JP5597905B2 - Curable composition, cured product, and liquid crystal display device using the same - Google Patents

Description

  The present invention relates to a curable composition, a cured product, and a liquid crystal display measure. Specifically, for example, in a color filter such as a liquid crystal display, a curable composition used for image formation, overcoat, rib and spacer, a cured product formed from the curable composition, and the cured product The present invention relates to a liquid crystal display measure.

  Conventionally, when forming a black matrix, an overcoat, a rib, a spacer, and the like in a color filter such as a liquid crystal display, a curable composition containing a resin, a photopolymerizable monomer, a photopolymerization initiator, and the like has been used. For this curable composition, various compositions have been proposed from the viewpoint of developability, pattern accuracy, adhesion, etc. As one of them, the efficiency in the forming process (shortening the curing time) and the yield are improved. For the purpose of, for example, an unsaturated group-containing resin obtained by further reacting a reaction product of an epoxy resin and an unsaturated group-containing carboxylic acid with a polybasic carboxylic acid or its anhydride as a resin contained in the curable composition. The technique used is disclosed (Patent Document 1).

  On the other hand, the curable composition for color filters may be required to have high curability and excellent mechanical properties. For example, a spacer (in the present specification, “spacer” is formed of a curable composition and indicates a so-called columnar spacer, photospacer, etc.) is a substrate of two substrates in a liquid crystal panel. Although it is used for the purpose of keeping the interval of the liquid crystal constant, it is not deformed by the high-temperature and high-pressure conditions at the time of pressure bonding because it undergoes a process of pressure bonding the color filter and the substrate under high temperature and high pressure when manufacturing the liquid crystal panel. The physical property that the spacer function is maintained is required. That is, the mechanical properties of the curable composition for color filters, such as the recovery rate and the elastic recovery rate, return to the original shape when the external pressure is removed even when the external pressure is deformed. Required as a property. As a material that satisfies this mechanical property, a curable composition that defines the content of a polyfunctional acrylate monomer has been proposed (Patent Document 2).

  In the field of liquid crystal displays, for example, in applications such as mobile phones, there is an increasing demand for higher-definition liquid crystal displays in order to perform high-quality display. In order to realize this, it is necessary to form higher-definition patterns while maintaining various conventional performances in the color pixel portion, the black matrix portion, the spacer portion, etc. among the constituent members of the color filter.

By the way, in order to satisfy such requirements, the present inventors tried to apply a phosphate ester-based adhesion improving material such as that described in Patent Document 3 for the curable composition for spacers. However, it has been found that the alkali resistance, which is one of the necessary performances of the spacer, is significantly impaired. Such a decrease in alkali resistance, for example, caused spacer peeling in the process of forming an alignment film of a liquid crystal panel, causing display defects.
JP 2001-174621 A JP 2002-174812 A Japanese Patent No. 3577754

An object of the present invention is a curable composition suitably used for forming a black matrix, an overcoat, a rib, a spacer and the like in a color filter such as a liquid crystal display, and without impairing these various performances. An object of the present invention is to provide a curable composition that forms a high-definition pattern and gives a cured product having excellent substrate adhesion and alkali resistance.
Another object of the present invention is to provide a cured product formed of such a curable composition and a liquid crystal display device having the cured product.

As a result of intensive studies on the above problems, the present inventors have found that the above object can be achieved by including an ethylenically unsaturated compound having a secondary hydroxyl group in the curable composition. It came to complete.
That is, the gist of the present invention is as follows.

［式中、Ｒ^１は、水素原子又はメチル基を表し、＊はエチレン性不飽和化合物（Ａ）中の他の部位との結合手を示す。］ 1. (A) an ethylenically unsaturated compound having a secondary hydroxyl group and containing at least one partial structure represented by the following formulas (i) to (iii); and (B) the double bond equivalent is 400 or less. A curable composition for a photospacer containing an ethylenically unsaturated compound , wherein (B) an ethylenically unsaturated compound having a double bond equivalent of 400 or less is obtained from an epoxy group-containing compound. A curable composition for a photospacer.

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and * represents a bond with another site in the ethylenically unsaturated compound (A). ]

2 . (B) The ethylenically unsaturated compound having a double bond equivalent of 400 or less contains a carboxyl group . Photospacer curable composition.

［式中、Ｒ¹は水素原子又はメチル基を表し、＊はエチレン性不飽和化合物（Ａ）中の他の部位との結合位置を示す。Ｙは任意の２価基を示す。］ 3 . (A) The ethylenically unsaturated compound having a secondary hydroxyl group contains at least one partial structure represented by the following formulas (iv) and (v), or is represented by the following formula (vi). Or 2 . Curable composition for photospacers.

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and * represents a bonding position with another site in the ethylenically unsaturated compound (A). Y represents an arbitrary divalent group. ]

4 . 1. ~ 3 . A photospacer characterized by being formed of the curable composition.

5 . 4 . A liquid crystal display device comprising a photo spacer.

According to the curable composition of the present invention, when forming a black matrix, overcoat, rib, spacer, etc. in a color filter such as a liquid crystal display, a high-definition pattern is formed without impairing these various performances. In addition, a cured product having excellent substrate adhesion and alkali resistance can be obtained.
According to such a curable composition of the present invention, a highly accurate, highly reliable and high quality cured product, and a liquid crystal display device are provided.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. The content of is not specified.
In the present invention, “(meth) acryl” means “acryl” and / or “methacryl”. In the present invention, the “total solid content” means all components except the solvent in the curable composition.

[1] Curable composition The curable composition of the present invention comprises (A) an ethylenically unsaturated compound having a secondary hydroxyl group (hereinafter sometimes referred to as “ethylenically unsaturated compound (A)”). It is essential to contain. Further, it preferably further contains (B) an ethylenically unsaturated compound having a double bond equivalent of 400 or less (hereinafter sometimes referred to as “ethylenically unsaturated compound (B)”). Moreover, other resin, a polymerizable monomer, a heat | fever and / or photoinitiator, etc. are contained as needed.
The curable composition of the present invention is usually used in a state where each component is dissolved or dispersed in a solvent in order to form a layer of the curable composition on the substrate by means of coating-drying or the like.

  The curable composition in the present invention is a state in which the curable composition is dissolved or dispersed in a solvent, a state in which the solvent component is volatilized and removed, and a state in which the curable composition is cured by heat and / or light. Both are included.

[1-1] Ethylenically unsaturated compound The ethylenic compound constituting the curable composition of the present invention contains (A) an ethylenically unsaturated compound having a secondary hydroxyl group as an essential component, preferably (B ) Contains an ethylenically unsaturated compound having a double bond equivalent of 400 or less.

  The ethylenically unsaturated compound is added by the action of a polymerization initiation system containing a photopolymerization initiator and / or a thermal polymerization initiator described later when the curable composition is irradiated with actinic rays or heated. It is a compound that has at least one radically polymerizable ethylenically unsaturated bond in the molecule that polymerizes and optionally crosslinks and cures. Hereinafter, these ethylenically unsaturated compounds will be described in detail.

[1-1-1] An ethylenically unsaturated compound having a secondary hydroxyl group (A)
The ethylenically unsaturated compound (A) having a secondary hydroxyl group according to the present invention is not particularly limited as long as it has at least one secondary hydroxyl group and one ethylenically unsaturated group in the molecule. Preferably, a compound containing at least one partial structure of the following formulas (i) to (iii) can be mentioned.

［式中、Ｒ¹は、水素原子又はメチル基を表し、＊はエチレン性不飽和化合物（Ａ）中の他の部位との結合手を示す。］

[Wherein R ¹ represents a hydrogen atom or a methyl group, and * represents a bond with another site in the ethylenically unsaturated compound (A). ]

  Among these, a compound having a partial structure represented by the formula (i) is particularly preferable.

［式中、Ｒ¹は水素原子又はメチル基を表し、＊はエチレン性不飽和化合物（Ａ）中の他の部位との結合位置を示す。Ｙは任意の２価基を示す。］ Another preferred compound includes a compound containing at least one partial structure represented by the following formulas (iv) and (v) or represented by the following formula (vi).

