TWI770294B - Polymer composition, photosensitive resin composition and color filter - Google Patents

Abstract

A photosensitive resin composition comprising two or more (meth)acrylic polymers having specific structural units and different acid values (mgKOH/g), a solvent, and a reactive diluent, which are combined with photopolymerization. A photosensitive resin composition of a starting agent, wherein the photosensitive resin composition comprises a (meth)acrylic polymer having the largest acid value among the two or more (meth)acrylic polymers described above. When the acid value of (a) is set to 1, the weight average of the (meth)acrylic polymer (b) having an acid value of 0.01 to 0.50 times the weight average of the aforementioned (meth)acrylic polymer (a) The molecular weight is 1,000 to 10,000, and the mass ratio [(a)/(b)] of the (meth)acrylic polymer (a) to the (meth)acrylic polymer (b) is 0.01 to 0.50 .

Description

Polymer composition, photosensitive resin composition and color filter

The present invention relates to a polymer composition, a photosensitive resin composition comprising the polymer composition, and a color filter manufactured using the photosensitive resin composition.

In recent years, photosensitive resin compositions curable by active energy rays such as ultraviolet rays and electron beams have been widely used in various fields such as coating, printing, paint, and adhesives from the viewpoint of saving resources and energy. In addition, in the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be cured by active energy rays are also used in solder resists, color filters, black matrices, black column spacers, photo spacers, Resistor for protective film, etc.

In general, a color filter is a transparent substrate such as a glass substrate; red (R), green (G), and blue (B) pixels formed on the transparent substrate; a black matrix formed at the boundary of the pixels ; and the protective film formed on the pixels and the black matrix. A color filter having such a configuration is usually produced by sequentially forming a black matrix, pixels, and a protective film on a transparent substrate. Various manufacturing methods are disclosed as methods of forming pixels and black matrices (hereinafter, pixels and black matrices are referred to as "colored patterns"). As a method for forming a colored pattern, there may be mentioned pigments/dyes in a photolithographic process in which a photosensitive resin composition is used as a resist, and the photosensitive resin composition is repeatedly coated, exposed, developed, and baked. dispersion method. This pigment/dye dispersion method has excellent durability such as light resistance and heat resistance, and can form a colored pattern with few defects such as pinholes, so it is widely used today.

However, the pigment/dye dispersion method has the above-mentioned advantages, but on the contrary, since the pattern of each pixel of the black matrix, R, G, and B is repeatedly formed by high temperature, the photosensitivity used in this method is In the resin composition, high thermal yellowing resistance is required.

In addition, in general, a liquid crystal display device is manufactured by sandwiching a liquid crystal between a separately produced color filter substrate and a TFT (Thin-Film-Transistor) substrate, and laminating these members. In order to align the liquid crystal when these structures are attached, an alignment film such as a polyimide film may be provided on the color filter substrate. At this time, the color filter layer is exposed to highly polar solvents such as N-methylpyrrolidone (NMP) contained in the polyimide resin. Therefore, the photosensitive resin composition used on the color filter layer needs to be Solvent resistance (NMP resistance).

For example, in Patent Documents 1 and 2, various photosensitive resin compositions for color filters having excellent heat resistance, solvent resistance, and the like have been proposed. However, photosensitive resin compositions used in the manufacture of color filters are required to further improve thermal yellowing resistance, solvent resistance, and alkali developability. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-029151 [Patent Document 2] Japanese Patent Laid-Open No. 2015-174930

[The problem to be solved by the invention]

The present invention is an invention for solving the above-mentioned problems, and an object of the present invention is to provide a photosensitive resin composition excellent in thermal yellowing resistance, solvent resistance, and alkali developability. Moreover, this invention aims at providing the color filter which consists of the said photosensitive resin composition and is excellent in thermal yellowing resistance and solvent resistance. [Methods to solve the problem]

In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, they have found a photosensitive resin composition which has a specific structural unit and contains two types of a specific acid value (mgKOH/g) in a specific mass ratio. The polymer composition of the above-mentioned (meth)acrylic polymer can solve the above-mentioned problems and achieve the present invention.

That is, the present invention is shown in the following [1] to [7].

[1] A polymer composition comprising polymerization of two or more (meth)acrylic polymers having a structural unit represented by the following formula 1 or formula 2 and having different acid values (mgKOH/g) composition, The polymer composition is characterized in that the acid value of the (meth)acrylic polymer (a) having the largest acid value among the above two or more (meth)acrylic polymers is set to 1. In this case, the (meth)acrylic polymer (b) having an acid value of 0.01 to 0.50 times, The weight average molecular weight of the aforementioned (meth)acrylic polymer (a) is 1,000 to 10,000, and The mass ratio [(a)/(b)] of the (meth)acrylic polymer (a) with respect to the (meth)acrylic polymer (b) is 0.01 to 0.50,

(In formula 1, R ¹ represents a hydrogen atom or a methyl group, in formula 2, R ² represents a hydrogen atom or a methyl group, and R ³ represents a C2-30 group having an acid group and an ethylenically unsaturated group ). [2] The polymer composition according to [1], wherein the (meth)acrylic polymer (a) and the (meth)acrylic polymer (b) have at least one of the above formula 1 or the above formula 2 represents the same constituent unit. [3] The polymer composition according to [1] or [2], wherein the (meth)acrylic polymer (b) has a weight average molecular weight of 1,000 to 10,000. [4] The polymer composition according to any one of [1] to [3], wherein the acid value of the (meth)acrylic polymer (b) is the (meth)acrylic polymer (a) 0.01 to 0.30 times the acid value.

[5] A photosensitive resin composition characterized by comprising the polymer composition (A) according to any one of [1] to [4], a solvent (B), a reactive diluent (C), and a light Polymerization initiator (D). [6] The photosensitive resin composition according to [5], further comprising a colorant (E).

[7] A color filter characterized by having a coloring pattern formed of the photosensitive resin composition according to [6]. [Effect of invention]

According to the present invention, a photosensitive resin composition excellent in thermal yellowing resistance, solvent resistance, and alkali developability can be provided. Furthermore, the present invention can provide a color filter having a colored pattern excellent in thermal yellowing resistance and solvent resistance.

Hereinafter, the present invention will be described in detail.

