JP4816372B2 - Thermosetting resin composition for color filter protective film - Google Patents

Description

  The present invention relates to a thermosetting resin composition for a color filter protective film used in a liquid crystal display device (LCD) and the like, and a color filter using the thermosetting resin composition.

  A color filter used as a member of a liquid crystal display-related device is manufactured through a number of harsh processes including an immersion treatment in an acid / alkali solution. From these harsh process conditions, it is common to provide various resistances by forming a protective film in the color filter in order to prevent performance degradation or failure due to deterioration or damage of the color filter. Has been done. Such a protective film has various resistances, and from the viewpoint of reliability, the RGB resist layer, which is a base material for forming the protective film, and the transparent electrode layer deposited (sputtered) on the protective film are both layers. Good adhesion, good ability to smooth the unevenness of RGB resist, good visible light transmittance in order not to deteriorate the image quality improvement performance of the liquid crystal display device, There is no change in appearance such as coloring or yellowing in the change, and the migration of impurities derived from pigments and dyes abundantly contained in the RGB resist layer to the liquid crystal layer or the transmission of gas components such as water vapor from the outside It is required to have a barrier function to suppress the above.

  In recent years, liquid crystal display-related devices have been required to have advanced performance in conjunction with technological advances, and higher performance has been strongly demanded for each member. In particular, there is a strong desire for higher image quality and higher definition of liquid crystal display devices. With this demand, it is necessary to reduce the resistance and thickness of transparent electrodes of color filters. Along with this, in the formation of the transparent electrode, it is necessary to perform sputtering at a higher temperature, which is a very severe manufacturing process. In the process of forming the transparent electrode, the surface of the pigment dispersion resist inside the color filter is exposed to a high temperature state, so that the surface of the protective film is likely to be wrinkled, cracked, and yellowed, which is recognized as a problem. ing.

On the other hand, various thermosetting compositions for color filter protective films have been proposed in the past, and they are required to be adapted to the above-described sophisticated characteristic requirements.
Patent Document 1 discloses a protective film using a polymer having an alkoxysilyl group and a glycidyl group and a polyvalent carboxylic acid or a polyvalent carboxylic acid anhydride. However, the physical properties of the protective film obtained by this technique are such that the heat resistance is improved by the siloxy bond generated by the reaction between alkoxysilyl groups, while the siloxy bond is a chemical bond having inferior chemical resistance. Insufficient process resistance during electrode formation. Furthermore, it is an unsolved problem that excessive alkoxysilyl groups remain unreacted and the cured film deteriorates with time.
Patent Document 2 discloses a resin composition using a polymer having an alkoxysilyl group, a saturated aliphatic epoxy resin, and a carboxylic anhydride compound. However, this curing system cannot originally obtain a sufficiently high crosslinking density, and cannot satisfy the requirements for process resistance at the time of forming a transparent electrode, that is, chemical resistance and heat resistance.
Thus, a thermosetting composition for a color filter protective film that satisfies the high adhesion required for color filter protective films in recent years and the process resistance when forming transparent electrodes is desired.

JP-A-61-2212218 JP 2005-213337 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 cured resin layer has adhesion, low thermal expansion, toughness. The object is to provide a resin composition for a color filter protective film that has basic properties such as properties and barrier properties and is excellent in process resistance when forming a transparent electrode.
The second object of the present invention is to provide a color filter having a layer of a cured resin product having the above-mentioned excellent characteristics.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymer (A) and an epoxy containing a structural unit having an epoxy group or a structural unit having an oxetanyl group and a structural unit having an alkoxysilyl group Polymer (B) containing a structural unit having a group or a structural unit having an oxetanyl group and an acrylate structural unit, and a polyvalent carboxylic acid hemiacetal ester (C) in which the carboxyl group of the polyvalent carboxylic acid compound is latentized by a vinyl ether compound The thermosetting resin composition for a color filter protective film, which is formulated in a specific amount), has obtained the knowledge to solve the above problems, and has completed the present invention.

That is, the present invention includes the following [1] and [2].
[1] The following three components (A), (B) and (C) (A) a structural unit having an epoxy group or 10 to 60% by weight of a structural unit having an oxetanyl group and a structural unit 40 having an alkoxysilyl group Polymer containing up to 90% by weight and having a weight average molecular weight (Mw) of 3,000 to 300,000 (B) A structural unit having an epoxy group or a structural unit having an oxetanyl group and a acrylate-based structure Polymer (C) Polyvalent carboxylic acid in which carboxyl group of polymer (C) Multivalent carboxylic acid compound containing 10 to 90% by weight and having weight average molecular weight (Mw) of 3,000 to 300,000 is made latent by vinyl ether compound It consists of a hemiacetal ester, and the mole of the above (epoxy group or oxetanyl group) / (alkoxysilyl group) / (carboxyl group) Ratio of degrees is 0.8 to 3.3 / 0.01 to 1.0 / 1, the thermosetting resin composition for a color filter protective film.

[2] A color filter having a layer of a cured resin obtained by curing the thermosetting resin composition according to [1].

  The thermosetting resin composition for the color filter protective film of the present invention is excellent in chemical resistance against acid and alkali and heat resistance at a very high temperature of 230 to 250 ° C. A layer of a cured product excellent in basic performance such as property, low thermal expansion, toughness, and barrier property, that is, a color filter protective film can be obtained. With this excellent protective film, a color filter having excellent optical characteristics and reliability can be obtained.

The present invention is described in detail below.
In the present invention, the color filter protective film widely means a protective film used for a display device having a color filter and a solid-state image sensor, and more specifically, a liquid crystal display device (LCD), a solid-state image sensor (CCD, etc.). , Color filter (CF) parts used in electroluminescence devices (ELD), etc., light-emitting or light-receiving element parts, electrode parts, etc., directly contacting and protecting these parts, or these parts through other materials This means a protective film that is indirectly protected.

1. Thermosetting resin composition for color filter protective film The thermosetting resin composition for a color filter protective film of the present invention comprises the following three components (A), (B) and (C).
(A) 10 to 60% by weight of a structural unit having an epoxy group or a structural unit having an oxetanyl group and 40 to 90% by weight of a structural unit having an alkoxysilyl group, and a weight average molecular weight (Mw) of 3,000 to 300, 000 polymer (B) derived from an alkyl (meth) acrylate monomer comprising 10 to 90% by weight of a structural unit having an epoxy group or a structural unit having an oxetanyl group and an alkyl group having 1 to 6 carbon atoms Polymer (C) Polyvalent Carboxylic Acid Containing Latent Carboxylic Carboxylic Acid Compound (C) Polyhydric Carboxylic Compound Comprising 10 to 90% by Weight of Constituent Unit and Weight Average Molecular Weight (Mw) of 3,000 to 300,000 Acid hemiacetal ester

<Polymer (A)>
The polymer (A) used in the present invention includes a structural unit having an epoxy group or a structural unit having an oxetanyl group and a structural unit having an alkoxysilyl group.
The structural unit having an epoxy group is specifically represented by any one of formulas (1) to (3), and the structural unit having an oxetanyl group is specifically represented by formula (4).

