TWI650611B - Photosensitive resin composition for gap control material and gap control material - Google Patents

Abstract

The present invention provides a photosensitive resin composition for a gap control material that has excellent adhesion to a substrate, can form a gap control material with high elastic recovery rate and high resistance strength, and has little development remaining. The photosensitive resin for a gap control material of the present invention The composition system is an adhesive polymer, which has a repeating unit having a cyclic structure in the main chain and a repeating unit having two or more oxyalkylene groups in a branched chain, and includes an acrylic resin. In one embodiment, the photosensitive resin composition for a gap control material of the present invention includes a polyfunctional monomer, a first photopolymerization initiator having a maximum absorption wavelength at a wavelength of 290 nm to 380 nm, and a maximum photopolymerization initiator at a wavelength of 230 nm to 290 nm. A second photopolymerization initiator that absorbs the wavelength.

Description

Photosensitive resin composition for gap control material and gap control material

The present invention relates to a photosensitive resin composition for a gap control material and a gap control material.

In a liquid crystal cell of a liquid crystal display device, a liquid crystal layer is formed between a pair of substrates, and a gap material is arranged in order to fix the interval between the substrates. In recent years, this gap material replaces gap material particles such as glass beads, resin beads, and the like, and a columnar gap material (gap control material) formed by photolithography can be used (for example, Patent Documents 1 and 2) . The gap control material is used for applying a photosensitive resin composition on a substrate, lithography is performed on a predetermined mask, and is then formed by development. The gap control material can be formed at any position, for example, it can be formed on a black matrix to prevent the display characteristics from being deteriorated due to the gap material.

The required characteristics of the gap control material include high elastic recovery to maintain a constant substrate interval, resistance strength, adhesion to the substrate, and the like. In addition, the photosensitive resin composition for a gap control material is required to have less development residue. These characteristics are required to have a higher level in improving the quality of the liquid crystal display device. Furthermore, in the case of a thin columnar shape, it is required to sufficiently satisfy the above-mentioned characteristics of the gap control material.

Patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2009-53663

Patent Document 2: Japanese Patent Laid-Open No. 2009-175647

The present invention is intended to solve the above-mentioned problems. An object of the present invention is to form a gap control material that has excellent adhesion to a substrate, high elastic recovery rate, and high resistance strength, and provides a photosensitive material for a gap control material with less development residue. Sexual resin composition.

The photosensitive resin composition for a gap control material of the present invention is an adhesive polymer, which has a repeating unit having a cyclic structure in the main chain and a repeating unit having two or more oxyalkylene groups in a branched chain, including acrylic acid. Department of resin.

In one embodiment, the photosensitive resin composition for a gap control material of the present invention includes a polyfunctional monomer, a first photopolymerization initiator having a maximum absorption wavelength at a wavelength of 290 nm to 380 nm, and a maximum photopolymerization initiator at a wavelength of 230 nm to 290 nm. A second photopolymerization initiator that absorbs the wavelength.

In one embodiment, the repeating unit having a ring structure on the main chain is selected from at least one of the general formulae (1) to (7) representing repeating units.

[Chemical 1]

In the general formulae (4) to (7), R ¹ , R ² , R ³ , R ⁴ , R ^5, and R ⁶ are each independently a hydrogen atom or a linear or branched carbon having 1 to 30 carbon atoms. alkyl.

In a preferred embodiment, the branched chain has a repeating unit having two or more oxyalkylene groups, and is a repeating unit represented by general formula (10).

In the general formula (10), R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkyl group having 1 to 20 carbon atoms and 2 to 20 carbon atoms. A linear or branched alkenyl group or an aromatic hydrocarbon group having 6 to 20 carbon atoms, where AO is an alkylene oxide group having 2 to 20 carbon atoms, x is an integer of 0 to 2, y is 0 or 1, and n is 2 or more.

In one embodiment, the acrylic resin further has a repeating unit having an acid group in a branched chain.

In one embodiment, the acrylic resin further has a repeating unit having a carbon double bond in a branched chain.

In another aspect of the present invention, an adhesive polymer for a gap control material is provided. This binder polymer for a gap control material is an acrylic resin, which has a repeating unit having a cyclic structure in the main chain and a repeating unit having two or more oxyalkylene groups in a branched chain.

In one embodiment, the branched repeating unit having two or more oxyalkylene groups is a repeating unit represented by general formula (10).

In other cases of the present invention, a gap control material is further provided. The gap control material is formed of the photosensitive resin composition for a gap control material.

In other cases of the present invention, a liquid crystal display is further provided. The liquid crystal display includes the gap control material described above.

The specific acrylic resin in the present invention can form a gap control material that has excellent substrate adhesion, high elastic recovery rate, and high resistance strength, and provides a photosensitive resin composition for a gap control material that has less development. Residual.

In addition, since the photosensitive resin composition for a gap control material in the present invention has two or more types of photopolymerization initiators having greatly different absorption wavelengths, the gap control material can be formed in a non-inverse tapered shape. The non-inverse tapered gap control material formed by the photosensitive resin composition for a gap control material significantly improves substrate adhesion, elastic recovery rate, and resistance strength. In addition, the room The gap control material can prevent air bubbles from being mixed into the liquid crystal layer, thereby improving the display performance of the display device.

10, 20‧‧‧ Gap control material

H1, H2 ‧‧‧ horizontal section

L, 1 / 2L, 1 / 4L‧‧‧height

1A and 1B are schematic cross-sectional views of a gap control material formed of a photosensitive resin composition according to the present invention.

Fig. 2 is a schematic cross-sectional view showing a gap control material having an inverse taper shape.

A. Photosensitive resin composition for gap control material

The photosensitive resin composition for a gap control material of the present invention is an adhesive polymer, which has a repeating unit (A) having a cyclic structure in the main chain and a repeating unit having two or more oxyalkylene groups in a branched chain. (B) including acrylic resin. This adhesive polymer can be used for various hardened materials with high resistance strength requirements. When this adhesive polymer is used as a gap control material, it can be a gap control material with a high elastic modulus. In practice, the photosensitive resin composition for a gap control material of the present invention may further include a polyfunctional monomer, a photopolymerization initiator, a solvent, and an additive.

A-1. Adhesive polymers

An acrylic resin (binder polymer) having a repeating unit (A) having a cyclic structure in the main chain and a repeating unit (B) having two or more oxyalkylene groups in a branched chain can be included in the main A monomer composition in which a monomer (a) having a cyclic structure on the chain and a monomer (b) having two or more oxyalkylene groups on a branched chain are combined. The monomer composition is composed of a monomer (c) composed of a repeating unit (C) having an acid group in a branched chain and / or a monomer (c) containing another repeating unit (E). And other monomers (e).

Repeating unit (A) with a cyclic structure in the main chain, such as maleimide structure, N-substituted maleimide structure, lactone ring structure, glutaric anhydride structure, anhydrous maleic anhydride structure, etc. Repeating unit. A maleimide structure or an N-substituted maleimide structure is preferred. An acrylic resin having a repeating unit having a maleimide structure or an N-substituted maleimide structure in the main chain can obtain a photosensitive resin composition for a gap control material having higher solubility than a developer Thing. Specifically, the repeating unit (A) having a ring structure on the main chain is preferably selected from at least one of the general formulae (1) to (3) representing the repeating unit, and the general formula (1) is particularly preferable. The indicated repeating unit. When an acrylic resin having a repeating unit represented by the general formula (1) is used, a hardening resin composition capable of forming a hardened product having higher resistance strength can be obtained, and it is particularly preferable to obtain a gap having higher resistance strength. A photosensitive resin composition for a gap control material for a control material.

The repeating unit (A) having a ring structure in the main chain may be selected from at least one of the general formulae (4) to (7) representing the repeating unit. Particularly preferred is a repeating unit represented by the general formula (4) or (7).

In the general formulae (4) to (7), R ¹ , R ² , R ³ , R ⁴ , R ^5, and R ⁶ are each independently a hydrogen atom or a linear or branched carbon having 1 to 30 carbon atoms. The alkyl group is preferably a linear or branched alkyl group having a hydrogen atom or a carbon number of 1 to 10, and more preferably a linear or branched alkyl group having a carbon atom of 1 to 5 or more This is more preferably methyl.

The repeating unit (A) having a cyclic structure in the main chain is composed of a monomer (a) having a cyclic structure in the main chain. Monomer (a) having a cyclic structure in the main chain, for example, maleimide, benzylmaleimide, phenylmaleimide, naphthylmaleimide, N -O-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-chlorophenylmaleimide , N-m-chlorophenylmaleimide, N-p-chlorophenylmaleimide, N-o-methylphenylmaleimide, N-m-methyl Phenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide Maleimides substituted by aromatics such as maleimide, N-p-methoxyphenylmaleimide; cyclohexylmaleimide, methylmaleimide, ethyl Maleimides substituted with alkyl groups such as propylmaleimide, propylmaleimide, and isopropylmaleimide. Preferred are maleimide, benzylmaleimide, phenylmaleimide, cyclohexylmaleimide, and more preferred are benzylmaleimide and phenylmaleimide. Imide, cyclohexylmaleimide, and particularly preferred is benzylmaleimide. The monomer (a) constituting the repeating unit represented by the general formulae (4) to (7) is, for example, a 1,6-diene represented by the general formulae (8) or (9).

