JP6657914B2 - Thermosetting resin composition for color filter protective film, and color filter having the cured film - Google Patents

Description

  The present invention relates to a thermosetting resin composition suitable for a color filter protective film used in a liquid crystal display device and the like, and a color filter having a protective film obtained by curing the composition.

  In recent years, with the rapid spread of liquid crystal display devices, demand for high quality color filters used in liquid crystal display devices has been increasing. The basic structure of a color filter has a structure in which a black matrix layer formed in a predetermined pattern, a colored layer in which red, green, and blue are arranged in a predetermined order, and a protective film are stacked on a transparent substrate. . In addition, the color filter creates three basic colors of red, green, and blue (RGB pixels) that pass through the colored layer, and creates an image color including an intermediate color and a white color by additively mixing those lights. Here, the protective film plays a role of physically and chemically protecting the color filter when manufacturing or using the liquid crystal display device. Therefore, for example, it has been conventionally performed to improve the transparency or smoothness of the protective film in order to improve the reproducibility of coloring by a color filter, and to increase the hardness in order to protect the liquid crystal portion from external impact. (Patent Document 1).

  Further, the color filter is manufactured through a severe process such as immersion treatment in an acid / alkali solution. Therefore, it is necessary to prevent performance deterioration and malfunction due to deterioration or damage of the color filter in such a manufacturing process. Therefore, various performance improvements of the protective film such as curability, adhesion, and processability of forming an ITO (tin-doped indium oxide layer) have been attempted (Patent Document 2).

JP 2001-350010 A JP 2006-276049 A

  By the way, recently, with the spread of mobile terminals such as smartphones and tablets, higher performance (higher image quality, higher definition, etc.) has been demanded for liquid crystal displays. Accordingly, an improvement in contrast is required, and an improvement in the OD value (optical density) of the black matrix is essential. The methods of improving the OD value are roughly classified into a method of increasing the pigment concentration in the resin of the black matrix and a method of increasing the thickness of the black matrix. The former method is mainly applied because there is a concern that other physical properties may be deteriorated.

  However, when the thickness of the black matrix increases, the level difference of the coloring layer (RGB pixel) formed thereon becomes larger than before. Therefore, higher flatness of the color filter protective film is required. If the flatness of the color filter protective film is low, the liquid crystal display performance is deteriorated due to the disorder of the liquid crystal alignment.

  Furthermore, in recent years, a color filter using a new technology called “white magic” has also appeared for the purpose of increasing luminance and reducing power consumption. “White magic” is an RGBW pixel obtained by adding W (white) to a conventional RGB pixel. The W pixels are roughly classified into a method of filling the holes in advance using a transparent resist when forming the W pixels, and a method of filling the W pixels with only the protective film. The latter is considered desirable in consideration of the number of steps. However, since the level difference of the W pixel is much higher than that of the RGB pixel, higher flatness is required for the protective film.

  As described above, with the improvement in the performance of the liquid crystal display device, higher flatness is also required for the color filter protective film, but in order to realize this requirement, the conventional color filter protective film is not sufficient, Further improvement was needed.

  Accordingly, an object of the present invention is to provide a thermosetting resin composition capable of forming a color filter protective film having excellent flatness while maintaining basic properties such as smoothness conventionally required. It is to provide a color filter provided with a protective film obtained by curing a color filter.

（Ｒ¹は水素またはメチル基。）
成分（Ｂ）：多価カルボン酸無水物又は多価ブロックカルボン酸
成分（Ｃ）：一分子中にエポキシ基を２個以上有する多官能エポキシ樹脂 As means for that purpose, the present invention provides a thermosetting resin composition for a color filter protective film containing the following components (A) to (C), wherein component (A) is 5 to 50 parts by weight, component (B) Is contained in an amount of 5 to 40 parts by weight, and the component (C) is contained in an amount of 25 to 80 parts by weight.
Component (A): (a1) a monomer having a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group; (a2) a monomer represented by the following formula (1); (a3) (a1) and (a2) (A1) is 10 to 65% by mass, (a2) is 10 to 60% by mass, (a3) is 15 to 55% by mass, and (a1) Tetrahydrofurfuryl group-containing polymer in which the total amount of (a2) and (a3) is 100% by mass

(R ¹ is hydrogen or a methyl group.)
Component (B): polycarboxylic acid anhydride or polyvalent block carboxylic acid Component (C): polyfunctional epoxy resin having two or more epoxy groups in one molecule

  Further, according to the present invention, it is possible to provide a color filter having a protective film obtained by curing the thermosetting resin composition for a color filter protective film.

