JP2011022490A - Substrate for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate for a color filter having excellent transparency, heat resistance and dimensional stability, and advantageous to be light-weight and low-profile. <P>SOLUTION: The substrate for the color filter uses an allyl ester thermosetting resin having a group expressed by a formula (2) as a terminal group and having an ester structure formed from a polyhydric alcohol and a dicarboxylic acid, (in the formula, R<SP>3</SP>denotes allyl or methallyl, and A<SP>2</SP>denotes one or more kinds of organic residue having an alicyclic structure and/or aromatic ring structure originating in dicarboxylic acid). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a color filter substrate. More specifically, the present invention relates to a substrate for a color filter that is excellent in transparency and heat resistance and excellent in productivity of a color filter that is advantageous for reduction in weight and thickness.

  Conventionally, glass plates have been widely used for substrates for liquid crystal display elements, substrates for organic EL display elements, color filter substrates, solar cell substrates, etc., but glass plates are heavy, fragile and cannot be bent. There are disadvantages. In recent years, flat panel displays have become thinner and lighter, and there has been a growing demand for flexible displays that can be freely deformed. In addition, flexible displays can be manufactured by a continuous roll-to-roll process, which is advantageous in terms of productivity. Therefore, plastic substrates for display devices are being studied.

  However, the conventional plastic substrate has insufficient heat resistance, and there is a problem that heat is applied in the process of forming a metal semiconductor or an insulating film, causing deformation.

  For example, a liquid crystal display device usually has a black matrix formed with high definition so as to have a plurality of openings on a base material, and a color filter and a base material having a plurality of colored layers formed in the openings. In other words, a TFT array in which an infinite number of thin film transistor electrodes (hereinafter referred to as TFTs) are regularly arranged is arranged so as to face each other through a liquid crystal layer.

  In general, when a plastic substrate is used as a substrate constituting a color filter or a TFT array, it is difficult to form a black matrix or a TFT electrode with a desired accuracy. That is, these forming steps are usually 160 ° C. or higher, and general-purpose polyethylene terephthalate, polymethacrylate, polycarbonate (see Patent Document 1), and cycloolefin copolymer (see Patent Document 2) are insufficient in heat resistance, and thus warp of the substrate. Occurs and changes in dimensions and cannot be used.

  In addition, when a transparent conductive film is added to a plastic substrate in the final step of the color filter, the transparent conductive film is formed at 150 ° C. or lower, which increases the surface resistance value of the transparent conductive film. It was.

  Incidentally, wholly aromatic polyimide is known as a plastic excellent in heat resistance and dimensional stability. Some aromatic polyimides have a heat resistance of 400 ° C. or higher, but the coloring is severe, and polyether sulfone (PES) (see Patent Document 3), which is also excellent in heat resistance, is insufficient in terms of transparency. It cannot be used for display devices.

  As a method for solving such problems, a color filter portion is formed on a heat-resistant base plate such as glass, and then transferred onto the plastic base plate, whereby a color using a plastic base plate is used. A method for obtaining a filter substrate is disclosed (see Patent Document 4).

  However, this method has the disadvantage that the production efficiency is low and it cannot be produced at a lower cost than a color filter substrate using a glass base plate.

JP 2000-227603 A Japanese Patent Laid-Open No. 2001-150584 JP 2000-284717 A JP 2000-47023 A

  An object of the present invention is to provide a substrate for a color filter which is excellent in transparency and heat resistance, in which the above-mentioned drawbacks are eliminated, and is advantageous for light weight and thinning.

  In order to solve the above problems, the present inventors have conducted intensive research. As a result, the present inventors have found that the allyl ester resin composition provides higher heat resistance and superior dimensional stability than the plastics used in conventional substrates for display devices, thereby completing the present invention. The present invention includes, for example, the following items [1] to [8].

