KR20060103072A - Resin composition for protective film of color filter, and color filter - Google Patents

Abstract

It provides not only the basic performance of visible light transmittance and solvent resistance of the layer of cured resin obtained after curing, but also excellent curability and storage stability, and provides a resin composition for color filter protective films excellent in adhesion and ITO formation processability. By using the resin composition which achieves the said objective, it provides not only the basic performance of visible light transmittance and solvent resistance, but also provides the color filter which has the layer of the resin cured material excellent in adhesiveness and ITO formation processability.

An epoxy group-containing polymer (A) polymerized using a monomer having a weight average molecular weight of 5000 to 40000, an epoxy equivalent of 140 to 400 g / mol, and containing at least a carbon-carbon unsaturated bond and an epoxy group, and a molecular weight of 330 to Epoxy group-containing compound (B), which is a derivative of bisphenol A having an epoxy equivalent of 150 to 3500 g / mol and having two or more epoxy groups, and a carboxylic acid (c1) having a specific structure are vinyl ether compounds (c2) It is a resin composition for color filter protective films containing the polyhydric carboxylic acid derivative (C) latent by using.

Color filter, protective film, resin composition

Description

Resin composition for color filter protective films, and color filter {RESIN COMPOSITION FOR PROTECTIVE FILM OF COLOR FILTER, AND COLOR FILTER}

[Document 1] Japanese Unexamined Patent Publication No. 7-126352

[Document 2] Japanese Unexamined Patent Publication No. 2001-350010

This invention relates to the resin composition for color filter protective films used for a liquid crystal display device (LCD), a solid-state image sensor (CCD, etc.), an electroluminescent device (ELD), etc., and the color filter using this resin composition.

Conventionally, color filters (hereinafter also referred to as CF) used in liquid crystal displays (LCDs), solid-state imaging devices (CCDs, etc.), electroluminescent devices (ELDs), and the like are used for the purpose of flattening irregularities of RGB resists or RGB resists. A layer called a protective film is provided between the RGB resist and the liquid crystal alignment film or the ITO layer or the like for the purpose of protecting the liquid crystal or the like from the ionic material bleed out. The protective film is required for performance such as transparency, chemical resistance, heat resistance, adhesion, ITO formation processability, and flatness. In particular, in recent years in the development of display devices for home television applications, the adhesion that greatly affects the lifespan and higher electrical characteristics have been required as the size has been increased, resulting in a more strict ITO forming process. CF protective films having ITO formation processability have been required.

Adhesion refers to the adhesion between the protective film and glass or RGB resist, and is an important performance related to the life of CF. Furthermore, the adhesive film is required for the protective film not to be peeled from the glass or the RGB resist even under high temperature, high distortion, acid or alkali immersion in the ITO forming step. In addition, the ITO formation processability is resistance to defects in forming an ITO circuit or in forming an alignment film, specifically, acid-alkali resistance (etching resistance) in forming an ITO circuit and heat resistance at 230 to 250 ° C. after forming an ITO circuit. Can be mentioned. In order to be excellent in the ITO formation processability, in addition to the above adhesiveness, it is required to be a material having excellent harmony in all of heat resistance, low thermal expansion, toughness, chemical resistance and the like.

As a resin composition for CF protective films, JP-A-7-126352 discloses a resin composition for CF protective films containing a combination of an epoxy compound, a curing agent, and a specific solvent. Especially, the CF protective film which thermosetted the epoxy resin composition containing an epoxy compound and a carboxylic acid compound (or carboxylic anhydride) has been used as a suitable material from the point of transparency, chemical-resistance, and heat resistance. However, the resin composition containing an epoxy compound and a hardening | curing agent was not necessarily excellent in adhesiveness or ITO formation processability. In addition, the epoxy compound reacts with the functional group of the curing agent even at room temperature, resulting in poor storage stability.

Storage stability is one of the performances required in resin compositions. When the resin composition is thickened at the time of storage, applicability | paintability falls remarkably, control of the film thickness of a protective film becomes difficult, and fatal nonuniformity arises in a protective film. In order to improve the storage stability at the time of storage, the method of storing each component reacting under low temperature and sealing which are storage conditions separately (two liquefaction), etc. is taken. However, any technique is a cause of the cost increase in storage and CF manufacture. In particular, when performing two-liquefaction, it is necessary to mix immediately before use, and since it is necessary to leave it for a long time until the bubble produced at this time disappears, there existed a problem in productivity. In addition, even when performing two-liquidization, the problem which precipitated and the thickening remained at the time of application | coating remained, and the resin composition excellent in storage stability was strongly requested | required.

Numerous studies have been made on the improvement of the storage stability of the resin composition for the CF protective film. For example, Japanese Patent Laid-Open No. 2001-350010 discloses a resin composition for CF protective film using an epoxy group-containing resin and a polyvalent carboxylic acid derivative. Since the polyhydric carboxylic acid derivative is a compound in which carboxylic acid was latent with vinyl ether, the said resin composition had the characteristic which was very excellent in storage stability. However, in order to satisfy the high adhesiveness and ITO formation processability which are currently requested | required of CF protective film, it was necessary to mix | blend comparatively many strong catalysts with active activity which promotes a thermosetting reaction with a resin composition. Since this catalyst having a high activity has some activity even at room temperature, it may not be able to exhibit the storage stability which is the greatest advantage when it is compounded relatively large.

On the other hand, in order to improve adhesiveness, the method of adding a silane coupling agent, a titanate coupling agent, etc. to a resin composition is generally taken. However, when the silane coupling agent and the titanate coupling agent were each used alone, the adhesiveness could not be sufficiently provided to the resin composition. In addition, when using a silane coupling agent and a titanate coupling agent together, the functional group and each coupling agent of a silane coupling agent, a titanate coupling agent, or a hardening | curing agent will react at room temperature. Therefore, when using a coupling agent together, although the adhesive improvement effect is high, there existed a problem that a resin composition thickens even at room temperature, and storage stability falls remarkably.

The present invention has been accomplished in view of the above facts, and its first object is to have excellent curability and storage stability, and not only to have the basic performance of the heat-resistant or solvent-resistant layer of the cured resin, but also the adhesion and ITO formation process. It is providing the resin composition for color filter protective films excellent in the property.

Moreover, the 2nd object of this invention is not only to provide the basic performance of heat resistance and solvent resistance, but also to provide the color filter which has a layer of the resin hardened | cured material excellent in adhesiveness and ITO formation processability.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, as a result, the specific resin composition has the outstanding curability and storage stability, and the layer of the cured resin product has not only good heat resistance and solvent resistance, but also the adhesiveness and ITO formation process. It was found that sex was superior and the present invention was completed.

That is, the resin composition for color filter protective films which concerns on this invention superposes | polymerizes using the monomer with a weight average molecular weight of 5000-40000, an epoxy equivalent of 140-600 g / mol, and containing at least a carbon-carbon unsaturated bond and an epoxy group. Epoxy group-containing polymer (A), an epoxy group-containing compound (B) which is a derivative of bisphenol A having a molecular weight of 330 to 7000, an epoxy equivalent of 150 to 3500 g / mol and having two or more epoxy groups, The carboxylic acid (c1) having a structure contains a polyvalent carboxylic acid derivative (C) latent with a vinyl ether compound (c2).

In the formula, the six-membered ring is an aromatic or alicyclic hydrocarbon. m1 is an integer of 0-2, t1 is an integer of 0-1, n is an integer of 1-4. In addition, 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.

example In the present invention, the poorly soluble polyvalent carboxylic acid used as the curing agent is blocked by carboxyl group of the polyvalent carboxylic acid, thereby dissolving in a solvent after being in the form of a highly soluble polyvalent carboxylic acid derivative (C). Disperse and use. Therefore, the reaction point of a carboxyl group can coexist in high concentration with an epoxy group in a resin composition, and when a layer is formed and heated using such a resin composition, the protective film of high crosslinking density is obtained. In addition, a polyhydric carboxylic acid derivative (C) does not regenerate a carboxyl group unless it heats more than predetermined temperature according to the said compound. Therefore, although the reaction point concentration of each of the epoxy group contained in the epoxy group-containing polymer (A) and the epoxy group-containing compound (B) and the carboxyl group contained in the polyvalent carboxylic acid derivative (C) is high, it is for a long time immediately after preparation. The storage stability is very excellent by continuing to maintain a good viscosity.

