color filter and each color, but the red, green and blue pixels are thinned from 200 to 300 μm to 100 μm, and the black matrix is thinned from 20 μm to 10 μm. High dimensional accuracy is required for the functional resin composition.

  For pattern formation, photocuring action by reaction of photoreactive resin and photopolymerization initiator is used, and i-line (365 nm) which is one of the line spectrum of mercury lamp is used for pigment-dispersed negative color resist. It is mainly used as an exposure wavelength for curing. In the photosensitive resin composition of red, green, blue and black, since the coloring material itself absorbs ultraviolet rays, and the content ratio of the coloring material in the photosensitive resin composition has recently increased, A difference in crosslink density with respect to the film thickness direction occurs, and even if photocured sufficiently on the surface of the coating, it is difficult to photocure on the base surface, so a color filter with good development margin, fine line adhesion, and pattern edge shape is obtained. It is becoming difficult. In addition, a coloring material such as a pigment that is hardly soluble in a developing solution is deposited on the substrate as a development residue even in an unexposed area, which causes a decrease in backlight transmittance when sequentially forming different hues. As a result, the brightness of the color filter is lowered. Furthermore, since the adhesion between the coating film and the substrate is lowered, there is a possibility that the development margin and the fine wire adhesion are lowered. These problems are particularly noticeable in a light-shielding photosensitive resin composition that forms a black matrix due to the spectral characteristics of the photosensitive resin composition.

  Furthermore, in recent years, in order to increase the productivity efficiency and reduce the cost of the color filter production line, the mother glass substrate tends to increase in size year by year, and the production of the mother glass substrate exceeding 1 m square is also performed. Further, in order to reduce the tact time and increase the productivity efficiency, there is a demand for a photosensitive resin composition for color filters that can be photocured with a short exposure time, that is, with a low exposure amount, in the exposure process. In this way, a photosensitive resin composition for color filters, which contains a large amount of colorant and is difficult to be photocured, has a pattern with good pattern dimensional stability, pattern adhesion, and sharpness of the edge shape of the pattern at low exposure. It is required to obtain a wide development margin. For this purpose, it is essential to increase the sensitivity of the photosensitive resin composition.

  Under such circumstances, photosensitive resin compositions for color filters are required to be cured with lower energy, cured faster, and capable of forming a finer pattern. However, depending on the type of pigment used in the photosensitive resin composition for a color filter, sufficient energy for starting photopolymerization cannot be obtained. In particular, a black matrix requires a resin black matrix having a high optical density, and the content of a colorant such as carbon black in the photosensitive resin composition increases, resulting in a problem that sufficient sensitivity cannot be obtained. . Various measures have been made to avoid these problems by irradiating with larger energy, adding an excessive amount of photopolymerization initiator, and installing an oxygen barrier film, but in order to save energy and reduce production costs. However, it cannot be said that it is appropriate, and a composition having more excellent photosensitivity is demanded.

Heretofore, in order to improve the sensitivity of the photosensitive composition, it has been proposed to use a polyfunctional thiol compound having a plurality of mercapto groups in the same molecule. However, those using the polyfunctional thiol compounds proposed so far have the disadvantage of poor storage stability. For example, regarding the use of a polyfunctional thiol compound in a photopolymerizable composition for a color filter suitable for forming a black matrix, Patent Document 1 discloses a photopolymerizable composition containing a polyfunctional thiol. Under high light shielding using a functional thiol (CB concentration of 52% or more), there is a problem that preservation stability is sacrificed when such high sensitivity is achieved by such a polyfunctional thiol, and a sensitizer is not used. High sensitivity has not been achieved. Accordingly, development of a black matrix resist for a color filter and a photosensitive composition used therefor that are highly sensitive, excellent in developability, and excellent in storage stability under high light shielding is demanded.
JP 2004-325733 A

  Accordingly, an object of the present invention is to provide a photosensitive resin composition for black resist having high sensitivity, good pattern adhesion, and wide storage stability even in a high light-shielding region. Another object of the present invention is to provide a black matrix for a color filter and a color filter formed using the photosensitive resin composition for a color filter.