（Ｒ^１、Ｒ^２は、それぞれ独立してアリル基またはメタリル基のいずれかの基を表し、Ａ^１はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）で表される化合物の中から選ばれる少なくとも１種以上の化合物を含む［２］に記載のカラーフィルター用基板。
［４］前記アリルエステル化合物の少なくとも一種が一般式（２）

（式中、Ｒ^３はアリル基またはメタリル基を表し、Ａ^２はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）で表される基を末端基として有し、かつ一般式（３）

（式中、Ａ^３はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表し、Ｘは多価アルコールから誘導された一種以上の有機残基を表す。ただし、Ｘはエステル結合によって、さらに上記一般式（２）を末端基とし、上記一般式（３）を構成単位とする分岐構造を有することが出来る。）で表される構造を構成単位として有する［２］に記載のカラーフィルター用基板。
［５］前記一般式（２）及び（３）におけるジカルボン酸が、テレフタル酸、イソフタル酸、フタル酸及び１，４−シクロヘキサンジカルボン酸からなる群から選ばれる少なくとも一種である［４］に記載のカラーフィルター用基板。
［６］前記アリルエステル樹脂組成物が、さらに反応性モノマーを含む［１］〜［５］のいずれかに記載のカラーフィルター用基板。
［７］前記基板の厚さが３０〜５００μｍである［１］〜［６］のいずれかに記載のカラーフィルター用基板。
［８］［１］〜［７］のいずれかに記載のカラーフィルター用基板を用いたカラーフィルター。 [1] A color filter substrate comprising a base material obtained by curing an allyl ester resin composition.
[2] The color according to [1], wherein the allyl ester resin composition includes an allyl ester compound having an allyl group and / or a methallyl group as an end group and having an ester structure formed from a polyhydric alcohol and a dicarboxylic acid. Filter substrate.
[3] The allyl ester resin composition further comprises the general formula (1)

(R ¹ and R ² each independently represents either an allyl group or a methallyl group, and A ¹ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. The color filter substrate according to [2], comprising at least one compound selected from the compounds represented by:
[4] At least one of the allyl ester compounds is represented by the general formula (2)

(Wherein R ³ represents an allyl group or a methallyl group, and A ² represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid). As a terminal group, and general formula (3)

(Wherein A ³ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol. However, X can have a branched structure having the above general formula (2) as a terminal group and the above general formula (3) as a structural unit by an ester bond.) The color filter substrate according to [2].
[5] The dicarboxylic acid in the general formulas (2) and (3) is at least one selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid and 1,4-cyclohexanedicarboxylic acid. Color filter substrate.
[6] The color filter substrate according to any one of [1] to [5], wherein the allyl ester resin composition further contains a reactive monomer.
[7] The color filter substrate according to any one of [1] to [6], wherein the thickness of the substrate is 30 to 500 μm.
[8] A color filter using the color filter substrate according to any one of [1] to [7].

  According to the present invention, by using a cured product of an allyl ester resin composition as a base material, a color filter substrate having excellent transparency, heat resistance, and dimensional stability and advantageous for lightening and thinning is provided.

  Hereinafter, the present invention will be described in more detail.

<Allyl ester resin>
The allyl ester resin used as the base material for the color filter substrate of the present invention is a kind of thermosetting resin.
In general, there are two cases where the term “allyl ester resin” refers to a prepolymer (including oligomers, additives, and monomers) before curing, and indicates a cured product thereof. Then, “allyl ester resin” indicates a cured product, and “allyl ester resin composition” indicates a prepolymer before curing.

<Allyl ester resin composition>
The allyl ester resin composition used as the base material of the color filter substrate of the present invention is mainly composed of an allyl group or a methallyl group (hereinafter sometimes referred to as a (meth) allyl group) and an ester structure. It is a composition contained as a curing component.

  The compound having a (meth) allyl group and an ester structure is (1) an esterification reaction between a compound containing a (meth) allyl group and a hydroxyl group (herein collectively referred to as allyl alcohol) and a compound containing a carboxyl group, (2) It can be obtained by an esterification reaction between a compound containing a (meth) allyl group and a carboxyl group and a compound containing a hydroxyl group, or (3) an ester exchange reaction between an ester compound consisting of allyl alcohol and dicarboxylic acid and a polyhydric alcohol. When the compound containing a carboxyl group is a polyester oligomer of a dicarboxylic acid and a diol, only the terminal can be an ester with allyl alcohol.

（Ｒ^１、Ｒ^２は、それぞれ独立してアリル基またはメタリル基のいずれかの基を表し、Ａ^１はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）で表される化合物の中から選ばれる少なくとも１種以上の化合物が挙げられる。この化合物は後述のアリルエステルオリゴマーの原料となるほか、反応性希釈剤（反応性モノマー）として本発明のアリルエステル樹脂組成物に含まれてもよい。一般式（１）中のＡ^１は後述の一般式（２）、一般式（３）におけるＡ^２、Ａ^３と同様のものが好ましい。 Specific examples of ester compounds composed of (meth) allyl alcohol and dicarboxylic acid include the following general formula (1)

(R ¹ and R ² each independently represents either an allyl group or a methallyl group, and A ¹ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. And at least one compound selected from the compounds represented by: This compound may be contained in the allyl ester resin composition of the present invention as a reactive diluent (reactive monomer) as well as a raw material for the allyl ester oligomer described later. A ¹ in general formula (1) is preferably the same as A ² and A ³ in general formula (2) and general formula (3) described later.