  In the present invention, “XX to XX” indicating a numerical range means “XX or more and XX or less” unless otherwise specified.

  According to the thermosetting resin composition for a color filter protective film of the present invention, a color filter protective film having excellent flatness can be formed while maintaining basic properties such as smoothness, transparency, and film hardness. . Particularly, by using a polymer containing a predetermined amount of the component (a2) having a specific structure as the component (A), the flatness is high.

熱 Thermosetting resin composition for color filter protective film≫
The thermosetting resin composition of the present invention can be suitably used as a protective film for a color filter. The essential components constituting the basic composition are (A) a polymer containing a tetrahydrofurfuryl group, (B) a polycarboxylic acid anhydride or a polyvalent block carboxylic acid compound, and (C) an epoxy group in one molecule. Includes multi-functional epoxy resin with more than one.

<(A) Tetrahydrofurfuryl group-containing polymer>
Component (A) includes (a1) a monomer having a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group, (a2) a monomer having a predetermined structure (details will be described later), and (a3) (a1) and (a2). ) Is a copolymer obtained by copolymerizing a monomer having a carbon-carbon unsaturated bond other than the above.

  (A1) The monomer having a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group only needs to have a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group. Monomers can also be utilized.

（式中、Ｒ^２は水素原子またはメチル基、kは１〜５の整数を示す。）

（式中、Ｒ^３は水素原子またはメチル基、Ｒ^４は−ＣＨ_２Ｏ−基または−ＣＨ_２−基、Ｒ^５は水素原子または炭素数１〜２のアルキル基、mは１〜７の整数を示す。）

（式中、Ｒ^６は水素原子またはメチル基、ｎは１〜８の整数を示す。） Preferred examples of the monomer having an epoxy group include monomers represented by the following formulas (2) to (4).

(In the formula, R ² represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 5.)

(Wherein, R ³ is a hydrogen atom or a methyl group, R ⁴ is a —CH ₂ O— group or a —CH ₂ — group, R ⁵ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and m is a 1 to 7 Indicates an integer.)

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8.)

（式中、Ｒ^７、Ｒ^８、Ｒ^９は水素原子またはメチル基、ｊは１〜８の整数を示す。） As a monomer having an oxetanyl group, for example, a monomer represented by the following formula (5) is a preferred example.

(In the formula, R ⁷ , R ⁸ , and R ⁹ represent a hydrogen atom or a methyl group, and j represents an integer of 1 to 8.)

（Ｒ¹は水素またはメチル基。） As (a2), a monomer represented by the following formula (1) is used.

(R ¹ is hydrogen or a methyl group.)

（式中、Ｒ^１０は水素原子またはメチル基、Ｒ^１１は炭素数１〜１２のアルキル基、アリール基、アリールオキシ基、ヒドロキシアルキル基、またはポリアルキレングリコール残基、もしくは主環構成炭素数３〜１２の脂環式炭素水素基を示す。）

（式中、Ｒ^１２は水素原子または炭素数１〜５のアルキル基、Ｒ^１３は炭素数１〜１２のアルキル基、アルコキシ基、ヒドロキシアルキル基、ヒドロキシル基、シロキシアルキル基、または芳香族炭化水素基を示す。）

（式中、Ｒ^１４は水素原子または炭素数１〜１２のアルキル基、シクロアルキル基、または芳香族炭化水素基を示す。）

（式中、Ｒ^１５は水素原子またはメチル基、ｐは１〜５の整数、Ｒ^１６、Ｒ^１７、Ｒ^１８は、それぞれ独立にメチル基またはエチル基を示す。） (A3) The monomer having a carbon-carbon unsaturated bond other than (a1) and (a2) may be any compound having a carbon-carbon unsaturated bond and not falling under (a1) and (a2). Any monomer known for such an application can be utilized. For example, monomers represented by the following formulas (6) to (9) are exemplified.

