JP2008233605A - Photosensitive resist composition for color filter and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resist composition for a color filter excellent in sensitivity, adhesion in development and pattern profile, to enhance the reliability of a color filter and a liquid crystal display device, to boost yield and to reduce the cost of manufacturing. <P>SOLUTION: The photosensitive resist composition comprises at least a pigment (A), an acrylic polymer (B), a monomer (C), a photopolymerization initiator (D) and a solvent (E), wherein the monomer (C) comprises a bisfluorene-based tetrafunctional acrylate compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resist composition for a color filter, and particularly to a photosensitive color resist composition for a color filter suitable for a resin black matrix and a color filter for a liquid crystal display device.

At present, a color filter used for a liquid crystal display device or the like is mainly a photosensitive color resist composition in which a pigment is dispersed. As an example of producing a color filter using a photosensitive color resist composition, a photosensitive color resist comprising acrylic polymer, acrylic polyfunctional monomer or oligomer, photopolymerization initiator, solvent, and pigment as constituent components, A photosensitive color resist in which titanium black or carbon black is dispersed is applied onto a substrate, dried, pattern exposure, developed with an alkaline aqueous solution, post-baked to form a resin black matrix, and then a colored photosensitive material in which each RGB pigment is dispersed. The color resist is implemented by repeating the same process as described above. Usually, an alkaline aqueous solution is used as a developer from the viewpoint of the working environment, and therefore the composition is designed to be soluble in the alkaline aqueous solution. In particular, a resin black matrix which is difficult to be photocured easily swells during development, and therefore a cardo compound having high hydrophobicity is applied and the composition is designed to be soluble in an alkaline aqueous solution. As compositions soluble in an alkaline aqueous solution, compositions obtained by modifying a cardo compound so as to have a carboxyl group are known in Patent Documents 1 to 3, Patent Document 6, Patent Document 7, and Patent Document 8. Patent Documents 4 and 9 disclose compositions soluble in an alkaline aqueous solution comprising a cardo compound having a specific structure having the same structure as that of the present invention and an acrylic polymer having a carboxyl group. Recent technological innovations have made it possible to increase the screen size of liquid crystal display devices, and liquid crystal display devices for television have been rapidly spreading, and high-contrast image quality is required. For this purpose, the light-shielding property of the resin black matrix is required to be 5 or more in terms of OD value, and as thin as possible is required to ensure the flatness of the color filter. In order to obtain a high OD value with a thin film, it is necessary to select a light shielding agent, optimize the primary particle size, and increase the content of the light shielding agent. However, when the content of the light-shielding agent is increased, there are various problems in sensitivity, adhesion during development (pattern peeling), pattern shape, and the like. In response to this problem, the compositions described in Patent Literature 1 to Patent Literature 3, Patent Literature 6, Patent Literature 7, and Patent Literature 8 use a cardo compound as a compound having a large molecular weight such as benzophenone tetracarboxylic anhydride. By modifying (in order to make it soluble in an aqueous alkali solution), the mass of the cardo compound (g / eq unsaturated group) per unsaturated bond (acrylic group, etc.) increases, resulting in a decrease in sensitivity. There's a problem. On the other hand, the compositions described in Patent Document 4 and Patent Document 9 have relatively good sensitivity, but have problems in adhesion (pattern peeling) and pattern shape (overhang shape) during development. This is presumed to be due to the slightly low hydrophobic performance. As a result of sincerity studies, the present inventor dimerized a cardo compound having an unsaturated bond (acrylic group) and a hydroxyl group via an aromatic ester group to form a tetrafunctional compound, and both sensitivity and hydrophobic performance were improved. It has been found that the adhesion and pattern shape during development are improved. In addition, although it is not this use in patent document 10, the curable resin composition using the high molecular weight polyfunctional ester acrylate connected with the aliphatic ester group is described. Since this product does not have a hydrophilic group (hydroxyl group, carboxyl group), there is a problem that even when combined with the above acrylic polymer having a carboxyl group, the developability in an alkaline aqueous solution is poor.
JP 05-70528 A Japanese Patent Laid-Open No. 08-278629 Japanese Patent Laid-Open No. 08-278630 Japanese Patent Application Laid-Open No. 08-327813 Japanese Patent Laid-Open No. 08-241339 JP 09-327813 A JP 2002-265840 A JP 2006-133338 A JP 2006-259716 A Japanese Patent No. 3621533

  The present invention was devised in view of the circumstances as described above. The object of the present invention is to provide a photosensitive resist composition for a color filter excellent in sensitivity, adhesion during development, and pattern shape. Another object is to increase the reliability of the liquid crystal display device, improve the yield, and reduce the manufacturing cost.

In order to solve the above problems, the present invention has the following configuration.
(1) In a photosensitive resist composition containing at least a pigment (A), an acrylic polymer (B), a monomer (C), a photopolymerization initiator (D), and a solvent (E), the monomer (C) is The photosensitive resist composition for color filters containing the compound (C1) represented by the following general formula (1).

(In formula (1), R ¹ represents a hydrogen atom or a methyl group. Both carboxyl groups of the phthalic acid moiety are meta or para oriented.

  In formula (1), X is a group represented by the following general formula (2).

In formula (2), R ³ and R ⁴ represent a hydrogen atom or a methyl group. R ² is an optionally substituted alkylene group having 1 to 10 carbon atoms, an alkenylene group or alkynylene group having 2 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, and an arylene group having 6 to 14 carbon atoms. Alternatively, it represents an aralkylene group having 7 to 20 carbon atoms. m is an integer of 0-5.

  In formula (1), Y1 and Y2 are a hydrogen atom or a group represented by the following general formula (3).

In formula (3), Z represents a divalent aliphatic group or an aromatic group. )
(2) Any compound of bisphenoxyethanol fluorene group, bisphenoxyfluorene group, biscresol fluorene group, wherein X is represented by the following general formulas (4) to (6)

The photosensitive resist composition for color filters as described in item (1), wherein
(3) In the compound represented by the general formula (1), R ¹ is a hydrogen atom, and one or both of Y1 and Y2 have a group represented by the general formula (3). The photosensitive resist composition for a color filter as described in (2), which is characterized.
(4) The photosensitive resist composition for a color filter as described in (3), wherein X is a bisphenoxyethanol type fluorene group represented by the general formula (4).
(5) The acrylic polymer (B) has a carboxyl group and has an ethylenically unsaturated group in a side chain, for the color filter according to any one of (1) to (4) Photosensitive resist composition.
(6) The photosensitive resist composition for a color filter according to any one of (1) to (5), wherein the pigment (A) is titanium black and / or carbon black.
(7) A color filter using the photosensitive resist composition for a color filter according to any one of (1) to (6).

  When the photosensitive resist composition for color filters according to the present invention is used, a color filter having excellent adhesion and pattern shape can be produced, and the reliability of the liquid crystal display device is improved, yield is improved and production cost is greatly reduced. it can.