<Polymer composition (A)> The polymer composition (A) of the present invention contains two or more (meth)acrylic-based structural units having an acid group represented by the following formula 1 or formula 2 and having different acid values (mgKOH/g) polymer. Furthermore, in the present invention, "(meth)acrylic acid" means at least one selected from methacrylic acid and acrylic acid.

(In formula 1, R ¹ represents a hydrogen atom or a methyl group, in formula 2, R ² represents a hydrogen atom or a methyl group, and R ³ represents a C2-30 group having an acid group and an ethylenically unsaturated group ).

Examples of the aforementioned acid group that R ³ has are polybasic acid groups such as dibasic acid groups (sulfonic acid groups, etc.), tribasic acid groups (phosphoric acid groups, etc.) in addition to carboxyl groups. Among them, carboxyl groups are relatively good. R ³ is preferably a group having 9 to 20 carbon atoms having a carboxyl group and an ethylenically unsaturated group. As a specific example of the structure containing the carboxyl group which R< ³ > has, the structure etc. which are represented by following formulae 3-20 are mentioned. Among these, the structures represented by the following formulae 4 and 11 are particularly preferred from the viewpoint of easy availability of raw materials and reactivity in synthesis. In addition, the carboxyl group of Formula 3 to Formula 20 may be substituted by the aforementioned polybasic acid group. Moreover, as a specific example of the structure containing the ethylenically unsaturated group which R< ³ > has, the structure etc. which are represented by following formulae 21 and 22 are mentioned. The structures represented by the following formulae 3 to 20 and the structures represented by the following formulae 21 and 22 may be individually bonded, and if the number of carbon atoms in R ³ is not more than 30, two or more types may be bonded.

A preferable specific example of R ³ is the following structure.

In the above structure, R ⁴ has an alkyl group having 1 to 5 carbon atoms of Formula 4 or Formula 11 and Formula 21 or 22 as a substituent. Among these, an alkyl group having 2 to 3 carbon atoms is particularly preferred from the viewpoint of easy availability of raw materials and reactivity in synthesis. Formula 4 or Formula 11 and Formula 21 or 22 may be bonded to the same carbon of the alkyl group or to a different carbon.

In addition, among the two or more (meth)acrylic polymers contained in the polymer composition (A), the polymer composition (A) of the present invention contains the (meth)acrylic polymer having the largest acid value. When the acid value of the acrylic polymer (a) is set to 1, it is characteristic of the (meth)acrylic polymer (b) having an acid value of 0.01 to 0.50 times. Here, the acid value in the present invention refers to the acid value of the (meth)acrylic polymer measured in accordance with JIS K6901 5.3, and means the amount of neutralizing the acidic component contained in 1 g of the (meth)acrylic polymer. mg of potassium hydroxide required.

Among the two or more (meth)acrylic polymers contained in the polymer composition (A), the acid value of the (meth)acrylic polymer (a) having the largest acid value is 50 mgKOH/g to 1000 mgKOH /g is preferable, and 100 mgKOH/g to 600 mgKOH/g is more preferable. When the acid value of the (meth)acrylic polymer (a) is in the above-mentioned range, the compatibility with the (meth)acrylic polymer (b) is good, and it is not necessary to do so when synthesizing or preparing a photosensitive resin composition. Separate and mix.

Moreover, among the two or more (meth)acrylic polymers contained in the polymer composition (A), the weight average molecular weight (Mw) of the (meth)acrylic polymer (a) having the largest acid value It is preferably 1,000 to 10,000 and 2,000 to 10,000. When the weight average molecular weight (Mw) of the (meth)acrylic polymer (a) is within the above-mentioned range, the compatibility with the (meth)acrylic polymer (b) is good, and the composition of the photosensitive resin is prepared during synthesis or preparation. When they are mixed, they can be mixed without separation.

Here, the weight-average molecular weight (Mw) in the present invention refers to the weight-average molecular weight in terms of standard polyethylene measured under the following conditions using a gel permeation chromatography (GPC). Column: Shodex (registered trademark) LF-804+LF-804 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40℃ Sample: 0.2% solution of (meth)acrylic polymer in tetrahydrofuran Developing solvent: tetrahydrofuran Detector: Differential Refractor (Shodex RI-71S) (manufactured by Showa Denko Co., Ltd.) Flow rate: 1mL/min

The (meth)acrylic polymer (b) has an acid value of 0.01 to 0.50 times the acid value when the acid value of the (meth)acrylic polymer (a) having the largest acid value is set to 1. Preferably, it has an acid value of 0.01 to 0.30 times. When the (meth)acrylic polymer (b) having an acid value of 0.01 to 0.50 times cannot be blended into the polymer composition (A), excellent thermal yellowing resistance, solvent resistance and alkali development cannot be achieved sex. From the viewpoint of alkali developability, it is more preferable that the (meth)acrylic polymer (b) is a mixture of two or more (meth)acrylic polymers having an acid value in the above range.

In addition, the weight average molecular weight (Mw) of the (meth)acrylic polymer (b) can be appropriately adjusted, but from the viewpoint of compatibility with the (meth)acrylic polymer (a), it is 1,000 to 10,000 More preferably, 2,000-10,000 are more preferable.

From the viewpoint of developability, the (meth)acrylic polymer (a) and the (meth)acrylic polymer (b) preferably have at least the same ones represented by Formula 1 or Formula 2 above. constituent unit.

Furthermore, in the polymer composition (A), with respect to the (meth)acrylic polymer (b), the mass ratio of the (meth)acrylic polymer (a) [(a)/(b)] is 0.01 to 0.50, preferably 0.01 to 0.30. When the mass ratio [(a)/(b)] is within the above range, excellent thermal yellowing resistance, solvent resistance and alkali developability can be achieved.