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k represents an integer of 1 to 5)

(In the formula, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ is a —CH ₂ O— group or —CH ₂ — group, R ⁴ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, m represents an integer of 1 to 7.)

(In the formula, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 8)

(Wherein R ⁶ , R ⁷ , and R ⁸ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and j represents an integer of 1 to 5)
Moreover, the structural unit which has an alkoxy silyl group is specifically represented by Formula (5).

(Wherein, ^{R 9} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, h is an integer of from 1 to ^{5, R 10, R 11, R} 12 represents a methyl group or an ethyl group independently.)

  The polymer (A) containing the structural unit having an epoxy group or oxetanyl group and the structural unit having an alkoxysilyl group in the thermosetting resin composition for a color filter protective film of the present invention is further represented by the following formulas (6) to (6): You may have the structural unit represented by (8).

(Wherein R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, or a polyalkylene glycol residue, or a main ring-constituting carbon. Represents an alicyclic hydrocarbon group of formula 3-12.)

Wherein R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a hydroxyalkyl group, a hydroxyl group, a siloxyalkyl group, or an aromatic Represents a hydrocarbon group.)

(In the formula, R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an alkaryl group.)

  The polymer (A) of the present invention can be obtained by polymerizing an epoxy group or oxetanyl group-containing monomer and an alkoxysilyl group-containing monomer, or by copolymerizing these monomers with 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 polymer (A) containing a structural unit having an epoxy group or oxetanyl group and a structural unit having an alkoxysilyl group in the thermosetting resin composition for a color filter protective film of the present invention is polymerized by a conventional polymerization method. can do. 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.
The structural units represented by the formulas (1) to (4) are each derived from an epoxy group or oxetanyl group-containing monomer represented by the following formulas (9) to (12).

(In the formula, each of R ¹ and k is the same as that in formula (1).)

(Wherein R ^{2 to} R ⁴ and m are the same as those in formula (2)).

(In the formula, each of R ⁵ and n is the same as that in formula (3).)

(Wherein R ^{6 to} R ⁸ and j are the same as those in formula (4).)
In the above formulas (1) and (9), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. Moreover, k is an integer of 1-5, and k = 1 is more preferable. If k exceeds 5, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
In the above formulas (2) and (10), R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. R ³ represents a —CH ₂ O— group or a —CH ₂ — group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, preferably a —CH ₂ — group. M is an integer of 1 to 7, and preferably m = 1. If m exceeds 7, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
In the above formulas (3) and (11), R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. N is an integer of 1 to 8, preferably n = 1. If k exceeds 8, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
In the above formula (4) and formula (12), (R ⁶ and R ⁷ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. In addition, R ⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom, and if it exceeds 5, it becomes inconvenient in terms of polymerizability. j is an integer of 1 to 5, preferably j = 1. If j exceeds 5, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
Of these epoxy group or oxetanyl group-containing monomers, glycidyl methacrylate is preferred from the standpoint of availability.
The structural unit represented by the formula (5) is derived from an alkoxysilyl group-containing monomer represented by the following formula (13).

(In formula, R < ⁹ > -R < ¹² > and h are respectively the same as the thing in Formula (5).)
In the above formulas (5) and (13), R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. H is an integer of 1 to 5, and h = 1 is more preferable. If h exceeds 5, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
The structural unit represented by the formula (6) is derived from a monomer represented by the following formula (14).

(In the formula, each of R ¹³ and R ¹⁴ is the same as that in formula (6).)
In the above formula (6) and formula (14), R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group. R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, or a polyalkylene glycol residue, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms constituting the main ring. The alicyclic hydrocarbon group having 3 to 12 ring carbon atoms includes an additional structure such as an intracyclic double bond, a side chain of a hydrocarbon group, a side chain of a spiro ring, an intracyclic bridged hydrocarbon group, and the like. You may go out. R ¹⁴ is preferably an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, or a dicyclopentanyl group. When the carbon number of R ¹³ exceeds 5 or the carbon number of R ¹⁴ exceeds 12, the reactivity is lowered, which is inconvenient.
The structural unit represented by the formula (7) is derived from a monomer represented by the following formula (15).

(In the formula, each of R ¹³ and R ¹⁴ is the same as that in formula (7).)
In the above formulas (7) and (15), R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably hydrogen or a methyl group, and R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, An alkoxy group, a hydroxyalkyl group, a hydroxyl group, a siloxyalkyl group, or an aryl group, preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. When the carbon number of R ¹³ exceeds 5 or the carbon number of R ¹⁴ exceeds 12, the reactivity is lowered, which is inconvenient.
The structural unit represented by the formula (8) is derived from a monomer represented by the following formula (16).

(Wherein R ¹⁷ is the same as in formula (6).)
In the formulas (8) and (16), R ¹⁷ is a hydrogen atom or a cycloalkyl group having 1 to 12 carbon atoms, an aryl group, or an alkaryl group, preferably a cyclohexyl group, and a phenyl group. If the number of carbon atoms exceeds 12, it is inconvenient in terms of polymerizability.
The structural unit represented by the above formulas (6) to (8) is a polymer (A) determined by the properties of a structural unit having an epoxy group or a structural unit having an oxetanyl group and a structural unit having an alkoxysilyl group. The monomers represented by the formulas (12) to (14) for introducing the structural unit without greatly changing the properties can be preferably used because they have good copolymerizability.

In the thermosetting resin composition for a color filter protective film of the present invention, the polymer (A) having a structural unit having an epoxy group or a structural unit having an oxetanyl group and a structural unit having an alkoxysilyl group is represented by the above formula ( At least one of the structural units having an epoxy group represented by 1) to (4) or the structural unit having an oxetanyl group in the polymer (A) is 10 to 60% by weight, preferably 20 to 40% by weight. Have. When the structural unit having an epoxy group represented by the formulas (1) to (4) or the structural unit having an oxetanyl group is less than 10% by weight in the polymer (A), it is desirable because the epoxy group or the oxetanyl group decreases. In some cases, the crosslink density cannot be obtained, and the physical properties of the protective film may be deteriorated. If it exceeds 60% by weight, the protective film may lose its toughness.
The polymer (A) having a structural unit having an epoxy group or a structural unit having an oxetanyl group and a structural unit having an alkoxysilyl group is a polymer having a structural unit having an alkoxysilyl group represented by the formula (5) ( A) 40 to 90% by weight, preferably 60 to 80% by weight. When the constituent unit having an alkoxysilyl group represented by the formula (5) is less than 40% by weight in the polymer (A), the effect of the present invention cannot be obtained. Decreases.

