JP4497003B2 - Resin composition for color filter protective film and color filter - Google Patents

Description

  The present invention relates to a resin composition for a color filter protective film used in a liquid crystal display device (LCD), a solid-state imaging device (CCD or the like), an electroluminescence device (ELD) or the like, and a color filter using the resin composition.

  Conventionally, the unevenness of RGB resist is flattened in color filters (hereinafter sometimes referred to as CF) used in liquid crystal display devices (LCD), solid-state imaging devices (CCD, etc.), electroluminescence devices (ELD), etc. For this purpose, or for the purpose of protecting the liquid crystal and the like from an ionic substance that bleeds out from the RGB resist, a layer called a protective film is provided between the RGB resist and the liquid crystal alignment film or the ITO layer. This protective film is required to have performance such as transparency, chemical resistance, heat resistance, adhesion, ITO forming process resistance, and flatness. Especially in recent years, when display devices are used in home TV applications, ITO has become more stringent as a result of the demand for adhesiveness that greatly affects its lifespan and higher electrical characteristics with the increase in size. A CF protective film having an ITO forming process resistance corresponding to the process conditions has been desired.

  The adhesion refers to the adhesion between the protective film and glass or RGB resist, and is an important performance related to the life of the CF. In recent years, as adhesion, high adhesion that does not peel from glass or RGB resist even under high temperature, high strain, acid or alkali immersion in the ITO formation process, and pressure that is an accelerated test of long-term reliability evaluation The protective film has been required to have reliable adhesion that does not cause peeling even after the cooker test (hereinafter referred to as the PCT test). In addition, the ITO process resistance is a resistance to defects such as cracks or wrinkles when forming an ITO circuit or an alignment film, and specifically, acid-alkali resistance (etching resistance) when forming an ITO circuit. ) And heat resistance at 230 to 250 ° C. after the ITO circuit is formed. In addition to the above-mentioned adhesion, it is required that the material has an excellent total balance of heat resistance, low thermal expansion, toughness, chemical resistance and the like in order to be excellent in ITO formation processability.

  As a resin composition for a CF protective film, Patent Document 1 discloses a resin composition for a CF protective film comprising a combination of an epoxy compound, a curing agent, and a specific solvent. Among them, a CF protective film obtained by thermosetting an epoxy resin composition composed of an epoxy compound and a carboxylic acid compound (or carboxylic acid anhydride) has been used as a suitable material in terms of transparency, chemical resistance, and heat resistance. . However, a resin composition comprising an epoxy compound and a curing agent is not necessarily excellent in adhesion and ITO forming process resistance. Furthermore, since the above epoxy compound reacts with the functional group of the curing agent even at room temperature, it has poor storage stability.

  Storage stability is one of the performances desired for a resin composition. When the resin composition is thickened during storage, the coating properties are remarkably lowered, it becomes difficult to control the thickness of the protective film, and fatal unevenness occurs for the protective film. In order to improve the storage stability at the time of storage, techniques such as keeping the storage conditions at a low temperature and hermetically, and storing each component that reacts separately (two-part liquefaction) are taken. However, both methods cause cost increase in storage and CF creation. In particular, when liquefaction is performed, it is necessary to mix immediately before use, and it is necessary to leave for a long time until bubbles generated at this time disappear. Furthermore, even if two-part liquefaction is performed, problems such as precipitation and thickening during coating remain, and a resin composition having excellent storage stability has been strongly desired.

  Many studies have been made so far for improving the storage stability of the resin composition for the CF protective film. For example, Patent Document 2 discloses a resin composition for a CF protective film using an epoxy group-containing resin and a polyvalent carboxylic acid derivative. Since the polyvalent carboxylic acid derivative is a compound in which the carboxylic acid is latentized with vinyl ether, the resin composition has a feature that the storage stability is extremely excellent. However, there have been cases where it has been insufficient to satisfy the high adhesion and ITO-resistant process properties required for CF protective films in recent years.

  On the other hand, a technique of adding a silane coupling agent, a titanate coupling agent, or the like to the resin composition is generally taken to improve adhesion. However, when a silane coupling agent or a titanate coupling agent is used alone, the above adhesiveness cannot be sufficiently imparted to the resin composition. Further, when a silane coupling agent and a titanate coupling agent are used in combination, the silane coupling agent and the titanate coupling agent, or the functional group of the curing agent and each coupling agent react even at room temperature. For this reason, when the coupling agent is used in combination, although the effect of improving the adhesion is high, there is a problem that the resin composition is thickened even at room temperature and the storage stability is remarkably lowered.

JP-A-7-126352 JP 2001-350010 A

The present invention has been accomplished in view of the above-mentioned circumstances, and the first object thereof is to have excellent curability and storage stability, and the resin cured product layer is basically such as heat resistance and chemical resistance. Another object of the present invention is to provide a resin composition for a color filter protective film that has excellent performance and is excellent in adhesion and ITO forming resistance.
In addition, the second object of the present invention is to provide a color filter having a layer of a cured resin product that has basic properties such as heat resistance and chemical resistance and is excellent in adhesion and ITO forming process resistance. is there.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific resin composition has excellent curability and storage stability, and the cured resin layer has heat resistance and resistance. In addition to having good chemical properties, the inventors have obtained knowledge that they have excellent adhesion and ITO forming process resistance, and have completed the present invention.
That is, the resin composition for a color filter protective film according to the present invention has a weight average molecular weight of 3000 to 100,000, an epoxy equivalent of 140 to 1000 g / mol, and contains a carbon-carbon unsaturated bond and an epoxy group. An epoxy group-containing polymer (A) polymerized by using at least a monomer to form a polycarboxylic acid derivative (B) in which the carboxyl group of the carboxylic acid (b1) is made latent by a vinyl ether compound (b2), and a titanium soap (C) containing 10 to 80% by weight of the (A), 5 to 70% by weight of the (B), and 0.001 to 20% by weight of the (C) with respect to the solid content. is there.

According to the present invention, the poorly soluble polyvalent carboxylic acid used as a curing agent is made latent by blocking the carboxyl group of the polyvalent carboxylic acid, thereby making the polyvalent carboxylic acid derivative (B) highly soluble. It is used after being shaped and dissolved and dispersed in a solvent. Therefore, the reaction point of a carboxyl group can coexist with an epoxy group at a high concentration in the resin composition, and a high crosslink density is obtained when a layer is formed using such a resin composition and heated. Further, the polyvalent carboxylic acid derivative (B) does not regenerate the carboxyl group unless it is heated to a predetermined temperature or higher according to the compound. Therefore, despite the high reaction point concentrations of the epoxy groups contained in the epoxy group-containing polymer (A) and the carboxyl groups contained in the polyvalent carboxylic acid derivative (B), a long period from immediately after preparation. It keeps a good viscosity for a long time and is very excellent in storage stability.
In the present invention, a CF protective film has recently been used by combining a specific amount of titanium soap (C) with the specific epoxy group-containing polymer (A) and the polyvalent carboxylic acid derivative (B). In addition to achieving the high adhesion required for the above, it is possible to obtain a material having an excellent total balance of heat resistance, low thermal expansion, toughness, chemical resistance, and the like. Therefore, according to the present invention, it has excellent curability and storage stability, and the layer of the cured resin has basic performance such as heat resistance and chemical resistance, and also has adhesion and ITO process formation. A resin composition for a color filter protective film having excellent properties can be obtained.

  In a preferred embodiment of the resin composition for a CF protective film according to the present invention, the polyvalent carboxylic acid derivative (B) is a latent carboxylic acid having the structure of the following formula (1) due to the vinyl ether compound (b2). Can be listed. In such a case, since the polyvalent carboxylic acid (B) has a low viscosity and a high solubility, there is an advantage that the coating property of the resin composition is improved.

（式中の６員環は芳香族又は脂環式の炭化水素である。ｍ１は０〜２の整数であり、ｔ１は０〜１の整数であり、ｎは１〜４の整数である。また、ｎが１の場合にはＲ¹は水素原子又は炭素数２〜８の炭化水素基であり、ｎが２〜４の場合にはＲ¹は炭素数２〜８の炭化水素基である。Ｒ²は、炭素数１〜５のアルキル基である。）

(The 6-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 2, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.)

  In addition, as a particularly preferred embodiment of the resin composition for a CF protective film according to the present invention, a carboxylic acid having a structure of the following formula (2) is latentized with a vinyl ether compound (b2). In such a case, even when cured at a lower temperature of 180 ° C. or lower, it has an advantage that it has a high crosslink density and is excellent in adhesion and ITO forming resistance.

（式中のｍ２は０〜２の整数である。）

(In the formula, m2 is an integer of 0 to 2.)

  As another particularly preferred embodiment of the resin composition for a CF protective film according to the present invention, the polyvalent carboxylic acid derivative (B) is a vinyl ether compound wherein the carboxylic acid having the structure of the following formula (3) is used. The one made latent by (b2) is mentioned. In such a case, the destabilizing temperature is high, so that the storage stability is remarkably excellent, and in particular, it is colorless and transparent, and it has the advantage of less discoloration under long-term high-temperature conditions or high-energy light irradiation. Have.

（式中のｍ３は０〜２の整数であり、ｔ３は０〜１の整数である。Ｒ²は、炭素数１〜５のアルキル基である。）

(An integer of m3 is 0 to 2 in the formula, .R ² is t3 is an integer from 0 to 1 is an alkyl group having 1 to 5 carbon atoms.)

In the resin composition for a color filter protective film according to the present invention, it is possible to impart toughness of the protective film by further containing an epoxy group-containing compound (D) having two or more epoxy groups in one molecule. To preferred.
In the resin composition for a color filter protective film according to the present invention, the titanium soap (C) is a reaction product of divalent to tetravalent titanium chloride and an aliphatic carboxylic acid having 4 to 16 carbon atoms. It is preferable from the viewpoint of solubility of titanium soap.

  The color filter according to the present invention has a layer of a cured resin obtained by curing the resin composition for a color filter protective film according to the present invention.

The resin composition for a color filter protective film according to the present invention has excellent curability and storage stability, and the cured resin layer has good heat resistance and chemical resistance. The required high adhesion and ITO process resistance can be achieved.
In addition, according to the present invention, it is possible to obtain a color filter having a layer of a cured resin product that has basic performance such as heat resistance and chemical resistance and is excellent in adhesion and ITO formation resistance.