  As a result of studies conducted by the present inventors to solve the above-mentioned problems, according to the photosensitive resin composition containing a specific thiol compound in combination with a photopolymerization initiator, the above-mentioned problems are solved. As a result, the present invention has been completed.

、及び
（Ｅ）黒色有機顔料、混色有機顔料及び遮光材から選ばれる１種以上の着色材を必須成分として含むブラックレジスト用感光性樹脂組成物であって、
溶剤を除いた全固形分に対して（Ｄ）成分を０．８〜６．４重量％含有すると共に、（Ａ）成分と（Ｂ）成分との重量割合（Ａ／Ｂ）が６０／４０〜９０／１０であり、（Ａ）成分と（Ｂ）成分の合計１００重量部に対して（Ｃ）成分を２０〜４５重量部含有し、（Ａ）〜（Ｅ）成分における溶剤を除いた固形分に対して（Ｅ）成分を重量分率で５０〜６０重量％含有することを特徴とするブラックレジスト用感光性樹脂組成物である。 That is, the present invention includes the following components (A) to (E):
(A) an alkali-soluble resin comprising an acid anhydride polycondensate of an epoxy acrylate having a fluorene skeleton,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) an acyloxime compound photopolymerization initiator,
(D) Polyfunctional thiol compound represented by the following chemical formula (III)

And (E) a photosensitive resin composition for a black resist containing, as an essential component, one or more colorants selected from black organic pigments, mixed color organic pigments and light-shielding materials,
The component (D) is contained in an amount of 0.8 to 6.4% by weight based on the total solid content excluding the solvent, and the weight ratio (A / B) between the component (A) and the component (B) is 60/40. ~ 90/10, containing 20 to 45 parts by weight of component (C) with respect to a total of 100 parts by weight of component (A) and component (B), and removing the solvents in components (A) to (E). A photosensitive resin composition for a black resist, comprising 50 to 60% by weight of the component (E) based on the solid content.

  In the present invention, the photosensitive resin composition for black resist is applied on a transparent substrate and dried, and then (a) exposure with an ultraviolet exposure device, (b) development with an alkaline aqueous solution, and (c) thermal baking. It is the black matrix for color filters characterized by being obtained through each process.

  Furthermore, the present invention is a color filter having the above black matrix.

  Hereinafter, the photosensitive resin composition for black resist of the present invention (hereinafter sometimes simply referred to as “photosensitive resin composition” or “composition”) will be described in detail. The composition of the present invention contains the components (A) to (E) as essential components.

  A preferred example of the alkali-soluble resin of component (A) is not particularly limited as long as it is a polymer compound capable of alkali development and having a film-forming ability. Specific examples are as follows: Compounds. 1) Polyolefin polymers such as polyethylene, polypropylene and polyisobutylene, 2) Diene polymers such as polybutadiene and polyisoprene, 3) Polymers having a conjugated polyene structure such as polyacetylene polymers and polyphenylene polymers, 4) Polyvinyl chloride, Polystyrene, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid, polyacrylic ester, polyacrylamide, polyacrylonitrile, polyvinylphenol and other vinyl polymers, 5) polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyether ketone, poly Polyethers such as ether ether ketone and polyacetal, 6) phenolic resins such as novolac resin and resole resin, 7) polyethylene terephthalate Polyesters such as polyphenolphthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin, 8) Polyamides such as nylon-6, nylon 66, water-soluble nylon, polyphenyleneamide, 9) Polypeptides such as gelatin and casein, 10) In addition to epoxy resins such as novolac epoxy resins, bisphenol epoxy resins, novolac epoxy acrylates and acid anhydride-modified resins, and modified products thereof, 11) polyurethane, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole, polypyrrole, polyaniline , Polysulfide, polysulfone, celluloses and the like.