The acid value of the above-mentioned (meth)acrylic polymer (a) and (meth)acrylic polymer (b) is determined by changing the amount and type of the radical polymerizable monomer used in the production of each polymer. Can be adjusted appropriately. Examples of the radically polymerizable monomer system that can be used for the production of the (meth)acrylic polymer (a) and the (meth)acrylic polymer (b) include dienes such as butadiene; ( Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate , isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isobutyl (meth)acrylate Amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (Meth)acrylate, (meth)acrylate rosin, (meth)acrylate norbornyl, (meth)acrylate 5-methylnorbornate, (meth)acrylate 5-ethylnorbornyl, Allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, (meth)acrylic acid Perfluoro-n-propyl ester, (meth)acrylic acid perfluoroisopropyl ester, (meth)acrylic acid triphenylmethyl ester, (meth)acrylic acid cumyl ester (cumyl), (meth)acrylic acid 3-(N, N-dimethylamino)propyl ester, glycerol mono(meth)acrylate, butanetriol mono(meth)acrylate, pentamethylenetriol mono(meth)acrylate, (meth)acrylic acid bicyclic Pentenyl ester, dicyclopentyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, etc. (meth)acrylates; norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2. 1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10]hept-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]hept-3-ene, 8-ethyl Tetracyclo[4.4.0.12,5.17,10]hept-3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]dec-8-ene, tricyclo[5.2.1.02,6]dec-3- ene, tricyclo[4.4.0.12,5]undec-3-ene, tricyclo[6.2.1.01,8]undec-9-ene, tricyclo[6.2.1.01,8]undec-4-ene, Tetracyclo[4.4.0.12,5.17,10.01,6]hept-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]hept-3-ene, 8-ethylenetetracyclo[ 4.4.0.12, 5.17,12]hept-3-ene, 8-ethylenetetracyclo[4.4.0.12,5.17,10.01, 6] Hept-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadec-4-ene, pentacyclo[7.4.0.12,5.19,12.08,13]pentadec-3-ene, 5-Norbornene-2-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride, (meth)acrylic acid amide, (methyl) base) acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-diethylamide N-diisopropylamide, (meth)acrylate anthrylamide, N-isopropyl (meth)acrylamide, (meth)acrylate morpholine, diacetone (meth)acrylamide, etc. (meth) acrylic acid amide; (meth) acrylic acid N-aniline, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl Vinyl compounds of pyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene, etc.; α-, o-, m-, p-alkyl, nitro, cyano, amide derivatives of styrene and styrene; Diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid and other unsaturated dicarboxylic acid diesters; N-phenylmaleimide, N-ring Monomaleimides such as hexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, etc.; maleic anhydride, itaconic anhydride, citron Unsaturated polybasic acid anhydrides such as conic anhydride, glycidyl (meth)acrylate having an alicyclic ether group, 3,4-epoxycyclohexylmethyl (meth)acrylate and their lactone adducts [for example ( Co., Ltd.) DAICEL Chemical Industry Co., Ltd. Cyclomer (registered trademark) A200, M100], mono(meth)acrylate of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, Epoxide of Dicyclopentenyl (Meth)acrylate, Epoxide of Dicyclopentenyloxyethyl (Meth)acrylate, (3-Ethyloxetane-3) (Meth)acrylate -yl) methyl ester, 4-[3-(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetane Alk-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy)pentyloxy]styrene, 2-vinyl -2-Methyl-oxetane, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-acryloic acid Oxyethyl phthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, and (methyl) 2-isocyanatoethyl acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, and the like.

Among the above-mentioned radically polymerizable monomers, (meth)acrylic polymer (a) and (meth)acrylic polymer (b) can be introduced into the above formula 1 or formula 2 by using The radical polymerizable monomer constituting the unit is obtained by carrying out a polymerization reaction. Specifically, the (meth)acrylic polymer system having the structural unit represented by the above formula 1 can be obtained by combining (meth)acrylic acid and other radically polymerizable monomers as required. After dissolving in a desired solvent, a radical polymerization initiator is added to this solution, and a suitable polymerization reaction is performed at 50 degreeC - 120 degreeC over 1 hour - 20 hours. Moreover, the (meth)acrylic-type polymer system which has the structural unit represented by the said formula 2 can be obtained by radical polymerization which has the group which reacts with the carboxyl group, such as an epoxy group, a propylene oxide group, etc. After the polymerizable monomer and other required radically polymerizable monomers are dissolved in the solvent as desired, a radical polymerization initiator is added to the solution, and the appropriate treatment is carried out at 50°C to 120°C for 1 to 20 hours. After the polymerization reaction, a radical polymerizable monomer having a carboxyl group is added to a part of the obtained polymer, and a polybasic acid anhydride is added to a part of the hydroxyl group generated by ring opening. The obtained (meth)acrylic polymer is purified according to the need, the polymer components are separated, the acid value is measured, and two or more (meth)acrylic polymers with different acid values are used as the designated acid value. The ratio and mass ratio were blended as the polymer composition (A).

Furthermore, the polymer composition (A) of the present invention may contain a (meth)acrylic polymer other than the range of the above-mentioned acid value (for example, will have the largest acid value) to such an extent that the effect of the present invention is not impaired. When the acid value of the (meth)acrylic polymer (a) is set to 1, the (meth)acrylic polymer having an acid value of less than 0.01 times or more than 0.50 times to less than 1 times Acid value (meth)acrylic polymers) or polymers other than (meth)acrylic polymers. In addition, from the viewpoint of developability, the average acid value of the polymer contained in the polymer composition (A) is preferably in the range of 50 mgKOH/g to 150 mgKOH/g, and preferably in the range of 80 mgKOH/g to 120 mgKOH/g range is better. Furthermore, the average acid value of the polymer contained in the polymer composition (A) is a calculated value calculated according to the following formula. Average acid value=(acid value of polymer 1×content of polymer 1+acid value of polymer 2×content of polymer 2+acid value of polymer 3×content of polymer 3+･･･)/polymerization The total mass of the polymers contained in the composition (A)

Usually, the radical polymerization initiator is a thermal radical polymerization initiator that generates thermal radicals by heat, and it is also possible to use one of organic peroxide-based radical polymerization initiators and azo-based radical polymerization initiators. either. As organic peroxide-based radical polymerization initiators, for example, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxycarbonic acids Esters, peroxydicarbonates, etc. are preferred, among which, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters (for example, tert-butylperoxy-2-ethylhexyl) acid esters) are particularly preferred. As an azo radical polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'- Azobis(methyl 2-propionate) and the like are preferred. These radical polymerization initiators may be used alone, or two or more of them may be used.