(In the formula, R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is an alkyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, a hydroxyalkyl group, a polyalkylene glycol residue, or a main ring carbon number 3 ~ 12 alicyclic hydrocarbon groups.)

(Wherein, R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹³ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a hydroxyalkyl group, a hydroxyl group, a siloxyalkyl group, or an aromatic hydrocarbon. Represents a group.)

(In the formula, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or an aromatic hydrocarbon group.)

(In the formula, R ¹⁵ is a hydrogen atom or a methyl group, p is an integer of 1 to 5, and R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently represent a methyl group or an ethyl group.)

  (A) The tetrahydrofurfuryl group-containing polymer can be obtained by polymerizing (a1) to (a3). At that time, the content of (a1) in the component (A) is 10 to 65% by mass, the content of (a2) is 10 to 60% by mass, and the content of (a3) is 15 to 55% by mass. If the total amount of (a1), (a2) and (a3) is 100% by mass, excellent flatness can be obtained in the finally obtained protective film. The polymerization mode of the component (A) may be linear or branched. (A1) to (a3) may be used alone or in combination of two or more. The branched polymerization mode is, for example, a radical is generated on carbon when methylene hydrogen of a polymer whose growth is terminated is extracted by a radical derived from a polymerization initiator, and the radical is a polymer in the growth process. This is the case when recombining.

  The polymerization methods (a1) to (a3) are not particularly limited, and polymerization methods such as radical polymerization and ionic polymerization can be used. More specifically, polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used in the presence of a polymerization initiator. If necessary, additives such as a catalyst and a solvent may be added to the polymerization reaction system. (A) The weight average molecular weight (Mw) of the tetrahydrofurfuryl group-containing polymer may be about 3,000 to 100,000.

<(B) polyvalent carboxylic anhydride or polyvalent block carboxylic acid>
As the component (B), a polyvalent carboxylic anhydride or a polyvalent block carboxylic acid can be used. In order to improve the flatness, polycarboxylic anhydrides are more preferable. The polycarboxylic anhydride is preferably an anhydride of a dicarboxylic acid having 2 to 8 carbon atoms and 4 to 20 carbon atoms. Preferred examples include anhydrides such as linear or branched aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, and aromatic polycarboxylic acids. Examples of the aliphatic polycarboxylic acid include itaconic acid, maleic acid, succinic acid, and citraconic acid. Examples of the alicyclic polycarboxylic acid include tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanedicarboxylic acid, cyclopentanetetracarboxylic acid, and cyclohexanetricarboxylic acid. Examples of the aromatic polycarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, melitic acid, trimellitic acid, pyromellitic acid, and benzophenonetetracarboxylic acid.

  Examples of the polyvalent block carboxylic acid include a vinyl ether block polyvalent carboxylic acid compound in which the carboxyl group of the above polyvalent carboxylic acid is latentized as a hemiacetal ester by a vinyl ether compound, that is, the carboxylic acid is blocked.

  Examples of the vinyl ether compound include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, i-propyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether. Is mentioned. Among these, n-propyl vinyl ether and i-propyl vinyl ether are preferred from the viewpoint that the availability and the curing temperature are compatible with the process of the protective film. In addition, a vinyl ether compound can be used individually or in combination of 2 or more types.

  The polyvalent block carboxylic acid compound can be obtained by reacting a polyvalent carboxylic acid with a vinyl ether compound at a temperature in the range of room temperature to 150 ° C. Since the blocking reaction is an equilibrium reaction, if the amount of the vinyl ether compound is slightly increased with respect to the polyvalent carboxylic acid, the reaction is accelerated and the yield can be improved. In the reaction between the polyvalent carboxylic acid and the vinyl ether compound, a catalyst or a solvent may be added according to the purpose.

  Examples of the catalyst include tertiary amines, imidazoles, organic phosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, quaternary ammonium salts, boron compounds, metal halides, and the like.

  Examples of the solvent include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphates, nitriles, aprotic polar solvents, propylene glycol alkyl ether acetates, and the like.