The weight average molecular weight (Mw) of the polymer (A) in the thermosetting resin composition for a color filter protective film of the present invention is 3,000 to 300,000, preferably 3,000 to 30,000. It is a range. When the weight average molecular weight (Mw) is less than 3,000, the hardness of the protective film decreases, and when it exceeds 300,000, the flatness after coating and curing decreases. In addition, a weight average molecular weight (Mw) is a weight average molecular weight of polystyrene conversion by gel permeation chromatography (GPC) method.
In the thermosetting resin composition for a color filter protective film of the present invention, the polymer (A) may be a mixture of two or more polymers having different molecular weights or comonomer types.

<Polymer (B)>
The polymer (B) containing a structural unit having an epoxy group or a structural unit having an oxetanyl group and an acrylate-based structural unit used in the thermosetting resin composition for a color filter protective film of the present invention is other than the polymer (A). And containing 10 to 90% by weight of a structural unit having an epoxy group or a structural unit having an oxetanyl group and 10 to 90% by weight of an acrylate-based structural unit.

The structural unit having an epoxy group or the structural unit having an oxetanyl group is represented by the following formulas (17) to (20).
The structural unit having an epoxy group is specifically represented by any one of formulas (17) to (19), and the structural unit having an oxetanyl group is specifically represented by formula (20).

(In the formula, R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 1 to 5)

Wherein R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ²⁰ is a —CH ₂ O— group or —CH ₂ — group, R ²¹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, q represents an integer of 1 to 7.)

(In the formula, R ²² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents an integer of 1 to 8)

(Wherein R ²³ , R ²⁴ , and R ²⁵ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and s represents an integer of 1 to 5)
The acrylate structural unit is specifically represented by the formula (21).

(Wherein R ²⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ²⁷ is an alkyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, or a polyalkylene glycol residue, or a main ring-constituting carbon. Represents an alicyclic hydrocarbon group of formula 3-12.)
In the thermosetting resin composition for a color filter protective film of the present invention, the polymer (B) containing a structural unit having an epoxy group or an oxetanyl group and an acrylate-based structural unit is further represented by the formula (22) or (23). It may have a structural unit represented by

Wherein R ²⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ²⁹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a hydroxyalkyl group, a hydroxyl group, a siloxyalkyl group, or an aromatic Represents a hydrocarbon group.)

(In the formula, R ³⁰ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an alkaryl group.)

  The polymer (B) of the present invention can be obtained by polymerizing an epoxy group or oxetanyl group-containing monomer and an acrylate monomer, or by copolymerizing these monomers with 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.

In the thermosetting resin composition for a color filter protective film of the present invention, the polymer (B) containing a structural unit having an epoxy group or oxetanyl group and an acrylate-based structural unit may be polymerized by a conventional polymerization method. it can. 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.
The structural units represented by the formulas (17) to (20) are each derived from an epoxy group or oxetanyl group-containing monomer represented by the following formulas (24) to (27).

(Wherein R ¹⁸ and p are the same as those in formula (17).)

(Wherein R ^{19 to} R ²¹ and q are the same as those in formula (18).)

(Wherein R ²² and r are the same as those in formula (19)).

(Wherein R ^{23 to} R ²⁵ and s are the same as those in formula (20).)
In the above formulas (17) and (24), R ¹⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. Moreover, p is an integer of 1-5, and p = 1 is more preferable. If p exceeds 5, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
In the above formulas (18) and (25), R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. R ²⁰ is a —CH ₂ O— group or —CH ₂ — group, and R ²¹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, preferably a —CH ₂ — group. Q is an integer of 1 to 7, preferably q = 1. If q exceeds 7, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
In the above formula (19) and formula (26), R ²² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. If the number of carbon atoms exceeds 5, it becomes inconvenient in terms of polymerizability. R is an integer of 1 to 8, preferably r = 1. If r exceeds 8, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
In the above formula (20) and formula (27), (R ²³ and R ²⁴ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group. In addition, R ²⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom, and if it exceeds 5, it is inconvenient in terms of reactivity. s is an integer of 1 to 5, preferably s = 1. If s exceeds 5, sufficient mechanical properties such as Tg of the cured product cannot be obtained after curing.
Of these epoxy group or oxetanyl group-containing monomers, glycidyl methacrylate is preferred from the standpoint of availability.
The structural unit represented by the formula (21) is derived from an acrylate monomer represented by the following formula (28).

(In the formula, each of R ²⁶ and R ²⁷ is the same as that in formula (21).)
In the above formulas (21) and (28), R ²⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group. R ²⁷ is an alkyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, or a polyalkylene glycol residue, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms constituting the main ring. The alicyclic hydrocarbon group having 3 to 12 ring carbon atoms includes an additional structure such as an intracyclic double bond, a side chain of a hydrocarbon group, a side chain of a spiro ring, an intracyclic bridged hydrocarbon group, and the like. You may go out. R ²⁷ is preferably an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, or a dicyclopentanyl group. If the number of carbon atoms in R ²⁶ exceeds 5 or the number of carbon atoms in R ²⁷ exceeds 12, the reactivity is lowered, which is inconvenient.
The structural unit represented by the formula (22) is derived from a monomer represented by the following formula (29).

(In the formula, each of R ²⁸ and R ²⁹ is the same as that in formula (29).)
In the above formulas (22) and (29), R ²⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably hydrogen or a methyl group, and R ²⁹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, An alkoxy group, a hydroxyalkyl group, a hydroxyl group, a siloxyalkyl group, or an aryl group, preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. If the number of carbon atoms in R ²⁸ exceeds 5 or the number of carbon atoms in R ²⁹ exceeds 12, the reactivity is lowered, which is inconvenient.
The structural unit represented by the formula (23) is derived from a monomer represented by the following formula (30).