The 10-hour half-life temperature of the radical polymerization initiator used in the present invention is preferably 50°C to 120°C, more preferably 50°C to 90°C. By using a radical polymerization initiator with a half-life temperature of 50°C to 120°C for 10 hours, the radical polymerization reaction is fully carried out, the heat-resistant yellowing of the obtained (meth)acrylic polymer is improved, and a stable quality product can be obtained. (Meth)acrylic polymer.

The usage amount of the radical polymerization initiator is not particularly limited, but relative to 100 parts by mass of the radical polymerizable monomer, 0.5 parts by mass to 100 parts by mass is preferable, and 1 part by mass to 50 parts by mass is more preferable . Deterioration of a (meth)acrylic-type polymer by decomposition|disassembly of a radical polymerization initiator at the time of storage can be suppressed by setting a usage-amount to 0.5 mass part - 100 mass parts.

In addition of radically polymerizable monomers and addition of polybasic acid anhydrides, an addition reaction catalyst can be used as required. Examples of the addition reaction catalyst system include triethylamine, benzyldimethylamine, tertiary amines such as triethylenediamine, quaternary ammonium salts such as triethylbenzylammonium chloride, triphenylene Phosphine compounds such as phosphine, tris-p-tolyl phosphine, ginseng (2,6-dimethoxyphenyl) phosphine, chelate compounds of chromium, and the like. These addition reaction catalysts may be used alone, or two or more of them may be used. The usage amount of the addition reaction catalyst is not particularly limited, but relative to 100 parts by mass of the radical polymerizable monomer, 0.1 part by mass to 1.0 part by mass is preferable, and 0.2 part by mass to 0.6 part by mass is more preferable. When it is 0.1 part by mass or more, a sufficient reaction rate can be obtained, which is preferable. When it is 1.0 part by mass or less, it is preferable to suppress the influence of coloration caused by the catalyst.

In addition of the radical polymerizable monomer and addition of the polybasic acid anhydride, a polymerization inhibitor can be used in order to prevent gelation. Examples of the polymerization inhibitor system include hydroquinone, methylquinone, methylhydroquinone, hydroquinone monomethyl ether, butylated hydroxytoluene, and the like. These polymerization inhibitors may be used alone, or two or more of them may be used. The usage amount of the polymerization inhibitor is not particularly limited, but relative to 100 parts by mass of the radical polymerizable monomer, it is preferably 0.1 part by mass to 1.0 part by mass, more preferably 0.2 part by mass to 0.6 part by mass. When the usage-amount of a polymerization inhibitor is 0.1 mass part or more, since gelation can be suppressed, it is preferable. When it is 1.0 parts by mass or less, when used in a photosensitive resin composition, curing is not inhibited, which is preferable.

The solvent used for the polymerization is not particularly limited, but a glycol ether solvent is preferable from the viewpoint of the solubility of the obtained (meth)acrylic polymer. Specifically, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol Alcohol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol Methyl ethyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether, etc. These solvent systems can be used individually or 2 or more types can be used. Among these, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable from the viewpoint of availability and reactivity.

The usage-amount of a solvent is not specifically limited, Preferably it is 30-1,000 mass parts with respect to 100 mass parts of radically polymerizable monomers, More preferably, it is 50-800 mass parts. In particular, by setting the amount of the solvent used to be 1,000 parts by mass or less, not only can the molecular weight decrease of the (meth)acrylic polymer due to chain transfer be suppressed, but also the (meth)acrylic polymer can be reduced The viscosity is controlled within an appropriate range. Moreover, by making the usage-amount of a solvent into 30 mass parts or more, an abnormal polymerization reaction can be prevented and a polymerization reaction can be stabilized and progressed, and the coloring and gelation of a (meth)acrylic-type polymer can also be prevented.

When the radically polymerizable monomer is dissolved in a solvent in advance and added, the solvent is preferably 1 to 500 parts by mass, more preferably 10 parts by mass relative to 100 parts by mass of the radically polymerizable monomer. Parts by mass to 300 parts by mass are mixed and added to the reaction vessel. Moreover, when the radical polymerization initiator is dissolved in a solvent in advance and added, the solvent is preferably 100 parts by mass to 10,000 parts by mass, more preferably 150 parts by mass relative to 100 parts by mass of the radical polymerization initiator. Parts by mass to 5000 parts by mass are mixed and added to the reaction vessel. Furthermore, when the radical polymerizable monomer and the radical polymerization initiator are mixed and added to the reaction vessel, the solvent is preferably 1 to 500 parts by mass, more preferably 100 parts by mass of the mixture. 10 parts by mass to 300 parts by mass are mixed and added to the reaction vessel.

The method of adding the radically polymerizable monomer and the radical polymerization initiator to the reaction vessel is not particularly limited. In terms of easy control of the addition amount, addition rate, addition time, etc., it is preferable to drop these and add them to the reaction vessel. Moreover, these can be mixed and can be added as a mixture, and can also be added individually.

The reaction vessel used in the present invention is not particularly limited as long as it is used to polymerize an industrial radical polymerizable monomer. For example, a reaction vessel having a mixing function and a temperature adjusting function, and having a supply port and an extraction port for supplying a raw material and taking out a reaction liquid can be mentioned.

The dropping time of the radically polymerizable monomer is not particularly limited, but it is preferably added over a period of 30 minutes to 300 minutes, and more preferably added over a period of 60 minutes to 250 minutes. Similarly, the dropping time of the radical polymerization initiator is not particularly limited, but it is preferably added over a period of 30 minutes to 300 minutes, and more preferably added over a period of 60 minutes to 250 minutes. Furthermore, from the viewpoint of work efficiency, it is preferable to adjust the dropping time of the radical polymerizable monomer and the radical polymerization initiator to be the same. Furthermore, when the mixture of the radical polymerizable monomer and the radical polymerization initiator is dropped into the reaction vessel, the addition time is not particularly limited, but it is preferably 30 to 300 minutes in the reaction vessel. Add, the better cost is added by 60 minutes to 250 minutes.