<(C) polyfunctional epoxy resin>
As the component (C), a polyfunctional epoxy resin having two or more epoxy groups in one molecule is used. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, diphenyl ether epoxy resin, hydroquinone epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, fluorene epoxy resin Epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, hydrogenated bisphenol A Epoxy resin, bisphenol A nucleated polyol epoxy resin, polypropylene glycol epoxy resin, glycidyl ester epoxy Fat, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. The polyfunctional epoxy resin (C) may be used alone or in combination of two or more.

<Additives>
If necessary, a leveling agent, a silane coupling agent, a catalyst, a stabilizer, a solvent, and the like can be added to the thermosetting resin composition of the present invention. In addition, as long as the curing of the present invention is not impaired, a carbon dioxide generation inhibitor, a flexibility imparting agent, an antioxidant, a plasticizer, a lubricant, a surface treatment agent, a flame retardant, an antistatic agent, a coloring agent, and an ion trapping agent , Sliding property improver, impact resistance improver, thixotropic agent, surfactant, surface tension lowering agent, defoamer, anti-settling agent, light diffusing agent, ultraviolet absorber, antioxidant, release agent , A fluorescent agent and the like can also be added.

  The leveling agent is compounded for the purpose of improving the appearance of the obtained protective film, and a silicon-based, fluorine-based, acrylic-based or the like can be used without any particular limitation. Commercially available leveling agents include, for example, Megafac F-410 (DIC), F-430 (f), F-444 (f), F-472SF (f), and F-577 (f). F-552 (same), F-553 (same), F-554 (same), F-555 (same), F-556 (same), F-558 (same) F-559 (same), F-561 (same), R-94 (same), RS-72-K (same), RS-75 (same), Novec FC-4430 (Sumitomo 3M) Co., Ltd.), FC-4432 (same), Surflon S-611 (AGC Seimi Chemical Co., Ltd.), S-651 (same), S-386 (same), Futergent 208G (Neos Co., Ltd.), 209F (same), 212P (same), 220P (same), 222F (same), 228P (same) 240G (same), 602A (same), 650A (same), 710FL (same), 710FM (same), FTX-218 (same), BYK-302 (Big Chemie Japan KK), BYK-307 (same), BYK-315 (same), BYK-320 (same), BYK-322 (same), BYK-323 (same), BYK-325 (same), BYK-330 (same), BYK -331 (same), BYK-337 (same), BYK-347 (same), BYK-370 (same), BYK-UV3500 (same), BYK-UV3510 (same), BYK-350 (same), BYK- 354 (same), BYK-392 (same), Polyflow KL-400HF (Kyoeisha Chemical Co., Ltd.), KL-401 (same), KL-402 (same), KL-403 (same), KL −404 (same), KL-100 (same), KL-600 (same), KL-700 (same), WS-30 (same), the same No. No. 75 (same), No. 75 No. 77 (same as above); 90 (the same), No. 95 (same), LE-604 (same) and the like can be used. These leveling agents may be used alone or in combination of two or more.

  The silane coupling agent is a linking agent that binds an organic material and an inorganic material using silane. As a functional group that reacts with an organic material, it generally has a vinyl group, an epoxy group, an amino group, and the like. These silane coupling agents may be used alone or in combination of two or more.

  Examples of the catalyst include tertiary amines, imidazoles, organic phosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, and organometallic compounds. These catalysts may be used alone or in combination of two or more.

  The solvent is added for the purpose of adjusting the viscosity and the like when the thermosetting resin composition is used. Specific examples include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphates, aprotic polar solvents, glycol derivatives and the like. These solvents may be used alone or in combination of two or more.

  Examples of the carbon dioxide gas generation inhibitor include aliphatic polyols such as ethylene glycol and propylene glycol, aliphatic or aromatic carboxylic acid compounds, and phenol compounds. Examples of the flexibility imparting agent include polyalkylene glycol and the like. Examples of the impact resistance improver include inorganic fillers such as various rubbers, organic polymer beads, glass beads, and glass fibers.

(Production of thermosetting resin composition for color filter protective film)
The thermosetting resin composition for a color filter protective film comprises 5 to 50 parts by weight of the component (A) and 5 to 40 parts by weight of the component (B) in a total of 100 parts by weight of the components (A) to (C). , And 25 to 80 parts by weight of the component (C). If the content of each component is out of this range, physical properties required in any of smoothness, flatness, transparency, and film hardness of the obtained protective film may not be obtained.