The present invention is described in detail below.
1. Resin composition for color filter protective film The resin composition for color filter protective film according to the present invention has a weight average molecular weight of 3000 to 100,000, an epoxy equivalent of 140 to 1000 g / mol, and carbon-carbon unsaturated. An epoxy group-containing polymer (A) polymerized using at least a monomer containing a bond and an epoxy group, and a polyvalent carboxylic acid derivative in which the carboxyl group of the carboxylic acid (b1) is made latent by the vinyl ether compound (b2) ( B) and titanium soap (C), and the solid content is 10 to 80% by weight, (B) is 5 to 70% by weight, and (C) is 0.001 to 20%. It is contained by weight.

  In the present invention, the CF (color filter) protective film widely means a display device having CF and a solid-state image sensor, and more specifically, a liquid crystal display (LCD), a solid-state image sensor (CCD). Etc.), an organic layer formed between an RGB pixel of a CF used in an electroluminescence device (ELD) or the like and a liquid crystal alignment film, an ITO layer, a light emitter, a light receiver, or the like. It is not particularly limited to what is generally referred to as a protective film, and includes cases such as a protective film that is not directly in contact with RGB pixels but indirectly protects through other materials, For example, an intermediate film used between the microlens of the solid-state imaging device and the color filter, or an intermediate film used between the color filter and the electrode is also included.

(Epoxy group-containing polymer (A))
The epoxy group-containing polymer (A) in the resin composition of the present invention was polymerized using at least a monomer containing a carbon-carbon unsaturated bond and an epoxy group (hereinafter sometimes referred to as an epoxy group-containing monomer). A polymer having two or more epoxy groups. The epoxy group-containing polymer (A) can be obtained by polymerizing an epoxy group-containing monomer alone or by copolymerizing an epoxy group-containing monomer and another monomer. The molecular form may be linear or may have a branched structure, and may be any form such as a random copolymer, a block copolymer, and a graft copolymer.

  The epoxy group-containing polymer (A) in the resin composition of the present invention can be copolymerized by a conventional polymerization method. That is, the polymerization method is not particularly limited, and a polymerization method such as radical polymerization or ionic polymerization can be employed. More specifically, in the presence of a polymerization initiator, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, A polymerization method such as an emulsion polymerization method can be employed. Depending on the polymerization method, a large amount of monomer may remain, but if this monomer affects the physical properties of the protective film after coating, the monomer may be removed by a vacuum distillation method or a reprecipitation formation method. good.

In the resin composition of the present invention, the epoxy group-containing polymer (A) may be used, for example, by mixing two or more types of polymers having different molecular weights or comonomer types.
Preferred examples of the epoxy group-containing polymer (A) in the resin composition of the present invention include structural units represented by the following formulas (4) to (6).

（式中のＲ³は水素原子または炭素数１〜５のアルキル基、Ｒ⁴は水素原子または炭素数１〜２のアルキル基であり、ｐ１＝１〜８の整数である。）

(In the formula, R ³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and p1 = 1 to 8 is an integer.)

（式中のＲ⁵は水素原子または炭素数１〜５のアルキル基、Ｒ⁶は−ＣＨ_２Ｏ−または−ＣＨ_２−、Ｒ⁷は水素原子または炭素数１〜２のアルキル基であり、ｑ１＝０〜７の整数である。）

(In the formula, R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁶ is —CH ₂ O— or —CH ₂ —, R ⁷ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, q1 is an integer of 0 to 7.)

（式中のＲ⁸は水素原子または炭素数１〜５のアルキル基であり、ｒ１＝１〜８の整数である。）

(R ⁸ in the formula is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r1 = 1 to 8 is an integer.)

  The epoxy group-containing polymer (A) in the resin composition of the present invention may further have structural units represented by the following formulas (7) to (9).

（式中のＲ⁹は水素原子または炭素数１〜１２のアルキル基であり、Ｒ^１０は水素原子、炭素数１〜１２のアルキル基、主環構成炭素数３〜１２の脂環式炭化水素基、芳香族炭化水素基、アリールオキシ基、または芳香族ポリアルキレングリコール残基である。）

(In the formula, R ⁹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon having 3 to 12 carbon atoms constituting the main ring. Group, aromatic hydrocarbon group, aryloxy group, or aromatic polyalkylene glycol residue.)

（式中のＲ^１１は水素原子または炭素数１〜１２のアルキル基であり、Ｒ^１２は水素原子、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、ヒドロキシ基、シロキシアルキル基、または芳香族炭化水素基である。）

(In the formula, R ¹¹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ¹² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a hydroxyalkyl group, a hydroxy group, a siloxyalkyl group, Or an aromatic hydrocarbon group.)

（式中のＲ^１３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である。）
前記式（４）〜（６）で表される構成単位は、それぞれ下記式（１０）〜（１２）で表されるエポキシ基含有モノマーから誘導される。

(In the formula, R ¹³ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or an aromatic hydrocarbon group.)
The structural units represented by the formulas (4) to (6) are derived from epoxy group-containing monomers represented by the following formulas (10) to (12), respectively.

（式中のＲ^１４は水素原子または炭素数１〜５のアルキル基、Ｒ^１５は水素原子または炭素数１〜２のアルキル基であり、ｐ２＝１〜８の整数である。）
前記式（１０）において、Ｒ^１４，およびＲ^１５として好ましいのは、それぞれ独立に水素原子またはメチル基であり、ｐ２として好ましいのは１〜３である。式（１０）で表されるモノマーとしては、具体的には、グリシジル（メタ）アクリレート、β−メチルグリシジル（メタ）アクリレートを例示することができ、その中ではグリシジルメタクリレート（以下、ＧＭＡ）が入手性の面等から好ましい。ここで、本発明における（メタ）アクリレートとは、アクリレートまたはメタクリレートのいずれであっても良いことを意味する。

(In the formula, R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and p2 = 1 to 8 is an integer.)
In the formula (10), R ¹⁴ and R ¹⁵ are each independently preferably a hydrogen atom or a methyl group, and p2 is preferably 1 to 3. Specific examples of the monomer represented by the formula (10) include glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate. Among them, glycidyl methacrylate (hereinafter, GMA) is available. It is preferable from the aspect of property. Here, the (meth) acrylate in the present invention means that either acrylate or methacrylate may be used.

（式中のＲ^１６は水素原子または炭素数１〜５のアルキル基、Ｒ^１７は−ＣＨ_２Ｏ−基または−ＣＨ_２−基、Ｒ^１８は水素原子または炭素数１〜２のアルキル基であり、ｑ２＝０〜７の整数である。）
前記式（１１）において、Ｒ^１６、およびＲ^１８として好ましいのは、それぞれ独立に水素原子またはメチル基であり、Ｒ^１７として好ましいのは−ＣＨ_２Ｏ−基であり、ｑ２として好ましいのは１〜３である。式（１１）で表されるモノマーとしては、ｏ−ビニルベンジルグリシジルエーテル、ｍ−ビニルベンジルグリシジルエーテル、ｐ−ビニルベンジルグリシジルエーテルが入手性の面等から好ましい。

(In the formula, R ¹⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁷ is a —CH ₂ O— group or —CH ₂ — group, and R ¹⁸ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. Yes, and q2 is an integer from 0 to 7.)
In the formula (11), R ¹⁶ and R ¹⁸ are each independently preferably a hydrogen atom or a methyl group, R ¹⁷ is preferably a —CH ₂ O— group, and q 2 is preferably 1. ~ 3. As the monomer represented by the formula (11), o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferable from the viewpoint of availability.

（式中のＲ^１９は水素原子または炭素数１〜５のアルキル基であり、ｒ２＝１〜８の整数である。）
前記式（１２）において、Ｒ^１９として好ましいのは、水素原子またはメチル基であり、ｒ２として好ましいのは１〜３である。式（１２）で表されるモノマーとしては３，４−エポキシシクロヘキシルメチル（メタ）アクリレートを例示することができる。その中で３，４−エポキシシクロヘキシルメチルメタクリレートが硬度等の樹脂硬化物の層の物性の面から好ましい。

(In the formula, R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r2 is an integer of 1 to 8.)
In the formula (12), R ¹⁹ is preferably a hydrogen atom or a methyl group, and r 2 is preferably 1 to 3. Examples of the monomer represented by the formula (12) include 3,4-epoxycyclohexylmethyl (meth) acrylate. Among them, 3,4-epoxycyclohexylmethyl methacrylate is preferable from the viewpoint of physical properties of the cured resin layer such as hardness.

  The structural units represented by the formulas (7) to (9) are derived from monomers represented by the following formulas (13) to (15).

（式中のＲ^２０は水素原子または炭素数１〜１２のアルキル基であり、Ｒ^２１は水素原子、炭素数１〜１２のアルキル基、主環構成炭素数３〜１２の脂環式炭化水素基、芳香族炭化水素基、アリールオキシ基、または芳香族ポリアルキレングリコール残基である。）

(In the formula, R ²⁰ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ²¹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon having 3 to 12 carbon atoms constituting the main ring. Group, aromatic hydrocarbon group, aryloxy group, or aromatic polyalkylene glycol residue.)

In the formula (13), the alicyclic hydrocarbon group having 3 to 12 carbon atoms constituting the main ring represented by R ²¹ has an additional structure such as an intracyclic double bond, a side chain of a hydrocarbon group, a spiro It may contain a ring side chain, an intra-ring bridged hydrocarbon group, and the like.
In the formula (13), R ²⁰ is preferably hydrogen or a methyl group, and R ²¹ is preferably an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, or a dicyclopentanyl group. Specifically, as the monomer represented by the formula (13), cyclohexyl methacrylate and dicyclopentanyl methacrylate are preferable from the viewpoint of physical properties of the cured resin layer such as hardness and heat resistance.

（式中のＲ^２２は水素原子または炭素数１〜１２のアルキル基であり、Ｒ^２３は水素原子、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、ヒドロキシ基、シロキシアルキル基、または芳香族炭化水素基である。）
前記の式（１４）において、Ｒ^２２としては好ましいのは水素またはメチル基であり、Ｒ^２３としては好ましいのは炭素数１〜６のアルキル基またはフェニル基である。式（１４）で表されるモノマーとしては、具体的には、スチレンが他種モノマーとの共重合性、および入手性の面等から好ましい。

(In the formula, R ²² is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ²³ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a hydroxyalkyl group, a hydroxy group, a siloxyalkyl group, Or an aromatic hydrocarbon group.)
In the formula (14), R ²² is preferably hydrogen or a methyl group, and R ²³ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. Specifically, as the monomer represented by the formula (14), styrene is preferable from the viewpoint of copolymerization with other monomers and availability.