When the radically polymerizable monomer is dissolved in a solvent and added dropwise to the reaction vessel, the dropping speed is not particularly limited, and when the total amount of the radically polymerizable monomer and the solvent is set to 100 ml , preferably 0.1ml/min～5ml/min, more preferably 0.2ml/min～4ml/min. In addition, when the radical polymerization initiator is dissolved in the solvent and added to the reaction vessel by dropwise addition, the dropping speed is the case where the total amount of the radical polymerization initiator and the solvent is set to 100 ml, It is preferably 0.1 ml/min to 5 ml/min, more preferably 0.2 ml/min to 4 ml/min. Furthermore, when the radical polymerizable monomer and the radical polymerization initiator are dissolved in the solvent through the mixture and added to the reaction vessel, the dropping rate is determined by combining the radical polymerizable monomer, the radical polymerization initiator, and the When the total amount of the solvent is set to 100 ml, it is usually 0.1 ml/min to 5 ml/min, preferably 0.2 ml/min to 4 ml/min.

<Photosensitive resin composition> In the present invention, the above-mentioned polymer composition (A), solvent (B), reactive diluent (C) and photopolymerization initiator (D) can be mixed as the photosensitive resin composition. The content of the polymer composition (A) in the photosensitive resin composition is preferably 5 parts by mass to 85 parts by mass when the sum of the components excluding the solvent in the photosensitive resin composition is set to 100 parts by mass parts, more preferably 9 parts by mass to 74 parts by mass, and more preferably 14 parts by mass to 64 parts by mass.

The solvent (B) is not particularly limited unless the solvent (B) is an inert solvent (B) which does not react with the (meth)acrylic polymer. As the solvent (B), the same solvent as the solvent used in the production of the above-mentioned (meth)acrylic polymer may be used, or the solvent included in the production of the (meth)acrylic polymer may be used as it is, and further can also be added. In addition, when other components are added, they may coexist with the other components. Specifically, examples of the solvent (B) include propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, and propylene glycol monomethyl ether. ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, etc. These solvents (B) may be used alone, or two or more of them may be used. In addition, among these, glycol ether solvents, such as propylene glycol monomethyl ether acetate used for the production of a (meth)acrylic-type polymer, are preferable.

The content of the solvent (B) in the photosensitive resin composition is generally 30 to 1,000 parts by mass when the sum of the components excluding the solvent (B) in the photosensitive resin composition is set to 100 parts by mass, It is preferably 50 parts by mass to 800 parts by mass, more preferably 100 parts by mass to 700 parts by mass. If it is the content of this range, it becomes the photosensitive resin composition which has suitable viscosity.

The reactive diluent (C) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule. By using such a reactive diluent (C) together with the polymer composition (A), the viscosity can be adjusted, and the strength to a cured product or the adhesion to a substrate can be improved.

The reactive diluent (C) is not particularly limited, and examples thereof include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, and phthalate diene. Aromatic vinyl monomers such as propyl ester and diallyl phenyl phosphate; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; methyl (meth)acrylate, (methyl) ) ethyl acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylic acid Esters, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylol Ethyl propane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(meth)acrylate, etc. (Meth)acrylic monomer; triallyl cyanurate, etc. These reactive diluents (C) can be used alone or in combination of two or more.

The content of the reactive diluent (C) in the photosensitive resin composition is preferably 10 to 90 parts by mass when the sum of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. The mass part is more preferably 20 to 80 parts by mass, still more preferably 25 to 70 parts by mass. If it is the content of this range, it becomes the photosensitive resin composition which has suitable viscosity, and the photosensitive resin composition has suitable photocurability.

The photopolymerization initiator (D) is not particularly limited, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, and other benzoin and their alkyl ethers; acetophenone, 2,2-dimethoxy - Acetophenones such as 2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, etc.; 2 -Anthraquinones such as methylanthraquinone, 2-pentylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc.; 2,4-dimethylthioxanthone, 2,4-diisoquinone Thioxanthones such as propyl thioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; diphenyl ketone, 4-(1 -t-butyldioxy-1-methylethyl) diphenyl ketone, 3,3',4,4'-tetra(t-butyldioxycarbonyl) diphenyl ketone and other diphenyl ketones Ketones; 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one; 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl)butanone-1; acylphosphine oxides; and xanthones and the like. These photopolymerization initiators (D) can be used individually by 1 type or in combination of 2 or more types.

The content of the photopolymerization initiator (D) in the photosensitive resin composition is preferably 0.1 parts by mass to 100 parts by mass when the sum of the components excluding the solvent (B) in the photosensitive resin composition is made 30 parts by mass, more preferably 0.5 parts by mass to 20 parts by mass, and still more preferably 1 part by mass to 15 parts by mass. When the content of the photopolymerization initiator (D) is within the above range, the photocurability of the photosensitive resin composition is more suitable.

By further blending the colorant (E) in the photosensitive resin composition of the present invention, it can be a photosensitive resin composition for a color filter. The colorant (E) is not particularly limited as long as it is dissolved or dispersed in a solvent, and examples thereof include dyes, pigments, and the like.

In particular, in the conventional photosensitive resin composition, when a dye is used, a coloring pattern with high precision can be obtained, but there is a problem that the heat-resistant yellowing of the coloring pattern is lower than that when a pigment is used. . In view of this, in the photosensitive resin composition of the present invention, even if a dye is used, a colored pattern excellent in thermal yellowing resistance can be obtained.

As the dye system, an acid dye having an acidic group such as a carboxylic acid is used from the viewpoints of solubility in a solvent or an alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, and the like. Salts with nitrogen compounds of acid dyes, sulfonamides of acid dyes, etc. are preferred. Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue38, 44; acid chrome violet K; acid Fuchsin; acid green1, 3, 5, 25, 27, 50; acid orange6, 7, 8, 10, 12 ,50,51,52,56,63,74,95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow1, 3, 9, 11, 17, 23, 25, 29 , 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow3; solvent yellow82 and derivatives thereof, etc. Among these, azo-based, xanthene-based, anthraquinone-based, or phthalocyanin-based acid dyes are preferred. These dyes can be used singly or in combination of two or more according to the intended pixel color.