In the general formula (8) or (9), R1, R2, and R3 are as described above.

In the above monomer composition, the content ratio of the monomer (a) constituting the repeating unit (A) having a cyclic structure in the main chain is such that the monomer (a) and the monomer ( b) 5% to 50% of the total weight of the monomer (c) and the monomer (e), more preferably 8% to 30%, and even more preferably 10% to 20%.

The acrylic resin as a binder polymer uses a repeating unit (A) having a cyclic structure in the main chain, and a photosensitive resin composition for a gap control material having higher solubility than a developer can be obtained. If such a photosensitive resin composition for a gap control material is used, a gap control material can be formed without causing a development residue. In addition, if a repeating unit with a ring structure on the main chain is used The acrylic resin of (A) can obtain the photosensitive resin composition for gap control materials which forms the gap control material which has a better substrate adhesion.

The repeating unit (B) having two or more oxyalkylene groups in the branched chain is, for example, a repeating unit represented by the general formula (10).

In the general formula (10), R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom or a methyl group, and preferably a hydrogen atom. R ¹⁰ is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a hydrogen atom 1, 1-20 carbon linear alkyl group, 2-20 carbon linear alkenyl group or 6-20 carbon aromatic hydrocarbon group, more preferably, 1-10 carbon linear group Alkyl group or aromatic hydrocarbon group having 6 to 12 carbon atoms, particularly preferably a linear alkyl group, phenyl group, or biphenyl group having 1 to 5 carbon numbers, particularly preferably methyl group, phenyl group, or biphenyl group base. The alkyl group, alkenyl group, and aromatic hydrocarbon group may have a substituent. Among them, AO is used to represent an oxyalkylene group. The carbon number of the oxyalkylene group represented by AO is 2-20, preferably 2-10, more preferably 2-5, and even more preferably 2. The repeating unit (B) may include one or more oxyalkylene groups. Among them, x represents an integer from 0 to 2, and y represents 0 or 1. n represents an average additional mole number of the oxyalkylene group, which is 2 or more, preferably 2 to 200, more preferably 2 to 50, and even more preferably 2 to 15.

The repeating unit (B) having two or more oxyalkylene groups in the branch is composed of a monomer (b) having two or more oxyalkylene groups in the branch. monomer (b) For example, the monomer represented by general formula (11).

In the general formula (11), R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , AO, x, y, and n are as described above.

Specific examples of the monomer represented by the general formula (11) are ethoxylated o-phenylphenol (meth) acrylate (EO2 Mol), phenoxydiethylene glycol (meth) acrylate, benzene Methoxy polyethylene glycol (meth) acrylate (EO4 mole), methoxy polyethylene glycol (meth) acrylate (EO9 mole), methoxy polyethylene glycol (meth) acrylate (EO13 mole), methoxytriethylene glycol (meth) acrylic acid, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, 2-ethyl Hexyl ester, diethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, nonylbenzene Oxypolyethylene glycol (meth) acrylate (EO4-17 mole), nonylphenoxy polyethylene glycol (meth) acrylate (PO5 mole), EO modified cresol (meth) Acrylic (EO2 Mor). In addition, in this specification, "EO2 mole", "PO5 mole", etc. are expressed as the average additional mole number of an oxyalkylene group.

In the above monomer composition, the content ratio of the monomer (b) constituting the repeating unit (B) having two or more oxyalkylene groups in the branch is relative to the monomers (a) and (a) in the monomer composition. 0.5% to 55% of the total weight of the monomer (b), the monomer (c), and the monomer (e), more preferably 1% to 50%, and even more preferably 1% ~ 45%.

The acrylic resin has a repeating unit (B) having two or more oxyalkylene groups in a branched chain, which can increase the crosslinking density, obtain an elastic recovery rate, and a photosensitive resin for a gap control material having a high resistance strength.组合 物。 Composition. When such an acrylic resin and a polyfunctional monomer (preferably a polyfunctional monomer having no oxyalkylene group) described later are combined to form a photosensitive resin composition for a gap control material, the above-mentioned effects are particularly significant.

In a preferred embodiment, the acrylic resin has a repeating unit (C) having an acid group on a branched chain. When the above-mentioned acrylic resin has a repeating unit (C) having an acid group in a branched chain, a photosensitive resin composition for a gap control material which is preferable for alkali development can be obtained. Monomer (c) for constituting repeating unit (C) having an acid group on a branched chain, such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, itaconic acid, ω -Carboxyl-monoacrylate and a monomer having a carboxyl group; a monomer having a carboxylic acid anhydride group such as maleic anhydride, itaconic anhydride. Among these, (meth) acrylic acid is preferred.

In the above monomer composition, the content ratio of the monomer (c) constituting the repeating unit (C) having an acid group in a branched chain is such that the monomer (a) and the monomer (b) in the monomer composition ), The total weight of the monomer (c) and the monomer (e) is 10% to 90%, more preferably 15% to 85%, and even more preferably 20% to 80%.

In a preferred embodiment, the acrylic resin has a repeating unit (D) having a carbon double bond in a branched chain. When the acrylic resin has a repeating unit (D) having a carbon double bond in a branched chain, the sensitivity of the lithography is improved, and the photosensitivity for the gap control material is obtained. Resin composition. Repeating units with carbon double bonds in the branch chain (D) can be obtained by adding a compound having a carbon double bond to a part or all (preferably a part) of the repeating unit (C) having an acid group in a branched chain as a reaction point.

When the acid group of the repeating unit (C) having an acid group in a branch is a carboxyl group, as the compound having a carbon double bond, a compound having an epoxy group and a double bond, an isocyanate group and a double bond can be used Compounds and more. Examples of the compound having an epoxy group and a double bond include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, M-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, and the like. Examples of the compound having an isocyanate group and a double bond include 2-isocyanatoethyl (meth) acrylic acid. When the acid group of the repeating unit (C) having an acid group in a branch is a carboxylic anhydride group, as the compound having a carbon double bond, a compound having a hydroxyl group and a double bond can be used. Examples of the compound having a hydroxyl group and a double bond include 2-hydroxyethyl (meth) acrylate.

The acrylic resin may further have another repeating unit (E) formed by other monomers (e) that can be polymerized together in the monomer (a), the monomer (b), and / or the monomer (c).

Other monomers (e) include, for example, meth (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (Meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (Meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, biphenyl (methyl Acrylate), methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, 2-ethylhexylethylene Alcohol di (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenol hydroxyethyl (meth) acrylate, dicyclopentyl (methyl Acrylate), tricyclodecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecyl ethylene oxide (meth) acrylate, nonylphenoxyglycol (Meth) acrylates such as (meth) acrylate, nonylphenoxy polypropylene glycol, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid Acylmorpholine (morpholinyl (meth) acrylate), (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl ( Methacrylamide, N-isobutyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-tert-octyl (meth) acrylamide, diacetone (meth) acrylamide , N-hydroxymethyl (meth) acrylamide, N-hydroxy (Meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl (methyl (Meth) acrylamide, (meth) acrylamide such as N, N-dimethyl (meth) acrylic acid, aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, butadiene Butadiene such as olefin, isoprene, etc. or alternative butadiene compounds, ethylene such as ethylene, propylene, vinyl chloride, acrylonitrile, or alternative vinyl compounds, vinyl acetate such as vinyl esters. Such monomers may be used singly or in combination of two or more kinds.

In the above monomer composition, the content ratio of the monomer (e) of the other repeating unit (E) is such that the monomer (a) and the monomer in the monomer composition are (b) The total weight of the monomer (c) and the monomer (e) is preferably 0% to 55%, more preferably 5% to 50%, and even more preferably 10% to 45%.

The acrylic resin may be a random copolymer or a segment copolymer.

The weight average molecular weight of the acrylic resin is preferably a value measured by a gel permeation chromatography (GPC) method of a tetrahydrofuran (THF) solvent, and is preferably 3,000 to 200,000, more preferably 4,000 to 100,000, especially More preferably, it is 5,000 ~ 50,000. Within this range, it is possible to obtain a photosensitive resin composition for a gap control material which can ensure heat resistance and have an appropriate viscosity in film forming.

The acid value of the acrylic resin is preferably 20 mg KOH / g to 300 mg KOH / g, more preferably 25 mg KOH / g to 200 mg KOH / g, and even more preferably 30 mg KOH / g to 150 mg KOH / g. In this range, the alkali developing characteristics are better, the development residue is less, and a photosensitive resin composition for a gap control material having a better adhesion to the gap control material can be formed.

The acrylic resin can be obtained by polymerizing a monomer composition including monomers (a) and (b), and monomers (c) and / or (e), which must be corresponding, by any appropriate method. The polymerization method includes, for example, a solution polymerization method.

The monomer composition may contain any appropriate solvent. The solvent may include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diglyme, propylene glycol monomethyl ether, and the like; ketones such as acetone, methyl ethyl ketone, and the like; ethyl acetate, Esters of butyl acetate, propylene glycol methyl ether acetic acid, 3-methoxybutyl acetate, etc .; alcohols of methanol, ethanol, etc .; aromatic hydrocarbons of toluene, xylene, ethylbenzene, etc .; chloroform ; Dimethyl sulfene and so on. This solvent can be used alone They can be used in combination of two or more solvents. The polymerization concentration when polymerizing the above-mentioned monomer composition is preferably 5% to 90% by weight, more preferably 5% to 50%, and even more preferably 10% to 50%.