In particular, according to the present invention, by using the specific epoxy group-containing polymer (A) and the specific epoxy group-containing compound (B) in combination with a specific amount of the specific polyvalent carboxylic acid derivative (C), it has excellent curability and storage stability. In addition, the layer of the cured resin product has not only good heat resistance and solvent resistance but also sufficiently excellent adhesion and ITO process formation resistance. Therefore, when the compounding quantity of the catalyst with a strong activity used conventionally is not reduced in storage stability, specifically, when the total weight of the said (A) component, the said (B) component, and the said (C) component is 100 weight part, 100 Even if it is suppressed to about 0.1 weight part or less as a metal atom with respect to a weight part, even if it is not used, the high adhesiveness and ITO formation processability currently requested | required of a CF protective film can be achieved, and further, it is very excellent without damaging storage stability. Do.

As a preferable embodiment in the resin composition for CF protective films which concerns on this invention, the said polyhydric carboxylic acid derivative (C) mentions that carboxylic acid which has a structure of following General formula (2) was latent by propyl vinyl ether. . In such a case, even when hardened at a lower temperature of 180 ° C. or lower, it has an advantage of having good adhesion and ITO formation processability at high crosslinking density.

In formula, m2 is an integer of 0-2.

Moreover, as another preferable embodiment in the resin composition for CF protective films which concerns on this invention, the said polyhydric carboxylic acid derivative (C) is the carboxylic acid which has a structure of following General formula (3) by a vinyl ether compound (c2). And latent ones. In this case, not only is it excellent in storage stability because of high de-latent temperature, but also it is colorless and transparent, and it has the advantage that there is little discoloration under long-term high temperature conditions but high energy light irradiation.

In formula, m3 is an integer of 0-2, t3 is an integer of 0-1. R ² is an alkyl group having 1 to 5 carbon atoms.

In the resin composition for CF protective films which concerns on this invention, it is preferable at the point which further improves adhesiveness to contain titanium soap and / or zirconium soap as an adhesive improving agent (D).

Moreover, in the resin composition for CF protective films which concerns on this invention, it is preferable to further contain a pentavalent phosphorus atom containing compound as a storage stability improving agent (E) from the point of further improving storage stability.

On the other hand, the color filter which concerns on this invention has a layer of the resin cured material formed by hardening | curing the resin composition for color filter protective films which concerns on the said invention.

The resin composition for color filter protective films which concerns on this invention has the outstanding curability and storage stability, and the layer of cured resin is good in heat resistance and solvent resistance, and can fully obtain adhesiveness and ITO process formation property. Therefore, even if the compounding amount of the active catalyst, which has been used conventionally, is suppressed or not used, it is possible to achieve high adhesion and ITO formation processability, which are required for the CF protective film in recent years, and further excellent without damaging the storage stability. Do.

Moreover, according to this invention, the color filter which has not only the basic performance of heat resistance and solvent resistance but also the layer of the resin hardened | cured material excellent in adhesiveness and ITO formation processability can be obtained.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in detail.

1. Resin composition for color filter protective film

The resin composition for color filter protective films according to the present invention contains an epoxy group polymerized using a monomer having a weight average molecular weight of 5000 to 40000, an epoxy equivalent of 140 to 600 g / mol, and a monomer containing at least a carbon-carbon unsaturated bond and an epoxy group. A polymer (A), an epoxy group-containing compound (B) which is a derivative of bisphenol A having a molecular weight of 330 to 7000, an epoxy equivalent of 150 to 3500 g / mol and having two or more epoxy groups, and a structure of the following general formula (1) The carboxylic acid (c1) contains a polyvalent carboxylic acid derivative (C) latent with a vinyl ether compound (c2).

<Formula 1>

In the formula, the six-membered ring is an aromatic or alicyclic hydrocarbon. m1 is an integer of 0-2, t1 is an integer of 0-1, n is an integer of 1-4. In addition, 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, in this invention, CF (color filter) protective film means what is widely used for the display apparatus and solid-state image sensor which have CF, More specifically, a liquid crystal display device (LCD), a solid-state image sensor (CCD etc.), an electric field It means an organic layer formed between an RGB pixel of CF used for a light emitting device (ELD), etc., and a liquid crystal aligning film, an ITO layer, a light emitting body, a light receiving body, etc. It is not specifically limited to what is generally called a protective film, and also the case where the protective film which protects indirectly through another material, even if it does not directly contact an RGB pixel, is included, for example, between the microlens of a solid-state image sensor, and a color filter. Also included are interlayers used, or interlayers used between color filters and electrodes.

(Epoxy group-containing polymer (A))

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

The epoxy group containing polymer (A) in the resin composition of this invention can be copolymerized by the polymerization method of a conventional method. That is, the polymerization method is not particularly limited, and polymerization methods such as radical polymerization and ionic polymerization can be used, and more specifically, in the presence of a polymerization initiator, such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method and the like. The polymerization method can be used. Depending on the polymerization method, a large amount of monomer may remain. However, when the monomer affects the protective film properties after coating curing, the monomer may be removed by a vacuum distillation method, a reprecipitation forming method, or the like.

In the resin composition of the present invention, the epoxy group-containing polymer (A) may be used by mixing two or more kinds having different molecular weights and comonomer species.

The epoxy group containing polymer (A) in the resin composition of this invention has what has a structural unit represented by following formula (4)-6 as a structural unit as a preferable example.

In formula, R <^3> is a hydrogen atom or a C1-C5 alkyl group, R <^4> is a hydrogen atom or a C1-C2 alkyl group, p1 is an integer of 1-8.

Wherein 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 0 It is an integer of -7.

In formula, R <^8> is a hydrogen atom or a C1-C5 alkyl group, and r1 is an integer of 1-8.

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

In formula, R <^9> is a hydrogen atom or a C1-C12 alkyl group, R <^10> is a hydrogen atom, a C1-C12 alkyl group, a C3-C12 alicyclic hydrocarbon group which comprises a main ring, an aromatic hydrocarbon group, an aryl Oxy or aromatic polyalkylene glycol moieties.

In formula, R <^11> is a hydrogen atom or a C1-C12 alkyl group, R <^12> is a hydrogen atom, a C1-C12 alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxy group, a siloxyalkyl group, or an aromatic hydrocarbon group.

In formula, R <^13> is a hydrogen atom or a C1-C12 alkyl group, a cycloalkyl group, or an aromatic hydrocarbon group.

The structural units represented by Chemical Formulas 4 to 6 are each derived from an epoxy group-containing monomer represented by the following Chemical Formulas 10 to 12.

In formula, R <^14> is a hydrogen atom or a C1-C5 alkyl group, R <^15> is a hydrogen atom or a C1-C2 alkyl group, p2 is an integer of 1-8.

In the above formula (10), preferred as R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a methyl group, and preferred as p 2 are 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 referred to as GMA) is It is preferable from the viewpoint of availability. Here, it means that the (meth) acrylate in this invention may be either an acrylate or a methacrylate.

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 a -CH ₂ -group, R ¹⁸ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, q2 is It is an integer of 0-7.

In the above formula (11), preferred as R ¹⁶ and R ¹⁸ are each independently a hydrogen atom or a methyl group, preferred as R ¹⁷ are a -CH ₂ O- group, and preferred as q2 are 1 to 3. Specific examples of the monomer represented by the formula (11) include o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether in terms of availability.

In the formula, R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 5, r2 is an integer of 1 to 8.

In Formula 12, R ¹⁹ is preferably a hydrogen atom or a methyl group, and r 2 is preferably 1 to 3. As the monomer represented by the formula (12), 3,4-epoxycyclohexylmethyl methacrylate is particularly preferable in view of physical properties of the cured resin layer such as hardness. However, when using the said monomer, since storage stability may fall by incorporation of a metal compared with another monomer, it is preferable to make the quantity of the transition metal atom contained in a resin composition below fixed as mentioned later. .

In addition, the structural units represented by Formulas 7 to 9 are derived from monomers represented by the following Formulas 13 to 15.

Wherein, R ²⁰ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ²¹ is group an alicyclic hydrocarbon group of 3 to 12 carbon atoms for a hydrogen atom, an alkyl group having 1 to 12 carbon atoms constituting the main ring, an aromatic hydrocarbon group, an aryl Oxy or aromatic polyalkylene glycol moieties.

In Formula 13, the alicyclic hydrocarbon group having 3 to 12 carbon atoms constituting the main ring represented by R ²¹ has an additional structure, for example, a double bond in a ring, a side chain of a hydrocarbon group, a side chain of a spiro ring, a crosslinked hydrocarbon group in a ring, and the like. It may include.

In 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. As the monomer represented by the formula (13), cyclohexyl methacrylate and dicyclopentanyl methacrylate are particularly preferable in terms of physical properties of the cured resin layer such as hardness and heat resistance.