(Wherein R ³⁰ is the same as in formula (23).)
In the formulas (23) and (30), R ³⁰ is a hydrogen atom or a cycloalkyl group having 1 to 12 carbon atoms, an aryl group, or an alkaryl group, preferably a cyclohexyl group, and a phenyl group. If the number of carbon atoms exceeds 12, it is inconvenient in terms of polymerizability.
The structural unit represented by the above formulas (22) and (23) greatly increases the properties of the polymer (B) determined by the properties of the structural unit having an epoxy group or the structural unit having an oxetanyl group and the acrylate-based structural unit. The monomers represented by the formulas (29) and (30) for introducing the structural unit without change are also preferably used since they have good copolymerizability.
The polymer (B) of the present invention can be obtained by polymerizing an epoxy group or oxetanyl group-containing monomer and an acrylate structural unit, or by copolymerizing these monomers with 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 polymer (B) containing the structural unit having an epoxy group or the structural unit having an oxetanyl group in the thermosetting resin composition for a color filter protective film of the present invention can be polymerized 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.

The polymer (B) containing the structural unit having an epoxy group or the structural unit having an oxetanyl group in the thermosetting resin composition for a color filter protective film of the present invention is represented by the above formulas (17) to (20). In the polymer (B), at least one of the epoxy group or oxetanyl group-containing structural units to be used is 10 to 90% by weight, preferably 25 to 70% by weight. When the structural unit having an epoxy group or an oxetanyl group represented by the above formulas (17) to (20) is less than 10% by weight in the polymer (B), the desired crosslinking density cannot be obtained, and the physical properties of the protective film are lowered. When it exceeds 90% by weight, the protective film loses toughness.
The weight average molecular weight (Mw) of the polymer (B) containing the structural unit having an epoxy group or oxetanyl group in the thermosetting resin composition for the color filter protective film of the present invention is 3,000 to 300,000. , Preferably 3,000 to 30,000. When the weight average molecular weight (Mw) is less than 3,000, a decrease in the hardness of the protective film is observed, and when it exceeds 300,000, the flatness after coating and curing may be deteriorated.

Moreover, the epoxy equivalent of the polymer (B) containing the structural unit having an epoxy group or oxetanyl group in the thermosetting resin composition for a color filter protective film of the present invention is 140 to 1,000 g / mol, preferably Is 200-800 g / mol. If the epoxy equivalent is less than 140 g / mol, the protective film after coating and curing tends to lose toughness, and if it exceeds 1,000 g / mol, the hardness of the cured film may be lowered. Furthermore, in the case of applications that require high adhesion, the protective film is required to have toughness, and is preferably 200 to 550 g / mol. When the epoxy equivalent of the polymer (B) containing a structural unit having an epoxy group or a structural unit having an oxetanyl group is 200 g / mol or less, the toughness is lowered, and there is a high possibility that an edge defect will occur in the adhesion test. . The epoxy equivalent in this case refers to the equivalent of the epoxy group of the resin, and is measured according to JIS K7236: 2001 “How to Determine Epoxy Equivalent of Epoxy Resin”.
In the thermosetting resin composition for a color filter protective film of the present invention, the polymer (B) containing a structural unit having an epoxy group or a structural unit having an oxetanyl group includes two types of polymers having different molecular weights and comonomer types. A mixture of the above may be used.

<Polyvalent carboxylic acid hemiacetal ester (C) in which carboxyl group of polyvalent carboxylic acid compound is made latent by vinyl ether compound>
In the thermosetting resin composition for a color filter protective film of the present invention, the polyvalent carboxylic acid hemiacetal ester (C) in which the carboxyl group of the polyvalent carboxylic acid compound is latentized with a vinyl ether compound is a polyvalent carboxylic acid ( In this compound, the carboxyl group of c1) is latentized (hereinafter referred to as blocking) by the vinyl ether compound (c2) (vinyl group and ether group-containing compound) represented by the following formula (31).

(Here, R ³¹ is a hydrocarbon group having 1 to 10 carbon atoms.)
More specifically, the polyvalent carboxylic acid hemiacetal ester (C) in which the carboxyl group of the polyvalent carboxylic acid compound is latentized with a vinyl ether compound is a compound having two or more functional groups represented by the formula (32) It is.

(In the formula, R ³¹ is the same as that in formula (31).)
Specific examples of the vinyl ether compound (c2) represented by the formula (31) include, for example, methyl vinyl ether, ethyl vinyl ether, i-propyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether. And aliphatic vinyl ether compounds such as 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether. Among them, n-propyl vinyl ether and i-butyl vinyl ether are preferable because they are available and the curing temperature is compatible with the process of the protective film.
A vinyl ether compound (c2) can be used individually by 1 type or in combination of 2 or more types.

As polyvalent carboxylic acid (c1) used for polyvalent carboxylic acid hemiacetal ester (C) used for this invention, it is preferable that it is C2-C20 and it is 2-8 carboxylic acid. From the viewpoint of fluidity that contributes to flatness, aliphatic polycarboxylic acids having a straight chain or branched chain such as itaconic acid, maleic acid, succinic acid, and citraconic acid are preferred examples;
Alicyclic polycarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanedicarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetricarboxylic acid; phthalic acid, terephthalic acid, isophthalic acid, merit acid, trimethyl Aromatic polyvalent carboxylic acids such as merit acid, pyromellitic acid, and benzophenone tetracarboxylic acid are listed.

As polyvalent carboxylic acid (c1), the half-ester body obtained by reaction with an alcohol compound and an acid anhydride can also be used.
Examples of the alcohol compound used in this reaction include monovalent alcohol compounds such as ethanol, propanol, hexanol, octanol, i-propyl alcohol; ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, cyclohexane Preferred examples include divalent alcohol compounds such as diols; trivalent alcohol compounds such as glycerin, pentanetriol, hexanetriol, cyclohexanetriol, benzenetriol, and trimethylolpropane; and tetravalent alcohol compounds such as pentaerythritol. Preferably hexanol, i-propyl alcohol, 1,2-propylene glycol, 1,3-propylene glycol, 1,6-hexanediol, glycerin Trimethylol propane, pentaerythritol.

  Specific examples of acid anhydrides used in this reaction include phthalic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 1,3,4-tricarboxylic acid-3,4-anhydride ( Hereinafter, it is called trimellitic anhydride), 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride, and methylhexahydrophthalic anhydride. 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 (c1), and among them, methylhexahydrophthalic anhydride is more preferably selected from the viewpoints of transparency and storage stability.