(Formation of color filter protective film)
The color filter includes, as a protective film, a layer of a cured product obtained by curing the thermosetting resin composition. The thermosetting resin composition is applied so as to cover the colored layer and the black matrix layer disposed on the substrate. The coating method is not particularly limited, and a conventionally known coating method such as a gravure coating method, a spin coating method, and a die coating method can be employed.

  The obtained coating film is dried and, if necessary, preheated (prebaked), followed by full curing heating (postbaked) to form a layer of a cured resin. The pre-bake conditions may be 40 to 140 ° C. and 0 to 1 hour. Post-bake conditions may be 150 to 280 ° C. and 0.2 to 2 hours. The heating method is not particularly limited, and for example, a curing device such as a closed curing furnace or a tunnel furnace capable of continuous curing can be employed. The heating source is not particularly limited, and the heating can be performed by a method such as hot air circulation, infrared heating, or high-frequency heating.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
<Polymerization Example 1: Synthesis of tetrahydrofurfuryl group-containing polymer (A-1)>
In a 300 mL four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 76.0 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was charged as a solvent, and heated to 90 ° C. while stirring. The temperature rose. Then, at a temperature of 90 ° C., 22.5 parts by weight of (3-ethyloxetane-3-yl) methyl methacrylate (OXE-30) as the monomer component (a1) and tetrahydrofurfuryl as the monomer component (a2) 5. methacrylate (THFMA) 36.5 parts by weight, butyl acrylate (BA) 41.0 parts by weight as a monomer component (a3), peroxide-based polymerization initiator (“Perhexyl O” manufactured by NOF Corporation) A mixture obtained by uniformly mixing 0 parts by weight and 18.0 parts by weight of PGMEA (dropping components) was dropped at a constant speed from the dropping funnel over 2 hours. Thereafter, the temperature of 90 ° C. was maintained for 5 hours to obtain a 50% PGMEA solution of the polymer (A-1) having an epoxy group and having a weight average molecular weight (Mw) of 20,000.

<Polymerization Examples-2 to 10: Synthesis of Tetrahydrofurfuryl Group-Containing Polymers (A-2 to A-10)>
The raw materials shown in Table 1 were mixed under the conditions shown in Table 1, and polymer solutions A-2 to A-10 were obtained in the same manner as in Polymerization Example-1. In Table 1, numerical values indicating the composition (content of each component) are parts by weight. Abbreviations in Table 1 are as follows.
GMA: glycidyl methacrylate 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether OXE-30: (3-ethyloxetane-3-yl) methyl methacrylate OXE-10: (3-ethyloxetane-3-yl) methyl acrylate THFMA: tetrahydrofurfuryl Methacrylate BA: Butyl acrylate BMA: Butyl methacrylate St: Styrene CHMA: Cyclohexyl methacrylate CHMI: Cyclohexyl maleimide Perhexyl O: Peroxide polymerization initiator manufactured by NOF Corporation PGMEA: Propylene glycol monomethyl ether acetate

  The weight average molecular weight (Mw) was measured using a gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation, using TSKgel HZM-M manufactured by Tosoh Corporation as a column, and using THF as an eluent. It was measured with an RI detector and determined in terms of polystyrene.

<Comparative Polymerization Examples -1 to 6: Synthesis of Comparative Polymers (A'-1 to A'-6)>
The raw materials shown in Table 2 were mixed under the conditions shown in Table 2, and comparative polymer solutions of A'-1 to A'-6 were obtained in the same manner as in Polymerization Example-1. In Table 2, the numerical values indicating the composition (content of each component) are parts by weight. Abbreviations in Table 2 not described in Table 1 are as follows.
MSMA: Methyl cellosolve methacrylate MPEGA: Methoxy polyethylene glycol acrylate PhMA: Phenoxy methacrylate

<Examples 1 to 10, Comparative Examples 1 to 10>
The components shown in Tables 3 and 4 were dissolved and mixed in the amounts shown in Tables 3 and 4, and the coating liquids of the color filter protective film resin compositions for Examples 1 to 10 and Comparative Examples 1 to 10 were prepared. It was adjusted. In Tables 3 and 4, numerical values indicating the content of each component are parts by weight. Abbreviations in Tables 3 and 4 are as follows.