  Among these resins, those having a carboxyl group or a phenolic hydroxyl group in the resin side chain or main chain are preferred. In particular, a resin having a carboxyl group, for example, an acrylic acid (co) polymer, a styrene / maleic anhydride resin, an acid anhydride-modified resin of novolak epoxy acrylate, and the like are preferable because of high alkali developability. Furthermore, an acrylic resin is preferable because it is excellent in developability, and a copolymer thereof is more preferable from the viewpoint of performance and production control because various monomers can be selected and polymerized.

  More specifically, as the acrylic resin containing a carboxyl group, monomers having a carboxyl group such as (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, styrene, α-methylstyrene , Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) Acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonic acid ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol acrylamide, N, N dimethyl acrylamide N- methacryloyl morpholine, N, N- dimethylaminoethyl (meth) acrylate, N, include polymers and comonomer are copolymerized, such as N- dimethylaminoethyl acrylamide. Among them, an acrylic resin containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ether as a constituent monomer is preferable, and an acrylic resin containing (meth) acrylic acid and styrene is more preferable.

  Moreover, the acrylic resin which has these carboxyl groups can also add an ethylenic double bond to the resin side chain. Since the photocurability is increased by imparting a double bond to the resin side chain, the resolution and adhesion can be further improved, which is preferable.

  The preferable range of the weight average molecular weight measured by GPC of the acrylic resin having these carboxyl groups is 1000 to 100,000, and if it exceeds this range, the developability tends to decrease. Moreover, the range of preferable content of a carboxyl group is 5-200 in an acid value. When the acid value is 5 or less, it becomes insoluble in an alkaline developer, and when it exceeds 200, the sensitivity may be lowered.

  Among the alkali-soluble resins of component (A), a propylene glycol monomethyl ether acetate solution of an acid anhydride polycondensate of an epoxy acrylate having a fluorene skeleton is particularly preferably used.

  The photopolymerizable monomer having at least one ethylenically unsaturated bond as component (B) includes a monomer that undergoes radical polymerization by the action of a radical generated by the photopolymerization initiator and an action of an acid generated from the photopolymerization initiator. Any known monomer such as a monomer that undergoes addition condensation at the above can be used. Typical examples of the former include monomers having an ethylenic double bond, and more specifically, isobutyl acrylate, t-butyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, Benzyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, tetrahydrofuryl acrylate, phenoxy polyethylene glycol acrylate, methoxypropylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxyp Pyrhydrogen phthalate, 2-acryloyloxypropyl tetrahydro phthalate, morpholinoethyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate , Heptadecafluorododecyl acrylate, trimethylsiloxyethyl methacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate , Tripropylene glycol diacrylate, propylene glycol diac Rate, glycerin methacrylate acrylate, bisphenol A ethylene oxide adduct diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, tris Acryloyloxyethyl phosphate, dipentaerythritol hexaacrylate, modified acrylic acid of novolac epoxy, modified acrylic acid and anhydride of novolac epoxy, N-vinylpyrrolidone, N-vinylcaprolactam, acrylated isocyanurate, dipenta Erythritol monohydroxypentaacrylate, urethane acrylate And one or more of these compounds can be used.

  Among these monomers, acrylic monomers, especially acrylic monomers having 3 or more double bonds, have high photosensitivity, so trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Poly (meth) acrylates such as erythritol hexa (meth) acrylate are particularly preferred. These monomers are used alone or in combination.

  In the photosensitive resin composition of this invention, (B) component is used in 10-40 weight part with respect to a total of 100 weight part of (A) component and (B) component. When the component (B) is less than 10 parts by weight, the ratio of the photoreactive functional group in the photosensitive resin composition of the present invention is small and the photosensitivity is insufficient, so the formed pattern is the target. It is thinner than the line width and the pattern is easily lost. On the other hand, if it exceeds 40 parts by weight, the photosensitivity is too strong and the pattern line width becomes thicker than the pattern mask, and the line width faithful to the mask cannot be reproduced, or the developability is high. Since it deteriorates, there is a possibility that the problem that the pattern edge becomes jagged and does not become sharp will occur.