  The polyvalent carboxylic acid hemiacetal ester (C) used in the present invention is obtained by reacting the polyvalent carboxylic acid (c1) with the vinyl ether compound (c2) at a temperature in the range of room temperature to 150 ° C. be able to. Since the blocking reaction is an equilibrium reaction, if the vinyl ether compound (c2) is used slightly more than the polyvalent carboxylic acid (c1), the reaction is promoted and the yield can be improved. Specifically, the molar equivalent ratio [the molar equivalent ratio of (vinyl group / carboxyl group)] of the vinyl group of the vinyl ether compound (c2) to the carboxyl group of the polyvalent carboxylic acid (c1) is 1/1 to 2/1. It is desirable that When this molar equivalent ratio exceeds 2/1, the reaction temperature cannot be increased, and the reaction rate may be extremely low. When the molar equivalent ratio is less than 1/1, a carboxyl group that is not blocked remains, so that the fluidity is lowered and the effect of the present invention cannot be obtained.

  When the blocking reaction is performed, an acid catalyst can be used for the purpose of accelerating the reaction. An example of such a catalyst is an acidic phosphate compound represented by the following formula (33).

(In the formula, R ³² represents an alkyl group, cycloalkyl group or aryl group having 3 to 10 carbon atoms, and t represents 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 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.

  In general, in the thermosetting resin composition for a color filter protective film, the concentration of alkoxysilyl groups in the polymer may be increased in order to improve the adhesion. However, simply increasing the concentration of alkoxysilyl groups in the polymer preferentially produces siloxy bonds that are inferior in chemical resistance. Therefore, in the transparent electrode formation process, under high temperature, high strain, acid or alkali immersion. Due to this severe condition, the adhesion to glass or RGB resist is lowered. In addition, since the alkoxysilyl group originally has poor affinity with the curing agent, component separation in the thermosetting resin composition has occurred, and it has been difficult to increase the concentration of the alkoxysilyl group itself.

  With respect to this problem, the polycarboxylic acid hemiacetal ester (C) used in the present invention has high solubility in a solvent or a resin composition, and even in a polymer containing a high concentration of alkoxysilyl groups, the resin composition It can mix | blend in arbitrary ratios in a thing. The protective film obtained by blending the molar concentration of the carboxyl group in the resin composition at a high concentration with respect to the molar concentration of the epoxy group can increase the crosslinking density. That is, the barrier property required for improving chemical resistance can be increased. When the concentration of the structural unit having an alkoxysilyl group in the polymer (A) is high, the contact of the surrounding alkoxysilyl group to the adhesion surface is promoted, and the number of alkoxysilyl groups bonded to the adhesion surface increases, and the adhesion surface A strong bond is formed, and adhesion can be effectively obtained.

<Blending ratio of each component of (A), (B), (C)>
The thermosetting resin composition for a color filter protective film of the present invention comprises a constituent unit having an epoxy group or a constituent unit having an oxetanyl group and an alkoxy with respect to the total weight of (A), (B), and (C). 5 to 70% by weight of the polymer (A) having a structural unit having a silyl group, 20 to 60% by weight of a polymer (B) containing a structural unit having an epoxy group or a structural unit having an oxetanyl group and an acrylate structural unit %, The polycarboxylic acid hemiacetal ester (C) in which the carboxyl group of the polyvalent carboxylic acid compound is made latent by the vinyl ether compound is contained in an amount of 10 to 80% by weight.

  The blending ratio of the polymer (A) component having a structural unit having an epoxy group or a structural unit having an oxetanyl group and a structural unit having an alkoxysilyl group is preferably 10 to 50% by weight, more preferably 10 to 40%. % By weight. When the blending ratio of the polymer (A) having a structural unit having an epoxy group or a structural unit having an oxetanyl group and a structural unit having an alkoxysilyl group is less than 10% by weight, the performance such as adhesion of the protective film is lowered. However, if it exceeds 70% by weight, the basic performance of the protective film may be impaired.

The blending ratio of the polymer (B) component containing a structural unit having an epoxy group or a structural unit having an oxetanyl group and an acrylate structural unit is preferably 25 to 50% by weight, more preferably 30 to 45% by weight. is there. When the blending ratio of the polymer (B) containing a structural unit having an epoxy group or a structural unit having an oxetanyl group and an acrylate-based structural unit is less than 20% by weight, the performance such as adhesion of the protective film is reduced. If it exceeds the weight percentage, the basic performance of the protective film may be impaired.
The blending ratio of the polycarboxylic acid hemiacetal ester (C) in which the carboxyl group of the polyvalent carboxylic acid compound is made latent by the vinyl ether compound is 10 to 80% by weight, preferably 20 to 30% by weight. When the blending ratio of the polyvalent carboxylic acid hemiacetal ester (C) is less than 10% by weight, it becomes difficult to obtain the effect of the present invention, and when it exceeds 80% by weight, the carboxylic acid becomes excessive and the transparency is lowered. There is.

In the thermosetting resin composition for a color filter protective film of the present invention, the blending ratio of the three components (A), (B), and (C) is derived from the polycarboxylic acid hemiacetal ester (C). The total molar concentration of the epoxy group or oxetanyl group derived from the polymers (A) and (B) at a ratio based on the carboxyl group concentration is 0.8 to 3.3 / 1, preferably 0.5 to It mix | blends so that it may become 1.1 / 1.
When the molar concentration ratio of the carboxyl group to the epoxy group or oxetanyl group is less than 0.8 / 1, the carboxyl group becomes excessive, and the physical properties of the resin are often lowered. In addition, when the molar concentration ratio of carboxyl group to epoxy group or oxetanyl group exceeds 3.3 / 1, a large amount of epoxy group or oxetanyl group remains after curing, resulting in a low crosslinking density and a protective film with basic performance. May be damaged.

  The molar concentration of the alkoxysilyl group derived from the polymer (A) is 0.01 to 1.0 / in a ratio based on the carboxyl group concentration derived from the polycarboxylic acid hemiacetal ester (C). 1, preferably 0.5 to 1.1 / 1, more preferably 0.1 to 0.4 / 1. If it is less than 0.01 / 1, the alkoxysilyl group is insufficient, so that the heat resistance in the transparent electrode forming process is insufficient. If it is 1.0 / 1 or more, the alkoxysilyl group becomes excessive, so that the chemical resistance in the transparent electrode forming process is insufficient.