The monomer composition may include any appropriate polymerization initiator. The polymerization initiator may include, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl isopropyl peroxide Organic peroxides of carbonate, tert-amylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoic acid, etc .; 2,2'-azobis (isobutyronitrile) , 1,1'-azobis (cyclohexane-nitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2 -Azo compounds and the like. The content ratio of the polymerization initiator with respect to 100 parts by weight of all the monomers in the monomer composition is preferably 0.1 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight.

When the acrylic resin is polymerized by a solution polymerization method, the polymerization temperature is preferably 40 ° C to 150 ° C, and more preferably 60 ° C to 130 ° C.

In the case of an acrylic resin having a repeating unit (D) having a carbon double bond in a branched chain, the compound obtained by adding the carbon double bond to the obtained acrylic resin after the above-mentioned polymerization. Any appropriate method can be adopted as the method of the compound having a carbon double bond. For example, in the presence of a polymerization inhibitor and a catalyst, a compound having a carbon double bond and a part or all (preferably a part) of the acid groups of the repeating unit (C) having an acid group in a branched chain react to In addition, a repeating unit (D) having a carbon double bond in a branched chain can be formed.

The additional amount of the compound having the carbon double bond is relative to the acrylic resin (that is, the compound having the carbon double bond before the addition of the 100 parts by weight of an enoic resin) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, particularly preferably 15 parts by weight or more, and particularly preferably 20 parts by weight or more. Within this range, alkali development characteristics are better, and a photosensitive resin composition for a gap control material having excellent development sensitivity can be obtained. If such a photosensitive resin composition for a gap control material is used, it is possible to form a precise hardened film, a better substrate adhesion, an elastic recovery rate, and a gap control material with high resistance strength. In addition, if the additional amount of the compound having a carbon double bond is within the above range, the hydroxyl group of the compound having a carbon double bond is sufficiently generated, and a photosensitive resin composition for a gap control material having good solubility in an alkali developer can be obtained. . The upper limit of the additional amount of the carbon double bond compound is preferably 170 parts by weight or less with respect to 100 parts by weight of the acrylic resin (ie, the acrylic resin before the compound having a carbon double bond) after the polymerization, It is more preferably 150 parts by weight or less, and even more preferably 140 parts by weight or less. When the amount of the compound having a carbon double bond is too large, the storage stability and solubility of the photosensitive resin composition for a gap control material may decrease.

The polymerization inhibitor may be, for example, an alkylphenol compound of 6-tert-butyl-2,4-dimethylphenol and the like. The catalyst may be a tertiary amine such as dimethylbenzylamine, triethylamine, and the like.

A-2. Polyfunctional monomer

The photosensitive resin composition for a gap control material of the present invention further contains a polyfunctional monomer. Polyfunctional monomers include polyfunctional aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, diallyl phenylphosphonic acid, and the like; (di) ethylene glycol di ( Meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, Pentaerythritol tri (a Acrylate), pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (pentaerythritol) ) Acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (pentaerythritol) ) Acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tris (hydroxyethyl) isocyanurate (meth) acrylate Polyfunctional (meth) acrylates such as esters; these monomers include polyfunctional monomers modified with lactone or alkylene oxide. Among these, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and tripentaerythritol octa ( Meth) acrylate and tris (hydroxyethyl) isocyanurate (meth) acrylate. If these polyfunctional monomers are used, a gap control material having a high crosslink density can be obtained due to the large number of functional groups. In the present invention, the adhesive polymer having an oxyalkylene group as described above may be used, and the polyfunctional monomer may have an oxyalkylene group, or may not have. Preferably, a polyfunctional monomer having an oxyalkylene group can be used.

The content ratio of the polyfunctional monomer is preferably 10 parts by weight to 90 parts by weight with respect to 100 parts by weight of the total weight of the adhesive polymer (acrylic resin) and the polyfunctional monomer, and more preferably 30 to 85 parts by weight, and particularly preferably 50 to 85 parts by weight.

A-3. Photopolymerization initiator

The photosensitive resin composition for a gap control material of the present invention may include any Suitable photopolymerization initiator. Photopolymerization initiators include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether and the like and their alkyl ethers; acetophenone, 2,2-dimethoxy-2- Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone; 2-methylanthraquinone, 2-pentylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone Anthraquinones, etc .; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc .; thioxanthone; Ketals such as ketals, benzyl dimethyl ketals, etc .; benzophenones such as benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2- Α-aminoketones of morpholino-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc .; 2-hydroxy Α-hydroxyketones of -1- {4- [4- (2-hydroxy-2-methyl-propanoyl) -benzyl] -phenyl} -2-methyl-propane-1-one; acylphosphines Oxides and thioxanthones. These photopolymerization initiators can be used alone or in a combination of two or more.

The content ratio of the photopolymerization initiator is preferably 0.1 to 50 parts by weight, and more preferably 100 parts by weight relative to 100 parts by weight of the total weight of the adhesive polymer (acrylic resin) and the polyfunctional monomer. 0.5 to 50 parts by weight, particularly preferably 0.5 to 30 parts by weight, particularly preferably 1 to 10 parts by weight, and most preferably 1.5 to 5 parts by weight.

In one embodiment, the photosensitive resin composition for a gap control material of the present invention includes two or more types of photopolymerization initiators having extremely large absorption wavelengths in different wavelength ranges. For example, the photosensitive resin composition for a gap control material of the present invention includes a first photopolymerization initiator having a maximum absorption wavelength at a wavelength of 290 nm to 380 nm, and a second photo polymerization start having a maximum absorption wavelength at a wavelength of 230 nm to 290 nm Agent. Photopolymerization initiators, by using different wavelength ranges Two or more types of photopolymerization initiators with extremely large absorption wavelengths can effectively use ultraviolet light during lithography. As a result, a gap control material having a shape having no substantial diameter difference in the height direction or a shape having a thinner upper portion than a lower portion is formed. The gap control material of this shape has better substrate adhesion, high elastic recovery rate and high resistance strength. In addition, the gap control material can prevent bubbles from being mixed into the liquid crystal layer, and can improve the display performance of the display device. In addition, in this specification, the shape which does not have a substantial diameter gap in a height direction, or the shape whose upper part is thinner than a lower part is called "non-inverse cone shape" as a general term.

The first photopolymerization initiator preferably has a maximum absorption wavelength at a wavelength of 290 nm to 380 nm, more preferably has a maximum absorption wavelength at a wavelength of 295 nm to 350 nm, and particularly preferably has a maximum absorption wavelength at 295 nm to 340 nm. By using this first photopolymerization initiator, it is possible to form a photosensitive resin composition for a gap control material formed of a gap control material having a non-inverse cone shape. In addition, when using a photopolymerization initiator with a maximum absorption wavelength above 380 nm, the thickness control of the gap control material is quite difficult, and a too thick gap control material may be formed. The "maximum absorption wavelength" in the present invention is a wavelength of a maximum absorption having a light absorbance of 0.5 or more measured with a light path length of 1 cm in a photopolymerization initiator solution having a concentration of 0.001% by weight.

The first photopolymerization initiator preferably uses an α-aminoketone compound, and more preferably uses an α-aminoketone compound represented by general formula (12). By using such a compound, a photosensitive resin composition for a gap control material having a non-inverse tapered shape and a narrow diameter gap control material can be formed.

[Chemical 8]

In the general formula (12), X ¹ and X ² are independently independent, and are methyl, ethyl, benzyl or 4-methylbenzyl, preferably methyl. -NX ³ X ⁴ is dimethylamino, morpholino or diethylamino, preferably dimethylamino or diethylamino, and more preferably diethylamino. X ⁵ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a dimethylamino group, or a morpholinyl group. An alkylthio group having 1 to 8 carbon atoms or a morpholinyl group is preferred, an alkylthio group having 1 to 3 carbon atoms or a morpholinyl group is more preferred, and a morpholinyl group is particularly preferred.

Specific examples of the aforementioned α-aminoketone compounds may include 2-dimethylamino-2-methyl-1-phenyl-1-one, 2-diethylamino-2-methyl-1-benzene Methyl-1-one, 2-methyl-2-morpholino-1-phenyl-1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan- 1-keto, 2-dimethylamino-1- (4-ethylphenyl) -2-methyl-propan-1-one, 2-dimethylamino-1- (4-isopropyl-benzene ) -2-methyl-propan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methyl-1-one, 2-dimethylamino-1- (4-methoxyphenyl) -2-methyl-propan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -But-1-one, 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -but-1-one, 2-dimethylamino-2-[( 4-methylphenyl) methyl] -1- [4- (4-Moruforuniru) phenyl] -1-butanone and many more. These compounds can be used individually or in combination of 2 or more types. Of these, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -but-1-one or 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-Moruforuniru) phenyl]- 1-butanone, more preferably 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one. If 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one is used as the first photopolymerization initiator, a non-inverse cone shape and a narrow diameter gap can be formed. Photosensitive resin composition for material gap control material.

As the first photopolymerization initiator, a commercially available product can be used. The first photopolymerization initiator on the market, for example, trade names "IRGACURE 907", "IRGACURE 369", "IRGACURE 379", etc. manufactured by BASF-JAPAN.