<Polycarboxylic anhydride (B)>
CHTA-an: cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride TMA-an: trimellitic anhydride <polyvalent block carboxylic acid (B)>
TMA-NPVE (a compound in which trimellitic acid is blocked with normal propyl vinyl ether): 1,2,4-benzenetricarboxylic acid-1,2,4-tris (1-propoxyethyl) ester CHTA-NPVE (cyclohexane tricarboxylic acid is normal) Compound blocked with propyl vinyl ether): 1,2,4-cyclohexanetricarboxylic acid-1,2,4-tris (1-propoxyethyl) ester CHTA-IPVE (compound obtained by blocking cyclohexanetricarboxylic acid with isopropyl vinyl ether): 1, 2,4-cyclohexanetricarboxylic acid-1,2,4-tris [1- (1-methylethoxy) ethyl] ester TMA-IPVE (compound obtained by blocking trimellitic acid with isopropyl vinyl ether): 1,2,2 - benzenetricarboxylic acid, 2,4-tris [1- (1-methylethoxy) ethyl] ester

<Polyfunctional epoxy resin (C)>
Ep-157: bisphenol A novolak type epoxy compound (manufactured by Mitsubishi Chemical Corporation, trade name: “jER157S70”, epoxy equivalent 210 g / eq)
Cel2021P: 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, Ltd., trade name: “Celoxide 2021P”, epoxy equivalent: 130 g / eq)
CG-500: Naphthyl group-containing fluorene type epoxy compound (manufactured by Osaka Gas Chemical Co., Ltd., trade name: "OGSOL CG-500", epoxy equivalent: 311 g / eq)
VG3101L: Glycidyl ether type epoxy compound (manufactured by Printec Co., Ltd., trade name: "Techmore VG3101L", epoxy equivalent 210 g / eq)

<Leveling agent>
F-554: Fluorine-based leveling agent (trade name: “MegaFac F-554” manufactured by DIC Corporation)
FTX-218: Fluorine-based leveling agent (manufactured by Neos Corporation, trade name: "FTX-218")
F-559: Fluorinated leveling agent (manufactured by DIC Corporation, trade name: "MegaFac F-559")
602A: Fluorine leveling agent (manufactured by Neos Co., Ltd., trade name: "Futhergent 602A")
F-177: Fluorine-based leveling agent (trade name: "Megafac F-177", manufactured by DIC Corporation)
BYK-307: silicone-based leveling agent (trade name: "BYK-307" manufactured by BYK Japan KK)

<Silane coupling agent>
OFS-6040: 3-glycidoxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd., trade name: “OFS-6040”)
X-41-1059A: silane compound (trade name: “X-41-1059A” manufactured by Shin-Etsu Chemical Co., Ltd.)
X-41-1053: silane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: "X-41-1053")

<Catalyst>
ZrOct: Zirconyl 2-ethylhexylate (manufactured by Nippon Chemical Industry Co., Ltd., trade name “Nikka Octix Zirconium 10% (K)”)
<Stabilizer>
IPVE: i-propyl vinyl ether NPVE: n-propyl vinyl ether <solvent>
PGMEA: Propylene glycol monomethyl ether acetate MMBA: 3-Methoxy-3-methyl-1-butyl acetate EDM: Diethylene glycol methyl ethyl ether EEP: Ethyl ethoxy propionate

  The coating liquids of the obtained resin compositions for a color filter protective film for Examples 1 to 10 and Comparative Examples 1 to 10 were each filtered through a membrane filter (material: PE, pore size: 0.2 μm), and then further filtered. Filtration was performed with a hollow filter (material: PP, pore size: 0.02 μm). The coating solution of the obtained resin composition for a color filter protective film was spin-coated on a 10 cm square quartz glass or non-alkali glass substrate by a spin coater (model 1H-DX-2, manufactured by Mikasa Corporation). After the application, the substrate was dried in a 90 ° C. clean oven for 2 minutes, and then heated in a 230 ° C. clean oven for 30 minutes to obtain a cured film having a thickness of 1.5 μm. The smoothness (applicability), flatness, transparency, and pencil hardness of the obtained cured film were evaluated as follows. The results are also shown in Tables 3 and 4.