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and * represents a bonding position with another site in the ethylenically unsaturated compound (A). Y represents an arbitrary divalent group. ]

  In the formula (vi), examples of the divalent group represented by Y include an alkylene group, alkenylene group, alkynylene group, and arylene group, which may have a substituent. Examples of the substituent that Y may have include a halogen atom, a hydroxyl group, an alkyl group, and an aryl group.

  Among these, a compound having a partial structure represented by formula (iv) and a compound represented by formula (vi) are particularly preferable.

  Specific examples of the ethylenically unsaturated compound (A) having a secondary hydroxyl group suitable for the present invention include propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, Diglycidylated compounds and (meth) acrylic compounds of glyceryl acrylate methacrylate and their modified C 2-5 alkylene oxides such as ethylene oxide or propylene oxide, aliphatic or aromatic dialcohols, polyalkylene glycols, or bisphenols Examples include a reaction product with an acid and a modified product thereof with an alkylene oxide.

As the ethylenically unsaturated compound (A), a commercially available product can be used, and examples of the commercially available product include the following.
Kyoei Chemical Co., Ltd .:
Light ester HOP, HOP-A, HOB, HO-MPP, G-101P, G-
201P
Epoxy ester M-600A, 40EM, 70PA, 200PA, 80MFA,
3002M, 3002A, 3000M, 3000A
Made by Nippon Oil & Fats Co., Ltd .:
BLEMMER GLM, GLM-R, GMR-H, GHR-R, GAM, GAM-R,
G-FA-80, QA, P
Shin-Nakamura Chemical Co., Ltd .:
NK ester 702A, 701A, TOPOLENE-M, 701
NK oligo EA-1020, EA-1025, EA-1026, EA-1028,
EA-5520

  The ethylenically unsaturated compound (A) having a secondary hydroxyl group as described above can be used alone or as a mixture of two or more.

  The content of the ethylenically unsaturated compound (A) in the curable composition of the present invention is usually 0.5 to 20% by weight, preferably 0.5%, based on the total solid content in the curable composition. -15% by weight, more preferably 0.5-10% by weight. If the content of the ethylenically unsaturated compound (A) is too small, the adhesion with the substrate is deteriorated and it is difficult to obtain a high-definition pattern, while the content of the ethylenically unsaturated compound (A) is low. If the amount is too large, the curability is impaired. For example, when used as a spacer, the necessary mechanical properties cannot be obtained.

[1-1-2] An ethylenically unsaturated compound (B) having a double bond equivalent of 400 or less
The curable composition of the present invention includes an ethylenically unsaturated compound (B) having a double bond equivalent of 400 or less as an ethylenically unsaturated compound other than the ethylenically unsaturated compound (A) having a secondary hydroxyl group. It is preferable to contain.

Here, the double bond equivalent is the weight per mole of the double bond of the compound, and is calculated by the following formula. The more double bonds per unit weight, the smaller the value of double bond equivalent. .
Double bond equivalent = weight of compound (g) / number of moles containing double bond of compound

  The ethylenically unsaturated compound (B) according to the present invention has a smaller double bond equivalent, and the more double bonds per unit weight, the greater the elastic recovery rate and recovery rate of the resulting cured product. Therefore, the double bond equivalent of the ethylenically unsaturated compound (B) according to the present invention is 400 or less, preferably 350 or less, more preferably 300 or less. The lower limit of the double bond equivalent of the ethylenically unsaturated compound (B) is usually 100 or more.

  In addition, since the double bond equivalent as the whole curable composition of the present invention is the same as the double bond equivalent of the ethylenically unsaturated compound (B), the smaller the elastic recovery rate and recovery rate of the cured product obtained. Since it becomes large, it is preferable, it is preferable that it is 300 or less, More preferably, it is 250 or less. The lower limit of the double bond equivalent of the curable composition as a whole is usually 100 or more.

Here, the double bond equivalent of the curable composition can be calculated by the above formula from the charged amount of the compound having an ethylenic double bond when preparing the curable composition, or a known method Then, after measuring the double bond equivalent of the curable composition solution, the solid content concentration of the curable composition can be measured by a known method and calculated by the following formula.
Double bond equivalent = double bond equivalent of the curable composition solution × solid content concentration

  The ethylenically unsaturated compound (B) preferably has an acid group. Here, “having an acid group” means having a group giving a value greater than 0 as an acid value determined by titration with KOH. Specifically, it means having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among them, it is particularly preferred to have a carboxyl group.

  Moreover, it is preferable that an ethylenically unsaturated compound (B) is a thing obtained from an epoxy compound so that it may mention later.

  The ethylenically unsaturated compound (B) preferably has a weight average molecular weight of 1,000 or more, more preferably 1,500 or more, and particularly preferably 2,000 or more. Moreover, the weight average molecular weight of an ethylenically unsaturated compound (B) is 100,000 or less normally, Preferably it is 10,000 or less. If the weight average molecular weight of the ethylenically unsaturated compound (B) is too small, the amount of displacement tends to be small, and if too large, the development tends to be poor.

  In addition, a weight average molecular weight is measured by polystyrene conversion by GPC (gel permeation chromatography).

The ethylenically unsaturated compound (B) according to the present invention is not particularly limited as long as the double bond equivalent is 400 or less, but is preferably obtained from an epoxy group-containing compound as described later. It preferably contains a carboxyl group.
Examples of such an ethylenically unsaturated compound (B) include compounds represented by the following general formula (I).

〔式（Ｉ）中、Ｒ¹¹は、置換基を有していても良いアルキレン基又は置換基を有していても良いアリーレン基を示す。Ｒ¹²は置換基を有していても良いエチレン性不飽和基含有カルボニルオキシ基を示す。Ｒ¹³及びＲ¹⁴は、それぞれ独立して任意の置換基を示す。ｎは０〜１０の整数である。ｍは１以上の整数である。Ｘは置換基を有していても良い任意の有機基を示す。〕

[In formula (I), R ¹¹ represents an alkylene group which may have a substituent or an arylene group which may have a substituent. R ¹² represents an ethylenically unsaturated group-containing carbonyloxy group which may have a substituent. R ¹³ and R ¹⁴ each independently represents an arbitrary substituent. n is an integer of 0-10. m is an integer of 1 or more. X represents an arbitrary organic group which may have a substituent. ]

In general formula (I), the alkylene group represented by R ¹¹ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and the arylene group may be a carbon atom. A number of 6 to 10 is preferable, and a phenylene group is more preferable. Of these, an alkylene group is preferred in the present invention.

Examples of the substituent that the alkylene group or arylene group of R ¹¹ may have include, for example, a halogen atom, a hydroxyl group, a C 1-15 alkyl group, preferably a C 1-10 alkyl group, and a C 2-10 alkenyl group. Group, phenyl group, carboxyl group, sulfanyl group, phosphino group, amino group, nitro group and the like.

  N is an integer of 0 to 10, preferably 0 to 5, and more preferably 0 to 3. When n exceeds the above range, when the resulting curable composition is a cured product, film loss or the like occurs as an image portion during development, or heat resistance decreases.

The lower limit of the carbon number of the ethylenically unsaturated group-containing carbonyloxy group which may have a substituent of R ¹² in the general formula (I) is usually 3, preferably 5, and more preferably 10. The upper limit is not particularly limited, but is preferably 50, more preferably 40, and particularly preferably 35. If the carbon number is too large or too small, the mechanical properties of the cured product formed by the curable composition of the present invention may not be obtained.
R ¹² is more preferably a group represented by the following general formula (II).

〔式（II）中、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷はそれぞれ独立して水素原子又はメチル基を示し、Ｑは任意の２価基を示す。〕

[In the formula (II), R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a methyl group, and Q represents an arbitrary divalent group. ]

  Q preferably represents a divalent group including an alkylene group which may have a substituent and / or an arylene group which may have a substituent and a carbonyloxy group, more preferably The divalent group containing the C1-C10 alkylene group which may have a substituent, and / or the C1-C10 arylene group which may have a substituent, and a carbonyloxy group is shown. .