The content ratio of the first photopolymerization initiator is preferably 0.1 to 30 parts by weight relative to 100 parts by weight of the total weight of the adhesive polymer (acrylic resin) and the polyfunctional monomer, and more It is preferably 0.5 to 10 parts by weight, and particularly preferably 1.0 to 5 parts by weight.

The second photopolymerization initiator preferably has a maximum absorption wavelength at a wavelength of 230 nm to 290 nm, more preferably a maximum absorption wavelength at a wavelength of 240 nm to 280 nm, and particularly preferably a maximum absorption wavelength at 250 nm to 270 nm.

As the second photopolymerization initiator, an α-hydroxy ketone compound can be preferably used, and an α-hydroxy ketone compound represented by the general formula (13) or the general formula (14) is more preferably used, and particularly preferably The α-hydroxy ketone compound represented by the general formula (14) is used. If this compound is used, it can form non-reverse A photosensitive resin composition for a gap control material having a tapered and narrow gap control material.

In the general formula (13), X ⁶ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or The alkoxy group having 1 to 5 carbon atoms is more preferably a hydrogen atom or an alkoxy group having 1 to 2 carbon atoms. X ⁷ and X ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. In addition, X ⁷ and X ⁸ may also combine a cycloalkyl group having 4 to 8 carbon atoms (preferably 6 to 8 and more preferably 6).

In the general formula (14), X ⁹ -X ¹² are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. In addition, X ⁹ and X ¹⁰ and / or X ¹¹ and X ¹² may be bonded to a cycloalkyl group having 4 to 8 carbon atoms.

The above-mentioned alkyl group, alkoxy group, alkyl group and cycloalkyl group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a halogen atom and the like.

Specific examples of the α-hydroxyketone-based compound include 2-hydroxy-2-methyl-1-phenyl-1-one and 2-hydroxy-2-methyl-1-phenylbutane-1-one , 1- (4-methylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-isopropyl-phenyl) -2-methyl-propan-1-one, 1- (4-butylphenyl) -2-hydroxy-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1- (4-octylphenyl) propan-1-one , 1- (4-dodecylphenyl) -2-methyl-propan-1-one, 1- (4-methoxyphenyl) -2-methylpropane-1-one, 1- ( 4-methylthiophenyl) -2-methyl-propan-1-one, 1- (4-chlorophenyl) -2-hydroxy-2-methyl-propan-1-one, 1- (4- Bromophenyl) -2-hydroxy-2-methyl-propan-1-one, 2-hydroxy-1- (4-hydroxyphenyl) -2-methyl-propan-1-one, 1- (4- (Dimethylaminophenyl) -2-hydroxy-2-methyl-propan-1-one, 1- (4-ethoxycarbonylphenyl) -2-hydroxy-2-methyl-propan-1-one, 1-hydroxycyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propanoyl) -benzyl] phenyl} -2-methyl-propane-1-one and the like. These compounds may be used alone or in combination of two or more. Among these, 1-hydroxycyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-1-one, or 2-hydroxy-1- {4- [ 4- (2-hydroxy-2-methyl-propanoyl) -benzyl] phenyl} -2-methyl-propane-1-one, more preferably 2-hydroxy-1- {4- [4- ( 2-hydroxy-2-methyl-propanoyl) -benzyl] phenyl} -2-methyl-propane-1-one. If the second photopolymerization initiator uses 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1 -Ketone can form a photosensitive resin composition for a gap control material having a non-reverse tapered gap control material with a small diameter.

The second photopolymerization initiator can be a commercially available product. The second photopolymerization initiator on the market, for example, trade names "IRGACURE 184", "IRGACURE 2959", manufactured by BASF-JAPAN, "IRGACURE 127", "DAROCUE 1173", and more.

The content ratio of the second photopolymerization initiator is preferably 0.01 to 30 parts by weight relative to 100 parts by weight of the total weight of the adhesive polymer (acrylic resin) and the polyfunctional monomer. It is preferably 0.05 to 10 parts by weight, and particularly preferably 0.07 to 1 part by weight.

In addition, the content ratio of the second photopolymerization initiator relative to the total weight of the first photopolymerization initiator and the second photopolymerization initiator is preferably 5% to 40%, more preferably It is 5% ~ 30%, especially more preferably 5% ~ 20%. If it is in the range, a photosensitive resin composition for a gap control material with a gap control material having high substrate adhesion, elastic recovery rate, and high resistance strength can be formed.

The total content ratio of the first photopolymerization initiator and the second photopolymerization initiator is preferably 100 parts by weight with respect to the total weight of the binder polymer (acrylic resin) and the polyfunctional monomer. 0.5 to 50 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 1.5 to 5 parts by weight.

The photopolymerization initiator can also be used in combination with a photopolymerization initiator. Multiple photopolymerization initiation aids can also be used. Specific examples of the photopolymerization initiation aid include 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanurate, 1,3,5-tris (3-mercaptopropionyloxy) Ethyl) -isocyanurate, 1,3,5-tris (3-mercaptooxyethyl) -isocyanurate (Karenz MT (registered trademark) NR1 manufactured by Showa Denko Corporation), three 3-functional thiol compounds such as methylolpropane tri (3-mercaptopropionate); pentaerythritol tetra (3-mercaptopropionate), pentaerythritol tetra (3-mercaptobutyrate) (produced by Showa Denko Corporation) Polyfunctional thiol compounds such as karenz MT (registered trademark) PE1) and the like; and 6-functional thiol compounds such as dipentaerythritol hexa (3-propionate).

A-4. Solvent

The photosensitive resin composition for a gap control material of the present invention contains any appropriate solvent. The solvent may include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diglyme, and the like; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cyclohexanone alcohol, and the like Ketones; Ethyl acetate, butyl acetate, propylene glycol methyl ether acetic acid, 3-methoxybutyl acetate, etc. esters; methanol, ethanol, isopropanol, n-butanol, ethylene glycol methyl ether , Propylene glycol methyl ether and the like; aromatic hydrocarbons such as toluene, xylene, ethylbenzene and the like; chloroform, dimethyl sulfene and the like. The amount of the solvent can be set to any appropriate amount in accordance with the viscosity of the photosensitive resin composition for a gap control material as required.

A-5. Additives

The photosensitive resin composition for gap control materials of this invention may contain arbitrary appropriate additives as needed. Additives can include fillers such as aluminum hydroxide, talc, clay, barium sulfate, dyes, pigments, defoamers, coupling agents, leveling agents, sensitizers, release agents, lubricants, plasticizers, antioxidants , UV absorbers, flame retardants, polymerization inhibitors, thickeners, dispersants, organic particles, inorganic fine particles (zinc oxide, silicon oxide, zirconia, titanium), porous particles such as silicon oxide, such as Hollow particles of silicon oxide, etc.

In one embodiment, the photosensitive resin composition for a gap control material according to the present invention includes a UV absorber. Use of a photosensitive resin composition for a gap control material including a UV absorber enables formation of a gap with a small gap between the upper and lower diameters Control material to obtain fine columnar gap control material. The gap control material formed by the photosensitive resin composition for a gap control material according to the present invention is thin and has sufficient resistance strength.

When the photosensitive resin composition for a gap control material of the present invention includes a UV absorber, the content ratio of the UV absorber is 100% by weight based on the total weight of the adhesive polymer (acrylic resin) and the polyfunctional monomer. It is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and particularly preferably 0.2 to 3 parts by weight.

B. Gap Control Material

The gap control material of the present invention can be obtained using the photosensitive resin composition for a gap control material. When the photosensitive resin composition for a gap control material is used, a gap control material having excellent substrate adhesion, high elastic recovery rate, and high resistance strength can be formed. The gap control material of the present invention can be suitable for a liquid crystal display, and more specifically, as a gap material for a liquid crystal cell of a liquid crystal display.

The gap control material can be formed by photoetching. Specifically, the photosensitive resin composition for a gap control material is dried immediately after the substrate is coated, and a photomask is arranged on the obtained coating film to perform lithography to harden the coating film. Thereafter, it is formed by development. Gap control material. The gap control material can be formed at an arbitrary position by photoetching. For example, in a liquid crystal display device, the gap control material is formed only on a black matrix, so that the display characteristics caused by the gap material can be prevented from being lowered.

The method of applying the photosensitive resin composition for a gap control material may be, for example, a method of a spin coater, a bar coater, a gravure coater, a roll coater, a blade coater, a coater, or the like. The drying temperature is preferably 40 ° C to 200 ° C, and more preferably The temperature is 70 ℃ ~ 100 ℃. The drying time is preferably 1 minute to 30 minutes, and more preferably 2 minutes to 10 minutes.

The arrangement position of the photomask can be set at any appropriate position according to the size of the target gap control material. When the photomask is disposed on the coating film, the distance between the coating film and the photomask is preferably 0 μm to 500 μm, more preferably 10 μm to 400 μm, particularly preferably 20 μm to 300 μm, and particularly preferably 30 μm to 200 μm.

The UV irradiation intensity (in terms of 365nm illumination) during the lithography is preferably 10mJ / cm ² to 200mJ / cm ² , more preferably 20mJ / cm ² to 150mJ / cm ² , and even more preferably 30mJ / cm ² ~ 100mJ / cm ² .