  As the photopolymerization initiator of component (C), at least one type of photopolymerization initiator is used. If it is a compound having an ethylenically unsaturated bond and capable of initiating addition polymerization, It is not particularly limited. Examples include acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, acyloxime compounds, and the like.

  Among them, examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- ( 2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino Examples include oligomers of -1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like.

  Examples of triazine compounds include 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroRmethyl) -1,3,5 -Triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis ( Trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (pipronyl) -4,6-bis And (trichloromethyl) -1,3,5-triazine.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxy). Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of imidazole compounds include 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer Etc.

  Examples of the acyloxime compound include 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptyl-1-one oxime-O-acetate, [9-Ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -adamantylmethane-1-oneoxime-O-benzoate, 1- [9-ethyl-6- (2- Methylbenzoyl) -9.H.-carbazol-3-yl] -adamantylmethane-1-oneoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazole- 3-yl] -tetrahydrofuranylmethane-1-oneoxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane- 1-Onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -thiophenylmethane-1-oneoxime-O-benzo 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -thiophenylmethane-1-oneoxime-O-acetate, 1- [9-ethyl- 6- (2-Methylbenzoyl) -9.H.-carbazol-3-yl] -morophonylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-Carbazol-3-yl] -morophonylmethane-1-oneoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazole-3 -Yl] -ethane-1-one oxime-O-bicycloheptanecarboxylate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime -O-tricyclodecane carbocichelate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-adamantane carbosichelate 1, 2-octanediene, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (product name: Irgacure OXE01, manufactured by Ciba Specialty Chemicals), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (product name Irgacure OXE02 manufactured by Ciba Specialty Chemicals).

  As the photopolymerization initiator of component (C), an active radical generator and an acid generator can also be used. Examples of active radical generators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like can also be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl, Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples thereof include benzoin tosylate. Among the compounds described above as active radical generators, there are compounds that generate an acid simultaneously with active radicals. For example, triazine compounds are also used as acid generators.

  (C) The photoinitiator of a component can be used individually or in mixture of 2 or more types. In addition, it does not act as a photopolymerization initiator or a sensitizer described later by itself, but increases the ability of the photopolymerization initiator and the sensitizer by using in combination with the photopolymerization initiator of the component (C). The resulting compound can also be added separately. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Ethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( And ethylmethylamino) benzophenone.

  Among the photopolymerization initiators of the component (C), triazine photopolymerization initiators and acyloxime photopolymerization initiators into which a trichloromethyl group has been introduced are particularly preferably used.

  (C) The usage-amount of the photoinitiator of a component is 5-50 weight part on the basis of a total of 100 weight part of each component of (A) and (B) which is a resin component, Preferably it is 20-45 weight. Part. When the blending ratio of the component (C) is less than 5 parts by weight, the speed of photopolymerization becomes slow and the sensitivity is lowered. On the other hand, when it exceeds 50 parts by weight, the sensitivity is too strong and the pattern line The width becomes thicker than the pattern mask, and there is a possibility that a line width that is faithful to the mask cannot be reproduced, or that the pattern edge does not become jagged and sharp.

  In addition to the photopolymerization initiator (C), a sensitizer can also be blended. As the sensitizer, a general sensitizer used for a normal photopolymerization initiator can be used. In order to increase sensitivity, a benzophenone compound, a thioxanthone compound, and a ketocoumarin compound are preferable. One or more compounds selected from the group consisting of:

  Specifically, benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis Benzophenone compounds such as (diethylamino) benzophenone, thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone , 3-acetylcoumarin, 3-acetyl-7-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-benzoyl-7-methoxycoumarin, 3,3′-camo Ketocoumarin compounds such as rubonyl biscoumarin, 3,3′-carbonyl bis (7-methoxycoumarin), 3,3′-carbonylbis (5,7-dimethoxycoumarin) can be used. You may use these 1 type or in mixture of 2 or more types.