R ¹³ is preferably a hydrogen atom, a substituent represented by the following general formula (IIIa), or a substituent represented by the following general formula (IIIb).

〔式（IIIａ），（IIIｂ）中、Ｒ²¹，Ｒ²²は、置換基を有していても良いアルキル基、置換基を有していても良いアルケニル基、置換基を有していても良いシクロアルキル基、置換基を有していても良いシクロアルケニル基又は置換基を有していても良いアリール基を示す。〕

[In the formulas (IIIa) and (IIIb), R ²¹ and R ²² may have an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good cycloalkyl group, an optionally substituted cycloalkenyl group, or an optionally substituted aryl group is shown. ]

Here, the alkyl group of R ²¹ and R ²² is preferably one having 1 to 20 carbon atoms, the alkenyl group is preferably one having 2 to 20 carbon atoms, and the cycloalkyl group is Those having 3 to 20 carbon atoms are preferred, those having 3 to 20 carbon atoms are preferred as the cycloalkenyl group, and those having 6 to 20 carbon atoms are preferred as the aryl group.

Examples of the substituent that R ²¹ and R ²² may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, Examples include a carbonyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group. In particular, R ²¹ preferably has a carboxyl group as a substituent.

The substituent represented by R ¹⁴ in the general formula (I) is not particularly limited, and examples thereof include a substituent represented by the following general formula (IV).

〔式（IV）中、Ｒ¹¹、Ｒ¹²、Ｒ¹³及びｎは前記一般式（Ｉ）におけると同義である。〕

[In the formula (IV), R ¹¹ , R ¹² , R ¹³ and n are as defined in the general formula (I). ]

  X in the general formula (I) represents an arbitrary organic group which may have a substituent. This X has the function of a base for bonding a double bond-containing group, and does not increase the double bond equivalent as a whole, so it provides a functional group serving as a site for bonding a moderate molecular weight and a moderate number of substituents. There is a function to do.

  The molecular weight of X is usually 14 or more, preferably 28 or more, and usually 1000 or less, preferably 800 or less.

Specific examples of the organic group that can be used as X include a linear or cyclic organic group.
As a linear thing, for example, alkane, alkene, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. Or an organic group derived from an acid-modified epoxy acrylate, polyolefin, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, or the like.

  In addition, the cyclic group includes an organic group derived from an alicyclic ring, an aromatic ring, an alicyclic heterocyclic ring, a heterocyclic ring or the like, or a condensed ring of these rings or a bonded group via a linking group. Can be mentioned. Among these, cyclopentane ring, cyclohexane ring, cyclohexene ring, tricyclodecane ring, etc. as alicyclic rings, and benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring as aromatic rings , Biphenylene ring, indene ring, etc., alicyclic heterocycle, and heterocycle include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring , Triazole ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and the like.

  Examples of the linking group via the bond of the cyclic organic group include a direct bond or a divalent or higher valent linking group. As the divalent or higher linking group, known ones can be used. For example, alkylene, polyoxyalkylene, amine, O atom, S atom, ketone group, thioketone group, —C (═O) O—, amide , Se, Te, P, As, Sb, Bi, Si, B and other metals, heterocycles, aromatic rings, heteroaromatic rings, and any combination thereof.

  Examples of the organic group of X include, for example, an alkylene group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, and 2 to 50 carbon atoms, preferably 2 to 30 carbon atoms. Examples include polyethers, bisphenols such as bisphenol A and bisphenol F shown below, and residues obtained by removing hydroxyl groups from polyol compounds such as trisphenol and novolak.

  In the above exemplary formula, z represents an integer of 0 or more. In the examples (X-13), (X-15), (X-18), (X-19), and (X-20), * represents a bond. In these exemplary structures, when there are 3 or more bonds *, the bonds as the linking group X take at least two of them. In this case, examples of the substituent linked to the remaining one or more bonds include an arbitrary substituent, and a group represented by the general formula (IV) is preferable.

  In addition, when the compound represented with the said general formula (I) has a benzene ring, as a substituent of the benzene ring, a C1-C15 alkyl group and a C1-C15 alkoxy group are mentioned, for example. , An acyl group having 2 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group having 1 to 16 carbon atoms, a carboxyl group, a halogen atom, and the like. More preferred are an alkyl group of ˜5, a phenyl group, and a halogen atom.

  As long as the compound represented by the general formula (I) has the structure, the production method is not particularly limited. For example, from the epoxy group-containing compound represented by the following general formula (V) If the compound obtained is described as an example, a compound represented by the following general formula (V) is used as a raw material, and an ethylenically unsaturated group-containing carbonyloxy group is formed on the compound. Examples thereof include a method of reacting one or more compounds selected from the group consisting of an anhydride and an isocyanate group-containing compound.

〔式（Ｖ）中、Ｒ¹¹、Ｘ及びｎは、それぞれ一般式（Ｉ）におけると同義である。Ｒ¹⁸は、一般式（Ｉ）におけるＲ¹¹と同義である。〕

[In the formula (V), R ¹¹ , X and n are as defined in the general formula (I). R ¹⁸ has the same meaning as R ¹¹ in formula (I). ]

As an epoxy group containing compound represented by the said general formula (V), the epoxy compound as described in the following [1-5-6] chapter, a bis (hydroxyphenyl) fluorene type epoxy compound, etc. are mentioned, for example. Examples of the bis (hydroxyphenyl) fluorene forming the bis (hydroxyphenyl) fluorene type epoxy compound include 9,9-bis (4′-hydroxyphenyl) fluorene and 9,9-bis (4′-hydroxy-3 ′). -Methylphenyl) fluorene, 9,9-bis (4'-hydroxy-3 ', 5'-dimethylphenyl) fluorene, 9,9-bis (4'-hydroxy-3'-methoxyphenyl) fluorene, 9,9 -Bis (4'-hydroxy-3'-fluorophenyl) fluorene, 9,9-bis (4'-hydroxy-3'-chlorophenyl) fluorene, 9,9-bis (4'-hydroxy-3 ', 5' -Dichlorophenyl) fluorene, 9,9-bis (4'-hydroxy-3'-bromophenyl) fluorene, 9,9-bis (4'-hydroxy-3 ', 5' Dibromophenyl) fluorene, and the like.
The epoxy group-containing compound represented by the general formula (V) may be used alone or in combination of two or more.

  In addition, the lower limit of the carbon number of the ethylenically unsaturated group-containing carbonyloxy group formed in the epoxy group-containing compound represented by the general formula (V) is usually 3, preferably 5, and more preferably 10. The upper limit is not particularly limited, but is preferably 50, more preferably 40, and particularly preferably 35. If the carbon number is less than the above range, when the curable composition is a cured product, the flexibility is insufficient and the adhesion to the substrate is inferior. On the other hand, if the carbon number is too large, the heat resistance is reduced. .

  These ethylenically unsaturated group-containing carbonyloxy groups are preferably groups represented by the general formula (II).

  Here, if the ethylenically unsaturated group-containing carbonyloxy group represented by the general formula (II) is formed as a result of a reaction using the compound represented by the general formula (V) as a raw material, The forming method is not limited. As the formation method thereof, specifically, a method of reacting the compound represented by the general formula (V) with an ethylenically unsaturated group-containing carboxylic acid (a), or first, no ethylenically unsaturated group is contained. After reacting the carboxylic acid (b), the compound (c) having a functional group that reacts with the generated hydroxyl group or carboxyl group is reacted to form an ethylenically unsaturated group-containing carbonyloxy group. I can list the methods.

The ethylenically unsaturated group-containing carboxylic acids (a) include, for example, reaction products of (meth) acrylic acid and lactone or polylactone; succinic anhydride, adipic anhydride, maleic anhydride, itaconic anhydride, tetrahydro Saturated or unsaturated dicarboxylic acid anhydrides such as phthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, phthalic anhydride, and hydroxyethyl (meth) Acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol Reaction with (meth) acrylate derivatives having one or more hydroxyl groups in one molecule such as (meth) acrylate such as di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Half-esters obtained by the above; saturated or unsaturated dicarboxylic anhydrides as described above, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 8,9-epoxy [bicyclo [4.3 0.0] non-3-yl] (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3-yl] oxymethyl (meth) acrylate and the like, Half-esters obtained by reaction; and the like. Among these, in the present invention, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride and the like, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, Half-esters obtained by reacting pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like are particularly preferable.
These ethylenically unsaturated group-containing carboxylic acids (a) may be used alone or in combination of two or more.