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 Chemical Formula 14, R ²² is preferably hydrogen or a methyl group, and R ²³ is preferably an alkyl or phenyl group having 1 to 6 carbon atoms. As the monomer represented by the general formula (14), styrene is particularly preferable in terms of copolymerizability with monomers of other species, availability and the like.

In formula, R <^24> is a hydrogen atom or a C1-C12 alkyl group, a cycloalkyl group, or an aromatic hydrocarbon group.

In the general formula (15), preferred as R ²⁴ are a cyclohexyl group and a phenyl group. As the monomer represented by the formula (15), N-cyclohexyl maleimide and N-phenylmaleimide are particularly preferable in terms of physical properties of the cured resin layer such as hardness and heat resistance.

When the epoxy group-containing polymer (A) of the resin composition of the present invention has an epoxy equivalent in the range of 140 to 600 g / mol, at least one or more of the epoxy group-containing structural units represented by the above formulas (4) to (6) may be selected from the epoxy group-containing polymer (A ), 10 to 100% by weight, more preferably 20 to 100% by weight. If the epoxy group-containing structural unit is less than 10% by weight, the toughness of the protective film after coating curing may be insufficient.

The weight average molecular weight (Mw) of the epoxy group containing polymer (A) in the resin composition of this invention is 5,000-40,000, Preferably it is the range of 5,000-20,000. If the weight average molecular weight (Mw) is less than 5,000, the fall of the hardness of a protective film is observed, and when it exceeds 40,000, the flatness after application hardening may fall. 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 this invention is 140-600 g / mol, Preferably it is 180-550 g / mol. If the epoxy equivalent is less than 140 g / mol, the protective film after coating hardening tends to lose toughness. If the epoxy equivalent exceeds 600 g / mol, the hardness of the cured resin layer and the lack of ITO forming process may occur. . In addition, since the toughness is required for a protective film in the case of the use which requires high adhesiveness, it is preferable that it is 260-550 g / mol. If the epoxy equivalent of an epoxy-group-containing polymer (A) is 260 g / mol or more, it will be excellent in toughness, and high adhesiveness will be obtained, so that an edge defect is hard to generate | occur | produce also in an adhesive test. Epoxy equivalent at this time refers to the equivalent of an epoxy group with respect to a polymer, and is measured according to JIS K 7236: 2001 "Method for obtaining the epoxy equivalent of epoxy resin".

Since the epoxy group-containing polymer (A) in the resin composition of the present invention has a weight average molecular weight (Mw) and an epoxy equivalent in terms of polystyrene in the above range, the crosslinking density is high and the ITO formation processability and toughness are excellent.

(Epoxy group-containing compound (B))

The epoxy group-containing compound (B) of the resin composition of the present invention has two or more epoxy groups in one molecule and is a derivative of bisphenol A.

Moreover, the molecular weight of the epoxy group containing compound (B) in the resin composition of this invention is 330-7,000, Preferably it is 330-6,500, More preferably, it is 330-6,000. If the molecular weight of an epoxy-group-containing compound (B) is less than 330, the hardness of a protective film may fall, and when it exceeds 7,000, the external appearance may fall, for example, the nonuniformity after application | coating hardening may arise. In addition, when an epoxy group containing compound (B) is a polymer, the said molecular weight is a weight average molecular weight.

The epoxy equivalent of the epoxy group-containing compound (B) is 150 to 3,500 g / mol, preferably 160 to 3,300 g / mol, more preferably 180 to 3,000 g / mol. If the epoxy equivalent of the epoxy group-containing compound (B) is less than 150 g / mol, the crosslinking density may increase, and the toughness of the protective film may be lowered, in particular, the hardness may be lowered. If the epoxy group-containing compound (B) exceeds 3,500 g / mol, the crosslinking density of the protective film is lowered and the hardness of the protective film is lowered. There is a possibility of a significant decrease.

The epoxy group-containing compound (B) of the resin composition of the present invention can be used alone or in combination of two or more as long as the above conditions are satisfied. When using in combination of 2 or more type, let this mixture be the epoxy group containing compound (B) in this invention.

Bisphenol A in the present invention refers to 4,4'-isopropylidenediphenol, and as the derivative thereof, bisphenol A type epoxy resin, 4,4'- which is a polycondensate with 1-chloro-2,3-epoxypropane. Bisphenol A novolac type epoxy resin which is a diglycidyl ether of the polycondensate of isopropylidene diphenol and formaldehyde, the diglycidyl ether of the bisphenol A ethylene oxide addition product, and the diglycidyl ether of the bisphenol A propylene oxide addition product Or these nuclear hydrogenated compounds. Especially, bisphenol-A epoxy resin and bisphenol-A novolak-type epoxy resin or these nuclear hydrogenated compounds are preferable, and a compound represented by following formula (16) or 17 is mentioned as a preferable compound. Moreover, these hydrogenated compounds are also mentioned as a preferable example.

In formula, n2 represents the integer of 0-19.

In formula, n3 represents the integer of 1-19.

Among these epoxy group-containing compounds, more preferable examples include epoxy group-containing compounds having n 2 of Formula 16 from 0 to 10 and epoxy groups containing compounds having n 3 of Formula 17 from 1 to 12 from the viewpoint of fluidity. Most preferable in terms of compatibility of the resin composition is a compound represented by the formula (16).

Since the epoxy group containing compound (B) in the resin composition of this invention is a derivative of bisphenol A, and since molecular weight and an epoxy equivalent are in the said range, the protective film which is high in hardness and excellent in transparency can be obtained.

In addition, although the epoxy group containing compound (B) in the resin composition of this invention is a derivative of bisphenol A which has 2 or more epoxy groups in 1 molecule, it is 1 as an additional component which is not contained in (A)-(C) which is an essential component. You may add epoxy group containing compounds other than the bisphenol A derivative which has one or more epoxy groups in a molecule | numerator. At this time, it is preferable to suppress the quantity of the epoxy group containing compound which is not contained in (B) to less than 100 weight% with respect to the total weight of the said (A) component, the said (B) component, and the (C) component mentioned later. If the amount of the epoxy group-containing compound not included in (B) is 100% by weight or more, the hardness and the applicability of the protective film after coating hardening will be reduced, and it will be difficult to obtain the effect of the present invention.

(Polyhydric carboxylic acid derivative (C))

Polyhydric carboxylic acid derivative (C) of the resin composition of this invention contains the vinyl ether compound (c2) (vinyl group and ether group) in which the carboxyl group of the carboxylic acid (c1) which has a structure of following formula (1) is represented by following formula (18) Compound), which is latent (hereinafter also referred to as blocking).

<Formula 1>

In the formula, the six-membered ring is an aromatic or alicyclic hydrocarbon. m1 is an integer of 0-2, t1 is an integer of 0-1, n is an integer of 1-4. In addition, 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 formula, R <^25> is a C1-C10 hydrocarbon group.

The carboxyl group is latent by reacting a vinyl group with the same formula (19). Since this reaction is relatively easy, the polyhydric carboxylic acid derivative (C) is obtained in excellent yield. Therefore, the polyhydric carboxylic acid derivative (C) has a structure of the following general formula (20) in which carboxylic acid is latent.

In formula, R <^25> is a C1-C10 hydrocarbon group.

In carboxylic acid (c1) represented by General formula (1), as a compound other than a hydrogen atom, R1 can mention the half ester body obtained by reaction of an alcohol compound and an acid anhydride.

Alcohol compounds used in this reaction include monohydric alcohol compounds such as ethanol, propanol, hexanol, octanol and isopropyl alcohol; Dihydric alcohol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol and cyclohexanediol; Trihydric alcohol compounds such as glycerin, pentane triol, hexane triol, cyclohexane triol, benzene triol and trimethylol propane; A tetrahydric alcohol compound, such as pentaerythritol, is mentioned as a preferable example, More preferably, hexanol, isopropyl alcohol, 1, 2- propylene glycol, 1, 3- propylene glycol, 1, 6- hexanediol, glycerin And trimethylolpropane and pentaerythritol.

 Moreover, as an acid anhydride used at the time of this reaction, the compound represented by following formula (21) is mentioned, Specifically, a phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1,3,4-tricarboxyl Acid-3,4- anhydride (henceforth a trimellitic anhydride), a 1,3,4-cyclohexane tricarboxylic acid-3,4- anhydride, and methylhexahydrophthalic anhydride are mentioned as a preferable example. In addition, in the above half ester body, since the protective film which has high crosslinking density and high adhesiveness is obtained, what is obtained by the combination of C3-C6 divalent or more polyhydric alcohol, trimellitic anhydride, or methylhexahydrophthalic anhydride is obtained. Preferred examples of the carboxylic acid (c1) represented by the general formula (1) include those in which methylhexahydrophthalic anhydride is selected from the viewpoints of transparency and storage stability.