Hereinafter, the components of the present invention will be described.
In the present invention, an organic pigment or an inorganic pigment is used as the pigment (A).
Examples of such pigments include compounds classified as pigments in Color Index CI (published by The Society of Dyers and Colorists). As a specific example, as a red pigment, Color Index No. Pigment Red (hereinafter abbreviated as PR) 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 254, and the like, and Color Index No. Pigment Green (hereinafter abbreviated as PG) 7, 36, and the like, as a blue pigment, Color Index No. Pigment Blue (hereinafter abbreviated as PB) 15: 3, 15: 4, 15: 6, 21, 22, 60, 64, and the like, and Color Index No. Pigment Yellow (hereinafter abbreviated as PY) 20, 24, 86, 93, 109, 110, 117, 129, 138, 139, 150, 153, and the like, and Color Index No. Pigment Violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 37, 40, 50, and the like are Color Index No. Pigment Orange (hereinafter abbreviated as PO) 36, 43, 51, 55, 59, 61 and the like are Color Index No. Pigment black 7 or the like, carbon black, titanium black, metal oxide, or the like can be used. These pigments may be used alone or in combination of two or more. In addition, pigment derivatives such as sulfonic acids of pigments obtained by sulfonated organic pigments, specifically sulfonic acids of copper phthalocyanine, sulfonic acids of diketopyrrolopyrrole (PR254), sulfonic acids of quinophthalone (PY138), etc. When added in an amount of 0.5 to 10% by mass, preferably 2 to 7% by mass, there is an effect of stabilizing the dispersion of the pigment, which is preferable. Furthermore, it is preferable to use a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, or a polyallylamine polymer dispersant in combination at the time of dispersion because of the effect of stabilizing the dispersion. Since these polymer dispersants do not have photosensitivity, there is a concern that the photosensitivity of the target color resist may be deteriorated if added in a large amount. Therefore, an appropriate addition amount considering dispersion stability and photosensitivity is required. Is desirable. In particular, when the polyethyleneimine polymer dispersant or polyallylamine polymer dispersant is added to the pigment in an amount of 5 to 50 (mass%), more preferably 7 to 40 (mass%), the photosensitive performance is not deteriorated. Furthermore, there is an effect of highly stabilizing dispersion, which is even more preferable. These polymer dispersants are “Solspers (registered trademark)” 24000 (or 24000SC, 32500, 33500) manufactured by Abyssia Co., Ltd. and “Disperbyk (registered trademark)” 163 (or 167) manufactured by BYK Chemi Japan Co., Ltd. Ajinomoto Fine Techno Co., Ltd. "Ajisper (registered trademark)" PB821 (or PB822, etc.) is commercially available.

  The composition of the present invention is particularly effective when a green pixel or a resin black matrix (hereinafter referred to as resin BM) having a high pigment ratio in the coating film is formed. As the pigment for the resin BM, a mixture of a red pigment and a blue and / or violet pigment, titanium black, and carbon black are preferable. In particular, when titanium black is contained when forming the resin BM, a material having excellent photosensitive characteristics such as sensitivity at the time of exposure can be obtained as compared with the case of carbon black alone. Among the titanium blacks, those having a high titanium nitride content are more preferable because a high optical density (OD) can be obtained with the same film thickness. Carbon black preferably has a primary particle diameter of 20 to 80 nm and its surface is oxidized with hypochlorous acid, nitric acid, hydrogen peroxide, or the like. Particularly, those having an acid value of 1 to 30 (mg KOH / g: according to JISK-5407), more preferably 5 to 25 (mg KOH / g: according to JIS K-5407) are preferable in terms of adhesion and solubility during development. preferable.

  In the present invention, the acrylic polymer (B) is an essential component, but an acrylic polymer having a carboxyl group is preferably used as the acrylic polymer (B). As the acrylic polymer having a carboxyl group, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid and the like.

  These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, methacryl Isopropyl acrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the terminals, Alternatively, polystyrene having a methacryloyl group, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and the like can be mentioned. Not shall. In particular, a quaternary copolymer selected from methacrylic acid and / or acrylic acid and methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and styrene has an average molecular weight Mw of 2,000 to 100,000, an acid value of 50 to 150 (mgKOH / g: According to JIS K-5407) is preferred from the viewpoint of solubility in an alkaline developer. Outside this range, the dissolution rate in the alkaline developer is undesirably lowered or increased too much.

  Further, when an acrylic polymer having an ethylenically unsaturated group in the side chain is used, the sensitivity at the time of exposure and development is improved, so that it can be preferably used. As an ethylenically unsaturated group, an acryl group and a methacryl group are preferable. Such an acrylic polymer can be subjected to an addition reaction of an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to a carboxyl group of an acrylic (co) polymer having a carboxyl group.

  Specific examples of the acrylic polymer having an ethylenically unsaturated group in the side chain include a copolymer described in Japanese Patent No. 3120476, JP-A-8-262221, or a commercially available acrylic polymer. Examples thereof include a curable resin “Cyclomer (registered trademark) P” (Daicel Chemical Industries, Ltd.). In particular, an acrylic polymer having an ethylenically unsaturated group in the side chain and an average molecular weight (Mw) of 2,000 to 100,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier, and using a standard polystyrene calibration curve) The polymer having an acid value of 50 to 150 (mg KOH / g: according to JIS K-5407) is most preferable from the viewpoints of photosensitive properties, solubility in an ester solvent, and solubility in an alkali developer.

The monomer (C1) in the present invention will be described. Monomer (C1) in the present invention
Is a compound represented by the following general formula (1).

(In formula (1), R ¹ represents a hydrogen atom or a methyl group. Both carboxyl groups of the phthalic acid moiety are meta or para oriented.

  In formula (1), X is a group represented by the following general formula (2).

In formula (2), R ³ and R ⁴ represent a hydrogen atom or a methyl group. R ² is an optionally substituted alkylene group having 1 to 10 carbon atoms, an alkenylene group or alkynylene group having 2 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, and an arylene group having 6 to 14 carbon atoms. Alternatively, it represents an aralkylene group having 7 to 20 carbon atoms. m is an integer of 0-5.

  In formula (1), Y1 and Y2 are a hydrogen atom or a group represented by the following general formula (3).

In formula (3), Z represents a divalent aliphatic group or an aromatic group. )
Here, the R ² group preferably has 1 to 5 carbon atoms, and more preferably a methylene group, an ethylene group, or a propylene group. m is an integer of 0 to 5, preferably 0 to 3, and more preferably 0 to 1. Further, X represents a bisphenoxyethanol fluorene group (corresponding to m = 1), a bisphenoxyfluorene group (corresponding to m = 0), a biscresol fluorene group (m) represented by the following general formulas (4) to (6). = Equivalent to 0) is preferable from the viewpoint of easy availability of raw materials.

Furthermore, in the compound represented by the general formula (1), it is preferable that R ¹ is a hydrogen atom because the reactivity is higher than the methyl group and the sensitivity is improved. In addition, a compound in which one or both of Y1 and Y2 have a group represented by the general formula (3) improves solubility in an alkaline developer, shortens the development time, and also improves adhesion during development. Since it improves, it is preferable. Therefore, a compound in which R ¹ is a hydrogen atom and one or both of Y 1 and Y 2 have a group represented by the general formula (3) is particularly preferable.