（式中のＲ^２４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である。）
前記式（１５）において、Ｒ^２４としては好ましいのはシクロヘキシル基、およびフェニル基である。式（１５）で表されるモノマーとしては、具体的には、Ｎ−シクロヘキシルマレイミド、およびＮ−フェニルマレイミドが硬度、および耐熱性等の樹脂硬化物の層の物性の面から好ましい。

(In the formula, R ²⁴ 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 (15), R ²⁴ is preferably a cyclohexyl group or a phenyl group. Specifically, as the monomer represented by the formula (15), N-cyclohexylmaleimide and N-phenylmaleimide are preferable from the viewpoint of physical properties of the cured resin layer such as hardness and heat resistance.

  The epoxy group-containing polymer (A) in the resin composition of the present invention is an epoxy group-containing structure represented by the above formulas (4) to (6) as long as the epoxy equivalent is 140 to 1000 g / mol. In the epoxy group-containing polymer (A), at least one of the units is preferably 10 to 100% by weight, more preferably 20 to 100% by weight. If the epoxy group-containing constitutional unit is less than 10% by weight, the protective film after coating may be poor in toughness.

The weight average molecular weight (Mw) of the epoxy group-containing polymer (A) in the resin composition of the present invention is 3,000 to 100,000, preferably 4,000 to 80,000. If the weight average molecular weight (Mw) is less than 3,000, a decrease in the hardness of the protective film is observed, and if it exceeds 100,000, the appearance after coating may be deteriorated. In addition, the weight average molecular weight (Mw) of an epoxy group containing polymer (A) is a weight average molecular weight of polystyrene conversion by a gel permeation chromatography (GPC) method.
Moreover, the epoxy equivalent of the epoxy group-containing polymer (A) in the resin composition of the present invention is 140 to 1000 g / mol, preferably 140 to 600 g / mol, and more preferably 260 to 550 g / mol. When the epoxy equivalent is less than 140 g / mol, the protective film after coating tends to lose toughness, and when it exceeds 1000 g / mol, the hardness of the cured resin layer is lowered and the ITO forming process is not suitable. there is a possibility. On the other hand, when the epoxy equivalent of the epoxy group-containing polymer (A) is 260 g / mol or more, it has excellent toughness, and high adhesion is obtained so that edge chipping hardly occurs even in the adhesion test after the pressure cooker test. Cheap. The epoxy equivalent in this case refers to the equivalent of the epoxy group of the polymer, and is measured according to JIS K 7236: 2001 “How to Determine Epoxy Equivalent of Epoxy Resin”.

  In the resin composition of the present invention, the blending ratio of the polymer (A) having an epoxy group is 10 to 80% by weight, preferably 15 to 65% by weight, more preferably 20 to 20% in the solid content of the resin composition. 60% by weight, more preferably 20 to 55% by weight. When the blending ratio of the epoxy group-containing copolymer (A) is less than 10% by weight, performance such as adhesion of the protective film may be deteriorated, and when it exceeds 80% by weight, the toughness of the protective film is impaired. Therefore, it is difficult to obtain the effects of the present invention. The solid content of the resin composition for specifying the blending ratio includes all components except the solvent, and liquid epoxy group-containing compounds are also included in the solid content.

(Polyvalent carboxylic acid derivative (B))
In the resin composition of the present invention, the polyvalent carboxylic acid derivative (B) is a vinyl ether compound (b2) in which the carboxyl group of the polyvalent carboxylic acid compound (b1) is represented by the following formula (16) (vinyl group and ether group). The compound is latent (hereinafter, sometimes referred to as “blocking”) by the contained compound). Since the polyvalent carboxylic acid derivative (B) has a latent carboxyl group, the storage stability of the composition can be remarkably improved, and it can coexist with the epoxy group at a high concentration. For this reason, it is a component that can improve adhesion and ITO forming resistance.

（式中のＲ^２5は炭素数１〜１０の炭化水素基である。）
カルボキシル基はビニル基と下記式（１７）のような反応をすることによって潜在化される。この反応は比較的容易であるため、多価カルボン酸誘導体（Ｂ）は収率良く得られる。従って、多価カルボン酸誘導体（Ｂ）は、カルボン酸が潜在化された下記式（１８）の構造を有している。

(R ²⁵ in the formula is a hydrocarbon group having 1 to 10 carbon atoms.)
The carboxyl group is latentized by reacting with the vinyl group as shown in the following formula (17). Since this reaction is relatively easy, the polyvalent carboxylic acid derivative (B) can be obtained in good yield. Therefore, the polyvalent carboxylic acid derivative (B) has a structure of the following formula (18) in which the carboxylic acid is latent.

（式中のＲ^２5は炭素数１〜１０の炭化水素基である。）

(R ²⁵ in the formula is a hydrocarbon group having 1 to 10 carbon atoms.)

  Examples of the polyvalent carboxylic acid compound (b1) that is a raw material of the polyvalent carboxylic acid derivative (B) in the resin composition of the present invention include oxalic acid, malonic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itacone. C2-C50 aliphatic dicarboxylic acid such as acid, succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, 2,4-diethylglutaric acid, decamethylene dicarboxylic acid; aromatic dicarboxylic acid; alicyclic Dicarboxylic acid; alicyclic tricarboxylic acid; aliphatic tricarboxylic acid having 2 to 50 carbon atoms; aliphatic tetracarboxylic acid having 2 to 50 carbon atoms; aromatic tetracarboxylic acid such as benzenetetracarboxylic acid; cyclohexanetetracarboxylic acid and the like Examples include polymers of carboxyl group-containing monomers such as alicyclic tetracarboxylic acid and (meth) acrylic acid. .

  As the polyvalent carboxylic acid derivative (B), a carboxylic acid having a structure represented by the following formula (1) is preferably latentized with a vinyl ether compound (b2). In such a case, since the polyvalent carboxylic acid derivative (B) has a low viscosity and a high solubility, there is an advantage that the coating property of the resin composition is improved.

（式中の６員環は芳香族又は脂環式の炭化水素である。ｍ１は０〜２の整数であり、ｔ１は０〜１の整数であり、ｎは１〜４の整数である。また、ｎが１の場合にはＲ¹は水素原子又は炭素数２〜８の炭化水素基であり、ｎが２〜４の場合にはＲ¹は炭素数２〜８の炭化水素基である。Ｒ²は、炭素数１〜５のアルキル基である。）

(The 6-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 2, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.)

Among the carboxylic acids represented by the formula (1), examples of the compound in which R ¹ is other than a hydrogen atom include a half ester obtained by a reaction between an alcohol compound and an acid anhydride.
Examples of alcohol compounds used in this reaction include monovalent alcohol compounds such as ethanol, propanol, hexanol, octanol, and isopropyl alcohol; ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, cyclohexanediol, and the like. Preferred examples include trivalent alcohol compounds such as glycerin, pentanetriol, hexanetriol, cyclohexanetriol, benzenetriol, and trimethylolpropane; and tetravalent alcohol compounds such as pentaerythritol. Preferably hexanol, isopropyl alcohol, 1,2-propylene glycol, 1,3-propylene glycol, 1,6-hexanediol, group Serine, trimethylolpropane, pentaerythritol.

  In addition, examples of the acid anhydride used in this reaction include compounds represented by the following formula (19). Specifically, phthalic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 1,3 Preferred examples include 1,4-tricarboxylic acid-3,4-anhydride (hereinafter referred to as trimellitic anhydride), 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride, and methylhexahydrophthalic anhydride. Can be mentioned. In addition, in the above half ester bodies, since a protective film with high crosslink density and high adhesion can be obtained, a polyhydric alcohol having 3 to 6 carbon atoms and divalent or higher polyhydric alcohol and trimellitic anhydride or methylhexahydroanhydride What is obtained by a combination with phthalic acid is preferably exemplified as (b1). Among them, methylhexahydrophthalic anhydride is preferably selected from the viewpoints of transparency and storage stability.

（式中の６員環は芳香族又は脂環式の炭化水素である。ｍ１は０〜２の整数であり、ｔ１は、０〜１の整数である。Ｒ²は、炭素数１〜５のアルキル基である。）

(6-membered ring in formula is an integer of .m1 is 0-2 aromatic or alicyclic hydrocarbons, t1 is an integer of 0 to 1 .R ² is C1-5 The alkyl group of

Among the carboxylic acids represented by the formula (1), a compound in which R ¹ is a hydrogen atom is represented by the formula (2) or the formula (3), and a polyvalent carboxylic acid derivative obtained by blocking these carboxylic acids ( Since B) has high dissolving power, it is preferably used in combination with the epoxy polymer (A) having low compatibility. Furthermore, in the case of the polyvalent carboxylic acid derivative (B) obtained by blocking the carboxylic acid represented by the formula (2), even when it is cured at a lower temperature of 180 ° C. or less, it has a high crosslinking density and adhesion and resistance. It has the advantage of excellent ITO processability. In addition, in the case of the polyvalent carboxylic acid derivative (B) obtained by blocking the carboxylic acid represented by the formula (3), the storage stability is remarkably excellent because the delatent temperature is high, and in particular, it is colorless. It is transparent and has the advantage of less discoloration under long-term high-temperature conditions and high-energy light irradiation.

（式中のｍ２は０〜２の整数である。）

(In the formula, m2 is an integer of 0 to 2.)

（式中のｍ３は０〜２の整数であり、ｔ３は０〜１の整数である。Ｒ²は、炭素数１〜５のアルキル基である。）

(An integer of m3 is 0 to 2 in the formula, .R ² is t3 is an integer from 0 to 1 is an alkyl group having 1 to 5 carbon atoms.)

Examples of the compound represented by formula (2) or formula (3) include aromatic dicarboxylic acids such as phthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Aromatic tricarboxylic acid such as merit acid); alicyclic tricarboxylic acid such as 1,2,4-cyclohexanetricarboxylic acid (hereinafter referred to as CHTA); 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), etc. Aromatic tetracarboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid and the like. These may have R ² as a substituent. R ² is an alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group. , N-pentyl group and the like are preferable, and a linear alkyl group having 1 to 3 carbon atoms is preferable. Among the carboxylic acids described above, pyromellitic acid, trimellitic acid or CHTA is preferably used as (b1) because a protective film having a high crosslink density and high adhesion can be obtained. From the viewpoint of stability, it is preferable to select CHTA.
The carboxylic acid that can be used as (b1) in the resin composition of the present invention can be used singly or in combination of two or more.