In the formula, the 6-membered ring is an aromatic or alicyclic hydrocarbon, m1 is an integer of 0 to 2, and t1 is an integer of 0 to 1. R ² is an alkyl group having 1 to 5 carbon atoms.

Among the carboxylic acids (c1) represented by the general formula (1), a compound in which R 1 is a hydrogen atom includes the general formula (2) or the general formula (3), and the polyvalent carboxylic acid derivatives (C) that block these carboxylic acids have high solubility. And in combination with (A) or (B) having low compatibility.

<Formula 2>

In formula, m2 is an integer of 0-2.

<Formula 3>

In formula, m3 is an integer of 0-2, t3 is an integer of 0-1. R ² is an alkyl group having 1 to 5 carbon atoms.

As a compound represented by Formula (2) or Formula (3), Aromatic dicarboxylic acid, such as a phthalic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Aromatic tricarboxylic acids such as 1,2,4-benzenetricarboxylic acid (hereinafter, trimellitic acid); Alicyclic tricarboxylic acids such as 1,2,4-cyclohexanetricarboxylic acid (hereinafter CHTA); Aromatic tetracarboxylic acids such as 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid); Alicyclic tetracarboxylic acids, such as 1,2,4,5-cyclohexane tetracarboxylic acid, are mentioned. In addition, they 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, etc. Although it is possible, Preferably it is a C1-C3 linear alkyl group. Among the above carboxylic acids, pyromellitic acid, trimellitic acid or CHTA can be preferably used as the carboxylic acid (c1) represented by the formula (1), in that a protective film having a high crosslinking density and high adhesion is obtained. Among them, it is preferable to select CHTA in terms of transparency and storage stability.

The carboxylic acid which can be used as carboxylic acid (c1) represented by General formula (1) in the resin composition of this invention can be used individually by 1 type or in combination of 2 or more types.

On the other hand, as a vinyl ether compound (c2) represented by General formula (18) which is a raw material of the polyhydric carboxylic acid derivative (C) in the resin composition of this invention, for example, isopropyl vinyl ether, n-propyl vinyl ether, n Alkyl vinyl ether, such as -butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether, is mentioned. As a vinyl ether compound (c2) which can be preferably used for the resin composition of this invention, n-propyl vinyl ether and isobutyl vinyl ether can be mentioned, It can be used individually by 1 type or in combination of 2 or more types.

The polyhydric carboxylic acid derivative (C) used in the present invention can be obtained by reacting the carboxylic acid (c1) with the vinyl ether compound (c2) at a temperature ranging from room temperature to 150 ° C. Since the blocking reaction is an equilibrium reaction, when the vinyl ether compound (c2) is slightly used with respect to the carboxylic acid (c1), the reaction can be promoted and the yield can be improved. Specifically, the molar equivalent ratio [molar equivalent ratio of (vinyl group / carboxyl group)] of vinyl group of vinyl ether compound (c2) to carboxyl group of carboxylic acid (c1) is preferably 1/1 to 2/1. When this molar equivalent ratio exceeds 2/1, reaction temperature cannot be raised and reaction rate may be remarkably low.

When performing the blocking reaction, an acid catalyst may be used for the purpose of promoting the reaction. As such a catalyst, the acidic phosphate ester compound represented by following formula (22) is mentioned, for example.

In formula, R <^26> is a C3-C10 alkyl group, a cycloalkyl group, or an aryl group, and k is 1 or 2.

In addition, when performing a blocking reaction, an organic solvent can also be used for the purpose of making a reaction system uniform and making reaction easy. Examples of the organic solvent used at this time include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphate esters, nitriles, aprotic polar solvents, propylene glycol alkyl ether acetates, and the like. More preferably, cyclohexanone and a propylene glycol monomethyl ether acetate are mentioned. It is preferable that it is an organic solvent except an alcohol or an ionic solvent as said organic solvent. It is known that deblocking reaction may be advanced with respect to an alcohol or an ionic solvent, since these may significantly reduce the storage stability of a resin composition, and it may become difficult to obtain the effect of this invention.

The said organic solvent can be used individually by 1 type or in combination of 2 or more type. Although the usage-amount of the said organic solvent is not specifically limited, Usually, 5-95 weight part with respect to 100 weight part of reaction raw materials, Preferably it is 20-80 weight part. Thus, even when the organic solvent is added, the content of the polyvalent carboxylic acid derivative (C) is considered to be the amount of the active ingredient (polyvalent carboxylic acid derivative (C) itself) excluding the organic solvent.

(Combination ratio of the above (A), (B), (C) component)

Since the optimum viscosity differs according to the kind of application | coating process, the resin composition of this invention shall be able to dilute arbitrarily with a solvent. In addition, the resin composition of this invention shall add the filler and additive which are mentioned later in arbitrary amounts. As mentioned above, in the resin composition of this invention, since the content rate in the final resin composition of the said (A)-(C) component changes, the said (A) component which is an essential component, the said (B) component, and the said (C) component Formulation ratios are defined based on the total weight of. Moreover, in the resin composition of this invention, it is preferable that 30-100 weight% of total weights of the said (A) component, the said (B) component, and the said (C) component are contained in solid content of a resin composition. Here, solid content of the resin composition for specifying a compounding ratio includes all components except a solvent, and liquid epoxy group containing compound etc. are contained in solid content.

The resin composition of the present invention is 20 to 65% by weight of the component (A) and 5 to 30% by weight of the component (B) to the total weight of the component (A), the component (B) and the component (C). It is preferable to contain 15 to 65 weight% of said (C) component.

In the resin composition of the present invention, the blending ratio of the epoxy group-containing polymer (A) in the composition is preferably 20 to 65% by weight, but more preferably the blending ratio depends on the polyvalent carboxylic acid derivative (C). As shown in the following formula (23), when the 6-membered ring of the formula (1) is an aromatic hydrocarbon, the blending ratio of the epoxy group-containing polymer (A) in the composition is more preferably 40 to 65% by weight, further 40 to 60% by weight desirable. When the compounding ratio of the epoxy group-containing polymer (A) is less than 40% by weight, the performance such as adhesion of the protective film may be deteriorated, and when it exceeds 65% by weight, the toughness of the protective film may be impaired. It's hard to get

In formula, m1 is an integer of 0-2, t1 is an integer of 0-1, n is an integer of 1-4. In addition, when n is 1, R <^1> is a hydrogen atom or a C2-C8 hydrocarbon group, and when n is 2-4, R <^1> is a C2-C8 hydrocarbon group. R ² is an alkyl group having 1 to 5 carbon atoms.

On the other hand, as shown in the following formula (24), when the 6-membered ring of the formula (1) is an alicyclic hydrocarbon, the blending ratio of the epoxy group-containing polymer (A) in the composition is more preferably 30 to 65% by weight, 35 to 55% by weight More preferred. When the blending ratio of the copolymer (A) having an epoxy group is less than 30% by weight, the performance such as adhesion of the protective film may be deteriorated, and when it exceeds 65% by weight, the processability of ITO formation may be impaired. It is difficult to obtain the effects of the invention.

In formula, m1 is an integer of 0-2, t1 is an integer of 0-1, n is an integer of 1-4. In addition, 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 the resin composition of this invention, 5-30 weight% is preferable for the compounding ratio of an epoxy group containing compound (B), but a more preferable compounding ratio changes with polyhydric carboxylic acid derivative (C). As shown in the formula (23), when the six-membered ring of the formula (1) is an aromatic hydrocarbon, the compounding ratio of the epoxy group-containing compound (B) in the composition is more preferably 5 to 30% by weight, still more preferably 10 to 25% by weight. Do. When the compounding ratio of an epoxy group containing compound (B) is less than 5 weight%, performance, such as adhesiveness of a protective film, may fall, and when it exceeds 30 weight%, the toughness of a protective film may be impaired. Therefore, the effect of this invention Is difficult to obtain.

On the other hand, as shown in Formula 24, when the 6-membered ring of Formula 1 is an alicyclic hydrocarbon, the blending ratio of the epoxy group-containing compound (B) in the composition is more preferably 5 to 25% by weight, and 5 to 20% by weight More preferred. When the blending ratio of the epoxy group-containing compound (B) is less than 5% by weight, the processability of ITO formation may decrease, and when it exceeds 25% by weight, the heat-coloring property may be impaired. Thus, the effect of the present invention is obtained. Is difficult.