<Smoothness>
A cured film formed with a film thickness of 1.0 μm, 1.5 μm, 2.0 μm, 2.5 μm on a non-alkali glass substrate was visually observed, and when no repelling was confirmed, it was evaluated as ○, and when repelling was confirmed. Was evaluated as x.

平坦化率Ｘ（％）が、９０％以上を◎、８０〜９０％を○、７０〜８０％を△、７０％以下を×と評価した。 <Flatness>
A dummy color filter for evaluating flatness, the difference in height between a red pixel and a green pixel center, the difference in height between a red pixel and a blue pixel center, and the difference in height between a green pixel and a blue pixel center ( (Step between pixels). Subsequently, after forming a cured film having a thickness of 1.5 ± 0.05 μm according to the above-described method of forming a cured film, the difference in height between the center portion of the red pixel and the green pixel in the same portion, the red pixel and the blue pixel The difference in height between the center portions and the difference in height between the center portions of the green and blue pixels were determined. These steps were measured by a stylus type surface roughness meter (model EK4000AK, manufactured by Kosaka Laboratory Co., Ltd.). Of the steps between pixels before the application of the protective film, a large value is defined as a maximum inter-pixel level difference (d1) before application, and a large value of the steps between pixels after the application of the protective film is defined as a maximum inter-pixel level (d2) after application. From these d1 and d2, the flattening rate X of the composition for a protective film was determined by the following formula (1).

The flattening rate X (%) was evaluated as ◎ when 90% or more, ○ when 80 to 90%, Δ when 70 to 80%, and X when 70% or less.

<Transparency>
The alkali-free glass substrate on which the cured film was formed was scanned from a wavelength of 300 nm to 800 nm using an ultraviolet-visible light spectrophotometer (model UV-3700, manufactured by Shimadzu Corporation) to measure the light transmittance. The average transmittance at 380 to 580 nm needs to be 98.0% or more.

<Hardness>
The alkali-free glass substrate on which the cured film was formed was subjected to a method according to JIS K5600-5-4: 1999 "General paint test method-Part 5: Mechanical properties of coating film-Section 4: Scratch hardness (pencil method)". evaluated. The evaluation result must be 3H or more.

  From the results in Table 3, in Examples 1 to 10, polymers containing an appropriate amount of components (A) to (C) and a predetermined amount of component (a2) having a specific structure in component (A) are used. As a result, excellent flatness has been obtained while maintaining the smoothness, transparency, and film hardness that have been conventionally required.

On the other hand, from the results in Table 4, in Comparative Examples 1 and 2, since the component (A) containing no (a3) was used, the transparency was poor. Further, Comparative Example 2 did not contain the component (C), so that the transparency was worse than Comparative Example 1. In Comparative Examples 3 to 6, the flatness was poor because the component (A) containing no (a2) was used. Comparative Example 7 was whitened because the component (A) excessively containing (a3) was used. For this reason, the smoothness and flatness also deteriorated. In Comparative Example 8, the content of the component (B) was excessive and the component (C) was not contained, so that the transparency was poor. Comparative Example 9 was poor in flatness because the content of the component (A) was too small. Comparative Example 10 was whitened because the content of the component (A) was excessive. For this reason, the smoothness and flatness also deteriorated.

Claims (2)

A thermosetting resin composition for a color filter protective film comprising the following components (A) to (C),
It contains 5 to 50 parts by weight of the component (A), 5 to 40 parts by weight of the component (B), and 25 to 80 parts by weight of the component (C), and the total of the components (A) to (C) is 100 parts by weight. A thermosetting resin composition for a color filter protective film.
Component (A): (a1) a monomer having a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group; (a2) a monomer represented by the following formula (1); (a3) (a1) and (a2) (A1) is 10 to 65% by mass, (a2) is 10 to 60% by mass, (a3) is 15 to 55% by mass, and (a1) Tetrahydrofurfuryl group-containing polymer in which the total amount of (a2) and (a3) is 100% by mass

(R ¹ is hydrogen or a methyl group.)
Component (B): polycarboxylic acid anhydride or polyvalent block carboxylic acid Component (C): polyfunctional epoxy resin having two or more epoxy groups in one molecule   A color filter having a protective film obtained by curing the thermosetting resin composition for a color filter protective film according to claim 1.