In the above development, an alkaline aqueous solution is preferably used. It has a low burden on the environment and enables highly sensitive development. As its basic component, for example, potassium hydroxide, sodium hydroxide, sodium carbonate and the like can be used. The alkaline concentration of the alkaline aqueous solution is preferably 0.01% to 5% by weight, more preferably 0.02% to 3%, and even more preferably 0.03% to 1%. If it is in this range, the photosensitive resin composition for gap control materials can be melt | dissolved suitably, and a gap control material with favorable developability can be formed. A surfactant may be further added to the alkaline aqueous solution.

You can also bake after development. The heating temperature during baking is preferably 150 ° C to 300 ° C, and more preferably 180 ° C to 250 ° C. The heating time is preferably 10 minutes to 90 minutes, and more preferably 20 minutes to 60 minutes. Regarding the photosensitive resin composition for a gap control material of the present invention, an acrylic resin having two or more repeating units (B) of an oxyalkylene group in a branched chain can form a high-crosslinking density after baking Gap control material.

The shape of the gap control material of the present invention may be, for example, a cylindrical shape, an angular column shape, a conical ladder shape, a pyramidal ladder shape, or the like. The thickness of the lowermost part of the gap control material is preferably 3 μm ² to 500 μm ² , and more preferably 15 μm ² to 100 μm ^{2 when} expressed by the horizontal cross-sectional area of the gap control material. The diameter of the lowermost part of the gap control material can be set within any appropriate range. In practice, it is preferably 2 μm to 20 μm, more preferably 3 μm to 10 μm, particularly preferably 5 μm to 8.5 μm, and particularly preferably 5 μm to 8 μm. Within this range, a high-definition gap control material corresponding to a display device can be obtained. This effect is particularly noticeable in the case of a gap control material having a diameter of 5 μm to 8.5 μm (preferably 5 μm to 8 μm) at the lowermost portion. In addition, in this specification, "diameter" means the length of a straight line which passes through the line of 2 points on the circumference of the lowermost part and passes through the center of gravity of the lowermost surface. Therefore, when the gap control material is in the shape of a column or a conical ladder (that is, when the lowermost surface is circular), it indicates the diameter of the lowermost surface. The height of the gap control material can be arbitrarily set to an appropriate height depending on the required substrate interval. The height of the gap control material is, for example, 1 μm to 10 μm.

The gap control material of the present invention preferably has a non-inverse cone shape. 1A and 1B are schematic cross-sectional views showing a non-inverse tapered gap control material formed by the photosensitive resin composition for a gap control material according to the present invention. FIG. 1A shows the gap control material 10 having substantially no diameter difference in the height direction. The 1B series shows the gap control material 20 having an upper portion thinner than a lower portion. As described above, in the present specification, a shape having no substantial diameter gap in the height direction or a shape having a thinner upper portion than a lower portion is referred to as a "non-inverse cone shape". More specifically, the "non-inverse cone shape" means the horizontal cross-sectional area A1 of the portion H1 spaced from the lower portion of the gap control material in the height direction (the height of the gap control material L * 1/2) and the lower portion of the gap control material in the height direction. Distance (gap control material The horizontal cross-sectional area A2 of the portion H2 with the height L * 1/4) is the same or smaller than the horizontal cross-sectional area A2. The non-inverse tapered gap control material can use, for example, a gap including two or more photopolymerization initiators having different absorption wavelengths (for example, the first photopolymerization initiator and the second photopolymerization initiator described above). The control material is formed using a photosensitive resin composition. In addition, the "inverse taper shape" may be the shape shown in the cross-sectional view of Fig. 2, specifically, a portion H1 spaced from the lower portion of the gap control material in the height direction (the height of the gap control material L * 1/2). The case where the horizontal cross-sectional area A1 is larger than the horizontal cross-sectional area A2 of the portion H2 of the lower part of the gap control material in the height direction (the height of the gap control material L * 1/4).

The horizontal cross-sectional area A1 of the portion H1 spaced from the lower part of the gap control material in the height direction (the height of the gap control material L * 1/2) and the lower part of the gap control material in the height direction (the height of the gap control material L * 1/4) The ratio (A2 / A1) of the horizontal cross-sectional area A2 of the part H2 is preferably 1 to 1.3, more preferably 1 to 1.2, particularly preferably 1 to 1.15, and particularly preferably 1 to 1.1. If A2 / A1 is in this range, the formed substrate of the gap control material has better adhesion, and the elastic recovery rate and resistance strength are high. In addition, the gap control material can prevent bubbles from being mixed into the liquid crystal layer, and can improve the display performance of the display device.

In one embodiment, the gap control material of the present invention has a compression ratio of 10% to 90%. The method of evaluating the compression ratio will be described in the following paragraphs.

The lower limit of the elastic recovery rate of the gap control material of the present invention is preferably 55% or more, more preferably 60% or more, particularly preferably 65% or more, more preferably 70% or more, and more preferably 75% or more In particular, it is more than 80%, and particularly preferably more than 90%. The larger the elastic recovery rate is, the better, the upper limit of the elastic recovery rate of the gap control material of the present invention is, for example, 100%. Evaluation of elastic recovery rate The valence method is described in the following paragraphs.

In one embodiment, when the diameter of the lowermost surface of the gap control material is 5 μm to 8.5 μm, the elastic recovery rate of the gap control material of the present invention is preferably 70% to 100%, and more preferably 80%. ~ 95%.

The relationship between the elastic recovery rate b (%) of the gap control material of the present invention and the diameter a (μm) of the lowermost surface of the gap control material, in the range of the diameter a in practice, preferably b> 3.1 a + 45, more preferably b> 3.1a + 50, and even more preferably b> 3.1a + 53.

The lower limit of the resistance strength of the gap control material of the present invention is preferably 20 mN or more, more preferably 50 mN or more, more preferably 100 mN or more, more preferably 110 mN or more, more preferably 120 mN or more, and more preferably It is 130 mN or more, more preferably 145 mN or more, particularly preferably 160 mN or more, particularly preferably 175 mN or more, and most preferably 190 mN or more. The larger the resistance strength is, the better the upper limit value of the resistance strength of the gap control material of the present invention is, for example, 300 mN. The method for evaluating the resistance strength will be described in the following paragraphs.

In one embodiment, when the diameter of the lowermost surface of the gap control material is 5 μm to 8.5 μm, the resistance strength of the gap control material of the present invention is preferably 100 mN to 300 mN, more preferably 145 mN to 300 mN, and more preferably It is 145mN ~ 250mN, more preferably 160mN ~ 250mN, particularly preferably 175mN ~ 210mN, and particularly preferably 175mN ~ 200mN.

Examples

Hereinafter, the present invention will be described more specifically with reference to examples. However, it should be understood that the present invention should not be limited thereto. The evaluation method performed is as follows.

(1) Weight average molecular weight: Mw uses GPC (HLC-8220 GPC; produced by TOSOH Co., Ltd.) to measure the column with THF as the eluent and uses TSKgcl Super HZM-N (manufactured by TOSOH Co., Ltd.). Calculated in polystyrene conversion.

(2) Solid content

Approximately 0.3 g of the copolymer solution prepared in the production example was obtained in an aluminum cup, and approximately 1 g of acetone was added to dissolve the copolymer solution, and then dried naturally at normal temperature. After that, it was dried at 140 ° C for 3 hours using a hot air dryer (trade name: PHH-101; manufactured by ESPEC Co., Ltd.), and then allowed to cool in a dryer to measure the weight. The solid content of the polymer solution (acrylic resin) was calculated from the weight reduction.

(3) Acid value

1.5 g of the copolymer solution prepared in the production example was accurately weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and then titrated with a 0.1 N KOH aqueous solution. The titration was performed using an automatic titration device (trade name: COM-555; manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mg KOH / g) corresponding to 1 g of the polymer was obtained from the solid content concentration.

(4) Remaining imaging

After development, it is visually judged whether the photosensitive resin composition for a gap control material remains.

(5) Tightness of gap control material

The presence or absence of defects in the formed gap control material was visually observed, and evaluated based on the following criteria.

○: No defect and excellent adhesion

△: Defective part and good adhesion

×: All defects and poor adhesion

(6) Compression ratio of gap control material

The compression ratio of the gap control material was measured using a micro compression tester (trade name: HM2000, manufactured by Fischer Instruments). With a 100μm square flat indenter, the load speed and no-load speed are both 4.7mN / s, and the load is loaded to 80mN to unload to 0.49mN, and the load-deformation curve under load and the load under no load- Deformation curve. At this time, the deformation amount of the loaded 80 mL load was L1, and the compression ratio was calculated by the following formula.

Compression ratio (%) = L1 * 100 / clearance material height

(7) Elastic recovery rate of gap control material

The elastic recovery rate of the gap control material was measured using a micro compression tester (trade name: HM2000, manufactured by Fischer Instruments). With a 100μm square flat indenter, the load speed and no-load speed are both 4.7mN / s, and the load is loaded to 80mN to unload to 0.49mN, and the load-deformation curve under load and the load under no load- Deformation curve. At this time, the amount of deformation of the loaded load of 80 mL is L1, and the amount of deformation of the unloaded load of 0.49 mL is L2, and the elastic recovery rate is calculated by the following formula.