In the resin composition of the present invention, the blending ratio of the polyvalent carboxylic acid derivative (C) is preferably 15 to 65% by weight, but more preferably the blending ratio depends on the structure of the polyvalent carboxylic acid derivative (C). As shown in the formula (23), when the six-membered ring of the formula (1) is an aromatic hydrocarbon, the blending ratio of the polyvalent carboxylic acid derivative (C) in the composition is more preferably 20 to 50% by weight, and 25 to 50% by weight More preferred. When the blending ratio of the polyhydric carboxylic acid derivative (C) is less than 20% by weight, the hardness of the protective film may be lowered, and when it exceeds 50% by weight, adhesion may occur to the protective film. Difficult to obtain

On the other hand, as shown in the said Formula (24), when the 6-membered ring of the said Formula (1) is an alicyclic hydrocarbon, the compounding ratio of the polyhydric carboxylic acid derivative (C) in a composition is more preferable 15 to 60 weight%. In the case where the blending ratio of the polyvalent carboxylic acid derivative (C) is less than 15% by weight, the process resistance of ITO formation may decrease, and if it exceeds 60% by weight, adhesion may occur to the protective film. Hard to get effect

It is preferable that the ratio of the total compounding quantity of the said epoxy group containing polymer (A) and an epoxy group containing compound (B) and the compounding quantity of a polyhydric carboxylic acid derivative (C) is the following range. The molar concentration of the carboxyl group produced after the separation (de-sublating, deblocking) of the vinyl ether compound of the polyvalent carboxylic acid derivative (C), and the molar concentration of the epoxy group of the epoxy group-containing polymer (A) and the epoxy group-containing compound (B) It is preferable to set it as the compounding quantity of ratio (carboxyl group / epoxy group) becoming 0.2 / 1.0-1.6 / 1.0, and more preferable molar concentration ratio is 0.4 / 1.0-1.2 / 1.0. If the molar concentration ratio between the carboxyl group and the epoxy group is less than 0.2 / 1.0, since the epoxy group remains in a large amount after curing, the crosslinking density may be low, and the effect of the present invention may not be obtained. Moreover, when the molar concentration ratio of a carboxyl group and an epoxy group exceeds 1.6 / 1.0, a carboxyl group will become excess and resin property will fall in most cases. Moreover, when adding the compound containing the carboxyl group and the functional group which can react with the carboxyl group containing an epoxy group as an additional component which is not contained in (A)-(C) which is an essential component in the resin composition of this invention, It is preferable to mix | blend so that ratio of the molar concentration of the carboxyl group in a composition, and the molar concentration of the functional group which can react with the carboxyl group containing an epoxy group will be in the said range.

In addition, the molar concentration of a carboxyl group here is simply computed from a compound structural formula (molecular weight) and a compounding concentration, and more accurately JIS K 0070: 1992 "The acid value, saponification value, ester value, iodine value, hydroxyl value, and ratio of a chemical product. It is calculated from the acid equivalent measured according to "Test Method of Saponified".

Next, the additive preferably added to the resin composition of the present invention will be described.

(Adhesive Enhancer (D))

In the resin composition of this invention, containing titanium soap and / or zirconium soap as an adhesive improving agent (D) is preferable at the point which improves adhesiveness further. Titanium soap or zirconium soap in the resin composition of this invention is a carboxylate salt which made titanium or zirconium the center metal, and is a mixture of the compound represented by following formula (25) although a structure is not limited.

Wherein M is a titanium atom or a zirconium atom, R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are each an organic group having the same or different hydrocarbon groups or carboxyl groups having 1 to 29 carbon atoms, and are bonded to each other to form a ring. Z1 may be 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, z6 and z7 are each independently 0 or 1.

It has been found by the present inventors that titanium soap or zirconium soap does not promote the reaction of the carboxyl group with the epoxy group and the deblocking reaction as compared with the titanium coupling agent having acetylacetone as a ligand. It is considered that this is because the titanium atom or the zirconium atom and the carboxyl group form a strong bond. Therefore, there is almost no thickening by crosslink formation at the time of resin composition storage. In general, when titanium soap or zirconium soap and carboxylic acid are mixed, ligand exchange reaction occurs between metal soap and carboxylic acid, but ligand exchange with polyhydric carboxylic acid derivative in which carboxyl group is latent It was also found that no reaction was observed. Thus, precipitation of gelling and insoluble metal soap does not occur. Therefore, titanium soap or zirconium soap is a preferred additive that can be added to the resin composition of the present invention not only to maintain high storage stability without lowering the storage stability of the resin composition but also to significantly improve the adhesion.

The method for synthesizing the titanium soap or zirconium soap used as the adhesion improving agent (D) in the resin composition of the present invention is not particularly limited, but the reaction between the carboxylic acid compound and the titanium or zirconium metal, the carboxylic acid compound and the titanium or Examples of the metathesis method, melt direct method, semi-melt direct method, wet direct method, solid phase direct method, solvent direct method, etc. using reaction of an oxide or hydroxide of zirconium, an alkali metal salt of a carboxylic acid compound and a water-soluble titanium or zirconium salt, etc. It can be mentioned as. Among the above synthesis methods, metathesis methods and semi-melt direct methods are preferable examples from the viewpoint of reaction rate and easy product separation. Properties, such as the solubility to the solvent of the titanium soap or zirconium soap obtained by the synthesis method, may differ.

When obtaining titanium soap in the adhesive improving agent (D) in the resin composition of this invention by metathesis method, it is preferable to make the sodium salt of a carboxylic acid compound and divalent tetravalent titanium chloride react in water.

In the resin composition of the present invention, as a carboxylic acid compound or an alkali metal salt thereof, which is a raw material of titanium soap or zirconium soap used as the adhesion improving agent (D), having a linear or branched or ring structure having 1 to 30 carbon atoms, or Unsaturated carboxylic acid or its alkali metal salt is mentioned preferably, Saturated or unsaturated aliphatic carboxylic acid or its alkali metal salt which has a C4-C15 linear or branched structure more preferably is mentioned preferably. . Among them, in the case of titanium soap, caproic acid, caprylic acid (n-octanoic acid), octylic acid (2-ethylhexanoic acid), capric acid (decanoic acid), naphthenic acid and the like from the viewpoint of solubility to the resin composition It is preferable to synthesize | combine using the alkali metal salt of. Moreover, in the case of zirconium soap, it is preferable to synthesize | combine using saturated C4-9 saturated aliphatic carboxylic acid or its alkali metal salt from a viewpoint of the solubility to a resin composition. In addition, as zirconium soap, what is represented by following formula (26) is used preferably especially.

In formula, j represents the integer of 4-9.

Specific examples of the zirconium soap represented by the formula (26) include zirconium valeric acid, zirconium caproate, zirconium heptane, zirconium n-octanoate (zirconium caprylate), zirconium octylate (zirconium 2-ethylhexanoate), and isononanoic acid Zirconium, zirconium decanoate (zirconium capricate), zirconium 3,5,5-trimethylhexanoate, and the like.

In the resin composition of this invention, an adhesive improving agent (D) can be used individually by 1 type or in combination of 2 or more type.

In the resin composition of the present invention, the blending ratio of the adhesion improving agent (D) is usually 0.010 to 100 parts by weight when the total weight of the component (A), the component (B) and the component (C) is 100 parts by weight. To 20 parts by weight, preferably 0.10 to 20 parts by weight, more preferably 0.2 to 15 parts by weight. In the case where the blending ratio of the adhesion improving agent (D) is less than 0.010 parts by weight in the above, the improvement of the adhesion of the protective film is insufficient, and when it exceeds 20 parts by weight, the transparency of the protective film is impaired, so that the effect of the present invention is difficult to be obtained.

In addition, since titanium content or zirconium soap used as an adhesive improving agent (D) differs in metal content according to the kind of ligand, it is preferable to prescribe the compounding quantity of the said metal soap by metal content. In this case, the compounding quantity of the titanium soap or zirconium soap used as an adhesive improving agent (D) is a metal with respect to 100 weight part, when the total weight of the said (A) component, the said (B) component, and the said (C) component is 100 weight part. The content is preferably 0.0030 to 3.0 parts by weight, more preferably 0.010 to 1.8 parts by weight.

(Storage stability improver (E))

Moreover, in the resin composition of this invention, it is preferable to further contain a pentavalent phosphorus atom containing compound as a storage stability improver (E) from the point of further improving storage stability. As a pentavalent phosphorus atom containing compound preferably used as a storage stability improving agent (E), a phosphate triester is mentioned preferably. As phosphoric acid ester, a triethyl phosphate, a tributyl phosphate, a triphenyl phosphate, etc. are mentioned, for example.