  The compound having an (meth) allyl group and an ester structure, which is the main curing component of the allyl ester resin composition used as the base material of the color filter substrate of the present invention, has an allyl group and / or a methallyl group as a terminal group. An allyl ester compound having an ester structure formed from a polyhydric alcohol and a dicarboxylic acid (hereinafter sometimes referred to as “allyl ester oligomer”) is preferable.

  Moreover, you may contain the hardening | curing agent mentioned later, a reactive monomer, an additive, other radical reactive resin components etc. as another component.

（式中、Ｒ^３はアリル基またはメタリル基を表し、Ａ^２はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）で表される基を末端基として有し、かつ下記一般式（３） <Allyl ester oligomer>
As said allyl ester oligomer, following General formula (2)

(Wherein R ³ represents an allyl group or a methallyl group, and A ² represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid). As a terminal group and the following general formula (3)

（式中、Ａ^３はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表し、Ｘは多価アルコールから誘導された一種以上の有機残基を表す。ただし、Ｘはエステル結合によって、さらに上記一般式（２）を末端基とし、上記一般式（３）を構成単位とする分岐構造を有することが出来る。）で表される構造を構成単位として有する化合物が好ましい。

(Wherein A ³ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol. However, X can have a branched structure having the above general formula (2) as a terminal group and the above general formula (3) as a structural unit by an ester bond.) The compound which has is preferable.

In the allyl ester oligomer, the number of terminal groups represented by the general formula (2) is at least 2 or more, but when X in the general formula (3) has a branched structure, the number is 3 or more. In this case, although also R ³ at each end groups there are a plurality, each of these R ³ may not necessarily be the same type, some end there in the structure of an allyl group, the other terminal methallyl group It doesn't matter.

Moreover, not all R ³ must be an allyl group or a methallyl group, and a part thereof may be a non-polymerizable group such as a methyl group or an ethyl group as long as the curability is not impaired.

Similarly, the structure represented by A ² may be different for each terminal group. For example, A ^{2 at} one terminal may be a benzene ring and the other may be a cyclohexane ring.

A ² in the general formula (2) is one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. Portion derived from dicarboxylic acid is shown by a carbonyl structure adjacent to A ^2. Therefore, the portion A ² represents a benzene skeleton or a cyclohexane skeleton.

There are no particular limitations on the dicarboxylic acid to induce A ² structure, from the viewpoint of ready availability of raw materials, terephthalic acid, isophthalic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-naphthalenedicarboxylic Acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl-m, m′-dicarboxylic acid, diphenyl-p, p′-dicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, p- Preferable are phenylenediacetic acid, p-carboxyphenylacetic acid, methylterephthalic acid and tetrachlorophthalic acid, and particularly preferable are terephthalic acid, isophthalic acid, phthalic acid and 1,4-cyclohexanedicarboxylic acid.

  In addition, within the range that does not impair the effects of the present invention, acyclic dicarboxylic acids (during the reaction) such as maleic acid, fumaric acid, itaconic acid, citraconic acid, endic acid anhydride and chlorendic acid are used. Also good.

  At least one structural unit represented by the general formula (3) is required in the allyl ester oligomer. However, when this structure is repeated, the molecular weight of the allyl ester oligomer as a whole increases to some extent. Is preferable because workability is improved and the toughness of the cured product is also improved. However, if the molecular weight is too large, the molecular weight between cross-linking points is too large, so that Tg is lowered and heat resistance may be lowered. The weight average molecular weight of the allyl ester oligomer is preferably from 500 to 200,000, more preferably from 1,000 to 100,000, but it is important to adjust to an appropriate molecular weight depending on the application.

In addition, A ³ in the general formula (3) is one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid, and examples of the definition and preferred compounds thereof are the general formula (2). The same as A ² in FIG.

X in the general formula (3) represents one or more organic residues derived from a polyhydric alcohol.
The polyhydric alcohol is a compound having two or more hydroxyl groups, and X itself represents a skeleton portion other than the hydroxyl groups of the polyhydric alcohol.