Here, the molar concentration of the carboxyl group is simply calculated from the compound structural formula (molecular weight) and the blending amount. More precisely, JIS K0070: 1992 “acid value, saponification value, ester value of chemical products, It is calculated from the acid equivalent measured according to the “Iodine value, hydroxyl value, and unsaponifiable test method”.
In general, in a thermosetting composition using a reaction of a hemiacetal ester, a part of a vinyl ether compound released during curing is recombined with a hydroxyl group generated by an acid-epoxy reaction to form an acetal structure. It has been known.
In the present invention, by using the three components (A), (B), and (C) in a specific ratio, a cured structure in which free hydroxyl groups are tightly bound by either alkoxysilyl groups or vinyl ether groups. It is considered that the process resistance at the time of forming the transparent electrode, which is a trade-off between the chemical resistance and the heat resistance, can be satisfied.
That is, the hydroxyl group by-produced by the reaction of the epoxy group and the carboxyl group serves as a reaction point with the alkoxysilyl group to form a bond, so that the crosslink density is further increased and the barrier property is improved. In addition, by reacting hydroxyl groups and alkoxysilyl groups, unreacted alkoxysilyl groups that cause changes in the protective film over time can be reduced, and a siloxy bond with weak chemical resistance is barriered to form a transparent electrode. The process resistance at the time can be improved.

  Polyhydric carboxylic acid hemiacetal esters are limited in solubility because they are used in the form of highly soluble polycarboxylic hemiacetal esters by blocking the carboxyl groups of poorly soluble polycarboxylic acids used as curing agents. It became possible to carry out compounding design without being carried out. However, by simply blending the carboxyl group to the same level as the epoxy group or oxetanyl group, the resulting cured film has been unable to meet the high heat resistance and process resistance when forming a transparent electrode, which are required in recent years. By introducing a polymer (A) containing a constitutional unit having an alkoxysilyl group at a high concentration in the resin composition, a siloxy bond is introduced to improve heat resistance, and a polycarboxylic acid hemiacetal ester (C) Has a high crosslinking density because the carboxyl group can be blended up to the same amount as the epoxy group or oxetanyl group, and the by-produced hydroxyl group has a reactive site of the unreacted alkoxysilyl group of the polymer (A). Become. Further, by blocking the siloxy bond having low alkali resistance, it is possible to satisfy the high heat resistance required in recent years and the process resistance when forming the transparent electrode.

  The thermosetting resin composition for a color filter protective film according to the present invention should be used by adjusting the viscosity to an optimum level according to the type of coating process by adding arbitrary amounts of solvents, fillers, and additives. Can do.

<Other ingredients>
The thermosetting resin composition for a color filter protective film of the present invention is used by adding a curing accelerator, an adhesion improving aid, a surface conditioner, an epoxy resin or oxetane resin, a viscosity conditioner, and other components. be able to.
<Organic solvent>
An organic solvent may be added to the thermosetting resin composition for a color filter protective film of the present invention for the purpose of adjusting viscosity and the like during use. 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.
These organic solvents can be used alone or in combination of two or more.
Moreover, there is no restriction | limiting in particular about the addition amount of these organic solvents, According to the predetermined film thickness, the smoothness of expression, a film-forming method, etc., arbitrary amounts can be added and the applicability | paintability can be provided. Usually, it is 5-2000 weight part with respect to 100 weight part of thermosetting resin compositions for color filter protective films.

<Curing accelerator>
In the thermosetting resin composition for a color filter protective film of the present invention, a curing accelerator is appropriately used as long as the colorless transparency of the cured resin obtained by curing the thermosetting resin composition of the present invention is not impaired. You can also Examples of the curing accelerator that can be added include tertiary amines such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine; 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl- Imidazoles such as 4-methylimidazole and 1-benzyl-2-methylimidazole; Organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; Quaternary compounds such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide Phosphonium salts; diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate, and aluminum acetylacetone complex; Tetraethylammoni Arm bromide, quaternary ammonium salts such as tetrabutylammonium bromide; boron trifluoride, boron compounds such as triphenyl borate; zinc chloride, metal halides such as stannic chloride. 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 Microcapsule type latent accelerators; latent curing accelerators represented by amine salt type latent curing accelerators, high temperature dissociation type latent curing accelerators such as Lewis acid salts, Bronsted acid salts, etc. are also used. be able to.

  The curing accelerator is preferably a halogen-free acidic catalyst from the viewpoint of liquid crystal non-contamination of the cured product. Furthermore, in view of the storage stability of the resin composition, among the halogen-free acidic catalysts, specifically, a Lewis acid salt high-temperature dissociation type latent curing accelerator is more preferable, and a commercial product is Nocure LCAT. -1 and Nocure-LCAT-2 (both are trade names, manufactured by NOF Corporation). These curing accelerators can be used singly or in appropriate combination of two or more. When using the said hardening accelerator, it is normally mix | blended in the ratio of 0.01 to 10 weight% with respect to 100 weight part of thermosetting resin compositions for color filter protective films of this invention.

<Adhesion improvement aid>
The thermosetting resin composition for a color filter protective film of the present invention includes a titanium cup containing a metal soap as an auxiliary agent for improving the adhesion when a higher degree of adhesion is required with the substrate. An adhesion improver such as a ring agent, a zirconium coupling agent, and an aluminum chelating agent can also be added. As the titanium coupling agent and the zirconium coupling agent, a metal soap type containing a carboxylate may be used. These coupling agents can be added individually by 1 type or in combination of 2 or more types.
<Surface conditioner>
The thermosetting resin composition for the color filter protective film of the present invention has the purpose of improving the appearance of the protective film obtained by curing the thermosetting resin composition, or improves the compatibility of each component. For the purpose of making it, a surface conditioner can be added. A surface conditioning agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
When the surface conditioner is added and used, the amount is usually 0.001 to 3% by weight with respect to 100 parts by weight of the thermosetting resin composition for the color filter protective film of the present invention.

<Epoxy resin or oxetane resin>
The epoxy resin or oxetane resin is usually used in an amount of 20% by weight or less, preferably 10% by weight or less, based on 100 parts by weight of the thermosetting resin composition for a color filter protective film of the present invention. May be.
The epoxy resin or oxetane resin can be used alone or in combination of two or more with respect to the thermosetting resin composition for the color filter protective film of the present invention.

The thermosetting resin composition for a color filter protective film of the present invention may further contain a viscosity adjusting agent such as a thickener or thixotropic agent 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 thermosetting resin composition for the color filter protective film of the present invention includes aliphatic polyols such as ethylene glycol and propylene glycol, phenolic compounds, and the like, as long as the effects of the present invention are not impaired. Carbon dioxide generation inhibitor, flexibility imparting agent such as polyalkylene glycol, antioxidant, plasticizer, lubricant, surface treatment agent, flame retardant, antistatic agent, colorant, leveling agent, ion trap agent, sliding Additives such as property improvers, various rubbers, organic polymer beads, glass beads, thixotropic agents, surface tension reducing agents, antifoaming agents, light diffusing agents, antioxidants, fluorescent agents, and the like can be blended.