  The blending ratio of the sensitizer to the photopolymerization initiator is not particularly limited, but is preferably 5 to 40% by mass, more preferably 10 to 30% by mass in the total amount of the photopolymerization initiator and the sensitizer. If the blending ratio of these sensitizers is too small, the sensitivity is lowered. If the blending ratio is too large, light transmission to the bottom of the resist is inhibited, so that the resist cross-sectional shape becomes an inverted trapezoid and the resolution accuracy is lowered.

（式中、Ｒ¹はアルキル基、Ｒ²は炭素以外の原子を含んでもよいｎ価の脂肪族基、Ｒ⁰はＨではないアルキル基、ｎは２〜４を表す。） The polyfunctional thiol compound as the component (D) of the present invention has two or more mercapto (SH) groups in the same molecule and can be represented by the following general formula (I).

(In the formula, R ¹ is an alkyl group, R ² is an n-valent aliphatic group that may contain atoms other than carbon, R ⁰ is an alkyl group that is not H, and n represents 2 to 4).

If the polyfunctional thiol compound represented by the general formula (I) is specifically exemplified, 1,4-bis (3-mercaptobutyryloxy) butane [formula (II)] having the following structural formula: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H5H) -trione [formula (III)] and pentaerythritol tetrakis (3 -Mercaptobutyrate) [formula (IV)] and the like. These polyfunctional thiols can be used alone or in combination.

  About the compounding quantity of the polyfunctional thiol in the photosensitive resin composition, it is 0.3-8.9 weight% with respect to the total solid content except a solvent, More preferably, it is the range of 0.8-6.4 weight%. It is desirable to add in. When the blending ratio deviates from the above range, the stability, odor, sensitivity, resolution, developability, adhesion, etc. of the photosensitive resin composition are deteriorated. Low addition amount decreases sensitivity and adhesion, and high addition amount reduces the ratio of initiator to thiol compound, slows the rate of photopolymerization, decreases sensitivity, is hard to solidify, and resist solubility. Also decreases.

  Although it is uncertain about the cause of such deterioration, it is related to the fact that the polyfunctional thiol radically or ionically adds to the carbon-carbon double bond, that is, the compound can also take monomeric behavior. It seems to do. That is, since the function as a monomer is lower than the desirable acrylic monomer of the above-mentioned component (B), since the function of the acrylic monomer is inhibited when the addition amount is the same as that of the normal monomer, the initiator as described above. It is considered that a high function is exhibited by adding a small amount.

  The colorant of component (E) is at least one selected from black organic pigments, mixed color organic pigments, or light-shielding materials that are light-shielding pigments. Examples of black organic pigments include perylene black and cyanine black. Examples of mixed color organic pigments include those obtained by mixing at least two pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like into a pseudo black color. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. Two or more colorants can be appropriately selected and used, but carbon black is particularly preferable in terms of good light shielding properties, surface smoothness, dispersion stability, and compatibility with the resin.

  Moreover, the coloring material of (E) component can be used with a dispersing agent if desired. Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Specific examples of this surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether.

  Furthermore, it is preferable to mix | blend the addition amount of the coloring material of (E) component so that it may become 50%-60% of solid content density | concentration except the solvent of the photosensitive resin composition. When this concentration is low, the light shielding property is not sufficient, and in order to obtain a desired contrast, it is necessary to increase the film thickness, so that it is difficult to obtain the surface smoothness of the black matrix. On the other hand, if the addition amount is too large, the dispersion stability of the photosensitive resin composition for black matrix containing the component (E) is lowered, and the content of the photosensitive resin that is the original binder is also reduced. There is a possibility that an undesired problem that an unsatisfactory development characteristic cannot be obtained may occur.