Elastic recovery rate (%) = (L1-L2) * 100 / L1

(8) Resistance strength of gap control material

The resistance strength of the gap control material was measured using a micro compression tester (trade name: HM2000, manufactured by Fischer Instruments). With a 100 μm square flat indenter, the load speed and no-load speed are both 4.7 mN / s, the load is loaded to 300 mN, and the gap material is read from the load-deformation curve Loads during destruction.

(9) Thickness (diameter of horizontal section) and height of gap control material

The diameter (diameter) and height of the lowermost surface of the gap control material were measured using a laser microscope (trade name "VK-9700", manufactured by KEYENCE Corporation).

(10) the shape of the gap control material (non-inverse taper shape / inverse taper shape)

The shape of the gap control material is a non-inverse taper shape or an inverse taper shape. FE-SEM (trade name "S-4800", manufactured by Hitachi, Ltd.) is used to determine the distance between the gap control material (L * 1/2 of the gap control material). The diameter (diameter) of the part H1 is D1 and the distance (the height of the gap control material L * 1/4) is the diameter (diameter) of the part H2 is D2. From the diameters D1 and D2, the horizontal cross-sectional area A1 of H1 and H2's horizontal cross-sectional area A2. When A2 / A1 is equal to or more than 1, it is a non-inverse cone shape.

Manufacturing Example 1

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzyl maleimide (BzMI), 44.5 g of acrylic acid (AA), 1 mole of ethoxyphenol phenyl acrylate, and 2 moles of ethoxyphenol. 1: 1 (mole ratio) mixture of phenyl acrylate (trade name "OPPE", produced by Daiichi Kogyo Co., Ltd., hereinafter referred to as OPPE) 40.5 g, t-butylperoxy-2-ethylhexanoic acid (Brand name "PERBUTYL (registered trademark) O, produced by Japan Oil Corporation, hereinafter referred to as PBO) 2 g, 42 g of propylene glycol methyl ether acetate (PGMEA), and 18 g of propylene glycol monomethyl ether (PGME) were put into the monomer Drop into the tank and mix with stirring. In addition, the chain transfer agent is added to the chain transfer agent drop via 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME. Lower into the tank and stir to complete.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in a reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol"), a polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd. ) 0.3 g, 0.5 g of dimethylbenzylamine (DMBA) as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared, and reacted at a temperature of 110 ° C. for 1 hour and at a temperature of 115 ° C. for 8 hours. After cooling to room temperature, a copolymer solution (A-1) containing 39.4% by weight of an acrylic resin was obtained. The weight average molecular weight (Mw) of the acrylic resin was 17,200, and its acid value was 55 mg KOH / g. The solid content concentration, the weight average molecular weight (Mw), and the acid value in the production conditions of the copolymer solution are shown in Table 1 together with Production Examples 2 to 20.

[Table 1]

Manufacturing Example 2

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzylmaleimide (BzMI), 55 g of acrylic acid (AA), 30 g of OPPE, 2 g of PBO, 30 g of propylene glycol methyl ether acetate (PGMEA), and propylene glycol monomethyl 30 g of phenyl ether (PGME) was put into the monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was added to the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 13 g of PGMEA, and 13 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in a reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol"), a polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd. ) 0.3 g, DMBA 0.5 g as a catalyst, PGMEA 11 g, and PGME 11 g were prepared at a temperature of 110 ° C. for 1 hour, and reacted at a temperature of 115 ° C. for 8 hours. After cooling to room temperature, a copolymer solution (A-2) containing 39.3% by weight of an acrylic resin was obtained. The weight average molecular weight (Mw) of the acrylic resin was 18,000, and its acid value was 103 mg KOH / g.

Manufacturing Example 3

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzyl maleimide (BzMI), 42 g of acrylic acid (AA), 4 g of OPPE, 2 g of PBO, 42 g of propylene glycol methyl ether acetate (PGMEA), and propylene glycol monomethyl 18 g of ether (PGME) was put into the monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98g and PGME 42g in the reaction tank, after replacing with nitrogen, the temperature of the reaction tank was increased by heating with an oil bath while stirring. 90 ° C. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in a reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol"), a polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd. ) 0.3 g, 0.5 g of DMBA as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. After that, it was cooled to room temperature to obtain a copolymer solution (A-3) containing 39.0% by weight of an acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 18,200, and its acid value was 44 mgKOH / g.

Manufacturing Example 4

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzyl maleimide (BzMI), 44.5 g of acrylic acid (AA), 40.5 g of OPPE, 2 g of PBO, 42 g of propylene glycol methyl ether acetate (PGMEA), and propylene glycol mono 18 g of methyl ether (PGME) was put into the monomer dropping tank and stirred and mixed. In addition, 1.2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME were charged into the chain transfer agent dropping tank and stirred to complete the chain transfer agent.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank is stabilized at 90 ° C, the monomer composition and Chain transfer agent. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in a reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol"), a polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd. ) 0.3 g, 0.5 g of DMBA as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-4) containing 39.5% by weight of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 25,200, and its acid value was 56 mgKOH / g.

Manufacturing Example 5

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzyl maleimide (BzMI), 44.5 g of acrylic acid (AA), 40.5 g of OPPE, 2 g of PBO, 42 g of propylene glycol methyl ether acetate (PGMEA), and propylene glycol mono 18 g of methyl ether (PGME) was put into the monomer dropping tank and stirred and mixed. In addition, 5 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME were charged into the chain transfer agent dropping tank and stirred to complete the chain transfer agent.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were maintained at a temperature of 90 ° C, respectively. It dripped over a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in a reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol"), a polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd. ) 0.3 g, 0.5 g of DMBA as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-5) containing 38.8 weight% of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 10,400, and its acid value was 55 mgKOH / g.

Manufacturing Example 6

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 10 g of benzylmaleimide (BzMI), 76 g of acrylic acid (AA), 14 g of OPPE, 2 g of PBO, 18 g of propylene glycol methyl ether acetate (PGMEA), and propylene glycol monomethyl 42 g of ether (PGME) was put into the monomer dropping tank and stirred and mixed. In addition, 1.5 g of dodecyl mercaptan (nDM), 8 g of PGMEA, and 18 g of PGME were added to the chain transfer agent dropping tank and stirred to complete the chain transfer agent.

In the preparation of PGMEA 42 g and PGME 98 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. Add PBO 30 minutes after dripping 0.5g. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in the reaction tank, 124 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol"), which is a polymerization inhibitor, were produced by Tokyo Chemical Industry Co., Ltd. ) 0.3 g, 0.7 g of DMBA as a catalyst, 32 g of PGMEA, and 74 g of PGME were prepared at a temperature of 110 ° C. for 1 hour, and reacted at a temperature of 115 ° C. for 12 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-6) containing 39.6% by weight of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 19,300, and its acid value was 54 mgKOH / g.

Manufacturing Example 7

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzyl maleimide (BzMI), 23 g of acrylic acid (AA), 62 g of OPPE, 2 g of PBO, 42 g of propylene glycol methyl ether acetate (PGMEA), and propylene glycol monomethyl 18 g of ether (PGME) was put into the monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, the separable flask was attached with a gas introduction tube and started with oxygen / nitrogen. Foaming of a mixed gas of 5/95 (v / v). Next, in a reaction tank, 30 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol"), which is a polymerization inhibitor, were produced by Tokyo Chemical Industry Co., Ltd. ) 0.3 g, 0.5 g of DMBA as a catalyst was prepared at a temperature of 110 ° C. for 1 hour, and reacted at a temperature of 115 ° C. for 8 hours. After that, it was cooled to room temperature to obtain a copolymer solution (A-7) containing 35.0% by weight of an acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 17,000, and its acid value was 56 mgKOH / g.

Manufacturing Example 8

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of cyclohexylmaleimide (CHMI), 44.5 g of acrylic acid (AA), 40.5 g of OPPE, 2 g of PBO, 42 g of propylene glycol methyl ether acetate (PGMEA), and propylene glycol mono 18 g of methyl ether (PGME) was put into the monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in the reaction tank, methyl propane 69 g of glycidyl enoate (GMA), 0.3 g of 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as polymerization inhibitors, and 0.3 g of catalyst DMBA 0.5g, PGMEA 16g, and PGME 6g were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-8) containing 39.0% by weight of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 17,500, and its acid value was 54 mgKOH / g.

Manufacturing Example 9

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition has 15 g of dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylic acid (MD), 44.5 g of acrylic acid (AA), 40.5 g of OPPE, and PBO. 2 g, 42 g of propylene glycol methyl ether acetate (PGMEA), and 18 g of propylene glycol monomethyl ether (PGME) were put into a monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in a reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2 as a polymerization inhibitor, 0.3 g of 4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of DMBA as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and at 115 ° C The temperature was reacted for 8 hours. After that, it was cooled to room temperature to obtain a copolymer solution (A-9) containing 38.8% by weight of an acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 17,000, and its acid value was 53 mgKOH / g.