<Method for producing resin composition>
The method of blending, stirring and dispersing the thermosetting resin composition for the color filter protective film of the present invention will be described below.
In the resin composition of the present invention, the components including the above 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 solutions are used during use (at the time of application). May be mixed to prepare a resin composition.

In the thermosetting resin composition for a color filter protective film of the present invention, with regard to stirring after mixing the components including the components (A) to (C), a blade-type stirrer, a desolver, a kneader, a ball mill Stirring may be performed using a blender, a roll disperser, or the like, or each component may be mixed in a container such as a gallon bottle and then stirred by rotating the whole container with a mix rotor. 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 thermosetting resin composition for a color filter protective film 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 using the components including the components (A) to (C) in the present invention in advance as a binder and mix them at the time of use. However, since the deblocking reaction proceeds with heat in the polycarboxylic acid hemiacetal ester (C), when the composition containing the polycarboxylic acid hemiacetal ester (C) is dispersed, it is not heated to 80 ° C. or higher. Consideration is necessary.

2. Color filter The color filter of this invention has the layer of the resin cured material formed by hardening | curing the thermosetting resin composition for color filter protective films of the said invention.
The layer of the cured resin obtained by curing the thermosetting resin composition for the color filter protective film is not particularly limited to what is generally referred to as a protective film, for example, on the substrate of the color filter. It refers to a layer of cured resin formed between the formed RGB pixel and a liquid crystal alignment film, a transparent electrode 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.

Since the color filter of the present invention has a layer of a cured resin obtained by curing the thermosetting resin composition for the color filter protective film of the present invention, heat resistance, solvent resistance, heat resistance colorability, adhesion In addition, a color filter having a layer of a cured resin with excellent flatness can be obtained.
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 on the black matrix, and a protective film formed so as to cover the pixel portion. Yes. 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 cured resin layer obtained by curing the thermosetting resin composition for the color filter protective film of the present invention is prepared by appropriately adjusting the viscosity of the thermosetting resin composition for the color filter protective film of the present invention. First, it is applied to the surface of the color filter on which the colored layer is formed.

The method for applying the thermosetting resin composition for the color filter protective film of the present invention is not particularly limited. Examples of commonly used coating methods include spin coater coating, dip coating, and spray coater. It can apply | coat to a base material by single or a combination, such as a coating method, a roll coater coating method, a screen printing coating method, an offset printing coating method, a slit coater coating method, and a die coater coating 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 this invention, it is preferable that the layer of a resin cured material is 0.2-5 micrometers as a film thickness after application | coating and hardening, More preferably, it is 0.5-4 micrometers. When the film thickness after coating and curing 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, the performance such as transparency may be deteriorated. Is not preferable. However, for applications where high flatness is desired, the film thickness after coating and curing may be 5 to 20 μm.
The cured resin layer for the color filter protective film obtained in the present invention has excellent curability and storage stability, and the cured resin layer has basic performance such as heat resistance and chemical resistance. Above, it has excellent adhesion and process resistance when forming transparent electrodes.

Next, the present invention will be described more specifically with reference to examples and comparative examples.
The measurement methods and evaluation methods used in the examples and comparative examples are shown below.
<Weight average molecular weight>
The weight average molecular weight (Mw) was measured by using a gel permeation chromatography apparatus 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.
<Solid content>
The solid content was calculated from the residual rate calculated from the weight change before and after drying after precisely weighing 1 g of the solution and drying at 170 ° C. for 1 hour in a hot air oven.
<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”.
<Total acid equivalent>
The total acid equivalent was measured by hydrolysis acid value measurement according to JIS K 0070: 1992 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”.

The process resistance at the time of forming the transparent electrode was evaluated from the following chemical resistance and heat resistance simulating the process conditions at the time of actual color filter production.
<Chemical resistance>
On the protective film of the sample on which the protective film is formed, the sputtering temperature is 250 ° C., the SiO ₂ layer thickness is 10 to 15 nm, the ITO layer thickness is 250 to 300 nm, and the resistance value is 10 to 15Ω / □. After forming the layer, 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 % NaOHaq, 60 ° C. × 5 minutes or 10 minutes), the appearance of the sample was observed.
Judgment criteria are as follows.
A: No abnormality was observed after 10 minutes of alkali treatment.
Δ: Abnormality was observed after 10 minutes of alkali treatment, but no abnormality was observed after 5 minutes.
In x, abnormality was observed after 5 minutes of alkali treatment.
In order to be put to practical use, ◎ or more is required.
<Heat resistance>
After forming an ITO layer similar to the post-ITO etching resistance, the appearance of the sample after treatment at 230 or 250 ° C. for 1 hour was observed.
Judgment criteria are as follows.
A: No abnormality was observed even after treatment at 250 ° C.
Δ: Abnormality was observed after 250 ° C. treatment, but no abnormality was observed after 230 ° C. treatment.
X: Abnormality was observed after treatment at 230 ° C.
In order to be put to practical use, ◎ or more is required.
<Storage stability>
Storage stability was evaluated by storing the resin composition solution in a sealed container for 120 hours at a constant temperature of 5 ° C. and 25 ° C., and observing the increase in viscosity relative to the initial viscosity after storage. The method for measuring the viscosity is as described above.
Judgment criteria are as follows.
A: Increase in viscosity after storage for 120 days at 5 ° C and 25 ° C is less than 1.5 times ○: Increase in viscosity after storage for 120 days at 5 ° C is less than 1.5 times ×: Viscosity after storage for 120 days at 5 ° C The increase is 1.5 times or more. In order to be put to practical use, ○ or more is required.
<Adhesion>
After the sample on which the protective film was formed was subjected to PCT treatment (left at 121 ° C. in an environment of 100% humidity for 8 hours), JIS K 5600-5-6: 1999 “Paint General Test Method—Part 5: Coating Adhesion was evaluated in accordance with “Mechanical Properties of Film—Section 6: Adhesion (Cross Cut Method)”.
Judgment criteria are as follows.
○: No peeling.
Δ: no peeling but edge chipping occurred during cross-cutting.
X: Peeled.
In order to be put to practical use, it is required to have a circle or more.