  On the other hand, examples of the vinyl ether compound (b2) represented by the formula (16) that is a raw material of the polyvalent carboxylic acid derivative (B) in the resin composition of the present invention include isopropyl vinyl ether, n-propyl vinyl ether, and n-butyl. Examples thereof include alkyl vinyl ethers such as vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether. As a vinyl ether compound (b2) which can be used suitably for the resin composition of this invention, n-propyl vinyl ether and isobutyl vinyl ether are mentioned, It can use individually by 1 type or in combination of 2 or more types.

  The polyvalent carboxylic acid derivative (B) used in the present invention can be obtained by reacting the carboxylic acid (b1) with the vinyl ether compound (b2) at a temperature ranging from room temperature to 150 ° C. . Since the blocking reaction is an equilibrium reaction, the reaction is promoted and the yield can be improved by using a little more vinyl ether compound (b2) than carboxylic acid (b1). Specifically, the molar equivalent ratio [the molar equivalent ratio of (vinyl group / carboxyl group)] of the vinyl group of the vinyl ether compound (b2) to the carboxyl group of the carboxylic acid (b1) is 1/1 to 2/1. It is desirable. When this molar equivalent ratio exceeds 2/1, the reaction temperature cannot be increased, and the reaction rate may be extremely low.

  When the blocking reaction is performed, an acid catalyst can be used for the purpose of accelerating the reaction. Examples of such a catalyst include an acidic phosphate compound represented by the following formula (20).

（式中のＲ^２６は炭素数３〜１０のアルキル基、シクロアルキル基またはアリール基、ｋは１または２である。）

(In the formula, R ²⁶ is an alkyl group, cycloalkyl group or aryl group having 3 to 10 carbon atoms, and k is 1 or 2.)

Moreover, when performing blocking reaction, you may use an organic solvent for the purpose of making a reaction system uniform and making reaction easy. Examples of organic solvents used here include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphate esters, nitriles, aprotic polar solvents, propylene glycol alkyl ether acetates, and the like. Is mentioned. More preferred are cyclohexanone and propylene glycol monomethyl ether acetate. The organic solvent is preferably an organic solvent excluding alcohol or ionic solvent. It is known that the deblocking reaction may proceed with respect to the alcohol or the ionic solvent, because the storage stability of the resin composition may be significantly reduced and it may be difficult to obtain the effects of the present invention. is there.
The said organic solvent can be used individually by 1 type or in combination of 2 or more types. Although the usage-amount of the said organic solvent is not specifically limited, It is 5-95 mass parts normally with respect to 100 mass parts of reaction raw materials, Preferably, it is 20-80 mass parts. Even when the organic solvent is added in this way, the content of the polyvalent carboxylic acid derivative (B) is the amount of the active ingredient (the polyvalent carboxylic acid derivative (B) itself) excluding the organic solvent. Think about it.

  In the resin composition of the present invention, the blending ratio of the polyvalent carboxylic acid derivative (B) is 5 to 70% by weight, preferably 5 to 60% by weight, more preferably 10 to 55% in the solid content of the resin composition. % By weight, more preferably 15 to 55% by weight. When the blending ratio of the polyvalent carboxylic acid derivative (B) is less than 5% by weight, the performance such as the flatness of the protective film is deteriorated. Difficult to get.

The ratio of the amount of the epoxy group-containing copolymer (A) and the polyvalent carboxylic acid derivative (B) is preferably in the following range. Ratio of the molar concentration of the carboxyl group generated after elimination (delatentization, deblocking) of the vinyl ether compound of the polyvalent carboxylic acid derivative (B) and the molar concentration of the epoxy group of the epoxy group-containing polymer (A) ( (Carboxyl group / epoxy group) is preferably blended so as to be 0.2 / 1.0 to 1.6 / 1.0, and a more preferable molar concentration ratio is 0.4 / 1.0 to 1. 2 / 1.0.
Further, when the epoxy group-containing compound (D) described later is further contained, the total amount of the epoxy group-containing copolymer (A) and the epoxy group-containing compound (D) described later and the polyvalent carboxylic acid derivative ( The blending ratio of B) is preferably in the following range. Molar concentration of carboxyl group generated after elimination (delatentization, deblocking) of vinyl ether compound of polyvalent carboxylic acid derivative (B), and epoxy of epoxy group-containing polymer (A) and epoxy group-containing compound (D) It is preferable to set the amount so that the ratio (carboxyl group / epoxy group) to the total molar concentration of groups is 0.2 / 1.0 to 1.6 / 1.0, and a more preferable molar concentration ratio is 0. 4 / 1.0 to 1.2 / 1.0.
If the molar concentration ratio between the carboxyl group and the epoxy group is less than 0.2 / 1.0, a large amount of the epoxy group remains after curing, so that the crosslinking density is lowered and the effect of the present invention may not be obtained. There is. On the other hand, if the molar concentration ratio between the carboxyl group and the epoxy group exceeds 1.6 / 1.0, the carboxyl group becomes excessive, and the physical properties of the resin are often lowered. In addition, as an additional component not included in the above-mentioned (A), (B), and (D) which is an essential component in the resin composition of the present invention, a functional group capable of reacting with a carboxyl group and a carboxyl group including an epoxy group. When adding the compound containing, it mix | blends so that ratio of the total molar concentration of the carboxyl group in a composition and the total molar concentration of the functional group which can react with the carboxyl group containing an epoxy group may become the said range. It is preferable.
Here, the molar concentration of the carboxyl group is simply calculated from the compound structural formula (molecular weight) and the compounding concentration, and more precisely, JIS K 0070: 1992 “acid value, saponification value, ester value of chemical products. , Iodine value, hydroxyl value and unsaponifiable product test method ".

(Titanium soap (C))
The resin composition of the present invention contains titanium soap in order to achieve the high adhesion required for the CF protective film in recent years and to obtain excellent ITO process resistance. The titanium soap in the resin composition of the present invention is a carboxylate salt having titanium as a central metal, and is typically a mixture of compounds represented by the following formula (21), although it is difficult to limit the structure.

（式中のＲ^２７、Ｒ^２８、Ｒ^２９およびＲ^３０はそれぞれ同一または相異なる炭素数１〜２９の炭化水素基またはカルボキシル基を有する有機基であり、互いに結合して環を形成していても良く、ｚ１は１以上の整数、ｚ２は０以上の整数、ｚ３は０または１、ｚ４およびｚ５はそれぞれ独立に０〜２の整数、ｚ６およびｚ７はそれぞれ独立に０または１である。）

(In the formula, R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are the same or different organic groups having 1 to 29 carbon atoms or a carboxyl group, and are bonded to each other to form a ring. Z1 is an integer of 1 or more, z2 is an integer of 0 or more, z3 is 0 or 1, z4 and z5 are each independently an integer of 0 to 2, and z6 and z7 are each independently 0 or 1.)

  The present inventors have clarified that the titanium soap (C) does not promote the reaction between the carboxyl group and the epoxy group and the deblocking reaction as compared with the titanium coupling agent having acetylacetone or the like as a ligand. Yes. This is considered due to the fact that the titanium atom and the carboxyl group form a strong bond. Therefore, when titanium soap is used, there is almost no thickening due to cross-linking during storage of the resin composition. Usually, when titanium soap and carboxylic acid are mixed, a ligand exchange reaction occurs between the metal soap and carboxylic acid. However, a polyvalent carboxylic acid derivative having a latent carboxyl group is defined as a ligand. It has been clarified by the present inventors that no exchange reaction is observed. Therefore, when the titanium soap (C) is used in combination with the polyvalent carboxylic acid derivative (B) in which the carboxyl group is latent, precipitation of gelled and insolubilized metal soap does not occur, and storage stability Is not impaired. Therefore, the titanium soap (C) is a suitable additive that can significantly improve the adhesion while maintaining high storage stability in the resin composition of the present invention. The titanium soap (C) can significantly improve the adhesion in the present invention because the titanium atoms are selectively transferred to the interface between the resin composition of the present invention and the substrate, and the protective film and the substrate. It can be presumed that this is due to the intermediary between chemical and physical bonds.

The method for synthesizing the titanium soap used in the resin composition of the present invention is not particularly limited, but the reaction between the carboxylic acid compound and titanium metal, the reaction between the carboxylic acid compound and titanium oxide or hydroxide. Examples include metathesis method, melt direct method, semi-melt direct method wet direct method, solid phase direct method, solvent direct method using reaction of alkali metal salt of carboxylic acid compound and water-soluble titanium salt, etc. . Among the synthesis methods described above, the metathesis method and the semi-melt direct method are preferable examples from the viewpoint of reaction rate and ease of product separation. Properties such as solubility of titanium soap obtained by the synthesis method in a solvent may be different.
When the titanium soap (C) in the resin composition of the present invention is obtained by the metathesis method, it is possible to react the sodium salt of the carboxylic acid compound with divalent to tetravalent titanium chloride in water so that the titanium soap can be obtained in a high yield. In addition to being obtained, a protective film in which the obtained titanium soap is blended is preferred from the viewpoint of better adhesion.

  In the resin composition of the present invention, the carboxylic acid compound or alkali metal salt thereof, which is a raw material of the titanium soap (C), is a saturated or unsaturated carboxylic acid having a linear, branched or cyclic structure having 1 to 30 carbon atoms. An acid or an alkali metal salt thereof is preferably exemplified, and more preferably, a saturated or unsaturated aliphatic carboxylic acid having a linear or branched structure having 4 to 15 carbon atoms or an alkali metal salt thereof. Among these, caproic acid, caprylic acid (n-octanoic acid), 2-ethylhexanoic acid (octylic acid), capric acid, naphthenic acid, and alkali metal salts thereof are preferably used from the viewpoint of solubility in the resin composition. .

In the resin composition of the present invention, the titanium soap (C) can be used singly or in combination of two or more.
In the resin composition of the present invention, the blending ratio of the titanium soap (C) is 0.001 to 20% by weight, preferably 0.01 to 20% by weight, more preferably 0.00% in the solid content of the resin composition. When the blending ratio of the titanium soap (C) of 1 to 20% by weight, more preferably 0.2 to 15% by weight is less than 0.01% by weight in the above, the adhesion of the protective film and the ITO-resistant formation process The improvement of the property is insufficient, and if it exceeds 20% by weight, it is difficult to obtain the effect of the present invention because the transparency of the protective film is impaired.
Further, since titanium soap (C) has a different metal content depending on the type of ligand, the blending amount of the titanium soap is preferably defined by the metal content. In this case, the blending amount of the titanium soap (C) is preferably 0.003 to 3% by weight, more preferably 0.01 to 1.8% by weight in terms of titanium metal content in the solid content of the resin composition. %.