  Among the bisphenoxyethanol fluorene group, bisphenoxyfluorene group, and biscresol fluorene group, the compound represented by the following general formula (4) has good solubility in an alkaline developer, shortening the development time, and high sensitivity can be obtained. So most preferred.

In the above formula (3), Z represents a divalent aliphatic group or aromatic group. Examples of the aliphatic or aromatic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, anhydrous Examples thereof include phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and endomethylenetetrahydrophthalic anhydride. These may be used alone, or two or more of them may be used as a mixture. Those having a relatively small molecular weight and good heat resistance, particularly phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferably used.
In the above formula (1), as the phthalic acid position, the position of meta and / or para is good in sensitivity and solubility in an alkali developer, and the position of meta is particularly preferable.

In the present invention, the monomer (C1) can be synthesized through 2 to 3 steps as follows.
First, in the first stage, a bisfluorene-type acrylate compound having a hydroxyl group as represented by the following general formula (7) is synthesized.

(In Formula (7), R < ¹ >, X is the same as the above. N represents the real number of 0-3.).

  Here, n represents a real number of 0 to 3, and preferable n is 0 to 2. n can be determined by analysis by GPC (measured by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve). In order to synthesize this, bisphenol fluorene type epoxy compounds such as bisphenoxyethanol fluorange glycidyl ether, bisphenoxy fluorange glycidyl ether, biscresol fluorange glycidyl ether, a compound having a carboxyl group and an ethylenically unsaturated double bond, for example, (Meth) acrylic acid, acryloyloxyethyl succinic acid, and acryloyloxyethyl phthalic acid are reacted at a ratio of 97 to 103 equivalents, preferably 100 equivalents, with respect to 100 equivalents of the epoxy compound. Acrylic acid is particularly preferable from the viewpoint of photosensitivity.

  In this reaction, if necessary, polymerization inhibitors such as 2,6-di-t-butyl-4-hydroxytoluene, hydroquinone monomethyl ether, t-butylcatechol, phenothiazine, triethylbenzylammonium chloride, triethylamine, benzyldimethyl Methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether added to adjust the viscosity as necessary, such as amine, methyltriethylammonium chloride, triphenylphosphine, tetraethylammonium bromide Acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-butyl acetate DOO, adding a solvent having a boiling point above the reaction temperature, such as γ- butyrolactone. Here, the amount of the polymerization inhibitor used is 1% by weight or less, preferably less than 0.5% by weight, based on the reaction raw material mixture, and the amount of the catalyst used is 0.001-5 relative to the reaction raw material mixture. The amount of the solvent used is 5 to 500% by weight, preferably 5 to 200% by weight, based on the reaction raw material mixture. The reaction conditions of the epoxy compound and (meth) acrylic acid are that the reaction temperature is usually 90 to 130 ° C., preferably 95 to 125 ° C., and the reaction time is usually 3 to 24 hours, preferably 4 to 18 hours. In order to suppress the polymerization of the double bond part, it is usually carried out while blowing dry air into the reaction system. The bisfluorene-type acrylate compound having a hydroxyl group thus obtained has an acid value (mgKOH / g, JIS K-5407) of 2 mgKOH / g or less in terms of solid content excluding the solvent.

  In the next second stage, the hydroxyl group of the bisfluorene-type acrylate compound having a hydroxyl group obtained above is esterified with isophthalic acid dichloride or terephthalic acid dichloride to form a dimer. Alternatively, isophthalic acid or terephthalic acid is esterified in the presence of a dehydrating agent such as dicyclohexylcarbodiimide to form a dimer. In this case, isophthalic acid or terephthalic acid may have a substituent such as a halogen or an alkyl group having 1 to 6 carbon atoms. Isophthalic acid or terephthalic acid is reacted at a ratio of 47 to 53 equivalents, preferably 50 equivalents, relative to the hydroxyl equivalent of the bisfluorene acrylate compound having a hydroxyl group. As the solvent at this time, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-butyl acetate, γ-butyrolactone, etc. can be used. . The reaction conditions may be 5 to 40 ° C. for 3 to 24 hours. When acid chloride is used, a tertiary amine such as triethylamine or benzyldimethylamine is usually used as a dehydrochlorination agent. The resulting hydrochloride or dicyclohexylurea is removed by filtration. Thus, the bisfluorene type | system | group tetrafunctional acrylate compound which has a hydroxyl group in which Y1 and Y2 of this invention correspond to a hydrogen atom is obtained. Here, the bisfluorene acrylate compound having a hydroxyl group to be reacted may have the same structure or a different structure.

In the next third stage, the bisfluorene-based tetrafunctional acrylate compound having a hydroxyl group is reacted with the aliphatic or aromatic acid anhydride. The reaction with an anhydride uses an anhydride in a range of 0.45 to 1.00 equivalent to 1 equivalent of a hydroxyl group, a reaction temperature of 60 to 150 ° C., preferably 70 to 125 ° C., and a reaction time of 1 to 12 hours. Preferably, the reaction is performed for 2 to 8 hours. By reacting the acid anhydride, a carboxyl group is formed, the solubility in the developer is improved, and the adhesion during development is improved. In this reaction, if necessary, the same catalyst as used in the first step such as benzyldimethylamine, tetraethylammonium bromide, triethylbenzylammonium chloride and the like can be used. In this way, the bisfluorene-based tetrafunctional acrylate compound having a carboxyl group of the present invention is obtained.

  As other components, polyfunctional or monofunctional acrylic monomers or oligomers can be used. Examples of the polyfunctional monomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylate, anhydrous Propylene phthalate (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, as described in JP-A-8-278630 Full orange acrylate oligomer, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, 2,2-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] methane, bis [4- (3- Acryloxy-2-hydroxypropoxy) phenyl] sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] ether, 4,4′-bis [4- (3-acryloxy-2-hydroxypropoxy) Phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (3-acryloxy-2-hydroxypropoxy) phenyl] Fluorene, 9,9-bis [3-chloro-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, biscresol full orange acrylate, biscresol full Examples include orange methacrylate.

Further, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate, tris-[(mercaptopropionyloxy) -ethyl]
-A polyfunctional thiol compound such as isocyanurate (abbreviation: TEMPIC) or a bisfluorene thiol compound described in JP-A-2006-259716. These can be used alone or in combination.

  By selecting and combining these polyfunctional monomers and oligomers, it is possible to control the sensitivity and processability characteristics of the resist. In particular, in order to increase sensitivity, it is desirable to use a compound having 3 or more, more preferably 5 or more functional groups, and dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable. In addition, when using a pigment that absorbs ultraviolet rays effective for photocrosslinking, such as resin BM, in addition to dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, the polyfunctional thiol compound, In particular, it is more preferable to use an isocyanurate-based polyfunctional thiol compound or a polyfunctional thiol compound having a fluorene ring having a large amount of aromatic rings and high hydrophobicity in the molecule because the pattern can be controlled to a desired shape at the time of development.