In the resin composition of this invention, when the compounding ratio of a storage stability improving agent (E) makes 100 weight part of total weights of the said (A) component, the said (B) component, and the said (C) component, it is 0.01 to 100 weight part normally. To 5 parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.05 to 1 part by weight. In the case where the blending ratio of the storage stability improving agent (E) is less than 0.01 part by weight in the above, the improvement of the storage stability is insufficient, and when it exceeds 5 parts by weight, the hardness and transparency of the protective film are impaired, so that the effect of the present invention is difficult to obtain. .

Next, the additive, organic solvent, and filler which can be added to arbitrary amounts to the resin composition of this invention are demonstrated.

(Adhesive Enhancement Aid)

A silane coupling agent can also be added to the resin composition of this invention as an adjuvant for improving the adhesiveness of the protective film which hardens a resin composition, and a base material. As a silane coupling agent which can be added, the silane coupling agent which has an epoxy group, the silane coupling agent which has an amino group, the silane coupling agent which has a (meth) acryloyl group, or its polymer etc. are mentioned, for example. These silane coupling agents can be added individually by 1 type or in combination of 2 or more types as appropriate.

When the said silane coupling agent makes the total weight of the said (A) component, the said (B) component, and said (C) component 100 weight part, it is 1-30 weight part normally with respect to 100 weight part, Preferably it is 2-25. It is added in parts by weight, more preferably 3 to 20 parts by weight. When the compounding quantity of a silane coupling agent is less than 1 weight part, the improvement of adhesiveness to the base material of the protective film obtained by hardening a resin composition is inadequate. Moreover, when silane coupling agent exceeds 30 weight part, performances, such as hardness of a protective film, fall.

(Surfactants)

Surfactant can also be added to the resin composition of this invention for the purpose of improving the external appearance of the protective film which hardens the resin composition of this invention, etc. Surfactant can be used individually by 1 type or in combination of 2 or more types. In addition, surfactant may be added in order to improve the compatibility of each component including the essential component of (A)-(C) of this invention.

When the said surfactant is made into 100 weight part of total weights of the said (A) component, the said (B) component, and the said (C) component, it is preferable to mix | blend normally with 0.001-3 weight part with respect to 100 weight part.

(Organic solvent)

An organic solvent can also be used for the resin composition of this invention in order to adjust viscosity, etc. Examples of the organic solvent used at this time include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphate esters, nitriles, aprotic polar solvents, propylene glycol alkyl ether acetates, and the like. As said organic solvent, it is preferable that it is an organic solvent except an alcohol or an ionic solvent. It is known that deblocking reaction may be advanced with respect to an alcohol or an ionic solvent, since these may significantly reduce the storage stability of a resin composition, and it may become difficult to obtain the effect of this invention. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

In addition, the usage-amount of these organic solvents is not specifically limited, Arbitrary quantity can be added according to predetermined | prescribed film thickness, surface smoothness, a film formation method, etc., and application | coating suitability can be provided.

(Other ingredients)

You may further add viscosity modifiers, such as a thickener and a thixo agent, to the resin composition of this invention for the purpose of viscosity adjustment. Moreover, infrared rays and an ultraviolet absorber can also be added.

In addition, any amount of filler can be added to the resin composition of the present invention for the purpose of adjusting the linear expansion coefficient, improving flatness, improving surface hardness, adjusting viscosity, adjusting refractive index, absorbing light at a predetermined wavelength, and improving adhesion. have. The filler used at this time is not particularly limited as long as it does not impede 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, in the resin composition of this invention, the carbon dioxide generation | occurrence | production agent, a softening agent, antioxidant, a plasticizer, a lubricating agent, a surface treating agent, a flame retardant, an antistatic agent, a coloring agent, and a leveling as needed in the range which does not impair the effect of this invention. Additives, such as an ion trap agent, a slidability improver, various rubber | gum, organic polymer beads, glass beads, a thixotropic imparting agent, a surface tension decreasing agent, an antifoamer, a light-diffusion agent, antioxidant, and fluorescent agent, can be mix | blended.

The additive may be used in any amount within the range that does not impair the effects of the present invention, but in this case transition metals, alkali metals, alkaline earth metals other than titanium and zirconium valences (A) component, (B) component and the When the total weight of the component (C) is 100 parts by weight, it is preferable not to mix 0.1 parts by weight or more with respect to 100 parts by weight. It is because storage stability may fall remarkably when it mixes 0.1 weight part or more.

(Method of producing a resin composition)

Below, the mixing | blending, stirring, and the dispersion method of the resin composition of this invention are demonstrated.

In the resin composition of this invention, each component including the essential component of said (A)-(C) may be mix | blended collectively, and it can also mix | blend sequentially after dissolving each component in a solvent. In addition, the addition order and working conditions at the time of compounding are not restrict | limited. For example, a resin composition may be prepared by dissolving all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions, and these solutions may be mixed at the time of use (at the time of application) as a resin composition. It can also manufacture.

In the resin composition of this invention, about stirring after each component mixing including the essential component of said (A)-(C), it stirs using a vane type stirrer, a dissolver, a kneader, a ball mill admixture, a roll disperser, etc. Alternatively, each component may be blended in a container such as a gallon bottle, and then rotated in a mix rotor for each container and stirred. Although the temperature of mixing and stirring also changes with blending components, in order to avoid condensation and volatilization of a solvent, 10-60 degreeC is preferable normally.

When adding a viscosity modifier and a filler to the resin composition of this invention, dispersion using high shear dispersers, such as a motor mill and a shaker, can also be performed. At this time, the method of preparing the master batch which used each component including the essential component of said (A)-(C) as a binder as a binder beforehand, and mix | blending at the time of use can also be taken. However, since the deblocking reaction proceeds by heat of the polyhydric carboxylic acid derivative (C) of the present invention, care should be taken not to be heated to 80 ° C or higher when dispersing the composition containing the polyvalent carboxylic acid derivative (C). need.

In the resin composition of the present invention produced in this way, the polysoluble carboxylic acid having high solubility by latent (blocking, capping, protecting) the carboxyl group of the poorly soluble polyvalent carboxylic acid to be used as a curing agent. It is used by dissolving and dispersing in a solvent from the form of derivative (C). Therefore, the reaction point of a carboxyl group can coexist with an epoxy group in high concentration in a resin composition, and when using this resin composition and forming a layer and heating, a high crosslinking density is obtained. In addition, a polyhydric carboxylic acid derivative (C) does not regenerate a carboxyl group unless it heats more than predetermined temperature according to the said compound. Therefore, although the reaction point concentration of each of the epoxy group contained in the epoxy group-containing polymer (A) and the epoxy group-containing compound (B) and the carboxyl group contained in the polyvalent carboxylic acid derivative (C) is high, it is for a long time immediately after preparation. It maintains a good viscosity and is very excellent in storage stability. After preparing a resin composition, it is preferable to restrain the viscosity after leaving in a sealed container for 5 days at 5 degreeC to 1.5 times or less of initial viscosity, and the viscosity after leaving at 25 degreeC for 120 days is 1.5 times or less of initial viscosity It is more preferable to suppress this.

Thus, the resin composition in this invention is excellent in storage stability compared with the prior art, long-term storage is possible in 1-liquid form, and it has the advantage that there is no generation | occurrence | production of precipitation at the time of storage and use. In addition, the balance of the resin composition which was once provided for use does not deteriorate in a short time of operation. Therefore, such a balance can be recovered or reused by continuously replenishing the fresh resin composition, which is economical.

 Moreover, since the composition ratio of the said specific essential component is optimal, the resin composition of this invention is not only excellent in adhesiveness with respect to the base material of a cured resin layer, but also excellent in all the harmony, such as heat resistance, low thermal expansion, toughness, chemical resistance, etc. It is excellent in the ITO formation process resistance. Moreover, since it can apply | coat with a uniform film thickness and is excellent in flatness, the resin composition of this invention can be used especially preferably for forming organic layers, such as a color filter protective film of a display apparatus and a solid-state image sensor.

2. color filter

The color filter which concerns on this invention has a layer of the resin cured material formed by hardening | curing the resin composition for color filter protective films which concerns on the said invention.

The layer of the cured resin product formed by curing the resin composition for color filter protective film is generally referred to as a protective film, and is not particularly limited. For example, an RGB pixel formed on a substrate of a color filter, a liquid crystal alignment film, an ITO layer, a light emitter, Or the layer of hardened | cured material of resin formed between a light receiver, etc. is meant. Also included is a case of a protective film which indirectly protects through another material even if it is not in direct contact with the RGB pixel, for example, an interlayer film used between a micro lens of a solid-state imaging device and a color filter, or of a color filter and an electrode. Also included is an interlayer used in between.