(Epoxy group-containing compound (D))
It is preferable to add an epoxy group-containing compound (D) having two or more epoxy groups in one molecule to the resin composition of the present invention. By adding the epoxy group-containing compound (D), the concentration of epoxy groups in the resin composition is increased, the crosslinking density of the color filter protective film is further increased, and the heat resistance can be improved.

  Examples of such an epoxy group-containing compound (D) include bisphenol A type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, and phenol novolak type epoxy. Resin, cresol novolac type epoxy resin, biphenol type or bixylenol type epoxy resin or a mixture thereof, naphthalene group-containing epoxy resin, stilbene type epoxy resin, alicyclic epoxy resin and its derivatives, hydroquinone type epoxy resin, fluorene skeleton Epoxy resin, tetraphenylolethane type epoxy resin, DPP (di-n-pentylphthalate) type epoxy resin, trishydroxyphenylmethane type epoxy resin, Aromatic polyglycidyl ethers such as cyclopentadiene phenol type epoxy resins; aliphatic polydioxy having 2 to 50 carbon atoms such as adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester Glycidyl ester; aromatic diglycidyl ester having 2 to 50 carbon atoms such as phthalic acid diglycidyl ester and isophthalic acid diglycidyl ester; aromatic amine such as N, N-diglycidyl-4-glycidyloxyaniline and tetraglycidyldiaminophenylmethane Epoxy resin, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether Aliphatic monoglycidyl ether having 1 to 50 carbon atoms; aromatic monoglycidyl ether, nonylphenyl glycidyl ether, cresyl glycidyl ether, s-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, N-glycidyl phthalimide and the like Glycidyl ether; aliphatic monoglycidyl ester having 2 to 50 carbon atoms such as glycidyl laurate, glycidyl stearate and glycidyl oleate, dicyclopentadiene skeleton-containing epoxy resin, brominated epoxy resin, trisphenol methane type epoxy resin , Aromatic glycidyl ethers such as resorcinol diglycidyl ether; hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, various aromatic glycidyl ethers Aliphatic glycidyl ethers such as hydrogenated or semi-hydrogenated epoxy resins of sidyl ethers and glycidyl ethers of aliphatic polyols (specifically, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,6-hexanediol diglycidyl ether, dipropylene glycol diglycidyl ether, tri Methylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl Ether, pentaerythritol polyglycidyl ether, sorbitan polyglycidyl ether, etc.); aromatic glycidyl esters such as diglycidyl phthalate and diglycidyl terephthalate; 1,2-cyclohexanedicarboxylic acid bis (2,3-epoxypropyl) ester, dimer Aliphatic glycidyl esters such as acid diglycidyl ester and tertiary carboxylic acid glycidyl ester; 1,2: 8,9 diepoxy limonene, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate , Ε-caprolactone modified 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 3,1-bis (3,4-epoxycyclohexylmethyl) adipate, 2- (7-oxabicycle [4.1.0] Heptyl 3-)-spiro [1,3-dione-5,3 ′-[7] Oxabicyclo [4.1.0] heptane, dicyclopentadiene dioxide, and other alicyclic compounds Epoxy compounds; N, N-diglycidyl-4-glycidyloxyaniline, tetraglycidyldiaminophenylmethane, aniline diglycidyl ether, N- (2-methylphenyl) -N- (oxiranylmethyl) oxiranemethanamine, N-glycidyl Examples thereof include glycidylamines such as phthalimide; heterocyclic epoxy compounds such as tris (2,3-epoxypropyl) isocyanurate; and butadiene homopolymer or copolymer epoxy group-containing compounds.

  Among these epoxy group-containing compounds, bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolak type epoxy resin, and low molecular weight alicyclic epoxy resin are preferable from the viewpoint of fluidity.

The molecular weight of the epoxy group-containing compound (D) in the resin composition of the present invention is usually 180 to 12,000, preferably 185 to 11,000, more preferably 250 to 8,000. If the molecular weight of the epoxy group-containing compound (D) is less than 180, the hardness of the protective film may be reduced, and if it exceeds 12,000, the appearance after coating may be reduced.
The epoxy equivalent of the epoxy group-containing compound (D) is preferably 60 to 4,000 g / mol, and more preferably 90 to 3,500 g / mol. If the epoxy equivalent of the epoxy group-containing compound (D) is less than 60 g / mol, the crosslink density increases, and the toughness of the protective film, particularly the hardness, may decrease. If the epoxy equivalent exceeds 4,000 g / mol, the protective film There is a possibility that the crosslink density of the protective layer becomes low and the hardness of the protective film is remarkably lowered.

The epoxy group-containing compound (D) in the resin composition of the present invention can be used alone or in combination of two or more.
In the resin composition of the present invention, the blending ratio when the epoxy group-containing compound (D) is contained is usually 1 to 45% by weight, preferably 2 to 40% by weight, more preferably in the solid content of the resin composition. 5 to 40% by weight. When the compounding ratio of the epoxy group-containing compound (D) is less than 1% by weight, it is difficult to obtain the toughness and the like obtained when the epoxy group-containing compound (D) is blended. Since the transparency of the protective film is impaired, it is difficult to obtain the effects of the present invention.

  In the resin composition of the present invention, an epoxy group-containing compound other than the epoxy group-containing compound (D) having one or more epoxy groups in one molecule may be added. In this case, the amount of the epoxy group-containing compound not included in (D) is preferably suppressed to less than 100% by weight based on the total weight of the component (A), the component (B) and the component (D). . When the amount of the epoxy group-containing compound not contained in the component (D) is 100% by weight or more, the hardness and applicability of the protective film after coating and curing are lowered, making it difficult to obtain the effects of the present invention.

Next, additives, organic solvents, and fillers that can be added in any amount to the resin composition of the present invention will be described.
(Storage stability improver)
Further, the resin composition of the present invention may further contain a pentavalent phosphorus atom-containing compound as a storage stability improver from the viewpoint of improving storage stability. Preferred examples of the pentavalent phosphorus atom-containing compound suitably used as a storage stability improver include phosphoric acid triesters. Examples of phosphoric acid triesters include triethyl phosphate, tributyl phosphate, triphenyl phosphate, and the like.
The blending ratio of the pentavalent phosphorus atom-containing compound arbitrarily blended as a storage stability improver in the resin composition of the present invention is usually 0.01 to 5% by weight, preferably in the solid content of the resin composition. It is 0.02 to 2 weight%, More preferably, it is 0.05 to 1 weight%. When the blending ratio of the pentavalent phosphorus atom-containing compound blended as the storage stability improver is less than 0.01% by weight in the above, the storage stability improving effect may be insufficient. If it exceeds 100%, the hardness and transparency of the protective film may be lowered.

(Curing accelerator)
In the present invention, a curing accelerator can be appropriately used as long as the colorless transparency of the protective film obtained by curing the resin composition of the present invention is not impaired.
However, since many of the curing accelerators are active even at room temperature, it is necessary to select a curing accelerator species and an addition amount that do not reduce the storage stability effect of the present invention. In the resin composition of the present invention, since the polyvalent carboxylic acid derivative (B) functions as a latent curing agent, the storage stability is good unless the deblocking reaction is accelerated. Therefore, a carboxyl group-epoxy group reaction accelerator that does not accelerate the deblocking reaction can be added to the resin composition as a curing accelerator.

Examples of the curing accelerator that can be added in the present invention include tertiary amines such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine; 1-cyanoethyl-2-ethyl-4-methylimidazole, 2 -Imidazoles such as ethyl-4-methylimidazole and 1-benzyl-2-methylimidazole; organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; tetraphenylphosphonium bromide, tetra-n-butylphosphonium bromide and the like Quaternary phosphonium salts; diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; quaternary ammonium such as tetraethylammonium bromide and tetrabutylammonium bromide S; boron trifluoride, boron compounds such as triphenyl borate and the like. Furthermore, high melting point dispersion type latent accelerators such as amine addition type accelerators added to epoxy resins such as high melting point imidazole compounds, dicyandiamide and amines; the surfaces of imidazole, phosphorus and phosphine accelerators are coated with a polymer A latent curing accelerator typified by a high-temperature dissociation type thermal cationic polymerization type latent curing accelerator such as an amine salt type latent curing accelerator can also be used. The curing accelerator is preferably halogen-free from the viewpoint of liquid crystal non-contamination property of the protective film.
These curing accelerators can be used singly or in appropriate combination of two or more. In the resin composition of the present invention, the blending ratio when these curing accelerators are included is usually 0.01 to 10% by weight in the solid content of the resin composition.

(Adhesion improvement aid)
A silane coupling agent can also be added to the resin composition of the present invention as an auxiliary agent for improving the adhesion between the protective film obtained by curing the resin composition and the substrate. Examples of the silane coupling agent that can be added include a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a (meth) acryloyl group, or a polymer thereof. Can be mentioned. These silane coupling agents can be added singly or in appropriate combination of two or more.
When the silane coupling agent is included, the blending ratio is usually 1 to 30% by weight, preferably 2 to 25% by weight, and more preferably 3 to 20% by weight in the solid content of the resin composition. If the blending amount of the silane coupling agent is less than 1% by weight, the effect of improving the adhesion of the protective film obtained by curing the resin composition to the substrate is insufficient. On the other hand, when the silane coupling agent exceeds 30% by weight, the performance such as the hardness of the protective film is lowered.

(Surfactant)
A surfactant may be added to the resin composition of the present invention for the purpose of improving the appearance of a protective film formed by curing the resin composition of the present invention. Surfactant can be used individually by 1 type or in combination of 2 or more types as appropriate. The surfactant may be added for the purpose of improving the compatibility of each component including the essential components (A) to (C) of the present invention.
When the surfactant is included, the blending ratio is preferably 0.001 to 3% by weight in the solid content of the resin composition.