  The photosensitive color resist composition for a color filter of the present invention contains a photopolymerization initiator (D) as an essential component. The photopolymerization initiator (D) is not particularly limited, and is a benzophenone compound, acetophenone compound, oxanthone compound, imidazole compound, benzothiazole compound, benzoxazole compound, oxime ester compound, carbazole compound, triazine. Known compounds such as inorganic photopolymerization initiators such as phosphinic compounds, phosphorus compounds, and titanates can be used. For example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl Ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, Ciba Specialty Chemical “Irgacure (registered trademark)” 369, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, Ciba Specialty Chemical Co., Ltd. CGI-113 2- [4-Methylbenzyl] -2-dimethylamino-1- (4-morpholinophenyl) -butanone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methyl Anthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4 , 5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” OXE01 1,2-octanedione, 1- [4 -(Phenylthio) -2- (O-benzoyl) Oxime)], an etanone that is CGI-242 of Ciba Specialty Chemicals Co., Ltd., 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O- Acetyloxime), 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine, “Adeka (registered trademark) optomer” N which is a carbazole-based compound manufactured by Asahi Denka Kogyo Co., Ltd. -1818, N-1919 and the like. These photopolymerization initiators can be used in combination of two or more. In particular, N, N′-tetraethyl-4,4′-diaminobenzophenone and Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” 369 or Ciba Specialty Chemical Co., Ltd. “Irgacure (registered trademark)” 379 and Asahi Denka Kogyo Co., Ltd. “Adeka (registered trademark) Optmer” N-1818, N-1919 or Ciba Specialty Chemical Co., Ltd. CGI It is preferable to use a combination of three types of carbazole-based compounds such as -242 because a photosensitive resist composition for color filters having high sensitivity and good pattern shape can be obtained. Although there is no limitation in particular as the addition amount of a photoinitiator, Preferably it is 2-50 mass% with respect to a color resist total solid, More preferably, it is 10-50 mass%.

  In the photosensitive resist composition for a color filter of the present invention, the resin component (total of polymer, monomer or oligomer and polymer dispersant) and the colorant containing at least the pigment are usually 20% by mass to 95% of the resin component. It is used by mixing in the range of mass%, preferably 25 mass% to 80 mass%. If the amount of the resin component is too small, the adhesion of the colored film to the substrate becomes poor. Conversely, if the amount of the pigment is too small, the color density or the optical density per unit thickness (OD value / μm) in the case of the resin BM. It becomes low and becomes a problem.

The solvent (F) of the photosensitive resist composition for color filters of this invention is demonstrated. As the solvent (F) used in the present invention, esters, aliphatic alcohols, ketones and the like can be used.
Specific esters include benzyl acetate (boiling point 214 ° C.), ethyl benzoate (boiling point 213 ° C.), γ-butyrolactone (boiling point 204 ° C.), methyl benzoate (boiling point 200 ° C.), diethyl malonate (boiling point 199 ° C.), 2-ethylhexyl acetate (bp 199 ° C.), 2-butoxyethyl acetate (bp 192 ° C.), 3-methoxy-3-methyl-butyl acetate (bp 188 ° C.), diethyl oxalate (bp 185 ° C.), ethyl acetoacetate ( Boiling point 181 ° C.), cyclohexyl acetate (bp 174 ° C.), 3-methoxy-butyl acetate (bp 173 ° C.), methyl acetoacetate (bp 172 ° C.), ethyl-3-ethoxypropionate (boiling point 170 ° C.), 2- Ethyl butyl acetate (boiling point 162 ° C), isopentyl propio (Boiling point 160 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), pentyl acetate (boiling point 150 ° C), propylene glycol monomethyl ether acetate (boiling point 146 ° C) ) And the like, but is not limited thereto.

  Among these solvents, acetate-type or propionate-type solvents include 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and 3-methoxy-butyl. Particularly preferred are acetate and propylene glycol monomethyl ether acetate.

  In addition to the above solvents, propylene glycol monomethyl ether (boiling point 120 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), propylene glycol tertiary butyl ether (boiling point 153 ° C.), dipropylene glycol monomethyl ether (boiling point 188 ° C.) Aliphatic ethers such as propylene glycol derivatives such as, aliphatic esters other than those described above, for example, ethyl acetate (boiling point 77 ° C.), butyl acetate (boiling point 126 ° C.), isopentyl acetate (boiling point 142 ° C.), or butanol ( Boiling point 118 ° C.), aliphatic alcohols such as 3-methyl-2-butanol (boiling point 112 ° C.), 3-methyl-3-methoxybutanol (boiling point 174 ° C.), ketones such as cyclopentanone and cyclohexanone, xylene ( Boiling point 14 ° C.), ethyl benzene (boiling point 136 ° C.), solvent naphtha (petroleum fraction: it is also possible to use a solvent such as boiling point 165 to 178 ° C.).

  Furthermore, since application by a die coating apparatus has become mainstream with the increase in the size of the substrate, it is preferable to use a mixed solvent of two or more components in order to achieve appropriate volatility and drying properties. When the boiling points of all the solvents constituting the mixed solvent are 150 ° C. or less, film thickness uniformity cannot be obtained, the film thickness of the coating end part is increased, and the pigment is applied to the base part for discharging the coating liquid from the slit. Aggregates are formed, causing many problems that streaks occur in the coating film. On the other hand, when the mixed solvent contains a large amount of solvent having a boiling point of 200 ° C. or higher, the surface of the coating film becomes sticky and sticking occurs. Therefore, a mixed solvent containing 30 to 75% by mass of a solvent having a boiling point of 150 ° C. or higher and 200 ° C. is desirable. In particular, as one component of the solvent constituting the mixed solvent, an ester solvent selected from 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and 3-methoxy-butyl acetate Is preferably a mixed solvent containing 30 to 75% by mass.

  The color resist for a color filter of the present invention can contain a silane coupling agent as an adhesion improver. Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane and the like are preferable because of easy availability of raw materials. Since the silane coupling agent has an effect of improving adhesion in a small amount, it is not necessary to add a large amount thereof, and is preferably 0.2 to 20% by mass, more preferably 0.8%, based on the total solid content of the color resist. 5 to 5% by mass.

  A surfactant can also be added to the photosensitive resist composition for color filters used in the present invention for the purpose of coating properties, smoothness of the colored coating and Benard cell. The addition amount of the surfactant is usually 0.001 to 10% by mass, preferably 0.01 to 1% by mass of the pigment. If the amount added is too small, the coating properties, smoothness of the colored coating and Benard cell are not effective, and if too large, the physical properties of the coating film may be poor. Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, and silicones based on polydimethylsiloxane Surfactants, fluorosurfactants and the like can be mentioned. In the present invention, the surfactant is not limited to these, and one or more surfactants can be used.

  The photosensitive resist composition for a color filter of the present invention has a solid content (a ratio of all components other than the solvent contained in the color resist to the color resist solution) of 5 to 30% by mass, more preferably 7 to 25% by mass. A range is desirable. When the viscosity is measured at 25 ° C., the molecular weight of the polymer and / or the type and amount of the solvent are adjusted so that the viscosity is in the range of 1 to 40 (mPa · s), preferably in the range of 2 to 20 (mPa · s). Thus, the coating film can be made more uniform, which is desirable.