Examples of pigments include C.I. Pigment Yellow-1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117 , 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I.Pigment Orange13, 31, 36, 38, 40, 42, 43, 51 , 55, 59, 61, 64, 65, 71, 73 and other orange pigments; Red pigments of 215, 216, 224, 242, 254, 255, 264, 265, etc.; blue pigments of C.I.Pigment Blue15, 15:3, 15:4, 15:6, 60, etc.; C.I.Pigment Violet 1, 19, Violet pigments of 23, 29, 32, 36, 38, etc.; green pigments of C.I.pigment green7, 36, 58, etc.; brown pigments of C.I.Pigment Brown23, 25, etc.; etc. black paint etc. These pigments can be used singly or in combination of two or more depending on the color of the intended pixel. Furthermore, the above-mentioned dyes and colors can also be combined according to the color of the pixel for the purpose.

The content of the coloring agent (E) in the photosensitive resin composition is preferably 5 parts by mass to 80 parts by mass, when the sum of the components excluding the solvent in the photosensitive resin composition is 100 parts by mass, more preferably It is 5 mass parts - 70 mass parts, More preferably, it is 10 mass parts - 60 mass parts.

When using a pigment as a coloring agent (E), a well-known dispersing agent may be mix|blended with a photosensitive resin composition from a viewpoint of improving the dispersibility of a pigment. As the dispersant, it is preferable to use a polymer dispersant having excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, Sorbitan aliphatic ester-based dispersant, aliphatic modified ester-based dispersant, and the like. As such a polymer dispersant, products such as EFKA (manufactured by FK Chemicals (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparlon (manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca), and the like can also be used Named commercial seller. The content of the dispersant in the photosensitive resin composition may be appropriately adjusted according to the types of pigments and the like to be used.

In addition to the above-mentioned components, known additives such as known coupling agents, leveling agents, and thermal polymerization inhibitors may be added to the photosensitive resin composition in order to impart predetermined properties. The addition amount of these additives is not particularly limited as long as the effect of the present invention is not inhibited.

The photosensitive resin composition can be produced by mixing the above-mentioned components using a known mixing device. Furthermore, if desired, after preparing the composition containing the polymer composition (A) and the solvent (B), the reactive diluent (C), the photopolymerization initiator (D) and the coloring agent (E) may be mixed. ) to manufacture.

Next, the color filter produced using the photosensitive resin composition of this invention is demonstrated. The color filter of the present invention has a colored pattern formed from the above-mentioned photosensitive resin composition. Hereinafter, the color filter of the present invention will be described using drawings. FIG. 1 is a schematic cross-sectional view showing a color filter according to an embodiment of the present invention. As shown in FIG. 1 , the color filter of the present invention includes: a substrate 1; RGB pixels 2 formed on one side of the substrate 1; and a black matrix 3 formed at the boundary of the pixels 2; 2 and the protective film 4 on the black matrix 3.

The color filter of the present invention uses the above-mentioned photosensitive resin composition in addition to one or more coloring patterns selected from R, G, and B constituting the pixels 2 and the black matrix 3 (coloring pattern). In addition to the formation, the other constitution systems can be those known in the art. Furthermore, the color filter shown in FIG. 1 is an example, and the color filter of the present invention is not limited to this configuration.

Next, the manufacturing method of the color filter of this invention is demonstrated. First, a colored pattern is formed on one side of the substrate 1 . Specifically, a black matrix 3 and a pixel 2 are sequentially formed on one surface of the substrate 1 . The base material 1 is not particularly limited, but glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamide imide substrates, polyimide substrates, aluminum substrates, Printed wiring substrates, array substrates, etc.

Shading patterns can be formed by photolithography. Specifically, after applying the above-mentioned photosensitive resin composition on one side of the substrate 1 to form a coating film, the coating film is exposed through a photomask of a predetermined pattern, and the exposed part is photocured. . In addition, after developing the unexposed portion with an alkaline aqueous solution, a predetermined color pattern can be formed by baking. The coating method of the photosensitive resin composition is not particularly limited, and a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, etc. can be used.

Moreover, after application|coating of the photosensitive resin composition, as needed, it heats by the heating method using a circulation oven, an infrared heater, a hotplate, etc., and can volatilize a solvent (B). The heating conditions are not particularly limited, and may be appropriately set according to the type of the photosensitive resin composition to be used. Generally, it is sufficient to heat at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

The light source used for exposing the coating film composed of the photosensitive resin composition is not particularly limited, and for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp and the like can be used. In addition, the exposure amount is not particularly limited either, and may be appropriately set according to the type of the photosensitive resin composition to be used.

The alkaline aqueous solution used for development is not particularly limited. Specific examples of the alkaline aqueous solution include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine. ; 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-beta-hydroxyethylaniline, 3-methyl-4 -Amino-N-ethyl-N-beta-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-beta-methoxyethylaniline and their Aqueous solutions of p-phenylenediamine-based compounds such as sulfate, hydrochloride, or p-toluenesulfonate, etc. Among these, it is preferable to use the aqueous solution of a p-phenylenediamine type compound. Furthermore, in these aqueous solutions, antifoaming agents or surfactants can also be added as required. Moreover, it is preferable to wash with water and dry it after making it develop with the said alkaline aqueous solution. The conditions of baking are not particularly limited, and the heat treatment may be performed according to the type of the photosensitive resin composition to be used. Generally, it is sufficient to heat at a temperature of 130°C to 250°C for 10 minutes to 60 minutes.

Using the photosensitive resin composition, the above-mentioned coating, exposure, development and baking are repeated in order by using the photosensitive resin composition for the black matrix 3 and the photosensitive resin composition for the pixel 2. The overlay operation can form the desired coloring pattern. In the above, the method of forming a colored pattern by photohardening has been described, but if a photopolymerization initiator (E) is replaced by a photosensitive resin composition blended with a curing accelerator and a well-known epoxy resin , the desired coloring pattern can also be formed by heating after coating by the inkjet method.

Next, a protective film 4 is formed on the colored pattern (pixel 2 and black matrix 3). The protective film 4 is not particularly limited, and is formed using known materials and forming methods.