Manufacturing Example 10

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of (α-allyloxymethyl) methacrylate (AMA), 44.5 g of acrylic acid (AA), 40.5 g of OPPE, 2 g of PBO, and propylene glycol methyl ether acetate. (PGMEA) 42g and 18g of propylene glycol monomethyl ether (PGME) were put into a monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in the reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor. 0.3 g, 0.5 g of DMBA as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-10) containing 38.9 weight% of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 17,500, and its acid value was 54 mgKOH / g.

Manufacturing Example 11

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzylmaleimide (BzMI), 44.5 g of acrylic acid (AA), 20.5 g of OPPE, and 1 mol of ethoxyphenylphenol acrylate (trade name "A -LEN-10 "; manufactured by Shin Nakamura Chemical Co., Ltd. (hereinafter referred to as A-LEN-10) 20 g, 2 g PBO, 42 g propylene glycol methyl ether acetate (PGMEA), and 18 g propylene glycol monomethyl ether (PGME) The monomer was dropped into the tank and the mixing was completed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in a reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol"), which is a polymerization inhibitor, were produced by Tokyo Chemical Industry Co., Ltd. 0.3g, DMBA 0.5g as catalyst, PGMEA 16g, PGME 6g were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-11) containing 39.1% by weight of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 18,100, and its acid value was 54 mgKOH / g.

Manufacturing Example 12

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzylmaleimide (BzMI), 44.5 g of acrylic acid (AA), 38.5 g of A-LEN-10, and methoxypolyethylene glycol (400) acrylate ( Trade name "LIGHT ACRYLATE 130A", manufactured by Kyoeisha Chemical Co., Ltd., Molar number of ethylene oxide n = 9, hereinafter referred to as 130A) 2g, PBO 2g, propylene glycol methyl ether acetate (PGMEA) 42g and 18 g of propylene glycol monomethyl ether (PGME) was put into the monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in a reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2 as a polymerization inhibitor, 0.3 g of 4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of DMBA as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and at 115 ° C The temperature was reacted for 8 hours. Then, it cooled to room temperature, and obtained the copolymer solution (A-12) containing 39.4 weight% of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 17,500, and its acid value was 55 mgKOH / g.

Manufacturing Example 13

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzylmaleimide (BzMI), 44.5 g of acrylic acid (AA), 38.5 g of A-LEN-10, and methoxypolyethylene glycol (550) acrylate ( Trade name "CD550", manufactured by Pakistan Industrial Corporation, Molar number of ethylene oxide n = 12 ~ 13, hereinafter referred to as CD550) 2g, PBO 2g, propylene glycol methyl ether acetate (PGMEA) 42g and propylene glycol mono 18 g of methyl ether (PGME) was put into the monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/05 (v / v) was started. Next, in the reaction tank, methyl propane 69 g of glycidyl enoate (GMA), 0.3 g of 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as polymerization inhibitors, and 0.3 g of catalyst DMBA 0.5g, PGMEA 16g, and PGME 6g were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-13) containing 39.0% by weight of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 18,000, and its acid value was 53 mgKOH / g.

Manufacturing Example 14

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzyl maleimide (BzMI), 44.5 g of acrylic acid (AA), phenoxydiethylene glycol acrylate (trade name "LIGHT ACRYLATE P2HA", Kyoeisha Chemical 40.5 g (hereinafter referred to as P2HA) manufactured by the company, 2 g of PBO, 42 g of propylene glycol methyl ether acetate (PGMEA), and 18 g of propylene glycol monomethyl ether (PGME) were put into a monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in the reaction tank, methyl propane 69 g of glycidyl enoate (GMA), 0.3 g of 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as polymerization inhibitors, and 0.3 g of catalyst DMBA 0.5g, PGMEA 16g, and PGME 6g were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. Then, it cooled to room temperature, and obtained the copolymer solution (A-14) containing 38.8 weight% of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 18,100, and its acid value was 56 mgKOH / g.

Manufacturing Example 15

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzylmaleimide (BzMI), 44.5 g of acrylic acid (AA), 20.5 g of OPPE, 20 g of 2-phenoxyethyl acrylate (POA), 2 g of PBO, 42 g of propylene glycol methyl ether acetate (PGMEA) and 18 g of propylene glycol monomethyl ether (PGME) were put into a monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in a reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4 as a polymerization inhibitor were used. -0.3 g of dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of DMBA as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and at 115 ° C. The temperature was reacted for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-15) containing 39.5% by weight of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 18,200, and its acid value was 54 mgKOH / g.

Manufacturing Example 16

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzyl maleimide (BzMI), 44.5 g of acrylic acid (AA), 20.5 g of OPPE, 20 g of dicyclopentyl acrylate (DCPA), 2 g of PBO, and propylene glycol methyl ether. 42 g of acetate (PGMEA) and 18 g of propylene glycol monomethyl ether (PGME) were put into the monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in the reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor. 0.3 g, 0.5 g of DMBA as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-16) containing 39.1% by weight of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 17,800, and its acid value was 56 mgKOH / g.

Manufacturing Example 17

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzyl maleimide (BzMI), 44.5 g of acrylic acid (AA), 38.5 g of OPPE, and methoxydipropylene glycol acrylate (trade name "LIGHT ACRYLATE DMP-A" Manufactured by Kyoeisha Chemical Co., Ltd., hereinafter referred to as DMP-A) 2g, PBO 2g, 42g of propylene glycol methyl ether acetate (PGMEA) and 18g of propylene glycol monomethyl ether (PGME) are put into a monomer dropping tank and Stirring is complete. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in the reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor. 0.3g, As catalysts, 0.5 g of DMBA, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-17) containing 39.0% of acrylic resin by weight. The weight average molecular weight (Mw) of the acrylic resin was 17,600, and its acid value was 54 mgKOH / g.

Manufacturing Example 18

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzyl maleimide (BzMI), 44.5 g of acrylic acid (AA), 40.5 g of A-LEN-10, 2 g of PBO, and propylene glycol methyl ether acetate (PGMEA). 42g and 18g of propylene glycol monomethyl ether (PGME) were put into the monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in the reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor Modulation of 0.3g, DMBA 0.5g as catalyst, PGMEA 16g, PGME 6g at 110 The temperature was 1 ° C for 1 hour, and the reaction was performed at 115 ° C for 8 hours. Then, it cooled to room temperature, and obtained the copolymer solution (A-18) containing 39.4 weight% of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin was 17,400, and its acid value was 54 mgKOH / g.

Manufacturing Example 19

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition consists of 15 g of benzylmaleimide (BzMI), 44.5 g of acrylic acid (AA), 40.5 g of DCPA, 2 g of PBO, 42 g of propylene glycol methyl ether acetate (PGMEA), and propylene glycol mono 18 g of methyl ether (PGME) was put into the monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in the reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor. 0.3 g, 0.5 g of DMBA as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. After cooling to room The copolymer solution (A-19) containing 39.6% by weight of the acrylic resin was obtained at a high temperature. The weight average molecular weight (Mw) of the acrylic resin was 18,000, and its acid value was 54 mgKOH / g.

Manufacturing Example 20

Prepare a separable flask with a cooling tube as a reaction tank. On the other hand, the monomer composition was composed of 44.5 g of acrylic acid (AA), 55.5 g of A-LEN-10, and 2 g of PBO. 42 g of propylene glycol methyl ether acetate (PGMEA) and 18 g of propylene glycol monomethyl ether (PGME) were put into a monomer dropping tank and stirred and mixed. In addition, the chain transfer agent was charged into the chain transfer agent dropping tank by stirring 2 g of dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME, and mixing was completed.

In the preparation of PGMEA 98 g and PGME 42 g in the reaction tank, the temperature of the reaction tank was increased to 90 ° C. by heating with an oil bath while stirring with nitrogen. After the temperature of the reaction tank was stabilized at 90 ° C, the monomer composition and the chain transfer agent were dropped. The monomer composition and the chain transfer agent were each kept at a temperature of 90 ° C. and dripped during a period of 180 minutes. 30 minutes after the end of the dripping, 0.5 g of PBO was added. After 30 minutes, the reaction tank was heated to 115 ° C. After maintaining the temperature at 115 ° C for 1.5 hours, a separable flask was attached with a gas introduction tube, and foaming with a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, in the reaction tank, 69 g of glycidyl methacrylate (GMA) and 6-tert-butyl-2,4-dimethylphenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor. 0.3 g, 0.5 g of DMBA as a catalyst, 16 g of PGMEA, and 6 g of PGME were prepared at a temperature of 110 ° C for 1 hour, and reacted at a temperature of 115 ° C for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-20) containing 38.6% by weight of acrylic resin. The weight average molecular weight (Mw) of the acrylic resin is 18,200, Its acid value is 56 mgKOH / g.

Example 1

89 g of the above-mentioned copolymer solution (A-1) (that is, 35 g of acrylic resin), 65 g of tripentaerythritol octaacrylate (trade name "Viscoat # 802", manufactured by Osaka Organic Chemical Co., Ltd.) as a polyfunctional monomer, and as Photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (trade name "IRGACURE (registered trademark) 907", BASF -Made by JAPAN) 1.75 g of the mixture was added with PGMEA having a solid content concentration of 35% by weight, and filtered through a filter having a pore size of 0.5 μm to prepare a photosensitive resin composition for a gap control material.