  In addition, since at least two hydroxyl groups in the polyhydric alcohol need only be bonded, when the polyhydric alcohol as a raw material is trivalent or more, that is, when there are three or more hydroxyl groups, unreacted hydroxyl groups remain. May be.

  Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6 -Hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, ethylene oxide 3 mol adduct of isocyanuric acid, pentaerythritol, tricyclodecane dimethanol, glycerin, trimethylolpropane, pentaerythritol ethylene oxide 3 mol adduct, D-sorbitol And hydrogenated bisphenol A and the like. Although there is no restriction | limiting in particular as a manufacturing method of these compounds, For example, it can manufacture by the method mentioned in Japanese Patent Publication No. 6-74239.

As the structural unit represented by the general formula (3) in the allyl ester oligomer, the same structural unit may be repeated, but different structural units may be included. That is, the allyl ester oligomer may be a copolymer type. In this case, several types of X exist in one allyl ester oligomer. For example, the structure may be such that one of X is a residue derived from propylene glycol and the other X is a residue derived from trimethylolpropane. In this case, the allyl ester oligomer will be branched at the trimethylolpropane residue. A ³ may also be present are several types as well. The structural formula (4) in the case where R ³ is an allyl group, A ² and A ³ are residues derived from isophthalic acid, and X is propylene glycol and trimethylolpropane is shown below.

<Curing agent>
A curing agent may be used for the allyl ester resin composition used as the base material of the color filter substrate of the present invention. There is no restriction | limiting in particular as a hardening | curing agent which can be used, What is generally used as a hardening | curing agent of polymeric resin can be used. Among these, it is desirable to add a radical polymerization initiator from the viewpoint of starting polymerization of the allyl group. Examples of the radical polymerization initiator include organic peroxides, photopolymerization initiators, azo compounds and the like.

  As the organic peroxide, known ones such as dialkyl peroxide, acyl peroxide, hydroperoxide, ketone peroxide, peroxy ester can be used. Specific examples thereof include benzoyl peroxide, 1,1. -Bis (t-butyl peroxy) cyclohexane, 2,2-bis (4,4-dibutylperoxycyclohexyl) propane, t-butylperoxy-2-ethylhexanate, 2,5-dimethyl 2,5-di (t -Butylperoxy) hexane, 2,5-dimethyl2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, t-butylcumyl peroxide, p-methylhydroperoxide, t-butylhydroper Oxide, cumene hydroperoxide, dicumyl Over peroxide, di -t- butyl peroxide and 2,5-dimethyl-2,5-dibutyl peroxy f relaxin -3, and the like.

  Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,4, Examples include 6-trimethylbenzoyldiphenylphosphine oxide.

  These radical polymerization initiators may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the compounding quantity of these hardening | curing agents, It is preferable to mix | blend 0.1-10 mass parts with respect to 100 mass parts of allyl ester resin compositions, and mixing 0.5-5 mass parts. More preferred. When the blending amount of the curing agent is less than 0.1 parts by mass, it is difficult to obtain a sufficient curing rate. When the blending amount exceeds 10 parts by mass, the final cured product becomes brittle and the mechanical strength decreases. There is a case.

<Reactive monomer>
The allyl ester resin composition used as the base material of the color filter substrate of the present invention is reactive for the purpose of controlling the curing reaction rate, adjusting the viscosity (improving workability), improving the crosslinking density, adding functions, etc. Monomers (reactive diluents) can also be added.

  These reactive monomers are not particularly limited, and various types can be used. However, in order to react with an allyl ester oligomer, a monomer having a radical polymerizable carbon-carbon double bond such as a vinyl group or an allyl group is used. preferable. Examples thereof include unsaturated fatty acid esters, aromatic vinyl compounds, vinyl esters of saturated fatty acids or aromatic carboxylic acids and derivatives thereof, crosslinkable polyfunctional monomers, and the like. Especially, if a crosslinkable polyfunctional monomer is used, the crosslinking density of hardened | cured material can also be controlled. Preferred specific examples of these reactive monomers are shown below.