  The example of the manufacturing method of the color filter by the die coating apparatus using the photosensitive resist composition for color filters of this invention is demonstrated. As the substrate, a transparent substrate such as soda glass, non-alkali glass, or quartz glass is usually used, but is not particularly limited thereto. Examples of the die coating apparatus include a single wafer coating apparatus disclosed in Japanese Patent No. 3139358 and Japanese Patent No. 3139359. With this apparatus, the color resist can be applied onto the substrate by discharging the photosensitive resist composition (coating solution) for the color filter of the present invention from the die and moving the substrate. In this case, since a large number of substrates are applied in a single sheet, when the apparatus is operated for a long time, agglomerates of pigments are formed in the base part for discharging the coating liquid from the slits, which may cause a coating defect and reduce the yield. In this case, by providing a step of wiping the base, which is a discharge port of the apparatus, with a solvent containing 40% by mass or more of the ester solvent having a boiling point of 150 ° C. or higher with respect to the total solvent, the coating defects are eliminated and the base is removed. The rate is improved. After the color resist is applied on the substrate as described above, the solvent is removed by air drying, reduced pressure drying, heat drying or the like to form a color resist coating film. In particular, after providing a vacuum drying step, additional heating and drying in an oven or a hot plate eliminates coating defects caused by convection and improves the yield. The drying under reduced pressure is preferably performed in the range of normal temperature to 100 ° C., 5 seconds to 10 minutes, and a degree of vacuum of 500 to 10 (Pa), and more preferably a pressure of 150 to 50 (Pa). Heat drying is preferably performed using an oven, a hot plate or the like at a temperature of 50 to 120 ° C. for 10 seconds to 30 minutes.

  Subsequently, a mask is placed on the coating and irradiated with ultraviolet rays using an exposure apparatus. Next, development is performed with an alkaline developer. It is preferable to use an alkaline developer added with 0.1 to 5% of a surfactant such as a nonionic surfactant because a better pattern can be obtained. Although it does not specifically limit as an alkaline substance used for an alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n- Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcohol amines, pyrrole, piperidine, 1,8-dia Bicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, organic alkalis such as cyclic amines such as morpholine.

  The concentration of the alkaline substance is 0.01% by mass to 50% by mass. Preferably it is 0.02 mass% to 10 mass%, More preferably, it is 0.02 to 1 mass%. In the case where the developer is an alkaline aqueous solution, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, N-methyl-2-pyrrolidone may be appropriately added to the developer.

Among these developers, an aqueous developer of an alkaline aqueous solution is preferable from the viewpoint of working environment and waste developer treatment.
The development method uses an immersion method, a spray method, a paddle method or the like, but is not particularly limited. After development, a washing process with pure water or the like is added.

  The resulting color resist coating film pattern is then subjected to heat treatment (post-baking) to become a colored filter patterned. The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at 150 to 300 ° C, preferably 180 to 250 ° C, continuously or stepwise for 0.25 to 5 hours. Done.

A color filter for a liquid crystal display device can be prepared by forming a colored pattern successively and repeatedly using the photosensitive resist composition for black, red, green and blue color filters of the present invention by the above method. Here, the patterning order of each color resist is not limited.
Further, after the manufacturing method of the present invention, a protective film and a transparent conductive film can be formed on the pixel.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Evaluation method and criteria)
1. Sensitivity PHOTORESIST STEP TABLET (Resolution Test Mask) manufactured by Optoline, Inc., exposure time (200 to 800 mJ / cm ^{2 at} 365 nm) after exposure with varying exposure amount, time for unexposed portion to dissolve (abbreviated as dissolution time) The surface of the patterned coating film formed on the substrate is observed, and the minimum exposure amount that is not rough and glossy is the sensitivity (mJ / cm ² ). It was.

2. Adhesion at the time of development Using PHOTORESIST STEP TABLET (resolution test mask) manufactured by Optoline Co., Ltd., exposure was performed at an exposure amount 1.5 times the sensitivity obtained in item 1, and the unexposed part was Development is performed 1.5 times the dissolution time (abbreviated as dissolution time), the presence or absence of peeling of the fine line pattern formed on the substrate is examined, and the minimum dimension (μm) remaining without peeling is determined at the time of development. Adhesiveness was assumed.

3. Pattern shape The fine line pattern formed on the substrate is observed with a microscope, and the edges of the pattern are observed with a microscope. A pattern with poor linearity is indicated by x.

4). OD value Y (viscosity corrected transmittance (%)) was measured with a microspectrophotometer (MCPD2000) manufactured by Otsuka Electronics Co., Ltd., and optical density OD = log (100 / Y) was calculated.

Reference example 1
Synthesis of acrylic polymer (P1) having carboxyl group and methacryl group in side chain According to the method described in Example 1 of Japanese Patent No. 3120476, methyl methacrylate / methacrylic acid / styrene copolymer (weight composition ratio 33/34 / 33), after adding 33 parts by weight of glycidyl methacrylate, reprecipitation with purified water, filtration and drying, an average molecular weight (Mw) of 9,000, an acid value of 70 (mgKOH / g: according to JISK-5407) An acrylic polymer (P1) powder having the following characteristics was obtained.

Reference example 2
Synthesis of Bisphenoxyethanol Fluorene Type Acrylate (A-1) Having Hydroxyl Group In a 500 ml separable flask, 296 g of bisphenoxyethanol fluorenediglycidyl ether (epoxy equivalent 296 g / eq), 3.4 g of dimethylbenzylamine, p-methoxyphenol 0. 34 g and 72.06 g (1 mol) of acrylic acid were charged, the temperature was raised while blowing air at a flow rate of 20 ml / min, and the reaction was performed at a temperature of 110 to 120 ° C. During this time, the acid value was measured, and heating and stirring were continued until it became less than 2.0 mgKOH / g. It took 10 hours for the acid value to reach the target. Thus, bisphenoxyethanol fluorene acrylate (A-1) was obtained.

Reference example 3
Synthesis of bisphenoxyfluorene-type acrylate (A-2) having a hydroxyl group Reference Example 2 except that 231 g (epoxy equivalent 231 g / eq) of bisphenoxyfluorene glycidyl ether was used instead of bisphenoxyethanol fluorenediglycidyl ether in Reference Example 2. In the same manner as above, bisphenoxyfluorene acrylate (A-2) was obtained.

Reference example 4
Synthesis of biscresol fluorene acrylate (A-3) having a hydroxyl group Reference Example 2 except that 258 g of biscresol fluorenediglycidyl ether (epoxy equivalent 258 g / eq) was used instead of bisphenoxyethanol fluorenediglycidyl ether in Reference Example 2. In the same manner as above, biscresol fluorene acrylate (A-3) was obtained.