(Organic solvent)
In the resin composition of the present invention, an organic solvent may be used for the purpose of adjusting viscosity and the like. Examples of organic solvents used here include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphate esters, nitriles, aprotic polar solvents, propylene glycol alkyl ether acetates, and the like. It is done. The organic solvent is preferably an organic solvent excluding alcohol or ionic solvent. It is known that the deblocking reaction may proceed with respect to the alcohol or the ionic solvent, because the storage stability of the resin composition may be significantly reduced and it may be difficult to obtain the effects of the present invention. is there.
These organic solvents can be used alone or in combination of two or more.
Moreover, there is no restriction | limiting in particular about the usage-amount of these organic solvents, According to the predetermined film thickness, the smoothness of expression, the film-forming method, etc., arbitrary amounts can be added and the applicability can be provided.

(Other ingredients)
To the resin composition of the present invention, viscosity adjusting agents such as thickeners and thixotropic agents may be further added for the purpose of adjusting the viscosity. Further, infrared rays or ultraviolet absorbers may be added.
Further, for the purpose of adjusting the linear expansion coefficient, improving the flatness, improving the surface hardness, adjusting the viscosity, adjusting the refractive index, absorbing light of a predetermined wavelength, improving the adhesiveness, etc., the resin composition of the present invention is filled with an arbitrary amount of filler. Can be added. The filler used in this case is not particularly limited as long as it does not hinder transparency, and examples thereof include silica sol, silica gel, titanium oxide, aluminum oxide, cerium oxide, tin oxide, zinc oxide, and zirconium oxide. These fillers can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, the resin composition of the present invention has a carbon dioxide gas generation inhibitor, a flexibility imparting agent, an antioxidant, a plasticizer, a lubricant, and a surface treatment as necessary, as long as the effects of the present invention are not impaired. Agent, flame retardant, antistatic agent, colorant, leveling agent, ion trap agent, sliding property improver, various rubber, organic polymer beads, glass beads, thixotropic agent, surface tension reducing agent, antifoaming agent, light Additives such as diffusing agents, antioxidants, and fluorescent agents can be blended.

(Method for producing resin composition)
Hereinafter, the blending, stirring, and dispersion methods of the resin composition of the present invention will be described.
In the resin composition of the present invention, the components including the essential components (A) to (C) may be blended together, or may be blended sequentially after each component is dissolved in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, a resin composition may be prepared by dissolving all components in a solvent at the same time, and if necessary, each component is appropriately made into two or more solutions, and these components are used at the time of use (coating). The solution may be mixed to prepare a resin composition.

In the resin composition of the present invention, with regard to stirring after mixing each component including the essential components (A) to (C), a blade-type stirrer, a desolver, a kneader, a ball mill mixer, a roll disperser, etc. The mixture may be used for stirring, or after each component is mixed in a container such as a gallon bottle, the container may be rotated by a mix rotor and stirred. Although the temperature of mixing and stirring is based also on a mixing | blending component, in order to avoid condensation and volatilization of a solvent, 10-60 degreeC is preferable normally.
When a viscosity modifier or filler is added to the resin composition of the present invention, dispersion using a high shear disperser such as a motor mill or a shaker may be performed. In this case, it is also possible to prepare a master batch in which each component including the essential components (A) to (C) in the present invention is used as a binder and mix it at the time of use. . However, since the deblocking reaction proceeds with heat in the polyvalent carboxylic acid derivative (B) of the present invention, when the composition containing the polyvalent carboxylic acid derivative (B) is dispersed, it should not be heated to 80 ° C. or higher. Consideration is required.

In the resin composition of the present invention thus prepared, the poorly soluble polyvalent carboxylic acid used as a curing agent is made latent (blocked, capped, protected) from the carboxyl group of the polyvalent carboxylic acid. Thus, the polycarboxylic acid derivative (B) having high solubility is used, and then dissolved and dispersed in a solvent. Therefore, the reaction point of a carboxyl group can coexist with an epoxy group at a high concentration in the resin composition, and a high crosslink density is obtained when a layer is formed using such a resin composition and heated. Further, the polyvalent carboxylic acid derivative (B) does not regenerate the carboxyl group unless it is heated to a predetermined temperature or higher according to the compound. Therefore, each of the epoxy group-containing polymer (A) and the epoxy group-containing compound (D) and the carboxyl group contained in the polyvalent carboxylic acid derivative (B) have high reaction point concentrations. Regardless, it maintains a good viscosity for a long period of time immediately after preparation and is extremely excellent in storage stability. Preferably, after preparing the resin composition, the viscosity after leaving in a sealed container for 120 days at 5 ° C. is 1.5 times or less of the initial viscosity, and more preferable, the viscosity after leaving for 120 days at 25 ° C. is the initial viscosity. The viscosity can be suppressed to 1.5 times or less.
As described above, the resin composition in the present invention is superior in storage stability as compared with the prior art, and has the advantage that it can be stored for one liquid for a long time and does not cause precipitation during storage or use. It is what. Moreover, the residual liquid of the composition (coating liquid) that has been once used is not deteriorated in a short work. Therefore, such residual liquid can be collected or reused by adding a fresh composition (coating liquid), which is economical.

  In addition, since the resin composition of the present invention is used in combination with a specific amount of the above-mentioned specific essential components including titanium soap, it is excellent in adhesion to the substrate of the layer of the resin cured product, heat resistance, low thermal expansion, It is a material excellent in total balance such as toughness and chemical resistance, and is excellent in ITO forming process resistance. Moreover, since the cured resin layer has visible light transmittance and can be applied to a uniform film thickness and is excellent in flatness, the resin composition of the present invention can be used for display devices and solid-state imaging devices. It can be particularly suitably used for forming an organic layer such as a filter protective film.

2. Color Filter The color filter according to the present invention has a layer of a cured resin product obtained by curing the resin composition for a color filter protective film according to the present invention.
The layer of the cured resin obtained by curing the resin composition for the color filter protective film is not particularly limited to what is generally referred to as a protective film. For example, RGB formed on the substrate of the color filter It refers to a layer of cured resin formed between a pixel and a liquid crystal alignment film, an ITO layer, a light emitter, or a light receiver. In addition, a case of a protective film that is not directly in contact with the RGB pixel but is indirectly protected through another material is also included. For example, an intermediate film used between a microlens and a color filter of a solid-state image sensor Alternatively, an intermediate film used between the color filter and the electrode is also included.

The color filter according to the present invention has a resin cured layer obtained by curing the resin composition for a color filter protective film according to the present invention. And a color filter having a layer of a cured resin having excellent ITO process resistance.
As an example, the color filter includes a black matrix formed in a predetermined pattern on a transparent substrate, a pixel portion formed in a predetermined pattern between the black matrix, and a protective film formed so as to cover the pixel portion. ing. A transparent electrode for driving liquid crystal may be formed on the protective film as necessary. Further, columnar spacers may be formed on the transparent electrode plate, the pixel portion, or the protective film in accordance with the region where the black matrix layer is formed.

The layer of the resin cured product obtained by curing the resin composition for a color filter protective film according to the present invention is a coating liquid by appropriately adjusting the viscosity of the resin composition for a color filter protective film according to the present invention. For example, it is applied to the surface of the color filter on which the colored layer is formed.
The method for applying the resin composition of the present invention is not particularly limited. Examples of commonly used application methods include spin coater application, dip application, spray coater application, roll coater application, screen, and the like. It can apply | coat to a base material individually or in combination, such as a printing application method, an offset printing application method, a slit coater application method, and a die coater application method.

Next, after drying the obtained coating film and performing preheating (hereinafter referred to as pre-baking) as necessary, a cured resin layer is formed through main curing heating (hereinafter referred to as post-baking). In this case, 40 to 140 ° C. and 0 to 1 hour are preferable as prebaking conditions, and 150 to 280 ° C. and 0.2 to 2 hours are preferable as post baking conditions. In addition, the heating method in this case is not particularly limited, and for example, a curing apparatus 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 can be performed by a method such as hot air circulation, infrared heating, high frequency heating or the like.
In addition to heat curing, when a photoacid generator or the like is added to the resin composition of the present invention, the protective film can be obtained by curing the resin composition with light. Examples of photoacid generators that can be selected include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts. Examples of these commercially available products include Sun-Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.).

Since the resin composition of the present invention is excellent in storage stability as described above, the viscosity does not increase during coating and the initial good coating property is maintained, and the coating composition is applied during the coating operation. It is not necessary to change the construction conditions frequently. Accordingly, it is possible to form a highly uniform coating film at high speed and continuously under the coating conditions set at the start of the operation. When the coating is heated after the coating is completed, the protective group of the polyvalent carboxylic acid derivative (B) contained in the coating is removed, and the carboxyl group is regenerated as shown in formula (1). A cross-linking reaction is caused with the epoxy group of the group-containing compound (components (A) and (D)), and the coating film is cured.
In addition, it is preferable that the layer of the resin cured material which concerns on this invention is 0.2-5 micrometers after coating, More preferably, it is 0.5-4 micrometers. When the film thickness after coating is less than 0.2 μm, it is difficult to obtain the performance required for a protective film such as barrier properties and flatness, and when it exceeds 5 μm, transparency, resistance to ITO formation process, etc. There is a possibility that the performance is lowered, which is not preferable. However, for applications where high flatness is desired, the film thickness after coating may be 5 to 20 μm.

  The layer of the resin cured product according to the present invention thus obtained is a cross-linked resin made of a compound containing a carboxylic acid compound and an epoxy group, so that it has chemical resistance and heat resistance (such as film reduction or discoloration due to heating). ). Furthermore, since the layer of the cured resin according to the present invention uses titanium soap (C) and the polyvalent carboxylic acid derivative (B) in combination, the adhesiveness to the substrate is remarkably high, and the ITO forming process resistance is improved. It has the advantage of being able to handle a wide variety of substrate types and CF forming processes that are excellent and diversified.

Specifically, the layer of the cured resin according to the present invention can be, for example, a layer having the following chemical resistance and heat resistance.
a) Chemical resistance: a resin cured product after a color filter provided with a layer of a cured resin according to the present invention is immersed in a solvent of either isopropyl alcohol, N-methylpyrrolidone or γ-butyrolactone at a liquid temperature of 40 ° C. for 1 hour. The film thickness reduction calculated by measuring the film thickness of each layer can be 10% or less even when immersed in any solvent.
b) Heat resistance: The film thickness reduction of the cured resin layer according to the present invention after leaving the color filter at 250 ° C. for 1 hour is 10% or less, and the color difference before and after the standing is 1 or less, more preferably 0. .3 or less.