As unsaturated fatty acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate Alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and methylcyclohexyl (meth) acrylate;
Phenyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, fluorophenyl (meth) acrylate, chlorophenyl (meth) acrylate, cyanophenyl (meth) acrylate, methoxyphenyl (meth) acrylate and biphenyl (meth) ) Acrylic acid aromatic esters such as acrylates;
Haloalkyl (meth) acrylates such as fluoromethyl (meth) acrylate and chloromethyl (meth) acrylate;
Furthermore, glycidyl (meth) acrylate, alkylamino (meth) acrylate, α-cyanoacrylic acid ester and the like can be mentioned.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, chlorostyrene, styrene sulfonic acid, 4-hydroxystyrene, vinyltoluene and the like.

  Examples of vinyl esters of saturated fatty acids or aromatic carboxylic acids and derivatives thereof include vinyl acetate, vinyl propionate and vinyl benzoate.

As the crosslinkable polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentadiol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, oligoester di (meth) acrylate, polybutadiene di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyphenyl) propane and 2,2-bis (4-ω- ( Meta) Di (meth) acrylates such as Leroy oxy pyridinium) phenyl) propane;
Diallyl phthalate, diallyl isophthalate, dimethallyl isophthalate, diallyl terephthalate, triallyl trimellitic acid, diallyl 2,6-naphthalenedicarboxylate, diallyl 1,5-naphthalenedicarboxylate, allyl 1,4-xylenedicarboxylate and 4,4 Aromatic carboxylic acid diallyls such as 4'-diphenyldicarboxylic acid diallyl;
Bifunctional crosslinkable monomers such as diallyl cyclohexanedicarboxylate and divinylbenzene;
Trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) allyl isocyanurate, tri (meth) allyl cyanurate, triallyl trimellitate and diallyl Trifunctional crosslinkable monomers such as chlorendate;
Furthermore, tetrafunctional crosslinkable monomers such as pentaerythritol tetra (meth) acrylate are exemplified.

  Said reactive monomer can be used individually by 1 type or in mixture or combination of 2 or more types. Although there is no restriction | limiting in particular in the usage-amount of the resin component of these reactive monomers, It is preferable that it is 1-1000 mass parts with respect to 100 mass parts of allyl ester oligomers, and it is more preferable that it is 2-500 mass parts. Preferably, it is 5 mass parts-100 mass parts. When the amount of the reactive monomer used is less than 1 part by mass, the effect of decreasing the viscosity is small, workability is deteriorated, and when a polyfunctional monomer is used as the reactive monomer, the crosslinking density is lowered. Since heat resistance may become insufficient, it is not preferable. Moreover, when the usage-amount exceeds 1000 mass parts, the outstanding transparency of allyl ester resin itself may not be expressed, or the mechanical strength derived from allyl ester resin may fall, and it is not preferable.

<Radically reactive resin component>
The allyl ester resin composition used as the base material of the color filter substrate of the present invention may contain a radical reactive resin component for the purpose of improving various physical properties. Examples of these resin components include unsaturated polyester resins and vinyl ester resins.

  Unsaturated polyester resin can be obtained by converting a condensation product obtained by esterification reaction of a polyhydric alcohol and an unsaturated polybasic acid (and a saturated polybasic acid if necessary) into a polymerizable unsaturated compound such as styrene. For example, the resins described in “Polyester Resin Handbook”, published by Nikkan Kogyo Shimbun, 1988, pages 16 to 18 and pages 29 to 37 can be given. This unsaturated polyester resin can be produced by a known method.

  Vinyl ester resin, also called epoxy (meth) acrylate, is a ring-opening reaction between a compound having an epoxy group typically represented by an epoxy resin and a carboxyl group of a carboxyl compound having a polymerizable unsaturated group such as (meth) acrylic acid. Polymerized by a ring-opening reaction between a resin having a polymerizable unsaturated group produced by the above, or a compound having a carboxyl group and an epoxy group of a polymerizable unsaturated compound having an epoxy group in the molecule such as glycidyl (meth) acrylate It refers to a resin having a polymerizable unsaturated group. Details are described in “Polyester Resin Handbook”, published by Nikkan Kogyo Shimbun, 1988, pp. 336 to 357, and can be produced by a known method.

The epoxy resin used as the raw material for the vinyl ester resin includes bisphenol A diglycidyl ether and its high molecular weight homologue, glycidyl ether of bisphenol A alkylene oxide adduct, bisphenol F diglycidyl ether and its high molecular weight homologue, and bisphenol F alkylene oxide. Examples include adduct glycidyl ethers and novolac-type polyglycidyl ethers.
The above radical-reactive resin components can be used alone or in combination of two or more.