  (E) About the mixture ratio of a component, 40-70 weight% by weight fraction with respect to solid content except the solvent which consists of (A)-(E) component in the composition of this invention, Preferably it is 50-. It is good that it is 60 weight%. If it is less than 40% by weight, the light shielding properties are not sufficient. If it exceeds 70% by weight, the content of the photosensitive resin as the original binder decreases, so that an undesired problem that the developing characteristics are impaired and the film forming ability is impaired.

  In the photosensitive resin composition for a black resist of the present invention, it is preferable to use a solvent in addition to the components (A) to (E). Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone. Ketones such as toluene, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol Glycol ethers such as ethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Examples include acetic acid esters such as ethyl ether acetate, and the like, and these can be dissolved and mixed to form a uniform solution-like composition.

  In addition, the photosensitive resin composition for a black resist of the present invention is blended with additives such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, and an antifoaming agent as necessary. be able to. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of antifoaming agents and leveling agents include silicon-based, fluorine-based, and acrylic compounds.

  The photosensitive resin composition for a black resist of the present invention contains the components (A) to (E) or these and a solvent as main components. It is desirable that the components (A) to (E) are contained in a total of 80% by weight, preferably 90% by weight or more, in the solid content excluding the solvent (the solid content includes a monomer that becomes a solid content after curing). Although the quantity of a solvent changes with target viscosity, it is desirable to contain in the range of 70 to 90 weight% in the photosensitive resin composition.

  The photosensitive resin composition for black resist of the present invention is excellent as a resin composition for forming a black matrix. Further, the black matrix of the present invention is formed, for example, by a photolithography method using the photosensitive resin composition for black resist of the present invention. As the manufacturing process, first, the photosensitive resin composition is applied to the substrate surface as a solution, and then the solvent is dried (prebaked), and then a photomask is applied on the coating thus obtained, Examples include a method in which an exposed portion is cured by irradiating ultraviolet rays, a pattern is formed by performing development in which an unexposed portion is eluted using an alkaline aqueous solution, and post baking (thermal baking) is performed as post-drying.

  As a substrate on which the solution of the composition of the present invention is applied, a glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) on which a transparent electrode such as ITO or gold is deposited or patterned is used. It is done.

  As a method for applying the solution of the composition onto the substrate, any method such as a method using a roller coater machine, a land coater machine, or a spinner machine can be adopted in addition to a known solution dipping method and spray method. . After applying to a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). Pre-baking can be performed by heating with an oven, a hot plate or the like, and the heating temperature and heating time in the pre-baking are appropriately selected according to the solvent to be used, for example, at a temperature of 80 to 120 ° C. for 1 to 10 minutes. You can do it.

  The exposure performed after pre-baking is performed by an exposure machine, and only the resist corresponding to the pattern is exposed by exposing through a photomask. The exposure machine and the exposure irradiation conditions are appropriately selected. For example, exposure is performed using a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a deep ultraviolet lamp, and a short wavelength (313 nm, 334 nm or less) is cut. The resin composition for black resist in the coating film is photocured.

  The alkali development after the exposure is performed for the purpose of removing the resist in the unexposed portion, and a desired pattern is formed by this development. Examples of the developer suitable for the alkali development include, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. Particularly, sodium carbonate, potassium carbonate, carbonate It is preferable to develop at a temperature of 20 to 30 ° C. using a weakly alkaline aqueous solution containing 0.05 to 3% by weight of a carbonate such as lithium, and a fine image using a commercially available developing machine or ultrasonic cleaner. Can be formed precisely.

  After the development as described above, a heat treatment (post-bake) is performed at a temperature of 180 to 250 ° C. and a condition of 20 to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned black matrix and the substrate. This is performed by heating with an oven, a hot plate or the like, as in the pre-baking. The patterned black matrix of the present invention is formed through each step by the above photolithography method.