The color filter produced in this way is produced using a photosensitive resin composition that imparts a color pattern that is excellent in alkali developability, and is excellent in thermal yellowing resistance and solvent resistance. Colored patterns (pixel 2 and black matrix 3) excellent in yellowing and solvent resistance. Therefore, the photosensitive resin composition of the present embodiment is suitable for use as various resists, especially for the manufacture of organic EL displays, liquid crystal displays, and color filters built in solid-state imaging elements. [Example]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The compounds used in the examples are as described below. GMA: Glycidyl methacrylate (manufactured by NOF Corporation) OXMA: (3-ethyloxetan-3-yl)methyl methacrylate (manufactured by Ube Industries, Ltd.) MAA: Methacrylic acid (manufactured by KURARAY) AA: Acrylic (manufactured by Toagosei Co., Ltd.) DCPMA: Dicyclopentadiene methacrylate (manufactured by Hitachi Chemical Co., Ltd.) SM: Styrene (manufactured by Idemitsu Kosan Co., Ltd.) THPA: Tetrahydrophthalic anhydride (manufactured by Nippon Chemical Co., Ltd.) V-601: Dimethyl-2,2'-azo(2-methylpropionate) ) (manufactured by Wako Corporation, 10-hour half-life temperature: 66°C) PERBUTYL O: tert-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, 10-hour half-life temperature: 72°C) Propylene glycol monomethyl ether (manufactured by KURARAY) Diethylene glycol methyl ethyl ether (manufactured by KURARAY) Propylene glycol monomethyl ether acetate (manufactured by KURARAY) DPHA: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Industry Co., Ltd.) IRGACURE907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (manufactured by BASF Japan) VALIFAST BLUE 2620 (solvent blue44): blue dye (manufactured by Orient Chemical Industry Co., Ltd.)

(Meth)acrylic polymers having different acid values shown in Synthesis Examples 1 to 15 below were synthesized. Furthermore, the acid value and weight average molecular weight of the (meth)acrylic polymer are measured according to the above-mentioned measurement methods.

[Synthesis Example 1] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 303.7 g of propylene glycol monomethyl ether was added, and the temperature was raised to 88° C. with stirring while substituting with nitrogen. Next, 23.3 g of dimethyl-2,2'-azobis(2-methylpropionate) and diethyl acetate were mixed with a monomer liquid composed of 116.7 g (1.0 mol) of methacrylic acid. 30.9 g of glycol methyl ethyl ether was dripped into the said flask from a dropping funnel over 2 hours. The temperature was raised to 120° C., and the polymerization reaction was carried out by stirring for 30 minutes, thereby producing a methacrylic polymer. This is taken as sample 1. The weight average molecular weight (Mw) of the obtained methacrylic polymer was 3,900, and the acid value was 543.6.

[Synthesis Examples 2 to 11] The polymerization reaction was carried out in the same manner as in Example 1 except that the raw materials in Tables 1 and 2 were used, and acrylic polymer samples 2 to 11 were obtained. However, in the case of using the raw materials described in Table 2, the polymerization reaction was carried out by stirring at 88° C. for 5 hours after the dropwise addition. The weight average molecular weight (Mw) and acid value of the obtained methacrylic polymer are shown in Tables 1 and 2.

[Synthesis Example 12] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 58.6 g of propylene glycol monomethyl ether acetate was added, and the temperature was raised to 118° C. with stirring while substituting with nitrogen. Next, 9.2 g of tert-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, PERBUTYL O, 0.068 moles) and 25.4 g of propylene glycol monomethyl ether acetate, and the resultant was dropped into the aforementioned flask from a dropping funnel over 2 hours. After completion of the dropping, the temperature was raised to 120° C., and the polymerization reaction was performed by stirring for 30 minutes to generate a polymer. Then, the inside of the flask was replaced with air, and 41.5 g (1.0 mol) of acrylic acid, 0.4 g of triphenylphosphine (addition reaction catalyst), and 0.2 g of methylhydroquinone (polymerization inhibitor) were put into the above-mentioned polymer In the solution, the reaction was continued at 110°C for 10 hours, and the epoxy group derived from glycidyl methacrylate was cleaved by the reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid, and vinyl was introduced at the same time. Unsaturation is in the side chain of the polymer. Next, 87.6 g (1.0 mol) of tetrahydrophthalic anhydride was added to the flask, and the reaction was continued at 110° C. for 3 hours to make the hydroxyl group generated by the cleavage of the epoxy group derived from glycidyl methacrylate. It reacts with the acid anhydride group of tetrahydrophthalic anhydride, introduces the carboxyl group into the side chain, and generates an acrylic polymer. Next, 145.2 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and this was used as sample 12. The weight average molecular weight (Mw) of the obtained acrylic polymer was 9,600, and the acid value was 146.9.

[Synthesis Examples 13 to 15] A polymerization reaction was carried out in the same manner as in Synthesis Example 12 except that the raw materials described in Table 3 were used, and acrylic polymer samples 13 to 15 were obtained. Dicyclopentadiene methacrylate and styrene-based glycidyl methacrylate were mixed and used as a monomer mixture. Table 3 shows the weight average molecular weight (Mw) and acid value of the obtained acrylic polymer.

[Examples 1 to 21 and Comparative Examples 1 to 18] <Preparation of photosensitive resin composition> Using the (meth)acrylic polymer samples 1 to 15 synthesized in Synthesis Examples 1 to 15, according to the blending components and blending amounts shown in Table 4, Examples 1 to 21 and Comparative Examples 1 to 18 were prepared. Photosensitive resin composition for color filters. In addition, the composition of the polymer composition (A) used for preparing the photosensitive resin compositions for color filters of Examples 1 to 21 and Comparative Examples 1 to 18 is shown in Tables 5 to 11. Furthermore, in the addition amount of the polymer composition (A) in Table 4, the solvent used for synthesizing the (meth)acrylic polymer is not included. That is, the amount of solvent (B) added is in Synthesis Examples 1 to 11, and the sum of propylene glycol monomethyl ether and diethylene glycol methyl ethyl ether when used to synthesize methacrylic polymers is in Synthesis Examples In 12 to 15, the total of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate added by additional addition when used for synthesizing an acrylic polymer.