Furthermore, the layer of the cured resin according to the present invention specifically includes, for example, the following excellent adhesiveness, ITO forming process resistance (acid-alkali resistance (etching resistance) after forming ITO circuit), ITO circuit It can be set as the layer which has the heat resistance in 230-250 degreeC after formation).
c) Adhesiveness: The color filter provided with the resin cured product layer according to the present invention was subjected to a PCT test (left at 121 ° C. in an environment of 100% humidity for 8 hours), and then JIS K5600-5. The mechanical property-adhesiveness (cross-cut method) test method of the coating film specified in 6 can be performed to prevent peeling.
d) Adhesion after heat treatment: After heating the color filter provided with the cured resin layer according to the present invention at 250 ° C. for 1 hour, PCT test (left at 121 ° C. in 100% humidity environment for 8 hours) After the treatment, a mechanical property-adhesiveness (cross-cut method) test method of the coating film defined in JIS K5600-5-6 can be performed to eliminate peeling.
e) Acid-alkali resistance (etching resistance) after forming the ITO circuit: After forming the ITO layer on the cured resin layer of the color filter provided with the cured resin layer according to the present invention, the etching resist is striped. After forming an etching resist at 60 ° C. for 10 minutes, acid treatment (H ₂ O / HCl / HNO ₃ = 1/1 / 0.04 <weight ratio>) is performed at 50 ° C. for 8 minutes. Even after alkali treatment (5% NaOHaq) is performed at 50 ° C. for 3 minutes or 18 minutes, the ITO layer and the cured resin layer can be free from cracks or wrinkles.
f) Heat resistance after forming the ITO circuit: After forming the ITO layer on the cured resin layer of the color filter provided with the cured resin layer according to the present invention, at 230 ° C. or 250 ° C. for 30 minutes or Even after the treatment for 1 hour, the ITO layer and the cured resin layer can be free from cracks or wrinkles.
The protective film prepared in the present invention exhibits superior adhesion and ITO forming process resistance as compared with the conventional one as described above, which contributes to the fact that the protective film has a very high crosslinking density. Presumed to be.
The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

(Production Example A-1: Synthesis of epoxy group-containing polymer (A))
A 500 mL four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel was charged with 160 parts by weight of propylene glycol monomethyl ether acetate (hereinafter PGMEA) and heated to 80 ° C. while stirring. did. Subsequently, 100 parts by weight of glycidyl methacrylate (hereinafter referred to as GMA), 100 parts by weight of cyclohexyl methacrylate (hereinafter referred to as CHMA) at a temperature of 80 ° C., a peroxide-based polymerization initiator “Perhexyl O” (trade name) manufactured by NOF Corporation. , Purity 93%) "(hereinafter, PHO) 8 parts by weight and PGMEA 32 parts by weight were mixed in advance (dropping component) at a constant rate from a dropping funnel over 2 hours. After completion of the dropping, the temperature was maintained at 98 ° C. for 7 hours, and then the reaction was terminated. Weight average molecular weight (Mw) 14,000, solid content 53%, viscosity 2.6 Pa · s (20 ° C.) and epoxy equivalent of solution 590 g / mol of polymer solution (epoxy equivalent of epoxy group-containing polymer) 310 g / mol) was obtained.

In addition, the measuring method of the said weight average molecular weight, solid content, a viscosity, and an epoxy equivalent is shown below.
<Weight average molecular weight>
The weight average molecular weight (Mw) was measured by using a gel permeation chromatography device HLC-8220GPC manufactured by Tosoh Corporation, using SHODEX K-801 manufactured by Showa Denko KK as a column, THF as an eluent, and using an RI detector. Measured and calculated by polystyrene conversion.
<Viscosity>
The viscosity was measured at a temperature of 20 ° C. using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.) equipped with a circulating constant temperature water bath.
<Epoxy equivalent>
The epoxy equivalent was measured by a method defined by JIS K 7236: 2001 “How to Determine Epoxy Equivalent of Epoxy Resin”.

(Production Examples A-2 to A-5, Comparative Production Example A′-6: Synthesis of Epoxy Group-Containing Polymer (A) and Comparative Epoxy Group-Containing Polymer (A ′))
In the same manner as in Production Example A-1, an epoxy group-containing polymer (A-2 to A-5) and a comparative epoxy group-containing polymer (A′-6) were obtained. The charging ratio, dropping temperature, weight average molecular weight, solid content, viscosity and epoxy equivalent of each raw material are shown in Table 1 together with Production Example A-1.

なお、表中の略号は以下の通りである。
＊１：サイクロマーＭ−１００、脂環式エポキシ基含有モノマー、ダイセル化学工業（株）製商品名
＊２：ビニルベンゼングリシジルエーテル、セイミケミカル（株）製
＊３：スチレン

The abbreviations in the table are as follows.
* 1: Cyclomer M-100, alicyclic epoxy group-containing monomer, product name manufactured by Daicel Chemical Industries, Ltd. * 2: Vinylbenzene glycidyl ether, manufactured by Seimi Chemical Co., Ltd. * 3: Styrene

(Production Example B-1: Synthesis of polyvalent carboxylic acid derivative (B))
In a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 27 parts by weight of PGMEA, 27 parts by weight of trimellitic acid (hereinafter, TMA) manufactured by Mitsubishi Gas Chemical Co., Ltd., n-propyl vinyl ether (hereinafter, nPr-VE) 46 parts by weight was charged and heated with stirring to 70 ° C. Next, stirring was continued while maintaining the temperature, and the reaction was terminated when the acid value of the mixture became 2.0 mgKOH / g or less, and two or more blocked carboxyl groups having an acid value of 0.64 mgKOH / g in the solution were obtained. The hardening | curing agent solution (B-1) which has was obtained.
The acid value and the total acid equivalent are measured by measuring the hydrolysis acid value according to JIS K 0070: 1992 “Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. did.

(Production Examples B-2 to B-5: Synthesis of polyvalent carboxylic acid derivative (B))
Polyvalent carboxylic acid derivatives (B-2 to B-5) were obtained in the same manner as in Production Example B-1. Table 2 shows the charging ratio, reaction temperature, acid value, and total acid equivalent of each raw material.

なお、表中の略号は以下の通りである。
＊１：ペンタエリスリトール（以下、ＰＥ）と無水トリメリット酸のハーフエステル化物。式（１）において、６員環がベンゼン環、Ｒ1が炭素数５のペンタエリスリチル残基、ｎ＝４、ｍ１＝１、ｔ１＝０に相当する。
＊２：１，２，４−シクロヘキサントリカルボン酸
＊３：プロピレングリコール（以下、ＰＧ）とメチルヘキサヒドロ無水フタル酸（以下、ＭＨＨＰＡ）のハーフエステル化物。式（１）において、６員環がシクロヘキシル環、Ｒ1が炭素数３のイソプロピレン残基、Ｒ２がメチル基、ｎ＝２、ｍ１＝０、ｔ１＝１に相当する。
＊４：イソプロピルビニルエーテル
＊５：アジピン酸

The abbreviations in the table are as follows.
* 1: Half-esterified product of pentaerythritol (PE) and trimellitic anhydride. In the formula (1), the 6-membered ring corresponds to a benzene ring, R 1 represents a pentaerythrityl residue having 5 carbon atoms, n = 4, m1 = 1, and t1 = 0.
* 2: 1,2,4-cyclohexanetricarboxylic acid * 3: Half-esterified product of propylene glycol (hereinafter referred to as PG) and methylhexahydrophthalic anhydride (hereinafter referred to as MHHPA). In the formula (1), a 6-membered ring corresponds to a cyclohexyl ring, R1 represents an isopropylene residue having 3 carbon atoms, R2 represents a methyl group, n = 2, m1 = 0, and t1 = 1.
* 4: Isopropyl vinyl ether * 5: Adipic acid

(Examples 1-8)
Each component was sufficiently stirred and dissolved at the blending ratio shown in Table 3 to obtain a resin composition for a color filter protective film.

なお、表中の略号は以下の通りである。
＊１：製造例の固形分のみを記述した。溶剤は全て最下段に計上した。
＊２：Ｃ−１は２−エチルヘキサン酸チタン、Ｃ−２はカプロン酸チタンを表す。
＊３：Ｄ−１はエピコート８２８（ジャパンエポキシレジン（株）製商品、エポキシ当量約１９０（ｇ／ｍｏｌ）、ビスフェノールＡ型エポキシ樹脂）；Ｄ−２はエピコート１００７（ジャパンエポキシレジン（株）製商品、エポキシ当量約２，０００（ｇ／ｍｏｌ）、ビスフェノールＡ重合型エポキシ樹脂）；Ｄ−３はエピコート１５７（ジャパンエポキシレジン（株）製商品、エポキシ当量約２１０（ｇ／ｍｏｌ）、ビスフェノールＡノボラック型エポキシ樹脂）、Ｄ−４はセロキサイド２０２１（ダイセル化学工業（株）製商品、エポキシ当量約１３０（ｇ／ｍｏｌ）、脂環式エポキシ樹脂）、Ｄ−５はエポトートＹＤＰＮ−６３８（東都化成（株）製商品、エポキシ当量約１８０（ｇ／ｍｏｌ）、フェノールノボラック型エポキシ樹脂）を表す。
＊４：ＫＢＭはγ−グリシドキシプロピルトリメトキシシラン「ＫＢＭ５０３（信越化学工業（株）製商品）」を表す。
＊５：ＰＧＭＥＡはプロピレングリコールモノメチルエーテルアセテートを表す。

The abbreviations in the table are as follows.
* 1: Only the solid content of the production example is described. All solvents were counted at the bottom.
* 2: C-1 represents titanium 2-ethylhexanoate, and C-2 represents titanium caproate.
* 3: D-1 is Epicoat 828 (product made by Japan Epoxy Resin Co., Ltd., epoxy equivalent of about 190 (g / mol), bisphenol A type epoxy resin); D-2 is Epicoat 1007 (made by Japan Epoxy Resin Co., Ltd.) Product, epoxy equivalent of about 2,000 (g / mol), bisphenol A polymerization type epoxy resin); D-3 is Epicoat 157 (product of Japan Epoxy Resin Co., Ltd., epoxy equivalent of about 210 (g / mol), bisphenol A Novolac type epoxy resin), D-4 is Celoxide 2021 (product of Daicel Chemical Industries, epoxy equivalent: about 130 (g / mol), alicyclic epoxy resin), D-5 is Epototo YDPN-638 (Tohto Kasei) Product made by Co., Ltd., epoxy equivalent of about 180 (g / mol), phenol novolac type epoxy tree ) Represents the.
* 4: KBM represents γ-glycidoxypropyltrimethoxysilane “KBM503 (product of Shin-Etsu Chemical Co., Ltd.)”.
* 5: PGMEA represents propylene glycol monomethyl ether acetate.