  As described above, the composition of the present invention is suitable for forming a fine pattern by an operation such as exposure and alkali development. However, even if the pattern is formed by conventional screen printing, the same light shielding property and adhesion A black matrix having excellent properties, electrical insulation, heat resistance, and chemical resistance can be obtained.

  The photosensitive resin composition for a black resist of the present invention can be suitably used as a coating material, and in particular, a color filter ink used for a liquid crystal display device or a photographing element, and a light-shielding film formed thereby. It is useful as a color filter, a black matrix for liquid crystal projection, and the like.

  The color filter of the present invention can be obtained by a known method such as coating, developing and curing each color ink in a predetermined pattern for each color on the substrate provided with the black matrix, and further forming a protective film. it can.

  The photosensitive resin composition for a black resist of the present invention is, for example, a light-shielding photosensitive resin composition that has a large content of colorant and is difficult to be photocured. A pattern having good characteristics and sharpness of the edge shape of the pattern can be obtained with a wide development margin, and a good light-shielding film is provided.

  Hereinafter, although an embodiment of the present invention is described concretely based on an example and a comparative example, the present invention is not limited to these. Here, the raw materials and abbreviations used in the production of the black matrices of Examples and Comparative Examples are as follows.

(A): propylene glycol monomethyl ether acetate solution of an acid anhydride polycondensate of epoxy acrylate having a fluorene skeleton (resin solid content concentration = 56.1% by weight, manufactured by Nippon Steel Chemical Co., Ltd., trade name V259ME)

(B): Trimethylolpropane triacrylate (Sartomer Japan, trade name SR351S)

(C) -1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (Ciba Specialty Chemicals) Product name Irgacure OXE02)
(C) -2: 4- (4′-ethylbiphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine (trade name STR-2BP manufactured by Respe Chemical Co., Ltd.)

(D) -1: 1,4-bis (3-mercaptobutyryloxy) butane, (trade name: Karenz MT BD1 (hereinafter abbreviated as BD1, manufactured by Showa Denko KK)
(D) -2: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H, 5H) -trione, (trade name: Karenz MT NR1 (hereinafter abbreviated as NR1: manufactured by Showa Denko KK)
(D) -3: pentaerythritol tetrakis (3-mercaptobutyrate), (trade name: Karenz MT PE1 (hereinafter abbreviated as PE1: manufactured by Showa Denko KK)
(D) -4: Pentaerythritol tetrakisthiopropionate (trade name: PETP (manufactured by Sakai Chemical Co., Ltd.)

(E): Propylene glycol monomethyl ether acetate dispersion having a carbon black concentration of 20% by weight and a polymer dispersant concentration of 4.0% by weight (solid content: 24.0%)

(F) -1: Propylene glycol monomethyl ether acetate (F) -2: Cyclohexanone

The said compounding component was mix | blended in the ratio of Table 1 , and Example 9, Reference Examples 1-8, 10 and Comparative Examples 1-6 (resist) were prepared. In Table 1, the number in () of the component (A) represents the solid content, and the number in () of the component (E) represents the solid content occupied by the pigment (colorant).

Each photosensitive resin composition for black resist according to Example 9, Reference Examples 1 to 8, 10 and Comparative Examples 1 to 6 obtained by uniformly mixing the components described in Table 1 was used with a spin coater. The film was applied on a 125 mm × 125 mm glass substrate (Corning 1737) so that the film thickness after post-baking was 1.1 μm, and prebaked at 80 ° C. for 2 minutes. After that, the exposure gap was adjusted to 80 μm, and a negative photomask with line / space = 10 μm / 10 μm and 20 μm / 20 μm was put on the dried coating film, and an ultrahigh pressure mercury lamp with i-line illuminance of 30 mW / cm ² A photocuring reaction of the photosensitive portion was performed by irradiating with 80 mj / cm ² of ultraviolet rays.