Synthesis example 1
Synthesis of bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1a) 184.0 g of bisphenoxyethanol fluorene acrylate (A-1) synthesized in Reference Example 2 (hydroxyl equivalent 368 g / eq, calculated value) in a 500 ml separable flask ), 100 g of 3-methoxy-3-methyl-butyl acetate and 26.6 g (0.263 mol) of triethylamine were dissolved and cooled in a water bath, and then 25.38 g of isophthal chloride (0.125 mol: half of the hydroxyl group was acid) (Amount required for reacting with chloride) in 100 g of 3-methoxy-3-methyl-butyl acetate was added dropwise. The mixture was further reacted at room temperature for 2 hours, diluted with 267.3 g of 3-methoxy-3-methyl-butyl acetate, and the resulting white precipitate was filtered under pressure to obtain 30 of bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1a). A mass% solution was obtained.

Synthesis example 2
Synthesis of bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1b) 184.0 g of bisphenoxyethanol fluorene acrylate (A-1) synthesized in Reference Example 2 (hydroxyl equivalent 368 g / eq, calculated value) in a 500 ml separable flask ), 100 g of 3-methoxy-3-methyl-butyl acetate and 26.6 g of triethylamine are charged and dissolved in a water bath, and then 25.38 g of terephthal chloride (0.125 mol: half of the hydroxyl group is reacted with the acid chloride). The amount required for 3) was dissolved dropwise in 100 g of 3-methoxy-3-methyl-butyl acetate. The mixture was further reacted at room temperature for 2 hours, diluted with 267.3 g of 3-methoxy-3-methyl-butyl acetate to 30% by mass, and the resulting white precipitate was filtered under pressure to give a bisphenoxyethanol fluorene-based tetrafunctional acrylate compound. A solution of (B-1b) was obtained.

Synthesis example 3
Synthesis of Bisphenol Fluorene-Based Tetrafunctional Acrylate Compound (B-2) In Synthesis Example 1, 151.5 g of bisphenoxyfluorene acrylate (A-2) instead of bisphenoxyethanol fluorene acrylate (A-1) (hydroxyl equivalent: 303 g / eq) , Calculated value) was used in the same manner as in Synthesis Example 1 except that 30% by mass of a bisphenolfluorene-based tetrafunctional acrylate compound (B-2) was obtained.

Synthesis example 4
Synthesis of biscresol fluorene-based tetrafunctional acrylate compound (B-3) In Reference Example 5, instead of bisphenoxyethanol fluorene acrylate (A-1), 165.0 g of biscresol fluorene acrylate (A-3) (hydroxyl equivalent: 330 g / eq, calculated value) was used in the same manner as in Synthesis Example 1 to obtain a 30% by mass solution of a biscresol fluorene-based tetrafunctional acrylate compound (B-3).

Synthesis example 5
Synthesis of acid-modified bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (C-1a) 667.6 g of a 30% by mass solution of bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1a) synthesized by the same method as Synthesis Example 1 (solid) 200.3 g), 19.02 g of 1,2,3,6-tetrahydrophthalic anhydride (0.125 mol: amount necessary to react all hydroxyl groups with acid anhydride) and 3-methoxy-3- After 44.4 g of methyl-butyl acetate was added at room temperature, the mixture was reacted at 100 ° C. for 3 hours, and an acid-modified bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (C-1a) having an acid value of 59 mg KOH / g (according to JIS K-5407) was obtained. A 30% by weight solution was obtained.

Synthesis Example 6
Synthesis of acid-modified bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (C-1b) 667.6 g (solid) 200.3 g), 19.02 g of 1,2,3,6-tetrahydrophthalic anhydride (0.125 mol: the amount necessary to react all hydroxyl groups with the acid anhydride) and 3-methoxy-3- After 44.4 g of methyl-butyl acetate was added at room temperature, the mixture was reacted at 100 ° C. for 3 hours. A 30% by weight solution was obtained.

Synthesis example 7
Synthesis of acid-modified bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (C-1c) 667.6 g of a 30% by mass solution of bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1a) synthesized by the same method as Synthesis Example 1 (solid) 200.3 g), 9.51 g of 1,2,3,6-tetrahydrophthalic anhydride (0.0625 mol: the amount required to react half of the hydroxyl group with the acid anhydride) and 3-methoxy-3- After 22.3 g of methyl-butyl acetate was added at room temperature, the mixture was allowed to react at 100 ° C. for 3 hours. A 30% by weight solution was obtained.

Synthesis Example 8
Synthesis of acid-modified bisphenol fluorene-based tetrafunctional acrylate compound (C-2) 559.3 g of a 30% by mass solution of bisphenol fluorene-based tetrafunctional acrylate compound (B-2) synthesized in the same manner as in Synthesis Example 3 (solid content: 167 8 g), 19.02 g of 1,2,3,6-tetrahydrophthalic anhydride (0.125 mol: the amount necessary to react all hydroxyl groups with acid anhydride) and 3-methoxy-3-methyl- After adding 44.4 g of butyl acetate at room temperature, the mixture was reacted at 100 ° C. for 3 hours, and a 30% by mass solution of acid-modified bisphenolfluorene-based tetrafunctional acrylate compound (C-2) having an acid value of 66 mgKOH / g (according to JISK-5407). Got.

Synthesis Example 9
Synthesis of acid-modified biscresol fluorene-based tetrafunctional acrylate compound (C-3) 604.2 g of a 30% by mass solution of biscresol fluorene-based tetrafunctional acrylate compound (B-3) synthesized in the same manner as in Synthesis Example 4 (solid 181.27 g), 19.02 g of 1,2,3,6-tetrahydrophthalic anhydride (0.125 mol: the amount necessary to react all hydroxyl groups with the acid anhydride) and 3-methoxy-3- After adding 44.4 g of methyl-butyl acetate at room temperature, the mixture was reacted at 100 ° C. for 3 hours, and 30 of acid-modified biscresol fluorene-based tetrafunctional acrylate compound (C-2) having an acid value of 64 mg KOH / g (according to JISK-5407). A mass% solution was obtained.

Comparative Synthesis Example 1
Synthesis of acid-modified bisphenoxyethanol fluorene acrylate compound (C-4) 1,2,3 to 184.0 g of bisphenoxyethanol fluorene acrylate (A-1) synthesized in Reference Example 2 (hydroxyl equivalent 368 g / eq, calculated value) , 6-Tetrahydrophthalic anhydride 19.02 g (0.125 mol: the amount necessary to react half of the hydroxyl group with the acid anhydride), 0.254 g of tetraethylammonium bromide, 3-methoxy-3-methyl-butyl acetate After adding 473.7 g at room temperature, the mixture was reacted at 115 ° C. for 5 hours to obtain a 30% by mass solution of acid-modified bisphenoxyethanol fluorene acrylate compound (C-4) having an acid value of 63 mg KOH / g (according to JIS K-5407). It was.