The above-mentioned photosensitive resin composition for a gap control material was applied on a 10 cm square glass substrate by a spin coater, and dried at 80 ° C. for 3 minutes in an oven. After drying, a photomask was placed at a distance of 100 μm from the coating film to install a UV aligner (trade name “TMEE-150RNS” manufactured by TOPCON Corporation) of a 2.0 kW ultrahigh-pressure mercury lamp. A 50 mJ / cm ² The intensity (in terms of 365 nm) was irradiated with ultraviolet rays. After the ultraviolet irradiation, the 0.05% potassium hydroxide aqueous solution on the smear film was spread by a rotary developing machine for 40 seconds, and the non-lithographic part was dissolved and removed. The remaining lithographic part was washed with pure water for 10 seconds for development. A cylindrical gap control material is formed. The presence or absence of development (evaluation (4)) is confirmed, and the above-mentioned evaluations (5) to (9) of the obtained gap control material are provided. The results are shown in Table 2.

Examples 2 to 26

A composition other than the composition of the photosensitive resin composition for a gap control material as shown in Table 2 was produced in the same manner as in Example 1, and was the same as in Example 1. Example 1 provides the evaluation. The results are shown in Table 2.

In addition, in Table 2, dipentaerythritol hexaacrylate (made by Kyoeisha Chemical Co., Ltd.) is represented by "DPHA", and pentaerythritol tetraacrylate (made by Kyoeisha Chemical Co., Ltd.) is represented by "PETA."

In addition, in Examples 4 to 8, a UV absorber was further added. This UV absorber is shown in Table 2 under the brand name "TINUVIN 479" manufactured by BASF-JAPAN company as "T479" and the trade name "Shiesorb707" manufactured by SHIPRO KASEI KAISHA company as "SB707".

Comparative Examples 1 to 7

A composition other than the composition of the photosensitive resin composition for a gap control material shown in Table 3 was produced in the same manner as in Example 1, and evaluation was also performed in the same manner as in Example 1. The results are shown in Table 3.

[Table 2]

[table 3]

Example 27

89 g of the copolymer solution (A-1) (i.e., 35 g of acrylic resin), 65 g of tripentaerythritol octaacrylate (trade name "Viscoat # 802", manufactured by Osaka Organic Chemical Co., Ltd.) as a polyfunctional monomer, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino group of a photopolymerization initiator (first photopolymerization initiator) having a maximum absorption wavelength at a wavelength of 290 nm to 380 nm- Propanol-1-one (trade name "IRGACURE (registered trademark) 907", manufactured by BASF-JAPAN) 1.75 g, 2-hydroxy-1 as a second photopolymerization initiator having a maximum absorption wavelength at a wavelength of 230 nm to 290 nm -{4- [4- (2-hydroxy-2-methyl-propanoyl) -benzyl] -phenyl} -2-methyl-propane-1-one (trade name "IRGACURE (registered trademark) 127" , Manufactured by BASF-JAPAN Co., Ltd.) 0.25 g, and 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole (trade name "SEESORB707", SHIPRO KASEI KAISHA company) as a UV absorber The manufactured, hereinafter referred to as SB707) 0.5 g of a mixture was added with PGMEA having a solid content concentration of 35% by weight and filtered through a filter having a pore size of 0.5 μm to prepare a photosensitive resin composition for a gap control material .

The above-mentioned photosensitive resin composition for a gap control material was applied on a 10 cm square glass substrate by a spin coater, and dried at 80 ° C. for 3 minutes in an oven. After drying, a photomask was placed at a distance of 100 μm from the coating film to install a UV aligner (trade name “TME-150RNS” manufactured by TOPCON) of a 2.0 kW ultra-high pressure mercury lamp. A 50 mJ / cm ² The intensity (in terms of 365 nm) was irradiated with ultraviolet rays. After the ultraviolet irradiation, the 0.05% potassium hydroxide aqueous solution on the smear film was spread by a rotary developing machine for 40 seconds, and the non-lithographic part was dissolved and removed. The remaining lithographic part was washed with pure water for 10 seconds for development. A gap control material is formed. The presence or absence of development (evaluation (4)) is confirmed, and the above-mentioned evaluations (5) to (10) of the obtained gap control material are provided. The results are shown in Table 4.

Examples 28 to 38

A composition other than the composition of the photosensitive resin composition for a gap control material as shown in Table 4 was produced in the same manner as in Example 27, and evaluation was provided in the same manner as in Example 27. The results are shown in Table 4.

In addition, in Table 4, dipentaerythritol hexaacrylate (made by Kyoeisha Chemical Co., Ltd.) is represented by "DPHA", and pentaerythritol tetraacrylate (made by Kyoeisha Chemical Co., Ltd.) is represented by "PETA."

[Table 4]

It is apparent from Tables 2 to 4 that if a photosensitive resin composition for a gap control material according to the present invention is used, no development residue is generated and a gap control material having excellent adhesion can be formed. This gap controls the material's excellent elastic recovery and resistance strength.

It is apparent from Examples 4 to 8 that if a UV absorber is used The photosensitive resin composition for a gap control material can form a finer gap control material. The gap control material in which the photosensitive resin composition for a gap control material according to the present invention is formed is thin and has sufficient resistance strength.

In addition, it is clear from Table 4 that if a photosensitive resin composition for a gap control material including two types of photopolymerization initiators having different absorption ranges in the maximum wavelength range is used, a gap control material having a non-inverse cone shape can be obtained.

[Industrial availability]

The photosensitive resin composition for a gap control material of the present invention can be suitably used for manufacturing a gap material for a liquid crystal cell.

Claims (12)

A photosensitive resin composition for a gap control material, comprising: an acrylic resin having a repeating unit having a cyclic structure in a main chain; and an acrylic resin having two or more repeating units of an oxyalkylene group in a branched chain for polymerization as an adhesive. The molecular weight of the acrylic resin is 5,000 to 25200 as determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent; a polyfunctional monomer; and a photopolymerization initiator. The photosensitive resin composition for a gap control material according to item 1 of the scope of patent application, wherein the photopolymerization initiator includes: a first photopolymerization initiator having a maximum absorption wavelength at a wavelength of 290 nm to 380 nm; and 230nm-290nm second photopolymerization initiator with a maximum absorption wavelength. The photosensitive resin composition for a gap control material according to item 1 or 2 of the scope of patent application, wherein the repeating unit having a ring structure in the main chain is as shown in the following general formulae (1) to (7) At least one of the repeating units represented: [化 1] Among them, in the general formulae (4) to (7), R ¹ , R ² , R ³ , R ⁴ , R ^5, and R ⁶ are each independently a hydrogen atom or a linear or branched chain having 1 to 30 carbon atoms. Like alkyl. The photosensitive resin composition for a gap control material according to item 1 of the scope of patent application, wherein the repeating unit having two or more oxyalkylene groups in the branched chain is a repeating unit represented by the following general formula (10) : Among them, in the general formula (10), R ⁷ , R ^8, and R ⁹ are each independently a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkyl group having 1 to 20 carbon atoms and a carbon number of 2 ~ 20 linear or branched alkenyl group or aromatic hydrocarbon group having 6 to 20 carbon atoms, in which AO is an alkylene group having 2 to 20 carbon atoms, x is an integer of 0 to 2, and y is 0 or 1, n is 2 or more. The photosensitive resin composition for a gap control material according to item 1 of the patent application range, wherein the acrylic resin further has a repeating unit having an acid group in a branched chain. The photosensitive resin composition for a gap control material according to item 1 of the patent application range, wherein the acrylic resin further has a repeating unit having a carbon double bond in a branched chain. The photosensitive resin composition for a gap control material according to item 6 of the patent application, wherein the acrylic resin further having a repeating unit having a carbon double bond in a branched chain is obtained by adding a carbon double bond The compound is obtained by adding the acrylic resin as described in item 1 of the scope of the patent application, and the carbon double bond compound is added to 100 parts by weight of the acrylic resin before the compound having the carbon double bond is added. The amount is 20 parts by weight to 170 parts by weight. A binder polymer for a gap control material, which has a repeating unit having a cyclic structure in a main chain, a repeating unit having two or more oxyalkylene groups in a branched chain, and a repeating having a carbon double bond in a branched chain. A unit acrylic resin, wherein the molecular weight of the acrylic resin is 5,000 to 25,200 as measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The adhesive polymer for a gap control material according to item 8 of the scope of the patent application, wherein the repeating unit having two or more oxyalkylene groups in the branched chain is a repeating unit represented by the following general formula (10): Among them, in the general formula (10), R ⁷ , R ^8, and R ⁹ are each independently a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkyl group having 1 to 20 carbon atoms and a carbon number of 2 ~ 20 linear or branched alkenyl group or aromatic hydrocarbon group having 6 to 20 carbon atoms, in which AO is an alkylene group having 2 to 20 carbon atoms, x is an integer of 0 to 2, and y is 0 or 1, n is 2 or more. The adhesive polymer for a gap control material according to item 8 of the scope of patent application, wherein the repeating unit having a carbon double bond in a branched chain is a repeating unit derived from a compound having an epoxy group and a double bond, or It is derived from a repeating unit of a compound having an isocyanate group and a double bond. A gap control material is formed by the photosensitive resin composition for a gap control material according to any one of claims 1 to 7 of the scope of patent application. A liquid crystal display includes the gap control material according to item 11 of the scope of patent application.