  The carboxylic acids (b) not containing the ethylenically unsaturated group include hydroxyl group-containing carboxylic acids such as lactic acid and dihydroxypropionic acid and anhydrides thereof, succinic acid, maleic acid, tetrahydrophthalic acid, phthalic acid, tartaric acid, etc. And saturated or unsaturated dicarboxylic acids and anhydrides thereof.

  Subsequently, the compound (c) having a functional group that reacts with the generated hydroxyl group or carboxyl group is reacted to form a functional group that reacts with the hydroxyl group or carboxyl group used when forming the ethylenically unsaturated group-containing carbonyloxy group. As the compound (c) having, an epoxy group, a carboxyl group, and a compound having an isocyanate group are preferable. Specifically, the ethylenically unsaturated group-containing carboxylic acid (a), the unsaturated group-containing glycidyl compound, etc. Examples of such an ethylenically unsaturated group-containing compound include, but are not limited to.

  The compounds (b) and (c) may be used alone or in combination of two or more.

In addition, as a raw material of the epoxy group-containing compound represented by the general formula (V), after forming an ethylenically unsaturated group-containing carbonyloxy group on this, a polyvalent carboxylic acid to be further reacted or an anhydride thereof, For example, succinic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, saturated or unsaturated dicarboxylic acids such as phthalic acid and the like Acid anhydride, trimellitic acid and its anhydride, and tetramellitic acid such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid And carboxylic acids and their acid anhydrides. . Among these, as a curable composition, from the viewpoint of dissolution and removal of non-image areas during alkali development, dicarboxylic acids such as oxalic acid, tetrahydrophthalic acid, and phthalic acid, and acid anhydrides thereof, trimellitic acid and its Preferred are acid anhydrides, pyromellitic acid, biphenyltetracarboxylic acid, tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, and acid dianhydrides thereof. Among them, acid dissociation constant (first dissociation constant) Is more preferably an acid anhydride of a polyvalent carboxylic acid having a value of 3.5 or more. The acid dissociation constant is further preferably 3.8 or more, and particularly preferably 4.0 or more. Such acid anhydrides include succinic acid and acid anhydrides of tetrahydrophthalic acid, and 1,2,3,4-butanetetracarboxylic acid dianhydrides, such as succinic acid and tetrahydrophthalic acid. The acid anhydride is particularly preferred.
The acid dissociation constant can be referred to Determination of Organic Structures by Physical Methods, Academic Press, New York, 1955 (Brown, HC et al.).
In the present invention, these polycarboxylic acids and acid anhydrides thereof may be used alone or in combination of two or more.

Moreover, after forming the ethylenically unsaturated group containing carbonyloxy group in the epoxy group containing compound represented by the said general formula (V), as a compound which has the isocyanate group made to react further, butane isocyanate, 3-chlorobenzene isocyanate , Cyclohexane isocyanate, organic monoisocyanates such as 3-isopropenoyl-α, α-dimethylbenzyl isocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene Aromatic diisocyanates such as 1,5-diisocyanate and tolidine diisocyanate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid Aliphatic diisocyanates such as diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), alicyclic diisocyanates such as ω, ω'-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α ', α Aliphatic diisocyanates having an aromatic ring such as' -tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6- Triisocyanates such as hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and the like Trimers, water adducts, and the like of these polyol adducts. Of these, preferred are dimers and trimers of organic diisocyanates, and most preferred are trimethylolpropane adduct of tolylene diisocyanate, trimer of tolylene diisocyanate, and trimer of isophorone diisocyanate.
The said compound may be used individually by 1 type, or may use 2 or more types together.

  In addition, as a compound represented by the said general formula (I) in this invention, it is preferable that an acid value is 30-150 mg-KOH / g, and it is still more preferable that it is 40-100 mg-KOH / g. Moreover, it is preferable that the weight average molecular weight of polystyrene conversion by GPC is 1,000-100,000, It is still more preferable that it is 1,500-10,000, It is especially 2,000-10,000. preferable.

An example of a specific method for synthesizing the compound represented by formula (I) in the present invention is as follows.
For example, the bis (hydroxyphenyl) fluorene type epoxy compound is dissolved in an organic solvent such as methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate by a conventionally known method described in JP-A-4-355450, etc., and triethylamine, benzyldimethyl Tertiary amines such as amine and tribenzylamine, or quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride, triphenylphosphine, etc. Hydroquinone, hydroquinone monomethyl ether in the presence of a catalyst such as a phosphorous compound or a stibine such as triphenylstibine In the presence of a thermal polymerization inhibitor such as methylhydroquinone, the ethylenically unsaturated group-containing carboxylic acid is usually 0.8 to 1.5 chemical equivalents, preferably 1 chemical equivalent of the epoxy group of the epoxy compound, preferably It is added in an amount of 0.9 to 1.1 chemical equivalents, and is usually subjected to an addition reaction at a temperature of 60 to 150 ° C., preferably 80 to 120 ° C. Subsequently, the polyvalent carboxylic acid or anhydride thereof is added in the reaction. Addition is usually made in an amount of 0.05 to 1.0 chemical equivalent, preferably 0.5 chemical equivalent, relative to 1 chemical equivalent of the resulting hydroxyl group, and the reaction is continued under the above conditions to obtain the desired compound.

  In addition, when the compound represented by the general formula (I) synthesized as described above is used for the curable composition of the present invention, it is caused by the influence of the mixture contained in the raw material or thermal polymerization during the reaction of the double bond. And may contain compounds other than the compound represented by formula (I).

〔式（VI）中、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は、それぞれ式（Ｉ）おけると同義である。〕 In the present invention, examples of the ethylenically unsaturated compound (B) include the following compounds in addition to the compound represented by the general formula (I).

[In the formula (VI), R ¹² , R ¹³ and R ¹⁴ have the same meanings in the formula (I). ]

  The production method of the compound represented by the general formula (VI) is not particularly limited as long as it has the structure. For example, the production method in the above general formula (I) using diglycidyl ether as a raw material. In the same manner as above, a compound obtained by reacting at least one compound selected from a compound having an ethylenically unsaturated group-containing carbonyloxy group and further having a polyvalent carboxylic acid, its anhydride, and an isocyanate group. Can be mentioned.

  In the curable composition of the present invention, the ethylenically unsaturated compound (B) having a double bond equivalent of 400 or less can be used alone or as a mixture of two or more.

  The content of the ethylenically unsaturated compound (B) in the curable composition of the present invention is usually 25% by weight or more, preferably 35% by weight or more, more preferably based on the total solid content in the curable composition. 45% by weight or more. The greater the content of the ethylenically unsaturated compound (B), the greater the total deformation of the cured product described later, which is preferable. On the other hand, when there is too little content, the total deformation of hardened | cured material cannot be enlarged, for example, the function as a spacer cannot fully be ensured.

[1-2] Other resins Other resins blended in the curable composition of the present invention are compounds other than the ethylenically unsaturated compound (A) and the ethylenically unsaturated compound (B), One kind or two or more kinds of resins used in known resin compositions for color filters can be used. Examples of such resins include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. Examples of the polymer include acid-modified epoxy acrylates, polyamides, polyesters, polyethers, polyurethanes, polyvinyl butyrals, polyvinyl alcohols, polyvinyl pyrrolidones, and acetyl celluloses. A resin containing resin, a copolymer containing a carboxyl group and an epoxy group, and acid-modified epoxy acrylates are preferable.

  Specific examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and other unsaturated carboxylic acids, and styrene. , Α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycy Zir (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, Examples thereof include copolymers with vinyl compounds such as N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, and vinyl acetate.