<Polymerization Example 1 Polymerization of Polymer (A-1)>
160 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PMA) was charged into a 500 mL four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, and heated to 80 ° C. while stirring. Next, “OXE-30” (trade name) 3-methyl-3-oxetane-ylmethyl ester 74 g, methacryloxypropyltrimethoxysilane (hereinafter referred to as MPS) manufactured by Osaka Organic Chemical Industry Co., Ltd. at a temperature of 80 ° C. ) 126 g, 7 g of a peroxide-based polymerization initiator “Perhexyl O (hereinafter PHO) (; trade name, purity 93%)” manufactured by NOF Corporation and 33 g of PMA (dropping component) It dropped at a constant speed from the dropping funnel over 2 hours. After completion of dropping, the temperature was maintained at 80 ° C. for 7 hours, and then the reaction was terminated. A polymer solution having a weight average molecular weight (Mw) of 30,000, a solid content of 52%, a viscosity of 1 Pa · s (20 ° C.) and an epoxy equivalent of 1,000 g / mol of the solution (epoxy equivalent of the polymer of 500 g / mol) was obtained. .
<Polymerization Examples 2 to 8 Polymer (polymerization of A-2 to 7 and A′-1 to 2)>
The same operation as in Polymerization Example 1 was performed to obtain polymers (A-2 to 7 and A′-1 to 2). Table 1 shows the charging ratio, dropping temperature, weight average molecular weight, solid content, viscosity, and epoxy equivalent of each raw material.
<Reaction of hydrolysis condensate (A'-3)>
In a 500 mL three-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, 169 parts by weight of vinyltrimethoxysilane and 210 parts by weight of propylene glycol monomethyl ether acetate were charged and stirred. Next, 62 parts by weight of distilled water and 0.02 part by weight of oxalic acid were added, and the temperature was raised to 120 ° C. The reaction was completed after stirring at 120 ° C. for 2 hours while distilling off methanol and water produced by the reaction.

<Polymerization of polymer (B)>
The same operation as in Polymerization Example 1 was performed to obtain polymers (B-1 to 8). Table 2 shows the charging ratio, dropping temperature, weight average molecular weight, solid content, viscosity, and epoxy equivalent of each raw material.

Synthesis example 1
<Synthesis of polyvalent carboxylic acid hemiacetal ester (C-1)>
In a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 33 g of PMA, 27 g of trimellitic acid (hereinafter, TMA) manufactured by Mitsubishi Gas Chemical Co., Ltd., n-propyl vinyl ether (hereinafter, nPr-VE) 40 g was charged and heated while stirring to raise the temperature 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. A solution of the polyvalent carboxylic acid and the polyvalent carboxylic acid hemiacetal ester (C) was obtained.
Synthesis Examples 2-6
<Synthesis of polyvalent carboxylic acid hemiacetal ester (C-2 to 6)>
In the same manner as in Synthesis Example 1, polyvalent carboxylic acid hemiacetal esters (C-2 to 6) were obtained. Table 2 shows the charging ratio, reaction temperature, acid value, and total acid equivalent of each raw material.

The meanings of the abbreviations used in the table are as follows.
TMA: trimellitic anhydride P-TMA: half-esterified product of pentaerythritol and trimellitic anhydride.
CHTA: 1,2,4-cyclohexanetricarboxylic acid G-HHPA: half esterified product of propylene glycol and methylhexahydrophthalic anhydride.
n-Pr-VE: n-propyl vinyl ether i-Pr-VE: i-propyl vinyl ether ADA: adipic acid MLA: maleic acid <Examples 1-7>
The performance of the thermosetting resin composition for the color filter protective film dissolved and mixed at the blending ratio shown in Table 4 was evaluated. The results are shown in Table 4 together with the blending ratio.
<Comparative Examples 1-4>
A cured film was obtained from the solution of the thermosetting resin composition for the color filter protective film dissolved and mixed at the blending ratio shown in Table 5 in the same manner as in the Examples, and the test was performed. The results are shown in Table 5 together with the blending ratio.
In all cases of Examples and Comparative Examples, the surface of the obtained coating film was extremely smooth, and no pinholes were observed.

The meanings of the abbreviations used in the table are as follows.
LCAT-1: Reaction product of zinc octylate and N-methylmorpholine (described in JP-A-2001-350010)
BYK-355: Surface conditioner (manufactured by Big Chemie Japan Co., Ltd.)
EXA-7015: Hydrogenated bisphenol A diglycidyl ether, trade name “Epicron EXA-7015” manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent 210 g / mol.

  From the results of the table, Examples 1 to 7 are extremely excellent in process resistance when forming a transparent electrode while satisfying the basic performance by using the thermosetting resin composition of the present invention. It can be seen that the effect of is obtained perfectly. On the other hand, in Comparative Examples 1 and 2, since the polyvalent carboxylic acid hemiacetal ester (C) used in the present invention is not used, sufficient barrier properties cannot be obtained. Was not obtained. In Comparative Example 3, since the polymer (B) was not used, sufficient process resistance when forming a transparent electrode could not be obtained. In Comparative Example 4, since the polymer (A) was not used, the crosslink density was low, so that sufficient process resistance and adhesion during formation of the transparent electrode could not be obtained. In Comparative Examples 5 and 6, since a polymer A′-1 different from the polymer (A) used in the present invention was used, sufficient process resistance at the time of forming a transparent electrode could not be obtained. In Comparative Example 7, since the polymer B′-1 different from the polymer (B) used in the present invention was used, sufficient adhesion could not be obtained. In Comparative Example 8, by not using the polyvalent carboxylic acid hemiacetal ester (C), a sufficient crosslinking density cannot be obtained, and the barrier property is low. In addition, A′-3 has a siloxane bond having poor solvent resistance. Since it has many, it resulted in the low process tolerance at the time of transparent electrode formation. In Comparative Example 9, since (epoxy group or oxetanyl group / carboxyl group) and (carboxyl group / silyl group) were out of the range in the thermosetting resin composition of the present invention, the effect of the present invention was not obtained. From the above, it is apparent that the object of the present application can be achieved only when the thermosetting resin composition of the present invention is used.

Claims (2)

The following three components (A), (B) and (C) (A) 10 to 60% by weight of a structural unit having an epoxy group or 10 to 60% by weight of a structural unit having an oxetanyl group and 40 to 90% by weight of a structural unit having an alkoxysilyl group A polymer having a weight average molecular weight (Mw) of 3,000 to 300,000 (B) 10 to 90% by weight of a structural unit having an epoxy group or 10 to 90% by weight of a structural unit having an oxetanyl group Polymer (C) Polyhydric Carboxylic Acid Hemiacetal Ester Containing 90% by Weight and Weight Average Molecular Weight (Mw) of 3,000 to 300,000 Concealed by Vinyl Ether Compound The molar concentration of the above (epoxy group or oxetanyl group) / (alkoxysilyl group) / (carboxyl group) The rate is 0.8 to 3.3 / 0.01 to 1.0 / 1, the thermosetting resin composition for a color filter protective film.   A color filter having a layer of a cured resin obtained by curing the thermosetting resin composition according to claim 1.