Comparative Synthesis Example 2
Synthesis of acid-modified bisphenoxyethanol fluorene acrylate compound (C-5) 1,2,3 to 184.0 g of bisphenoxyethanol fluorene acrylate (A-1) synthesized in Reference Example 2 (hydroxyl equivalent 368 g / eq, calculated value) , 6-Tetrahydrophthalic anhydride 38.04 g (0.25 mol: amount necessary to react all hydroxyl groups with acid anhydride) and tetraethylammonium bromide 0.254 g, 3-methoxy-3-methyl-butyl acetate After adding 517.9 g at room temperature, the mixture was reacted at 115 ° C. for 5 hours to obtain a 30% by mass solution of acid-modified bisphenoxyethanol fluorene acrylate compound (C-5) having an acid value of 107 mg KOH / g (according to JIS K-5407). It was.

Comparative Synthesis Example 3
As in Synthesis Example 1 of Patent Document 3, in a 500 ml four-necked flask, 231 g of bisphenoxyfluorenedin glycidyl ether (epoxy equivalent 231), 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-di-isobutylphenol, acrylic acid 72.0 g was charged and mixed, and dissolved by heating at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised and the mixture was heated to 120 ° C. and stirred for 8 hours. The acid value of this solution was 1.0 mgKOH / g. And it cooled to room temperature and obtained the colorless and transparent solid. Next, 151.5 g of this was weighed, and 1 kg of cellosolve acetate was added to make a solution. Then, 19 g of 1,2,3,6-tetrahydrophthalic anhydride and 40.25 g of benzophenonetetracarboxylic dianhydride and tetraethylammonium bromide 0.5 g was mixed and gradually heated to react at 110 to 115 ° C. for 2 hours to obtain Compound (C-6). The reaction of the acid anhydride during this reaction was confirmed by the disappearance of the 1780 cm ⁻¹ peak in the IR spectrum.

Example 1
842.22g of acid-treated carbon black 9930CF manufactured by Daido Kasei Co., Ltd., 82.53g of carbon black Special Black250 manufactured by Degussa Co., Ltd. 56.14 g of 45% by weight 3-methyl-3-methoxybutanol solution of polymer (P1), 24.29 g of “Disperbyk (registered trademark)” 167 (dispersing agent) manufactured by Big Chemi Japan Co., Ltd. and 751 of propylene glycol monomethyl ether acetate 0.1 g was weighed and dispersed at 2500 rpm for 3 hours using a mill type disperser filled with zirconia beads to obtain a pigment dispersion (CB1) having a pigment concentration of 16.843 mass%. To this pigment dispersion (CB1) 54.36 g, 1.16 g of a 45% by weight 3-methyl-3-methoxybutanol solution of acrylic polymer (P1), 3-methyl bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1a) 8.22 g of a 3-methoxy-butyl acetate 30% by mass solution, 3-methyl-3-methoxy-butyl acetate 30% by mass solution of dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer 3 .52 g, “Irgacure (registered trademark)” 369 0.26 g as photopolymerization initiator, Ciba-Specialty Chemical Co., Ltd. CGI-242 1.60 g and N, N′-tetraethyl-4,4′-diaminobenzophenone 0 .26 g, vinyltrimethoxysilane as an adhesion improver 15 g, a solution obtained by dissolving 0.30 g of a 10% by weight propylene glycol monomethyl ether acetate solution of a silicone surfactant in 30.23 g of 3-methyl-3-methoxy-butyl acetate was added and mixed to obtain a black color resist (solid content A concentration of 17.5% by mass) was prepared. The prepared color resist was filtered through a 2 μm Teflon (registered trademark) filter, and then applied onto an alkali-free glass substrate so that the film thickness was 1.2 μm (after post-baking). The coated substrate was dried under reduced pressure (100 Pa) and then heat-treated on a hot plate at 100 ° C. for 2 minutes to produce a color resist coating film. Subsequently, this coating film was exposed with a different exposure amount (200 to 800 mJ / cm ^{2 at} 365 nm) through a resolution test mask, and “Emulgen (registered as a nonionic surfactant) was added to a 0.04 mass% KOH aqueous solution. Trademark) “A-60 (HLB 12.8, polyoxyethylene derivative) (manufactured by Kao Corporation) added with 0.2% of the total amount of the developer in an alkaline developer 1. A patterning substrate was obtained by spray development 5 times and then washing with pure water. The obtained patterning substrate was held in a hot air oven at 230 ° C. for 30 minutes and post-baked to obtain a patterning substrate. The substrate was examined for dissolution time, sensitivity, adhesion during development, and pattern shape according to the evaluation method and evaluation criteria. The results are shown in Table 1.

Examples 2 to 10, Comparative Example 1
A patterned substrate was obtained in the same manner except that the compound described in the monomer (C) in Table 1 was used instead of the bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1a) of Example 1. This substrate was examined for dissolution time, sensitivity, adhesion during development, and pattern shape according to the evaluation method and evaluation criteria. The results are shown in Table 1.

Comparative Example 2
Except for using the acid-modified bisphenoxyethanol fluorene acrylate compound (C-4) synthesized in Comparative Synthesis Example 1 instead of the acrylic polymer (P1) and the bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1a) in Example 1. Obtained a patterned substrate in the same manner. The substrate was examined for dissolution time, sensitivity, adhesion during development, and pattern shape according to the evaluation method and evaluation criteria. The results are shown in Table 1.

Comparative Example 3
The same except that the bisphenoxyethanol fluorene acrylate compound (C-5) synthesized in Comparative Synthesis Example 2 was used instead of the acrylic polymer (P1) and the bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1a) in Example 1. Thus, a patterning substrate was obtained. This substrate was examined for dissolution time, sensitivity, adhesion during development, and pattern shape according to the evaluation method and evaluation criteria. The results are shown in Table 1.

Comparative Example 4
Patterning substrate in the same manner except that the compound (C-6) synthesized in Comparative Synthesis Example 3 was used instead of the acrylic polymer (P1) of Example 1 and the bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1a). Got. The substrate was examined for dissolution time, sensitivity, adhesion during development, and pattern shape according to the evaluation method and evaluation criteria. The results are shown in Table 1.

From comparison between Examples 1 to 4 and Comparative Example 1 in Table 1, in the various bisfluorene acrylate compounds having a hydroxyl group, the compounds of the present invention are all excellent in adhesion and pattern shape. Among them, bisphenoxyethanol It can be seen that the fluorene-based tetrafunctional acrylate compound exhibits the most excellent performance in terms of dissolution time, sensitivity, adhesion during development, and pattern shape. Further, from comparison between Examples 1 to 4 and Examples 5 to 9, it can be seen that when acid modification is performed, the dissolution time is shortened according to the amount of modification, and the adhesion during development is improved. On the other hand, the sensitivity tends to decrease. Comparing Examples 5 to 9 and Comparative Examples 2 to 4, it can be seen that Comparative Examples 2 to 3 have a fast dissolution time and the pattern shape tends to be inversely tapered, that is, poor in hydrophobicity. Comparative Example 5 is a comparison with the case of acid modification with an aromatic tetracarboxylic acid anhydride. Although this has good dissolution time and adhesion at the time of development, it can be seen that it is inferior in sensitivity and pattern shape as compared with Examples 5-9. This is presumably because the mass (g / eq unsaturated group) of the cardo compound per unsaturated bond (such as acrylic group) is too large. In Examples 5-9, it turns out that an acid-modified bisphenoxyethanol fluorene type | system | group tetrafunctional acrylate compound shows the most outstanding performance. Further, Example 10 shows the effect when a part of DPHA of Example 5 is replaced with the polyfunctional thiol compound tris-[(mercaptopropionyloxy) -ethyl] -isocyanurate (abbreviation: TEMPIC). The sensitivity is 2.7 times that of 5, indicating that there is a significant sensitizing effect.