  The storage stability test of each color filter protective film resin composition was performed by the following method. Each resin composition was filtered through a membrane filter having a pore size of 0.2 μm, and then rotated at 800 rpm on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd .; trade name: OA-10, non-alkali glass) using a spin coater. Applied. After coating, the glass substrate was dried in a clean oven at 80 ° C. for 5 minutes and then treated in a clean oven at 230 ° C. for 30 minutes to cure the coating film. In all cases of the examples, the surface of the obtained coating film was very smooth and no pinholes were observed. The film thickness measured by a fine shape measuring instrument (manufactured by Kosaka Laboratory Ltd .; trade name: SURFCORDER ET400) was 2.0 to 2.5 μm. Moreover, about the layer of the resin cured material of each obtained resin composition for color filter protective films, the adhesiveness after a PCT test, the adhesiveness after a PCT test after heat processing, and ITO formation process resistance (ITO circuit) by the following method Each test of acid-alkali resistance after formation and heat resistance after ITO circuit formation was performed. The results are shown in Table 4.

<Storage stability>
The storage stability was evaluated by observing the rate of increase in viscosity (/ initial viscosity) after storing the resin composition solution in a sealed container at a constant temperature of 5 ° C. and 25 ° C. for 120 days. The viscosity was measured by the above method.
<Adhesion after PCT test>
After the sample on which the protective film is formed is subjected to a pressure cooker test (PCT) (left at 121 ° C. in an environment of 100% humidity for 8 hours), the mechanical properties of the coating film specified in JIS K5600-5-6 A property-adhesion (cross-cut method) test method was performed.
<Adhesiveness after PCT test after heat treatment>
The sample on which the protective film is formed is heated at 250 ° C. for 1 hour and then subjected to PCT treatment (left at 121 ° C. in an environment of 100% humidity for 8 hours), and then the coating specified in JIS K5600-5-6. A mechanical property-adhesion (cross-cut method) test method of the film was performed.
<Etching resistance after ITO>
On the protective film of the sample on which the protective film is formed, the sputtering temperature is 230 ° C., the SiO ₂ layer film thickness is 100 to 150 mm, the ITO layer film thickness is 2,500 to 3,000 mm, and the resistance value is 10 to 15Ω / □. After the ITO layer was formed as described above, an etching resist was applied in a stripe shape. After forming an etching resist at 60 ° C. × 10 minutes, acid treatment (H ₂ O / HCl / HNO ₃ = 1/1 / 0.04 <weight ratio>, 50 ° C. × 8 minutes) and alkali treatment (5 With respect to the sample after being subjected to% NaOHaq, 50 ° C. × 3 minutes or 18 minutes, it was visually confirmed that no cracks or wrinkles occurred in the ITO layer and the protective film.
<Heat resistance after ITO>
As with the post-ITO etching resistance, after the ITO layer is formed on the sample on which the protective film is formed, cracks or wrinkles are not generated on the ITO layer and the protective film with respect to the sample after being treated at 230 or 250 ° C. for 1 hour. Was confirmed visually.

なお、表４において○および◎は要求性能を満たしていることを、×または△は要求性能を満たしていないことを示す。また、表中の略号は以下の通りである。
＊１：◎は２５℃で１２０日間、○は５℃で１２０日間貯蔵後の粘度上昇率が１．５未満であったことを示し、×は５℃で１２０日間貯蔵後の粘度上昇率が１．５以上であったことを示す。
＊２：○は剥離が無くクロスカット時に縁欠けも無いことを、△は縁欠けが観測されるか１００マス中１〜５０マス剥離したことを、×は５１マス以上剥離したことを示す。
＊３：○はアルカリ処理後もクラックまたはシワが観測されなかったことを、×はアルカリ処理１８分間後にクラックまたはシワが観測されたことを示す。
＊４：◎は２５０℃処理後もクラックまたはシワが観測されなかったことを、○は２５０℃処理後にはクラックまたはシワが観測されたが、２３０℃処理後にはクラックまたはシワが観測されなかったことを、×は２３０℃処理後にクラックまたはシワが観測されたことを示す。

In Table 4, ◯ and ◎ indicate that the required performance is satisfied, and x or Δ indicates that the required performance is not satisfied. Abbreviations in the table are as follows.
* 1: ◎ indicates that the viscosity increase rate after storage at 25 ° C. for 120 days, and ○ indicates that the viscosity increase rate after storage at 5 ° C. for 120 days was less than 1.5, and × indicates the viscosity increase rate after storage at 5 ° C. for 120 days. It shows that it was 1.5 or more.
* 2: ◯ indicates no peeling and no edge chipping at the time of cross-cutting, Δ indicates that edge chipping is observed or 1-50 squares peeled out of 100 squares, and x indicates that 51 squares or more were peeled off.
* 3: ◯ indicates that no cracks or wrinkles were observed even after the alkali treatment, and x indicates that cracks or wrinkles were observed 18 minutes after the alkali treatment.
* 4: ◎ indicates that no cracks or wrinkles were observed even after 250 ° C treatment, ○ indicates that cracks or wrinkles were observed after 250 ° C treatment, but no cracks or wrinkles were observed after 230 ° C treatment. This indicates that cracks or wrinkles were observed after the treatment at 230 ° C.

(Comparative Examples 1-6)
Each component was sufficiently stirred and dissolved at the blending ratio shown in Table 5 to obtain a resin composition for a color filter protective film of a comparative example.

なお、表中の略号は以下の通りである。
＊１：Ｂ’−６は無水トリメリット酸
＊２：Ｃ’−３は２−エチルヘキサン酸亜鉛とＮ−メチルモルホリンの反応物（潜在性触媒）、Ｃ’−４は２−エチルヘキサン酸スズ、Ｃ’−５はプレンアクトＫＲＴＴＳ（味の素ファインテクノ（株）製商品、チタンカップリング剤）を表す。

The abbreviations in the table are as follows.
* 1: B'-6 is trimellitic anhydride * 2: C'-3 is a reaction product (latent catalyst) of zinc 2-ethylhexanoate and N-methylmorpholine, C'-4 is 2-ethylhexanoic acid Tin and C′-5 represent Preneact KRTTS (Ajinomoto Fine Techno Co., Ltd. product, titanium coupling agent).

  Further, the storage stability of the comparative resin composition was evaluated in the same manner as in the Examples. Moreover, the layer of the resin cured material was obtained by the completely same method as the Example using the resin composition of the comparative example. In all cases of the comparative examples, the surface of the obtained coating film was smooth and no pinholes were observed. The film thickness measured in Examples was 2.0 to 2.5 μm. Moreover, each test of adhesiveness and ITO formation process property was done like the Example about the layer of the obtained resin cured material. The results are shown in Table 6.

なお、表中の評価基準及び略号は表４と同じである。

The evaluation criteria and abbreviations in the table are the same as those in Table 4.

From the results of Table 4 and Table 6, in the case of Examples 1 to 8 using the resin composition of the present invention, the obtained composition had excellent storage stability, and the adhesion of the protective film after curing It can be seen that the processability and the ITO-proof processability are excellent so that the performance required in recent years can be achieved. Moreover, since the resin composition of this invention consists of an epoxy compound and a carboxylic acid compound, the protective film after hardening is excellent in transparency, chemical resistance, and heat resistance.
In Comparative Example 1, although the storage stability satisfies the required performance, since titanium soap is not included, the adhesion after heating and the etching resistance after ITO resistance were inferior. In Comparative Example 2, although the storage stability satisfies the required performance, titanium soap is not included, resulting in poor adhesion and ITO formation resistance. In Comparative Example 3, trimellitic anhydride was used as the curing agent, so that the storage stability was inferior, and the adhesion and the ITO forming process resistance were remarkably inferior. In Comparative Example 4, since tin metal soap was used instead of titanium, the storage stability was inferior, and the adhesion and the ITO forming process resistance were remarkably inferior. In Comparative Example 5, since a general titanium coupling agent was used, the adhesion and the ITO forming process resistance satisfied the required performance, but the storage stability was extremely inferior. In Comparative Example 6, although the storage stability was excellent, the epoxy group-containing polymer and the titanium soap were not included, so that the adhesion and the ITO forming process resistance were inferior.

Claims (7)

An epoxy group-containing polymer (A) having a weight average molecular weight of 3000 to 100,000 and an epoxy equivalent of 140 to 1000 g / mol and polymerized using at least a monomer containing a carbon-carbon unsaturated bond and an epoxy group. ), A polyvalent carboxylic acid derivative (B) in which the carboxyl group of the carboxylic acid (b1) is made latent by the vinyl ether compound (b2), and a titanium soap (C). 10 to 80 wt%, (B) 5 to 70 wt%, and (C) 0.001 to 20 wt% resin composition for a color filter protective film. The resin composition for a color filter protective film according to claim 1, wherein the polyvalent carboxylic acid derivative (B) is obtained by latentizing a carboxylic acid having a structure represented by the following formula (1) with a vinyl ether compound (b2). object.

(The 6-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 2, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.) The color filter protective film according to claim 1 or 2, wherein the polyvalent carboxylic acid derivative (B) is a carboxylic acid having a structure represented by the following formula (2) latentized by a vinyl ether compound (b2). Resin composition.

(In the formula, m2 is an integer of 0 to 2.) The color filter protective film according to claim 1 or 2, wherein the polyvalent carboxylic acid derivative (B) is a carboxylic acid having a structure represented by the following formula (3) latentized by a vinyl ether compound (b2). Resin composition.

(An integer of m3 is 0 to 2 in the formula, .R ² is t3 is an integer from 0 to 1 is an alkyl group having 1 to 5 carbon atoms.)   Furthermore, the resin composition for color filter protective films in any one of Claims 1 thru | or 4 containing the epoxy group containing compound (D) which has 2 or more of epoxy groups in 1 molecule.   The color filter protective film according to any one of claims 1 to 5, wherein the titanium soap (C) is a reaction product of divalent to tetravalent titanium chloride and an aliphatic carboxylic acid having 4 to 16 carbon atoms. Resin composition.   A color filter having a layer of a cured resin obtained by curing the resin composition for a color filter protective film according to any one of claims 1 to 6.