Although there is no restriction | limiting in particular in the usage-amount of these radical reactive resin components, It is preferable that it is 1-1000 mass parts with respect to 100 mass parts of allyl ester oligomers, and it is more preferable that it is 2-500 mass parts. Preferably, it is 5 mass parts-100 mass parts.
When the amount of the reactive monomer used is less than 1 part by mass, the effect of improving the mechanical strength derived from the radical reactive resin component is small, and workability is deteriorated or moldability is deteriorated. Moreover, when the usage-amount exceeds 1000 mass parts, the heat resistance of allyl ester resin itself may not appear, and it is unpreferable.

<Additives>
The allyl ester resin composition used as the base material of the color filter substrate of the present invention has an ultraviolet absorber, an antioxidant, and an antifoaming agent for the purpose of improving hardness, strength, moldability, durability, and water resistance. Additives such as leveling agents, mold release agents, lubricants, water repellents, flame retardants, low shrinkage agents, and crosslinking aids can be added as necessary.

  There is no restriction | limiting in particular as antioxidant, What is generally used can be used. Among them, a phenolic antioxidant and an amine antioxidant which are radical chain inhibitors are preferable, and a phenolic antioxidant is particularly preferable. Phenol antioxidants include 2,6-t-butyl-p-cresol, 2,6-t-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6-t-butylphenol) and 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and the like can be mentioned.

  There is no restriction | limiting in particular as a lubricant, What is generally used can be used. Among these, metal soap lubricants, fatty acid ester lubricants, aliphatic hydrocarbon lubricants and the like are preferable, and metal soap lubricants are particularly preferable. Examples of the metal soap lubricant include barium stearate, calcium stearate, zinc stearate, barium stearate, magnesium stearate, and aluminum stearate. These may be used as a complex.

There is no restriction | limiting in particular as said ultraviolet absorber, What is generally used can be used. Among these, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers are preferable, and benzophenone ultraviolet absorbers are particularly preferable. Examples of benzophenone ultraviolet absorbers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-butylphenyl) benzotriazole and 2- (2-hydroxy-3). '-Tert-butylphenyl) benzotriazole and the like.
However, these additives are not limited to the specific examples described above, and any additive can be added within a range that does not impair the object or effect of the present invention.

<Solvent>
When the allyl ester resin composition used as the base material of the color filter substrate of the present invention is cured, a solvent may be used if it is necessary to reduce the viscosity by a curing method. However, since it is necessary to remove the solvent later, the viscosity is preferably adjusted with the aforementioned reactive monomer.
Examples of solvents that can be used for viscosity adjustment include aromatic hydrocarbons such as toluene and xylene, acetates such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones, ethers such as tetrahydrofuran and 1,4-dioxane, alcohols such as ethyl alcohol, (iso) propyl alcohol, and butyl alcohol.

<Viscosity of allyl ester resin composition>
The viscosity of the allyl ester resin composition used as the base material of the substrate for a color filter of the present invention is not particularly limited, but is preferably a viscosity suitable for the molding method.
For example, in cast molding, the viscosity at 25 ° C. is preferably in the range of 0.01 (Pa · s) to 1,000 (Ps · s). When the viscosity is lower than 0.01 (Pa · s) or higher than 1,000 (Pa · s), workability is deteriorated, which is not preferable.
The viscosity of the curable resin can be measured by a method based on JIS K6901.

<Base material for color filter substrate>
The base material of the color filter substrate of the present invention will be described.
The base material of the color filter substrate of the present invention is a cured product of the allyl ester resin composition. The allyl ester resin composition can be obtained by mixing the allyl ester oligomer, the reactive monomer, the curing agent, and various additives by a known method. The composition can be cured using a coating method such as a roll coater or a spin coater, a casting method, an optical modeling method, or the like using heat, ultraviolet rays, or an electron beam.

  Moreover, the shape of the obtained allyl ester resin cured product can be a film or a sheet. The thickness is usually 10 μm to 1000 μm, preferably 30 μm to 500 μm. If it is less than 10 μm, the strength as a self-supporting film is lowered, and if it exceeds 1000 μm, the flexibility of the film tends to be lowered.

  The transparency of the substrate used in the present invention varies depending on the transparency required for the color filter substrate, but usually the transmittance in the visible light region is preferably 80% or more, more preferably 85% or more. If the transmittance is low, the haze of the color filter substrate of the present invention becomes larger than a desired value, which is not preferable.