Examples 11-16, Comparative Examples 5-6
Mitsubishi Materials Co., Ltd. titanium black 13M-T (titanium nitride) 42.11 g, Daido Kasei Co., Ltd. acid-treated carbon black 9930CF 62.32 g, Degussa Co. carbon black PRINTEX25 62.32 g, (Registered trademark) “12000 (manufactured by Abyssia Co., Ltd.) 1.68 g and acrylic polymer (P1) 3-methyl-3-methoxybutanol 45% by mass 56.14 g, manufactured by BYK Japan Japan Co., Ltd.“ Disperbyk (registered trademark) Trademark) "167 (dispersant) 24.29 g and propylene glycol monomethyl ether acetate 751.1 g were weighed and dispersed for 3 hours at 2500 rpm using a mill type disperser filled with zirconia beads, and the pigment concentration was 16.843 mass % Pigment dispersion (TCB1) was obtained. 57.74 g of this pigment dispersion (TCB1), 0.63 g of a 45% by weight 3-methyl-3-methoxybutanol solution of acrylic polymer (P1), and 3-methyl bisphenoxyethanol fluorene-based tetrafunctional acrylate compound (B-1a) 7.56 g of a 30% by mass solution of -3-methoxy-butyl acetate, 30% by mass of a 3-methyl-3-methoxy-butyl acetate solution of dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer 3 .24 g, “Irgacure (registered trademark)” 379 0.24 g as a photopolymerization initiator, Asahi Denka Kogyo Co., Ltd. “Adeka (registered trademark) Optomer” N-1919 1.47 g and N, N′-tetraethyl-4, 0.19 g of 4'-diaminobenzophenone, vinyltrimethoxy as an adhesion improver A black color resist was prepared by adding and mixing 0.14 g of silane and 0.28 g of a 10% by mass solution of propylene glycol monomethyl ether acetate of a silicone surfactant in 28.51 g of 3-methyl-3-methoxy-butyl acetate. (Solid content concentration 17.5 mass%) was prepared. The prepared color resist was filtered through a 2 μm Teflon (registered trademark) filter, and then applied onto an alkali-free glass substrate so that the film thickness was 1.2 μm (after post-baking). The coated substrate was dried under reduced pressure (100 Pa) and then heat-treated on a hot plate at 100 ° C. for 2 minutes to produce a color resist coating film. Subsequently, this coating film was exposed with a different exposure amount (200 to 800 mJ / cm ^{2 at} 365 nm) through a resolution test mask, and “Emulgen (registered as a nonionic surfactant) was added to a 0.04 mass% KOH aqueous solution. Trademark) “A-60 (HLB 12.8, polyoxyethylene derivative) (manufactured by Kao Corporation) added with 0.2% of the total amount of the developer in an alkaline developer 1. A patterning substrate was obtained by spray development 5 times and then washing with pure water. The obtained patterning substrate was held in a hot air oven at 230 ° C. for 30 minutes and post-baked to obtain a patterning substrate. The substrate was examined for dissolution time, sensitivity, adhesion during development, and pattern shape according to the evaluation method and evaluation criteria. The results are shown in Table 2.

  Tables 1 and 2 have the same OD value (optical density OD = log ((100 / Y (transmissivity (%) corrected for visibility)), but Example 11 and Example 1, Example 12 and Example 5) From the comparison of Example 13 and Example 7, Example 14 and Example 8, Example 15 and Example 9, it can be seen that the sensitivity is improved when titanium black is contained. From comparisons of Examples 5 to 6, it can be seen that the compounds of the present invention are excellent in adhesion and pattern shape, and among the compounds of the present invention, acid-modified bisphenoxyethanol fluorene-based tetrafunctional acrylate compounds (C- It can be seen that 1a and C-1b) show the most excellent performances in terms of dissolution time, sensitivity, adhesion during development, and adhesion during development. Functional thiol compound tris-[(mercaptopropionyloxy -Ethyl] -isocyanurate (abbreviation: TEMPIC) shows the effect, but the sensitivity is higher than that of Example 12, and the sensitization is remarkable even when added in a small amount of 5% by mass of monomer component (C). It turns out that there is an effect.

  The mechanism of this action is not clear, but the cardo-based tetrafunctional acrylate compound used in the composition of the present invention has a mass of cardo-based compound per unsaturated bond (such as an acrylic group) (compared to the conventional technique) ( g / eq unsaturated group) is not so large, and a cardo compound such as bisphenoxyethanol fluorene having an unsaturated bond (acrylic group) and a hydroxyl group is dimerized via a hydrophobic aromatic ester group. Thus, it is considered that the number of photoreactive groups becomes four, the sensitivity and hydrophobic performance are improved, and the adhesion and pattern shape during development are improved.

Claims (7)

In the photosensitive resist composition containing at least the pigment (A), the acrylic polymer (B), the monomer (C), the photopolymerization initiator (D), and the solvent (E), the monomer (C) is represented by the following general formula: A photosensitive resist composition for color filters, comprising a compound (C1) represented by the formula (1).

(In formula (1), R ¹ represents a hydrogen atom or a methyl group. Both carboxyl groups of the phthalic acid moiety are meta or para oriented.
In formula (1), X is a group represented by the following general formula (2).

In formula (2), R ³ and R ⁴ represent a hydrogen atom or a methyl group. R ² is an optionally substituted alkylene group having 1 to 10 carbon atoms, an alkenylene group or alkynylene group having 2 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, and an arylene group having 6 to 14 carbon atoms. Alternatively, it represents an aralkylene group having 7 to 20 carbon atoms. m is an integer of 0-5.
In formula (1), Y1 and Y2 are a hydrogen atom or a group represented by the following general formula (3).

In formula (3), Z represents a divalent aliphatic group or an aromatic group. ) A compound in which X is a bisphenoxyethanol fluorene group, bisphenoxyfluorene group, or biscresol fluorene group represented by the following general formulas (4) to (6):

The photosensitive resist composition for a color filter according to claim 1, wherein: In the compound represented by the general formula (1), R ¹ is a hydrogen atom, and one or both of Y1 and Y2 have a group represented by the general formula (3). The photosensitive resist composition for color filters according to claim 2. 4. The photosensitive resist composition for a color filter according to claim 3, wherein X is a bisphenoxyethanol type fluorene group represented by the general formula (4). The photosensitive resist composition for a color filter according to any one of claims 1 to 4, wherein the acrylic polymer (B) has a carboxyl group and has an ethylenically unsaturated group in a side chain. The photosensitive resist composition for a color filter according to any one of claims 1 to 5, wherein the pigment (A) is titanium black and / or carbon black. A color filter using the photosensitive resist composition for a color filter according to claim 1.