  Among these, a styrene- (meth) acrylate- (meth) acrylic acid copolymer is preferable, and 3-30 mol% of styrene, 10-70 mol% of (meth) acrylate, 10-60 mol% of (meth) acrylic acid. A copolymer consisting of 5 to 25 mol% of styrene, 20 to 60 mol% of (meth) acrylate, and 15 to 55 mol% of (meth) acrylic acid is particularly preferable. These carboxyl group-containing vinyl resins preferably have an acid value of 30 to 250 mg · KOH / g and a polystyrene-equivalent weight average molecular weight of 1,000 to 300,000.

  Further, as the carboxyl group-containing vinyl-based resin, those having an ethylenically unsaturated bond in the side chain are suitable. Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate is added to the carboxyl group-containing polymer. , Α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Group epoxy group-containing unsaturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1. ] Dec-2-yl] An alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate, 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer Reaction products obtained by reacting, and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, Compounds having two or more unsaturated groups such as N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1- Propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) a The ratio of the compound having two or more kinds of unsaturated groups such as chloramide and the unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester to the whole compound having the unsaturated group. The reaction product etc. which were copolymerized so that it may become 10-90 mol%, preferably about 30-80 mol% are mentioned. In addition, a reaction product of an epoxy group-containing polymer and an ethylenically unsaturated compound having a functional group capable of reacting with an epoxy group such as a carboxyl group or a hydroxyl group, and a compound obtained by further reacting an acid anhydride with this product. I can do it.

  Examples of the copolymer containing a carboxyl group and an epoxy group include unsaturated carboxylic acids, unsaturated compounds having an epoxy group, and copolymers with other compounds as required. Examples include alkali-soluble resins used in the composition described in No. 133600.

  The content of these other resins is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content of the curable composition of the present invention. When there is too much content of other resin, since it exists in the tendency to reduce sclerosis | hardenability and the mechanical characteristic of hardened | cured material, it is unpreferable.

[1-3] Polymerizable monomer The curable composition of the present invention contains a polymerizable monomer separately from the ethylenically unsaturated compounds (A) and (B) described in [1-1] above. Is preferred. The term “monomer” in the present invention means a concept relative to a so-called polymer substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “oligomer”. Means a concept that also includes

  Examples of the polymerizable monomer include compounds having at least one ethylenically unsaturated group in the molecule. Specific examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylic acid, alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond and many ( And monoesters of monohydric alcohols.

  In the present invention, it is desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule as the polymerizable monomer. Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, methacrylic acid esters in which the acrylates of these exemplified compounds are replaced with methacrylates, and similarly itaconic acid esters in which itaconate is replaced, and clonates And crotonic acid ester or maleate instead of maleate.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.

  The ester obtained by the esterification reaction of a polyvalent hydroxy compound with a polybasic carboxylic acid and an unsaturated carboxylic acid is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, And a condensate of ethylene glycol, a condensate of acrylic acid, maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin.

  In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.

  One kind of these polymerizable monomers may be contained alone in the curable composition, or two or more kinds thereof may be contained.

  The content of the polymerizable monomer in the curable composition of the present invention is usually less than 80% by weight, preferably less than 70% by weight, and preferably 10% by weight or more based on the total solid content. When the content of the polymerizable monomer is out of the above range, it is difficult to obtain an image with a good pattern.

[1-4] Photopolymerization initiator and / or thermal polymerization initiator The curable composition of the present invention includes a photopolymerization initiator and / or a thermal polymerization initiator depending on the curing method of the curable composition. May be included. The photopolymerization initiator and / or thermal polymerization initiator according to the present invention is not particularly limited as long as it is a compound that polymerizes an ethylenically unsaturated group by actinic rays and / or heat, and a known photopolymerization initiator and / Or thermal polymerization initiator A polymerization initiator can be used.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Halomethylated triazine derivatives such as ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2'-benzofuryl) vinyl] -1,3,4-oxa Halomethylated oxadiazole derivatives such as diazole;
2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- ( Imidazole derivatives such as 2'-fluorophenyl) -4,5-diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl- [ Acetophenone derivatives such as 4- (methylthio) phenyl] -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-2,6-di-fluoro-3- (pyr-1-yl ) -Titanocene derivatives such as phen-1-yl;
Acetophenone oxime-o-acetate, 1,2-octanedione-1- [4- (phenylthio) -2- (o) described in JP-A No. 2000-80068, Japanese Patent Application No. 2004-183593, etc. -Benzoyloxime)], 1- [9-ethyl-6- (2-benzoyl) -9H-carbazol-3-yl] ethanone-1- (o-acetyloxime) and the like.

  In addition, photopolymerization initiators that can be used in the present invention are described in Fine Chemical, March 1, 1991, Vol. 20, no. 4, P. 16-P26, JP-A-59-152396, JP-A-61-151197, JP-B-45-37377, JP-A-58-40302, JP-A-10-39503, etc. Have been described.

  One of these photopolymerization initiators may be included alone in the curable composition, or two or more thereof may be included.

  Specific examples of the thermal polymerization initiator used in the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used.

  As the azo compound, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2-azobis [2-Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2 , 2'-azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2'-azobis [N-butyl-2-methylpropionamide], 2,2'-azobis (N-cyclohexyl- 2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionate), 2,2'-azobis (2,4 , 4-Trimethylpen Emissions), or the like can be cited, among these, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like are preferable.

  Examples of the organic peroxide include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like. Specifically, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di (2-ethoxyethyl) peroxy Dicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t -Butylperoxypivalate, di (3,5,5-trimethylhexanoyl) peroxy , Di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 2, 5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2- Ethylhexanoate, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy)- 3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di- ( t-Butylperoxy) cyclohexyl) Bread, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl -2,5-di- (3-methylbenzoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5- Di-methyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl4, 4-di- (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (T-Butylpas Oxy) hexane, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1 , 3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyltrimethylsilyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, di (3-methylbenzoyl) And a mixture of peroxide, benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide.

  One of these thermal polymerization initiators may be contained alone in the curable composition, or two or more thereof may be contained. Moreover, you may use together a photoinitiator and a thermal-polymerization initiator.

  The content of these photopolymerization initiator and / or thermal polymerization initiator is usually 0.01% by weight or more, preferably 0.1% by weight or more, based on the total solid content of the photosensitive composition of the present invention. More preferably, it is 0.5 weight or more, and is usually 30 weight% or less, preferably 20 weight% or less. If the content is too low, the sensitivity may be lowered. On the other hand, if the content is too high, the solubility of the unexposed portion in the developer is lowered, and development defects are likely to be induced.

[1-5] Other components In addition to the above components, the curable composition of the present invention includes a solvent, a colorant, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, and a polymerization inhibitor. An antioxidant, a silane coupling agent, an epoxy compound, an amino compound, a polymerization accelerator and the like can be appropriately blended.

[1-5-1] Solvent The solvent used in the curable composition of the present invention is not particularly limited. For example, water, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n- Hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, Barsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl Nonyl ketone, propyl ether, dodecane, Social solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec, t), hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene Recall monobutyl ether acetate, diethylene glycol monobutyl ether, dipentene, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol , Cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl acetate Ter, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether , 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxy It can be mentioned solvents such as butyl acetate specifically.

  The solvent can dissolve or disperse each component and is selected according to the method of using the curable composition of the present invention, but it is preferable to select a solvent having a boiling point in the range of 60 to 280 ° C. More preferably, it has a boiling point of 70 to 260 ° C. These solvents can be used alone or in combination of two or more.

  These solvents are used in such an amount that the ratio of the total solid content in the curable composition of the present invention is usually 10% by weight or more and 90% by weight or less.

[1-5-2] Colorant As the colorant used in the curable composition of the present invention, known colorants such as pigments and dyes can be used. For example, when a pigment is used, a known dispersant or dispersion aid may be used in combination so that the pigment can be stably present in the curable composition without agglomeration. Although there is no restriction | limiting in particular in content of a coloring agent, Usually, it is 70 weight% or less with respect to the total solid of a curable composition.

[1-5-3] Coating property improver, development improver Examples of the coating property improver or development improver used in the curable composition of the present invention include, for example, known cationic, anionic, nonionic, and fluorine. And silicon surfactants can be used. As the development improver, known ones such as organic carboxylic acids and / or anhydrides thereof can be used. Moreover, the content is 20 weight% or less normally with respect to the total solid of a curable composition, Preferably it is 10 weight% or less.