Since the color filter which concerns on this invention has the layer of the cured resin material which hardens the resin composition for color filter protective films which concerns on the said invention, it does not only have the basic performance of heat resistance and solvent resistance, but also the adhesiveness and ITO formation process The color filter which has a layer of the resin composition excellent in the characteristic can be obtained.

The color filter includes, for example, a black matrix formed in a predetermined pattern on a transparent substrate, a pixel portion formed in a predetermined pattern between the black matrices, and a protective film formed to cover the pixel portion. The transparent electrode for liquid crystal drive may be formed on a protective film as needed. In addition, a columnar spacer may be formed on a transparent electrode plate, a pixel part, or a protective film according to the area | region in which the black matrix layer was formed.

The layer of the cured resin product which hardens the resin composition for color filter protective films which concerns on the said invention adjusts the resin composition for color filter protective films which concerns on this invention to appropriate viscosity, and makes it a coating liquid, First, for example, a color filter It applies to the surface of the side which formed the colored layer of.

It does not specifically limit about the method of apply | coating the resin composition of this invention, As a coating method used normally, for example, a spin coater coating method, the dip coating method, the spray coater coating method, the roll coater coating method, the screen printing coating method It can apply | coat to a base material individually or in combination, such as the offset printing coating method, the slit coater coating method, and the die coater coating method.

Next, the obtained coating film is dried, and further preliminary heating (henceforth preliminary baking) is performed as needed, and the layer of hardened | cured material of resin is formed through this hardening heating (henceforth a post-baking). At this time, 40-140 degreeC, 0 to 1 hour as a preliminary baking condition, 150-280 degreeC and 0.2 to 2 hours are mentioned as a preferable baking condition. In addition, it does not specifically limit as a heating method at this time, For example, hardening apparatuses, such as a closed hardening furnace and the tunnel furnace which can continuously cure, can be used. The heating source is not particularly limited and can be performed by hot wind circulation, infrared heating, high frequency heating or the like.

Since the resin composition of this invention is excellent in storage stability as mentioned above, a viscosity does not rise and it maintains the initial favorable applicability | paintability continuously, and it does not need to change coating conditions frequently during application | coating operation, during this application | coating. . Therefore, a coating film with high uniformity can be formed at high speed and continuously under the coating conditions set at the start of the work. When the coating film is heated after the coating is finished, the protecting group of the polyvalent carboxylic acid derivative (C) contained in the coating film is released, and the carboxyl group is regenerated as shown in Formula 1 to contain an epoxy group ((A) and (b) A crosslinking reaction occurs with the epoxy group of the component) and the coating film is cured.

 Moreover, it is preferable that the film thickness after application hardening is 0.2-5 micrometers, and, as for the layer of the cured resin product which concerns on this invention, it is more preferable that it is 0.5-4 micrometers. When the film thickness after application | coating hardening is less than 0.2 micrometer, the performance required for protective films, such as barrier property and flatness, is difficult to obtain, and when it exceeds 5 micrometers, there exists a possibility that the performances, such as transparency and ITO formation processability, may fall, and are not preferable. not. However, the film thickness after application hardening may be 5-20 micrometers about the use which requires high flatness.

Since the layer of the cured resin product which concerns on this invention obtained in this way is a crosslinked resin by the compound containing a carboxylic acid compound and an epoxy group, it is excellent in chemical-resistance and heat resistance (degree of film | membrane reduction or discoloration by heating, etc.). Furthermore, since the layer of the cured resin product according to the present invention contains an appropriate resin composition, not only the adhesiveness and the ITO formation processability are excellent, but also the layer of the cured resin product according to the present invention further contains titanium soap and / or zirconium soap. In combination with, the adhesiveness to the substrate is remarkably high, and has the advantage of being able to cope with a wide variety of substrate types and CF forming processes that are diversified.

The layer of the cured resin product which concerns on this invention can be made into the layer which specifically has the following chemical-resistance and heat resistance, for example.

a) Chemical resistance: The color filter having the layer of cured resin according to the present invention is immersed in a solvent of any one of isopropyl alcohol, N-methylpyrrolidone or γ-butyrolactone at a liquid temperature of 40 ° C. for 1 hour. Even if the film thickness reduction calculated by measuring the film thickness of the layer of cured resin after that is immersed in either solvent can be made into 10% or less.

b) Heat resistance: The film thickness reduction of the layer of cured resin 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.

Moreover, the layer of the resin composition which concerns on this invention specifically has the following outstanding adhesiveness, ITO formation processability (acid-alkali resistance (etch resistance) after ITO circuit formation, 230-250 degreeC after ITO circuit formation), for example. Heat resistance) can be used as the layer.

c) Adhesiveness: The color filter which provided the layer of the hardened | cured material of the resin which concerns on this invention was subjected to the pressure cooker test (henceforth PCT) which is long-term reliability evaluation (it left for 8 hours in 121 degreeC 100% humidity environment). Then, the mechanical property-adhesiveness (cross-cutting method) test method of the coating film prescribed | regulated to JISK5600-5-6 can be performed, and peeling can be eliminated in the layer of resin cured material.

d) Acid-alkali resistance after etching of ITO circuit (etching resistance: after forming an ITO layer on this resin cured product layer of the color filter provided with the resin cured product layer of this invention, an etching resist is apply | coated in stripe form, and , then forming an etching resist by 60 ℃ × 10 minutes, and acid treatment _{(H 2 O / HCl / HNO} 3 = 1/1 / 0.04 ( weight ratio)) for 8 minutes at 50 ℃, and alkali treatment (5% NaOH aqueous solution ) Can be prevented from cracking or wrinkles in the ITO layer and the layer of the cured resin.

e) Heat resistance after the formation of the ITO circuit: After forming an ITO layer on the layer of the cured resin of the color filter provided with the layer of the cured resin according to the present invention, even after treatment for 1 hour at 230 ° C or 250 ° C, It is possible to prevent cracks or wrinkles from occurring in the ITO layer and the layer of the cured resin.

As described above, the protective film produced in the present invention exhibits excellent adhesion and ITO formation processability in addition to the conventional ones, and it is estimated that the crosslinking density of the protective film is very high due to the optimization of the resin composition.

In addition, this invention is not limited to the said embodiment. The said embodiment is an illustration, and what has substantially the same structure as the technical idea described in the claim of this invention, and exhibits the same effect is contained in the technical scope of this invention.

<Example>

Production Example A-1: Synthesis of Epoxy Group-Containing Polymer (A)

160 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PMA) was put into a 500 mL four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping lot, heated with stirring to raise the temperature to 80 ° C. Subsequently, 114 parts by weight of glycidyl methacrylate (hereinafter referred to as GMA), 86 parts by weight of cyclohexyl methacrylate (hereinafter referred to as CHMA) at a temperature of 80 ° C., and peroxide-based polymerization of Nippon Yushi Co., Ltd. 7 parts by weight of the initiator "perhexyl O (product name, purity 93%)" (hereinafter referred to as PHO) and 33 parts by weight of PMA were uniformly mixed in advance by a dropping lot over 2 hours. It dripped. After completion of the dropwise addition, the temperature was maintained at 98 ° C for 7 hours, and then the reaction was completed. A polymer solution having a weight average molecular weight (Mw) of 34,000, a solid content of 53%, a viscosity of 25 Pa · s (20 ° C.) and an epoxy group having an epoxy equivalent of 520 g / mol of the solution (the epoxy equivalent of the epoxy group-containing polymer 280 g / mol) Got it.

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) is a gel permeation chromatography apparatus HLC-8220GPC manufactured by Toso Corporation, and SHODEX K-801 manufactured by Showa Denko Co., Ltd. is used as a column, and THF (tetrahydrofuran) is used. It was set as the eluent, measured by RI (refractive index) detector, and calculated | required by polystyrene conversion.

<Viscosity>

The viscosity was measured at the temperature of 20 degreeC using the Brookfield viscometer (made by AX Sangyo Co., Ltd.) equipped with the circulating constant temperature water bath.

<Epoxy equivalent>

Epoxy equivalent was measured by the method prescribed by JIS K 7236: 2001 "Method of obtaining 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 preparation ratios, the dropping temperature, the weight average molecular weight, the solid content, the viscosity, and the epoxy equivalent of each raw material in Production Examples A-2 to A-5 and Comparative Production Example A'-6 were added to those of Production Example A-1. Shown in

(Production Example C-1: Synthesis of Polyvalent Carboxylic Acid Derivative (C))

27 parts by weight of PMA, 27 parts by weight of trimellitic acid (hereinafter referred to as TMA) manufactured by Mitsubishi Gas Chemical Co., Ltd., n-propyl vinyl ether, in a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping lot. Hereinafter, 46 parts by weight of nPr-VE) was put, heated with stirring to raise the temperature to 70 ° C. Subsequently, stirring was continued while maintaining the temperature, the reaction was terminated as soon as the acid value of the mixture became 2.0 mg KOH / g or less, and the curing agent solution having two or more blocked carboxyl groups having an acid value of 0.64 mg KOH / g (C -1) was obtained.