Next, this exposed coated plate (photosensitive resin composition coated on a glass substrate and photocured photosensitive portion) was showered at 23 ° C. in 0.04% potassium hydroxide aqueous solution at 1 kgf / cm ² . After developing for 30 seconds from the development time (break time = BT) at which the pattern begins to appear at the development pressure, spray with 5 kgf / cm ² of spray water to remove the unexposed areas of the paint film and form the pixel pattern on the glass substrate. Formed. Then, the line | wire width and saturation exposure amount with respect to each mask width | variety after heat-baking for 30 minutes at 230 degreeC using a hot air dryer were measured. The results are shown in Table 2.

Moreover, each photosensitive resin composition for black resists according to Example 9, Reference Examples 1 to 8, 10 and Comparative Examples 1 to 6 is stored at room temperature (22 ° C. to 24 ° C.) for 2 weeks and 1 month. The resulting film was exposed and developed in the same manner using a negative photomask of line / space = 20 μm / 20 μm, and the line width / line width reduction ratio and surface appearance were evaluated. The results are shown in Table 3.

Evaluation items and methods of the black matrix obtained in Examples and Comparative Examples are as follows, and the results are shown in Tables 2 and 3.
Line width: Development was further performed for +30 seconds from the development time (break time) at which the pattern began to appear, and then measurement was performed using a side length microscope (Nikon Corporation, trade name: XD-20).
OD: Appearance of optical density surface when converted to a thickness of 1 μm: Surface roughness (Ra) of the coating film after development and baking is less than 150 mm ○ <good>, 150 mm or more x <bad> evaluated.

When Comparative Examples 5 and 6 to which a primary thiol compound was added were compared with Examples 9 (and Reference Examples 1 to 8 and 10) to which a secondary thiol compound was added, those to which a primary thiol compound was added had a aging period of 2 The weekly breakage time +30 seconds from the break time showed a significant thinning of the 20 μm pattern, and no 20 μm pattern remained in one month. However, the addition of the secondary thiol compound can leave a good line width even with a aging period of 2 weeks or 1 month. Further, in Comparative Example 3 in which the thiol compound is excessively added to the initiator, the temporal stability is poor, and in Comparative Example 4 in which the thiol compound is excessively added, pattern formation itself is difficult.

Further, as is apparent from the results of Tables 2 and 3, according to the results of Example 9 (and Reference Examples 1 to 8, 10) compared with Comparative Examples 1 and 2 in which no thiol compound was added, It was clarified that the addition of a functional thiol compound shows a significant improvement in line width.

Claims (3)

The following components (A) to (E),
(A) an alkali-soluble resin comprising an acid anhydride polycondensate of an epoxy acrylate having a fluorene skeleton,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) an acyloxime compound photopolymerization initiator,
(D) Polyfunctional thiol compound represented by the following chemical formula (III)

And (E) a photosensitive resin composition for a black resist containing, as an essential component, one or more colorants selected from black organic pigments, mixed color organic pigments and light-shielding materials,
The component (D) is contained in an amount of 0.8 to 6.4% by weight based on the total solid content excluding the solvent, and the weight ratio (A / B) between the component (A) and the component (B) is 60/40. ~ 90/10, containing 20 to 45 parts by weight of component (C) with respect to a total of 100 parts by weight of component (A) and component (B), and removing the solvents in components (A) to (E). A photosensitive resin composition for a black resist, comprising 50 to 60% by weight of the component (E) based on the solid content. The photosensitive resin composition for black resist according to claim 1 is applied on a transparent substrate and dried, and then each of (a) exposure with an ultraviolet exposure device, (b) development with an alkaline aqueous solution, and (c) thermal baking is performed. A black matrix for a color filter, which is obtained through a process. A color filter comprising the black matrix according to claim 2 .