[1-5-4] Polymerization inhibitor, antioxidant Further, the curable composition of the present invention has a polymerization inhibitor such as hydroquinone and methoxyphenol, and 2,6-di- It is preferable to contain a hindered phenol antioxidant such as tert-butyl-4-cresol (BHT). The content thereof is usually 5 ppm or more, preferably 10 ppm or more, and usually 1000 ppm or less, preferably 600 ppm or less, based on the total solid content of the curable composition. If this content is small, the stability tends to deteriorate, and if it is too large, for example, curing by heat and / or light may cause insufficient curing, which is not preferable. In particular, when used in a normal photolithography method, it is necessary to set the optimum amount in view of both storage stability and sensitivity of the curable composition.

[1-5-5] Silane Coupling Agent The curable composition of the present invention preferably contains a silane coupling agent in order to improve adhesion to the substrate. As for the type of silane coupling agent, various types such as epoxy, (meth) acrylic, amino and the like can be used singly or as a mixture of two or more, and in particular, epoxy silane coupling agents Is preferred. The content is usually 20% by weight or less, preferably 15% by weight or less, based on the total solid content in the curable composition.

[1-5-6] Epoxy Compound It is also preferable to add an epoxy compound in order to improve curability and adhesion to the substrate.

  As the epoxy compound, constituting a repeating unit of a so-called epoxy resin, a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin, a polyglycidyl ester compound obtained by reacting a polycarboxylic acid compound and epichlorohydrin, and And compounds ranging from a low molecular weight substance to a high molecular weight substance, such as a polyglycidylamine compound obtained by reacting a polyamine compound and epichlorohydrin.

  Examples of the polyglycidyl ether compound include diglycidyl ethers of alkylene glycols having 1 to 20 carbon atoms such as ethylene glycol, propylene glycol, butanediol, and hexanediol, and polyalkylene glycols having 2 to 50 carbon atoms such as polyethylene glycol and polypropylene glycol. Polyglycidyl ethers of polyols such as diglycidyl ether, glycerol and pentaerythritol, diglycidyl ethers of aromatic diols, polyglycidyl ethers of aromatic polyols and the like. Specifically, for example, diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), diglycidyl ether type epoxy of bis (3,5-dimethyl-4-hydroxyphenyl), Diglycidyl ether type epoxy of bisphenol F, diglycidyl ether type epoxy of bisphenol A, diglycidyl ether type epoxy of tetramethylbisphenol A, diglycidyl ether type epoxy of ethylene oxide-added bisphenol A, diglycidyl ether type epoxy of fluorene type bisphenol, Examples thereof include phenol novolac type epoxy and cresol novolac type epoxy. These polyglycidyl ether compounds have acid anhydrides and 2 Or the like may be those obtained by introducing carboxyl group by reacting the acid compound.

  Examples of the polyglycidyl ester compound include a diglycidyl ester type epoxy of hexahydrophthalic acid and a diglycidyl ester type epoxy of phthalic acid, and examples of the polyglycidyl amine compound include bis (4- Aminophenyl) methane diglycidylamine type epoxy, isocyanuric acid triglycidylamine type epoxy, and the like.

One of these epoxy compounds may be included alone in the curable composition, or two or more thereof may be included. The content of the epoxy compound in the curable composition is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content. When there is too much content of an epoxy compound, the storage stability of a curable composition may deteriorate.
In this case, a known epoxy curing agent may be used in combination.

[1-5-7] Amino compound Further, the curable composition of the present invention improves its curability (curing speed of the curable composition, mechanical properties of the cured product) and adhesion to the substrate. It is also preferable to add one or more amino compounds. The content thereof is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content in the curable composition. Moreover, it is 0.5 weight% or more normally, Preferably it is 1 weight% or more. When there is too much this content, the storage stability of a curable composition may deteriorate. Moreover, when there is too little content, the improvement effect of the said sclerosis | hardenability and adhesiveness with a board | substrate will become low.
In particular, when the curing rate is expected, the content is usually 10% by weight or less, preferably 5% by weight or less. Moreover, it is 0.5 weight% or more normally, Preferably it is 1 weight% or more. If this content is too large, the pattern formability may deteriorate.

  Examples of the amino compound include a methylol group as a functional group and an amino compound having at least two alkoxymethyl groups obtained by condensing and modifying the alcohol with 1 to 8 carbon atoms. For example, melamine obtained by polycondensation of melamine and formaldehyde. Resin, benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde, glycoluril resin obtained by polycondensation of glycoluril and formaldehyde, urea resin obtained by polycondensation of urea and formaldehyde, melamine, benzoguanamine, glycoluril, urea, etc. And a resin obtained by copolycondensation of two or more of the above and formaldehyde, and a modified resin obtained by alcohol condensation modification of the methylol group of these resins. Among them, in the present invention, a melamine resin and a modified resin thereof are preferable, a modified resin having a methylol group modification ratio of 70% or more is more preferable, and a modified resin having a methylol group modification ratio of 80% or more is particularly preferable.

  Specific examples of these amino compounds include “Cymel” (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, Mitsui Cytec Co., Ltd. 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and “Nicarac” (registered trademark) MW-390, MW-100LM, MX- from Sanwa Chemical Co., Ltd. 750LM, MW-30M, MX-45, and MX-302 are also benzoguanamine resins and modified resins thereof, “Cymel” (registered trademark) 1123, 1125, and 1128, and glycoluril resins and modified resins thereof as “ Cymel "(registered trademark) 1170, 1171, 1174, 117 "Nikarak" (registered trademark) MX-270, BX-4000, and urea resin and modified resins thereof, "UFR" (registered trademark) 65, 300 and "Nicarak" (registered) of Mitsui Cytec Co., Ltd. (Trademark) MX-290, etc.

[1-5-8] Polymerization Accelerator Moreover, it is also preferable to add one or more polymerization accelerators to the curable composition of the present invention in order to promote polymerization and curing.

  Examples of the polymerization accelerator include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, Mercapto group-containing compounds such as β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakis Derivatives such as polyfunctional thiol compounds such as thiopropionate, N, N-dialkylaminobenzoic acid ester, N-phenylglycine or its ammonium salt, sodium salt, etc. Niruaranin, or salts such as its ammonium and sodium salts, derivatives, and the like, such as amino acid or a zwitterionic compound having an aromatic ring such as derivatives of esters.

  The content of these polymerization accelerators is usually 10% by weight or less, preferably 5% by weight or less, based on the total solid content in the curable composition. When this content is too large, there are problems such as poor developability and adhesion, which is not preferable.

[1-6] Total deformation, displacement and elastic recovery rate during loading, recovery rate The curable composition of the present invention is used in a load-unloading test with a microhardness meter, particularly when used in a spacer application ( It is characterized in that a cured product satisfying 1) and / or (2) and satisfying the following (3) and / or (4) can be formed.
(1) Deformation amount is 1.35 μm or more (2) Load N when displacement at load is 0.25 μm is 0.7 gf or less (3) Elastic recovery rate is 50% or more (4) Recovery rate is 80% or more

For example, a spacer provided in a liquid crystal display device (hereinafter sometimes referred to as a “panel”) of a large-sized liquid crystal screen television is easily subjected to a load in the manufacturing process of the panel, and the total deformation amount of the spacer is large. Tend to be. In particular, in a large screen panel, the load tends to be uneven in each part.
Even in such a case, the curable composition of the present invention is significant in that the cured product (spacer) has a high elastic recovery rate and / or high recovery rate.

Here, the load-unloading test using a micro hardness tester is performed in a later-described [2] chapter or a spacer pattern formed by a known method, with an upper cross-sectional area of 80 ± 10 μm ² and a height of 4 ± 0.3 μm. For one pattern, a microhardness meter is used as follows.