In addition, the acid value and total acid equivalent were measured by the hydrolysis acid value measurement of JIS K 0070: 1992 "Test method of the acid value, saponification value, ester value, iodine value, hydroxyl value, and non-soapide of a chemical product."

Preparation Example C-2 to C-4 and Comparative Production Example C'-5: Synthesis of Polyvalent Carboxylic Acid Derivative (C) and Comparative Polyvalent Carboxylic Acid Derivative (C ')

In the same manner as in Production Example C-1, a polyhydric carboxylic acid derivative (C-2 to C-4) and a comparative polyhydric carboxylic acid derivative (C'-5) were obtained. The input ratio, reaction temperature, acid value and total acid equivalent of each raw material are shown in Table 2 below.

(Examples 1 to 9)

Each component was fully stirred and dissolved at the blending ratio shown in Table 3 below to obtain a resin composition for a color filter protective film.

The storage stability test of each resin composition for color filter protective films was done with the following method. In addition, after filtering each resin composition with the membrane filter of 0.2 micrometer of pore diameters, it spin-coated to a glass substrate (made by Nippon Denki Glass Co., Ltd .; brand name: OA-10, an alkali free glass) using a spin coater at 800 rpm. It was. After apply | coating, the glass substrate was dried for 5 minutes in a 80 degreeC clean oven, and then processed for 30 minutes in a 230 degreeC clean oven, and hardened the coating film. In all cases of the examples, the surface of the obtained coating film was very flat, and no pinholes or the like were seen at all. The film thickness measured by the fine shape measuring device (made by Kosaka Co., Ltd .; brand name: SURFCORDER ET400) was 2.0-2.5 micrometers. Moreover, about the layer of the resin cured material of each obtained resin composition for color filter protective films, each test of adhesiveness and ITO formation processability (acid-alkali resistance after ITO circuit formation, heat resistance after ITO circuit formation) was performed by the following method. It was done. The results are shown in Table 4 below.

<Storage stability>

Storage stability was evaluated by observing the rate of rise (/ initial viscosity) of the solution after storing the solution of the resin composition for 120 days in a 5 degreeC and 25 degreeC thermostat in a closed container. The viscosity was measured by the method mentioned above.

<Adhesiveness>

After the sample which formed the protective film was processed by PCT (staying for 8 hours in the environment of 100% humidity at 121 degreeC), the mechanical property-adhesiveness (cross-cutting method) test method of the coating film prescribed | regulated to JISK5600-5-6. Was performed.

<Etch resistance after ITO>

On the protective film of the sample to form a protective film, a sputtering temperature of 230 ℃, 100 to 150 Å is SiO ₂ layer thickness, an ITO layer having a thickness of 2,500 to 3,000 Å film, the ITO layer so that the resistance value is 10 to 15 Ω / □ After formation, the etching resist was applied in the form of stripes. After the etching resist was formed at 60 占 폚 for 10 minutes, acid treatment (H ₂ O / HCl / HNO ₃ = 1/1 / 0.04 <weight ratio>, 50 占 폚 for 8 minutes), and alkali treatment (5% NaOH aqueous solution, About the sample after 50 degreeC * 3 minutes or 18 minutes), it confirmed visually that the ITO layer and the protective film did not generate | occur | produce a crack or a wrinkle.

<Heat resistance after ITO>

After the ITO layer was formed on the sample in which the protective film was formed in the same manner as the etching resistance after the ITO, the sample after the 230 ° C. or 250 ° C. × 1 hour treatment was not cracked or wrinkled in the ITO layer and the protective film. It was visually confirmed.

(Comparative Examples 1 to 6)

Each component was fully stirred and dissolved at the blending ratio shown in Table 5 to obtain a resin composition for a color filter protective film of Comparative Example.

In addition, storage stability was evaluated like the Example about the resin composition of the comparative example. Moreover, the layer of resin cured material was obtained using the resin composition of a comparative example by the method exactly the same as an Example. In all cases of the comparative example, the surface of the obtained coating film was flat and no pinholes or the like were seen. The film thickness measured in the Example was 2.0-2.5 micrometers. Moreover, each test of adhesiveness and ITO formation processability (acid-alkali tolerance after ITO circuit formation, heat resistance after ITO circuit formation) was performed about the obtained resin cured layer similarly to an Example. The results are shown in Table 6 below.

In the case of Examples 1-9 using the resin composition of this invention from the result of Table 4 and Table 6, the adhesiveness of the protective film after hardening and ITO formation, while the storage stability of the obtained compound liquid satisfy | fill the performance currently calculated | required in recent years. It was found that the processability is excellent. Moreover, since the resin composition of this invention contains an epoxy compound and a carboxylic acid compound, the protective film after hardening was excellent in transparency, chemical-resistance, and heat resistance.

In the comparative example 1, since the epoxy equivalent of the epoxy group containing polymer (A) was large compared with the Claim of this invention, the crosslink density of a protective film was low, and the result that adhesiveness and ITO formation processability were inferior was obtained. In Comparative Examples 2, 3 and 6, the epoxy group-containing compound (B) was not included in the claims of the present invention, respectively, and the results showed that the adhesion and the lTO formation processability were poor. In Comparative Examples 4 and 5, the polyvalent carboxylic acid derivative (C) is not included in the claims of the present invention, and in Comparative Example 4, since the crosslinking density is low, the adhesion and the ITO formation processability are inferior, and Comparative Example 5 Since the carboxylic acid was not blocked, the storage stability was significantly lower.

The resin composition for color filter protective films which concerns on this invention has the outstanding curability and storage stability, and the layer of cured resin is good in heat resistance and solvent resistance, and can fully obtain adhesiveness and ITO process formation property. Therefore, even if the compounding amount of the active catalyst, which has been used conventionally, is suppressed or not used, it is possible to achieve high adhesion and ITO formation processability, which are required for the CF protective film in recent years, and further excellent without damaging the storage stability. Do.

Moreover, according to this invention, the color filter which has not only the basic performance of heat resistance and solvent resistance but also the layer of the resin hardened | cured material excellent in adhesiveness and ITO formation processability can be obtained.

Claims (6)

An epoxy group-containing polymer (A) polymerized using a monomer having a weight average molecular weight of 5000 to 40000, an epoxy equivalent of 140 to 600 g / mol, and containing at least a carbon-carbon unsaturated bond and an epoxy group, and a molecular weight of 330 to 7000 Epoxy group-containing compound (B), which is a derivative of bisphenol A having an epoxy equivalent of 150 to 3500 g / mol and having two or more epoxy groups, and a carboxylic acid (c1) having a structure represented by the following formula (1) are vinyl ether compounds ( The resin composition for color filter protective films containing the polyhydric carboxylic acid derivative (C) latent by c2). <Formula 1>

(Wherein 6-membered ring is an aromatic or alicyclic hydrocarbon, m1 is an integer of 0 to 2, t1 is an integer of 0 to 1, n is an integer of 1 to 4, when n is 1, R ¹ is A hydrogen atom or a hydrocarbon group of 2 to 8 carbon atoms, when n is 2 to 4, R ¹ is a hydrocarbon group of 2 to 8 carbon atoms, and R ² is an alkyl group of 1 to 5 carbon atoms) The resin composition for color filter protective films of Claim 1 in which the said polyhydric carboxylic acid derivative (C) has the carboxylic acid which has a structure of following General formula (2) latent by propyl vinyl ether. <Formula 2>

(Wherein m2 is an integer of 0 to 2) The resin composition for color filter protective films of Claim 1 in which the said polyhydric carboxylic acid derivative (C) is latent by the vinyl ether compound (c2) which has the structure of following General formula (3). <Formula 3>

(Wherein m3 is an integer of 0 to 2, t3 is an integer of 0 to 1, and R ² is an alkyl group having 1 to 5 carbon atoms) The resin composition for color filter protective films as described in any one of Claims 1-3 which further contains titanium soap and / or zirconium soap as an adhesive improving agent (D). The resin composition for color filter protective films as described in any one of Claims 1-4 which further contains a pentavalent phosphorus atom containing compound as a storage stability improving agent (E). The color filter which has a layer of the resin cured material formed by hardening | curing the resin composition for color filter protective films of any one of Claims 1-5.