  The substrate of the color filter substrate used in the present invention is excellent in heat-resistant dimensional stability, and the glass transition temperature (Tg) of the substrate is preferably 160 ° C. or higher. Tg can be adjusted by changing the main chain structure of the allyl ester oligomer and the crosslinking density of the cured product. Tg is increased by blending a large amount of polyfunctional radical polymerizable monomers or by making the main chain structure of the allyl ester oligomer rigid such as an aromatic ring. Further, Tg can be adjusted by the kind, amount, and curing conditions of the polymerization initiator.

  Although the heat-resistant dimensional change rate at 160 ° C. of the substrate is appropriately determined according to the application, it is preferably within 0.1%, and more preferably within 0.05%. The dimensional change rate of the color filter substrate of the present invention can be adjusted within a desired range by adjusting the glass transition temperature of the allyl ester resin.

<Color filter substrate>
Next, the color filter substrate of the present invention will be described.
The color filter substrate of the present invention can be produced by a known method such as a fosography method or an ink jet method.

  For example, the surface of the color filter substrate of the present invention is washed, and a black matrix material such as chromium or black resin is formed on one surface of the base material using a technique such as sputtering. A resist is coated on the surface of the black matrix material film, and after heating, the resist is patterned by exposure and development using a photomask. Thereafter, etching and resist stripping are performed to leave only a necessary portion of the black matrix material, thereby forming a black matrix.

  Each color pixel portion such as R (red), G (green), and B (blue) can also be formed by a known method. For example, when forming a red pixel, a red pigment material is applied and pre-baked. After the red pigment is coated with a resist on the surface of the material film and baked, exposure and development are performed using a photomask to pattern the red pigment material. Thereafter, etching and resist stripping are performed to leave only a necessary portion of the red pigment material, and post baking is performed to form a red pixel portion. Each remaining color such as GB can be formed by the same operation.

  As a patterning method for the black matrix and each dye portion, in addition to the above-described method using a photoresist, a method of directly patterning with a photomask without using a resist using a photosensitive black matrix material or each dye material, a screen The black matrix and each pixel portion can be patterned by printing methods such as printing, gravure printing, and ink jet printing.

  An overcoat layer may be provided as necessary for the purpose of protecting the surface of the color pixel portion. For the overcoat layer, epoxy resin, acrylic resin, or the like is used.

  Moreover, a transparent conductive film can be formed as needed. A known metal film or metal oxide film can be applied as the transparent conductive film, but a metal oxide film is desirable from the viewpoint of conductivity and mechanical characteristics. As these metal oxide films, for example, tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium added indium oxide, cadmium oxide, tin oxide as impurities, zinc oxide added aluminum as impurities, Examples thereof include metal oxide films such as titanium oxide. In particular, indium tin oxide containing 2 to 15% by mass of tin oxide is preferable in terms of transparency and conductivity.

  When the color filter substrate of the present invention is used as a color filter substrate for a liquid crystal display element or an organic EL element, a gas barrier layer can be provided on one side or both sides of the substrate. Examples of the gas barrier layer include metal oxides or metal nitrides mainly composed of one or more metals selected from silicon, aluminum, magnesium, and zinc. These oxide and nitride layers are formed by sputtering, vacuum deposition, ion plating, plasma CVD, or the like, for example.

  The substrate for color filters of the present invention can be used as various substrates used for color filters for display devices such as liquid crystal and organic EL. The substrate of the color filter substrate of the present invention can also be used as a substrate material for solar cells, lighting, etc., in addition to TFTs using amorphous silicon, low-temperature polysilicon, and organic semiconductors.

Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is further demonstrated, this invention is not limited by these description.
In addition, the physical-property value described in the present Example and the comparative example was measured with the following method.

<Measurement of glass transition temperature (Tg)>
Measurement was performed in a tensile mode using TMA / SS6100 manufactured by SII Nanotechnology. The film-shaped test piece has a thickness of 100 μm × 2 mm × 12 mm (distance between chucks: 10 mm), tension: 0.003 kgf, and the temperature is raised to 250 ° C. at a temperature rising rate of 5 ° C./min in an atmosphere of 100 mL / min. After cooling to 50 ° C. or less, the temperature of the discontinuity of the elongation rate in the plane direction of the test piece between 50 ° C. and 250 ° C. is increased again at a heating rate of 5 ° C./min. ).