Here, the upper cross-sectional area of the spacer pattern means the following area.
First, a vertical cross section passing through the central axis of the spacer pattern is profiled for one spacer pattern using an ultra-deep color 3D shape measuring microscope “VK-9500” manufactured by Keyence Corporation. The spacer pattern profile method will be described with reference to FIGS. FIG. 1 is a schematic diagram showing a position where a spacer pattern is profiled when viewed from above, and FIG. 2 is a schematic diagram showing a profile of a vertical cross section of the spacer pattern. 1 and 2, 1 is a spacer pattern, 2 is a central axis of the spacer pattern, 3 is a profile position, 4 is a profile of a vertical cross section of the spacer pattern, 5 is a height from the substrate surface to the highest position, and 6 is from the substrate surface. 90% of the height to the highest position, 7 is the diameter AA 'of the circle in the upper section.
Thus, the straight line AA parallel to the substrate surface in the spacer pattern graphic at the height (6) of 90% of the height (5) from the substrate surface of the profiled graphic (4) to the point Q at the highest position. The length (7) of ′ is measured. The area of a circle having the diameter AA ′ is defined as the upper cross-sectional area of the spacer pattern.

As a microhardness meter for the load-unloading test, Shimadzu Corp. (Shimadzu dynamic ultra microhardness meter DUH-W201S) is used.
The test conditions were a measurement temperature of 23 ° C. and a flat indenter with a diameter of 50 μm. A load was applied to the spacer at a constant speed (0.22 gf / sec). When the load reached 5 gf, the load was held for 5 seconds, and then the same speed. Unload at. From the load-displacement curve as shown in FIG. 3 obtained from this test, the maximum displacement H [max], the final displacement H [Last], and the load N (gf) when the displacement at the time of loading is 0.25 μm (hereinafter, (Referred to as “0.25 μm displacement load N”). The maximum displacement H [max] is defined as the total deformation amount.

  In the present invention, the total deformation amount is preferably 1.4 μm or more, more preferably 1.5 μm or more, preferably 2 μm or less, more preferably 1.8 μm or less.

  The 0.25 μm displacement load N is preferably 0.45 gf or less, and preferably 0.1 gf or more.

  If the total deformation amount is too large and / or the 0.25 μm displacement load N is too small, the elastic recovery rate and / or the recovery rate deteriorates. On the other hand, if the total deformation amount is too small and / or the 0.25 μm displacement load N is too large, the cured product cannot cope with load unevenness at the time of manufacturing the panel.

The elastic recovery rate and recovery rate are calculated as follows based on the values measured by the load-unloading test using the micro hardness tester.
Recovery rate (%) = final displacement H [Last] / (pattern height before test) × 100
Elastic recovery rate (%) = (maximum displacement H [max]-final displacement H [Last])
/ Maximum displacement H [max] × 100

The recovery rate is preferably 85% or more, more preferably 90% or more.
The elastic recovery rate is preferably 60% or more, more preferably 80% or more.
If the recovery rate and / or elastic recovery rate is too small, the cured product cannot cope with load unevenness during panel manufacture.

[1-7] Bottom cross-sectional area, elastic recovery rate, recovery rate The curable composition of the present invention also forms a cured product satisfying the following (3) and / or (4) and satisfying the following (5). It is a feature.
(3) Elastic recovery rate is 50% or more (4) Recovery rate is 80% or more (5) Bottom cross-sectional area is 25 μm ² or less

For example, a spacer provided for a screen panel of a mobile phone has a small bottom area so as not to damage an image because the pixel is small. On the other hand, a product such as a mobile phone is easily subjected to an impact during use, and thus is easily loaded.
Even in such a case, the curable composition of the present invention is significant in that the cured product (spacer) has a high elastic recovery rate and / or high recovery rate.

  Here, the bottom cross-sectional area refers to the contact area of the cured product formed of the curable composition of the present invention such as a spacer with the substrate, and is measured by observing the spacer pattern with an optical microscope.

The bottom cross-sectional area is preferably 20 μm ² or less, more preferably 15 μm ² or less, preferably 1 μm ² or more, and more preferably 5 μm ² or more.
When the bottom cross-sectional area is too large, it is not suitable for a panel such as a cellular phone having a small pixel. On the other hand, if the bottom cross-sectional area is too small, a sufficient elastic recovery rate and / or recovery rate cannot be obtained.

The elastic recovery rate and recovery rate are calculated in the same manner as described above based on the values measured by the load-unloading test using the micro hardness tester. The recovery rate is preferably 90% or more, and the elastic recovery rate The rate is preferably 60% or more, more preferably 80% or more.
If the recovery rate and / or elastic recovery rate is too small, the cured product cannot cope with a load such as a panel impact.

  When the cured product formed by the curable composition of the present invention has the mechanical properties described in the chapters [1-6] and [1-7], the curable composition of the present invention is the above-mentioned second grade. The composition is not particularly limited as long as it contains an ethylenically unsaturated compound (A) having a hydroxyl group, but such mechanical properties are, for example, that the curable composition is an ethylenically unsaturated compound (A ) And the ethylenically unsaturated compound (B) having a double bond equivalent of 400 or less.

[2] Method of using curable composition The curable composition of the present invention is used in the same manner as a known curable composition for a color filter. A description will be given of the case.

  Usually, a curable composition dissolved or dispersed in a solvent is supplied in a film or pattern by a method such as coating on a substrate on which a spacer is to be provided, and the solvent is dried and then supplied in a film. If necessary, pattern formation is performed by a method such as photolithography in which exposure and development are performed as necessary. Thereafter, if necessary, additional exposure or thermosetting treatment is performed to form spacers on the substrate.

[2-1] Supply Method to Substrate The curable composition of the present invention is usually supplied onto the substrate in a state dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred. The coating amount varies depending on the application. For example, in the case of a spacer, the dry film thickness is usually 0.5 μm or more, preferably 1 μm or more, and usually 10 μm or less, preferably 9 μm or less, particularly preferably 7 μm or less. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation in the spacer height is large, a nonuniformity defect occurs in the liquid crystal panel. Further, the curable composition may be supplied in a pattern by an ink jet method or a printing method.

[2-2] Drying method Drying after supplying the curable composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature. Drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 130 ° C., preferably 30 to 50 to 110 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of seconds to 3 minutes.

[2-3] Exposure Method Exposure is performed by superimposing a negative mask pattern on the coating film of the curable composition and irradiating an ultraviolet or visible light source through the mask pattern. Further, a scanning exposure method using a laser beam without using a mask pattern may be used. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, it is carried out in a deoxygenated atmosphere or oxygen such as a polyvinyl alcohol layer on the photopolymerizable layer made of the curable composition of the present invention. Exposure may be performed after the blocking layer is formed.

  The light source used for said exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[2-4] Development Method After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. This aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids. These may be used individually by 1 type, or may use 2 or more types together.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. An organic solvent may be used individually by 1 type, may be 2 or more types of mixed solvents, and may be used as aqueous solution.

[2-5] Additional exposure and thermosetting treatment The substrate after development may be subjected to additional exposure by a method similar to the above-described exposure method, if necessary, or may be subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. It is particularly preferable to perform such a thermosetting treatment.

  In the present invention, preferable conditions for forming the cured product having the mechanical properties described in the above [1-6] and [1-7] chapters are, for example, 200 to 250 ° C., particularly 230 ° C. and 15 to 15 ° C. A 30-minute heat curing treatment can be mentioned.

  Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

<Synthesis Example 1: Synthesis of ethylenically unsaturated compound (B1)>
By reacting 118 parts by weight of succinic anhydride with 596 parts by weight of commercially available pentaerythritol triacrylate at 85 ° C. for 5 hours in the presence of 2.5 parts by weight of triethylamine and 0.25 parts by weight of hydroquinone, A polyfunctional acrylate mixture having an acid value of 92.7 mg-KOH / g comprising 66% by weight of a polyfunctional acrylate having one carboxyl group and two or more acryloyl groups and 34% by weight of pentaerythritol tetraacrylate was obtained (ethylene Unsaturated group-containing carboxylic acid mixture (B0)).