<Evaluation of photosensitive resin composition> (1) Heat-resistant yellowing The prepared photosensitive resin composition was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after exposure was 2.5 μm, then heated at 90° C. for 3 minutes to volatilize the solvent, and applied to the glass substrate. A coating film is formed thereon. Next, on the obtained coating film, light with an exposure wavelength of 365 nm was performed, and after the exposure part was photocured, it was baked at 230° C. for 30 minutes to prepare a cured coating film. The color conversion of the coating film before and after baking was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). By investigating the change in transmittance (ΔEab) before and after the aforementioned baking operation at 230° C. for 30 minutes, the evaluation of thermal yellowing was performed. The basis for this evaluation is as follows. The results are shown in Tables 12 and 13. ◎: ΔEab is 5 or less ○: ΔEab is more than 5 and 10 or less △: ΔEab is more than 10 and 15 or less ×: ΔEab is greater than 15

(2) Solvent resistance The prepared photosensitive resin composition was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after exposure was 2.5 μm, then heated at 90° C. for 3 minutes to volatilize the solvent, and applied to the glass substrate. A coating film is formed thereon. Next, on the obtained coating film, light with an exposure wavelength of 365 nm was performed, and after the exposure part was photocured, it was baked at 230° C. for 30 minutes to prepare a cured coating film. The glass substrate with the above-mentioned cured coating film was immersed in n-methyl-2-pyrrolidone at 23° C. for 1 hour. The change in transmittance (ΔEab) before and after immersion in n-methyl-2-pyrrolidone was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation), and solvent resistance was evaluated based on the results. The basis for this evaluation is as follows. The results are shown in Tables 12 and 13. ◎: ΔEab is 1 or less ○: ΔEab is more than 1 and 3 or less Δ: ΔEab is more than 3 and 5 or less ×: ΔEab is greater than 5

(3) Alkali imaging The prepared photosensitive resin composition was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after exposure was 2.5 μm, then heated at 90° C. for 3 minutes to volatilize the solvent, and applied to the glass substrate. A coating film is formed thereon. Next, a photomask of a predetermined pattern was arranged at a distance of 100 μm from the coating film, and light with a wavelength of 365 nm was exposed through the photomask, and the exposed part was photocured. Next, by spraying an aqueous solution containing 0.1 part by mass of sodium carbonate at a temperature of 23° C. and a pressure of 0.3 MPa to dissolve the unexposed part and develop the image, bake at 230° C. for 30 minutes. to form the specified pattern. The residue after alkali imaging was observed using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation, and the pattern after alkali imaging was confirmed. The basis for this evaluation is as follows. The results are shown in Tables 12 and 13. ◎: No residue ○: Almost no residue △: A little residue ×: There is residue and no pattern remains

From the results shown in Tables 12 and 13, it was confirmed that the photosensitive resin compositions of Examples 1 to 21 had excellent thermal yellowing resistance and solvent resistance compared with the photosensitive resin compositions of Comparative Examples 1 to 18. and alkali imaging. In particular, it was confirmed that the more types of the (meth)acrylic polymer (b) having a low acid value, the more excellent the alkali developability. In Examples 3, 6, 9, 12, 15, 18 and 21, four kinds of (meth)acrylic polymers with different acid values were used, but even if five or more kinds of (meth)acrylic polymers with different acid values were used based) acrylic polymers, it is also believed that the same results can be obtained. On the other hand, as shown in Comparative Examples 1 to 8 and 15 to 18, the photosensitive resin composition containing only one type of (meth)acrylic polymer, as shown in Comparative Example 12, is relatively A photosensitive resin composition in which the mass ratio of the acrylic polymer (b) to the (meth)acrylic polymer (a) exceeds 0.50, and as shown in Comparative Examples 13 and 14, the (meth)acrylic polymer ( b) The acid value of the (meth)acrylic polymer (a) is more than 0.50 times the acid value of the photosensitive resin composition system, at least one of thermal yellowing resistance, solvent resistance and alkali developability is not full. Moreover, as shown in Comparative Examples 9 to 11, even if two or more (meth)acrylic polymers having different acid values were blended, the weight average molecular weight of the (meth)acrylic polymer (a) was too large. In this case, it was confirmed that the mixture was separated. [Industrial Availability]

The cured coating film using the photosensitive resin composition obtained by the present invention is excellent in thermal yellowing resistance, solvent resistance, and alkali developability, so it has extremely high utility value in the field of various resists, so it is suitable as an organic EL display device , Liquid crystal display devices, built-in color filters for solid-state photographic elements.

1‧‧‧Substrate 2‧‧‧Pixels 3‧‧‧Black Matrix 4‧‧‧Protective film

1 is a schematic cross-sectional view showing a color filter according to an embodiment of the present invention.

Claims (7)

A polymer composition comprising two or more (meth)acrylic polymers having structural units represented by the following formula 1 or formula 2 and having different acid values (mgKOH/g) , characterized in that the polymer composition system comprises setting the acid value of the (meth)acrylic polymer (a) having the largest acid value among the above two or more (meth)acrylic polymers to 1 In the case of (meth)acrylic polymer (b) having an acid value of 0.01 to 0.30 times, the weight average molecular weight of the (meth)acrylic polymer (a) is 1,000 to 10,000, and relative to The mass ratio [(a)/(b)] of the aforementioned (meth)acrylic polymer (b) and the aforementioned (meth)acrylic polymer (a) is 0.01 to 0.50,

(In formula 1, R ¹ represents a hydrogen atom or a methyl group, in formula 2, R ² represents a hydrogen atom or a methyl group, and R ³ represents a C2-30 group having an acid group and an ethylenically unsaturated group ). The polymer composition according to claim 1, wherein the (meth)acrylic polymer (a) and the (meth)acrylic polymer (b) have at least one A constituent unit that is the same as that represented by the aforementioned formula 1 or the aforementioned formula 2. The polymer composition according to claim 1 or 2, wherein the weight-average molecular weight of the (meth)acrylic polymer (b) is 1,000 to 10,000. The polymer composition according to claim 1 or 2, wherein the mass ratio of the aforementioned (meth)acrylic polymer (a) to the aforementioned (meth)acrylic polymer (b) [(a)/(b) ] is 0.01~0.30. A photosensitive resin composition, characterized by comprising the polymer composition (A) as claimed in any one of claims 1 to 4, a solvent (B), a reactive diluent (C), and a photopolymerization initiator ( D). The photosensitive resin composition according to claim 5, further comprising a colorant (E). A color filter characterized by having a colored pattern formed by the photosensitive resin composition of claim 6.

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