<Total light transmittance>
A test piece having a thickness of 100 μm × 30 mm × 30 mm was measured according to JIS K7361-1 using a fully automatic haze meter TC-H3DPK manufactured by Tokyo Denshoku.

<Dimensional stability>
Measurement was performed in a tensile mode using TMA / SS6100 manufactured by SII Nanotechnology. The film-shaped test piece has a thickness of 100 μm × 2 mm × 12 mm (distance between chucks: 10 mm), tension: 0.003 kgf, and a surface when the temperature is raised to 160 ° C. and maintained constant in an atmosphere of 100 mL / min. The direction dimensional change rate was calculated.

[Synthesis Example 1]
A 2-liter three-necked flask equipped with a distillation apparatus was charged with 1625 g of diallyl terephthalate, 167 g of propylene glycol and 0.813 g of dibutyltin oxide, and heated while distilling off the alcohol produced at 180 ° C. in a nitrogen stream. . When the distilled alcohol reached about 170 g, the pressure in the reaction system was gradually reduced to 6.6 kPa over about 4 hours to increase the alcohol distillation rate. When the distillate almost disappeared, the pressure in the reaction system was reduced to 0.5 kPa and the reaction was further continued for 1 hour, and then the reaction product was cooled. Hereinafter, the reaction product thus obtained is referred to as “oligomer (1)”.

[Example 1]
For 100 parts by mass of the oligomer (1) prepared in Synthesis Example 1, 10 parts by mass of pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester A-TMMT”), 1-hydroxycyclohexyl phenyl ketone (Ciba 3 parts by mass of “Irgacure 184” manufactured by Specialty Chemicals Co., Ltd.) was added and sufficiently stirred, and UV cured at a UV irradiation amount of 1200 mJ / cm ² to prepare a film having a thickness of 100 μm. When the Tg of this film was measured, no discontinuities were observed.
The resulting film had a total light transmittance of 92% and a dimensional change rate of 160 ° C. of 10 ppm.

[Example 2]
The film obtained in Example 1 was used as a substrate for a color filter. After cleaning and drying a 100 mm square film, a silicon oxide layer having a thickness of 500 nm was formed on one side as a gas barrier layer by sputtering. Next, a chromium film was formed on the opposite side of the gas barrier layer by sputtering, and after photographic processing with a positive photoresist, etching was performed to form a black matrix. A red facial color dispersion type dye (acrylic negative photosensitivity) was applied by spin coating and then pre-baked on a hot plate. Thereafter, the photomask was exposed and developed, and unnecessary portions were removed to form red pixel portions, which were post-baked at 200 ° C. for 20 minutes. Green and blue pixels were formed by the same operation. Further, an epoxy resin-based overcoat agent was applied by spin coating, and an overcoat layer was formed by heat treatment at 200 ° C. for 20 minutes.
The color filter was good with no displacement of each pixel.

[Comparative Example 1]
An attempt was made to produce a color filter on a polycarbonate resin plate with a hard coat (Tg of 145 ° C.) in the same manner as in Example 2, but warpage was confirmed during heating at 200 ° C.

Claims (8)

A substrate for a color filter comprising a base material obtained by curing an allyl ester resin composition. 2. The color filter substrate according to claim 1, wherein the allyl ester resin composition includes an allyl ester compound having an ester structure formed from a polyhydric alcohol and a dicarboxylic acid having an allyl group and / or a methallyl group as a terminal group. . The allyl ester resin composition further comprises the general formula (1)

(R ¹ and R ² each independently represents either an allyl group or a methallyl group, and A ¹ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. The color filter substrate according to claim 2, comprising at least one compound selected from the compounds represented by: At least one of the allyl ester compounds is represented by the general formula (2)

(Wherein R ³ represents an allyl group or a methallyl group, and A ² represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid). As a terminal group, and general formula (3)

(Wherein A ³ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol. However, X can have a branched structure having the above general formula (2) as a terminal group and the above general formula (3) as a structural unit by an ester bond.) The color filter substrate according to claim 2. 5. The color filter according to claim 4, wherein the dicarboxylic acid in the general formulas (2) and (3) is at least one selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, and 1,4-cyclohexanedicarboxylic acid. substrate. The color filter substrate according to claim 1, wherein the allyl ester resin composition further contains a reactive monomer. The color filter substrate according to claim 1, wherein the substrate has a thickness of 30 to 500 μm. A color filter using the color filter substrate according to claim 1.