  In a 1500 ml four-necked flask, 231 g of diglycidyl etherified product (epoxy equivalent 231) of 9,9-bis (4′-hydroxyphenyl) fluorene, 605 g of the ethylenically unsaturated group-containing carboxylic acid mixture (B0), triethyl Charge 6.06 g of benzylammonium chloride, 0.15 g of p-methoxyphenol and 170 g of propylene glycol monomethyl ether acetate, heat and dissolve at 80 to 90 ° C., and heat for 8 hours until the acid value reaches 0.8 mg-KOH / g Stirring was continued to obtain a colorless and transparent reaction product. Propylene glycol monomethyl ether acetate was added to the obtained reaction product to adjust the solid content to 50% by weight.

  Subsequently, 8.7 g of 1,2,3,6-tetrahydrophthalic anhydride is added to 100 g of the obtained solution having a solid content of 50% by weight, and the temperature is gradually raised and reacted at 80 to 90 ° C. for 3 hours. A solution of the ethylenically unsaturated compound (B1) was obtained.

  The obtained ethylenically unsaturated compound (B1) had a solid content acid value of 55 mg-KOH / g, a weight average molecular weight of 2,500, and a double bond equivalent of 250.

<Synthesis Example 2: Synthesis of ethylenically unsaturated compound (B2)>
280 parts by weight of an epoxy compound (epoxy equivalent 260) represented by the following structural formula, 442.7 parts by weight of the ethylenically unsaturated group-containing carboxylic acid mixture (B0), 0.36 parts by weight of p-methoxyphenol, triphenylphosphine 14.4 parts by weight and 722.7 parts by weight of propylene glycol monomethyl ether acetate were charged into a reaction vessel and stirred at 85 ° C. until the acid value was 5 mg-KOH / g or less. It took 10 hours for the acid value to reach the target (acid value 4.0 mg-KOH / g).

  80 parts by weight of propylene glycol monomethyl ether acetate was added to the reaction solution obtained by the above reaction, 97.9 parts by weight of tetrahydrophthalic anhydride was further added, and the mixture was allowed to react at 85 ° C. for 3 hours to give an acid value of 58 mg-KOH / g, an ethylenically unsaturated compound (B2) solution having a weight average molecular weight of 2,700 and a double bond equivalent of 305 was obtained.

<Examples 1 to 3 and Comparative Examples 1 and 2>
<1> Preparation of curable composition As the ethylenically unsaturated compound (A) having a secondary hydroxyl group, 6 parts by weight of the compound shown in Table 1 and an ethylenically unsaturated compound (B) having a double bond equivalent of 400 or less ), 100 parts by weight of the ethylenically unsaturated compound (B1) or (B2) obtained in Synthesis Examples 1 and 2, and 80 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the polymerizable monomer. 6 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a heat and / or photopolymerization initiator and 0.2 part by weight of FC430 (manufactured by Sumitomo 3M, fluorine-based surfactant) as a surfactant Then, after dissolving in propylene glycol monomethyl ether acetate so that the solid content concentration becomes 35% by weight, it is filtered through a Millipore filter (2 μm) and hardened. A curable composition was obtained.
However, in Comparative Examples 1 and 2, the ethylenically unsaturated compound (A) was not used, and in Comparative Example 2, 6 parts by weight of phosphoric acid acrylate (“KAYARAD PM-21” manufactured by Nippon Kayaku Co., Ltd.) was added.

<2> Formation of Spacer Pattern After applying the curable composition obtained in the above <1> on the ITO film of the glass substrate having an ITO film formed on the surface using a spinner, hot at 80 ° C. for 3 minutes A film was formed by heating and drying on a plate. The obtained coating film was exposed to ultraviolet rays having an intensity at 365 nm of 32 mW / cm ² using a predetermined pattern mask so that the exposure amount was 100 mJ / cm ² . The ultraviolet irradiation at this time was performed under air. Subsequently, spray development was carried out with a 0.1 wt% potassium hydroxide aqueous solution at 23 ° C. for twice the minimum development time, followed by rinsing with pure water for 1 minute. Here, the minimum development time means a time during which the unexposed area is completely dissolved under the same development conditions. By these operations, the substrate on which the unnecessary portion was removed and the spacer pattern was formed was heated and cured in an oven at 230 ° C. for 30 minutes to obtain cylindrical spacer patterns having a height of 4 μm and different sizes.

<3> Evaluation The following evaluation was performed on the spacer pattern obtained in the above <2>, and the results are shown in Table 2.

(1) Evaluation of adhesion The obtained cylindrical spacer pattern was observed with an optical microscope, and the adhesion was evaluated according to the following criteria.
A pattern with a bottom diameter of less than 50 μm ² was obtained: ○
A pattern having a bottom diameter of less than 50 μm ² could not be obtained: ×

(2) Evaluation of alkali resistance The obtained substrate with a columnar spacer pattern was immersed in a 2 wt% aqueous sodium hydroxide solution at room temperature for 10 minutes, then washed with water and dried. This substrate was observed with an optical microscope and evaluated as “x” when the spacer pattern was observed to be peeled off, and “◯” when the substrate was not peeled off at all.

(3) Evaluation of recovery rate About the obtained columnar spacer pattern, using the ultra deep color 3D shape measurement microscope "VK-9500" by Keyence Corporation, as shown in FIG. A longitudinal section was profiled. The straight line AA ′ parallel to the substrate surface in the spacer pattern graphic at 90% of the height from the substrate surface of the profiled graphic (schematic diagram shown in FIG. 2) to the point Q at the highest position. The length was measured. Next, the area of a circle having a diameter of AA ′ was defined as the upper cross-sectional area of the spacer pattern.

Among these, the strength of the spacer pattern having an upper cross-sectional area of 80 ± 10 μm ² was evaluated by a load-unloading test using a Shimadzu dynamic ultra-micro hardness meter DUH-W201S. The test condition was that the load was applied to the spacer at a constant speed (0.22 gf / sec) with a flat indenter with a diameter of 50 μm at a measurement temperature of 23 ° C., and held for 5 seconds when the load reached 5 gf. Unloaded at From the load-displacement curve obtained from this test (shown schematically in FIG. 3),
Maximum displacement H [max]
Final displacement H [Last]
0.25μm displacement load N
Recovery rate (%) = H [last] / (pattern height before test) × 100
Elastic recovery rate (%) = (H [max] −H [last]) / H [max] × 100
The bottom cross-sectional area was determined.

  From Tables 1 and 2, it can be seen that according to the present invention, a cured product having excellent substrate adhesion and alkali resistance and excellent mechanical properties such as recovery rate and elastic recovery rate is provided.

It is a schematic diagram which shows the position to profile when a spacer pattern is seen from the top. It is a schematic diagram which shows the profile of the longitudinal cross-section of a spacer pattern. It is a schematic diagram which shows the load-displacement curve in the load-unloading test of a spacer.

Explanation of symbols

1 Spacer pattern 2 Center axis of spacer pattern 3 Profile position 4 Profile of spacer pattern longitudinal section 5 Height from substrate surface to highest position 6 Height 90% of height from substrate surface to highest position 7 Circle of upper section Diameter AA '

Claims (5)

(A) an ethylenically unsaturated compound having a secondary hydroxyl group and containing at least one partial structure represented by the following formulas (i) to (iii); and (B) the double bond equivalent is 400 or less. A curable composition for a photospacer containing an ethylenically unsaturated compound , wherein (B) an ethylenically unsaturated compound having a double bond equivalent of 400 or less is obtained from an epoxy group-containing compound. A curable composition for a photospacer.

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and * represents a bond with another site in the ethylenically unsaturated compound (A). ] (B) The curable composition for photospacers of Claim 1 in which the ethylenically unsaturated compound whose double bond equivalent is 400 or less contains a carboxyl group. (A) The ethylenically unsaturated compound having a secondary hydroxyl group contains at least one partial structure represented by the following formulas (iv) and (v), or represented by the following formula (vi). Or the curable composition for photospacers of 2.

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and * represents a bonding position with another site in the ethylenically unsaturated compound (A). Y represents an arbitrary divalent group. ] A photospacer formed from the curable composition according to any one of claims 1 to 3 . A liquid crystal display device comprising the photospacer according to claim 4 .

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