JP6041571B2 - Photosensitive resin composition for spacer formation, spacer, display device, and method for forming spacer - Google Patents

Description

  The present invention relates to a photosensitive resin composition for forming a spacer, a spacer, a display device, and a method for forming the spacer.

  In display devices such as a liquid crystal display device and an organic EL display device, a spacer for forming a space of a predetermined height between two substrates is used for various purposes. For example, a liquid crystal panel has a structure in which a liquid crystal material is sandwiched between two transparent substrates such as a glass substrate, so that it is necessary to form a spacer between the two substrates so that the liquid crystal material can be filled. is there.

  Conventionally, in order to form a spacer, a method of dispersing bead particles serving as a spacer over the entire surface of a substrate has been adopted. However, with this method, it is difficult to form spacers with high positional accuracy, and beads adhere to the pixel display portion, so that there is a problem that image contrast and display image quality deteriorate. Therefore, in recent years, various methods for forming this spacer with a photosensitive resin composition have been proposed (see Patent Documents 1 and 2, etc.). In this method, a photosensitive resin composition is applied onto a substrate, exposed through a predetermined mask, and then developed to form a dot-like spacer. A predetermined portion other than a pixel display portion Only the spacer can be formed.

JP 2006-184841 A JP 2006-308961 A

  In display devices such as liquid crystal display devices, the number of display pixels increases year by year in order to obtain a high-definition image, and accordingly, the diameter of a spacer formed on a substrate needs to be reduced. However, the conventional photosensitive resin composition used for spacer formation has a problem that it is difficult to form a small-diameter spacer.

  In recent years, it has been desired to reduce the price of various display devices, and cost reduction is strongly desired in various manufacturing processes of display devices.

  From the viewpoint of cost reduction, it is preferable to use a proximity exposure apparatus as the exposure apparatus in the step of forming the spacer using the photosensitive resin composition. This is because the proximity exposure apparatus is inexpensive and can reduce the amount of capital investment. However, when a proximity exposure apparatus is used, an exposure gap is generated between the photomask and the substrate, which makes it difficult to form a small-diameter spacer.

  The present invention has been made in view of such a conventional situation, and even when a spacer is formed using a proximity exposure apparatus as an exposure apparatus, a photosensitive resin for spacer formation that can easily form a small-diameter spacer. It aims at providing the formation method of the spacer using the composition, the spacer formed from the said photosensitive resin composition, the display apparatus provided with the said spacer, and the said photosensitive resin composition.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, by blending a compound having a specific structure with the photosensitive resin composition for spacer formation containing the alkali-soluble resin (A), the photopolymerizable monomer (B), and the photopolymerization initiator (C), The present inventors have found that the problem can be solved and have completed the present invention. Specifically, the present invention provides the following.

（式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又は有機基を示す。ただし、Ｒ^１及びＲ^２の少なくとも一方は有機基を示す。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^３は、単結合又は有機基を示す。Ｒ^４及びＲ^５は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基を示す。Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基を示す。ただし、Ｒ^６及びＲ^７が水酸基となることはない。Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^１０は、水素原子又は有機基を示す。） The first aspect of the present invention is for forming a spacer containing an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a compound represented by the following formula (1). It is a photosensitive resin composition.

(Wherein, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2} are they are attached It may form a cyclic structure and may contain a heteroatom bond, R ³ represents a single bond or an organic group, and R ⁴ and R ⁵ each independently represents a hydrogen atom, a halogen atom, or a hydroxyl group , mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group .R ^6, R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group Shows a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group. However, never R ⁶ and R ⁷ is a hydroxyl group .R ^6, R ⁷ , R ⁸ , and R ⁹ may be bonded to each other to form a cyclic structure, and may include a heteroatom bond, and R ¹⁰ may be a hydrogen atom or an organic group. Show.)

  The 2nd aspect of this invention is the spacer formed from the photosensitive resin composition for spacer formation of a 1st aspect.

  3rd aspect of this invention is a display apparatus provided with the spacer of 2nd aspect.

A fourth aspect of the present invention is a coating process in which the photosensitive resin composition for forming a spacer of the first aspect is coated on a substrate to form a photosensitive resin layer;
An exposure step of exposing the photosensitive resin layer according to a predetermined spacer pattern;
And a developing step of developing the exposed photosensitive resin layer to form a spacer pattern.

  According to the present invention, even when a spacer is formed using a proximity exposure apparatus as an exposure apparatus, the spacer-forming photosensitive resin composition that easily forms a small-diameter spacer is formed from the photosensitive resin composition. A spacer, a display device including the spacer, and a method for forming the spacer using the photosensitive resin composition can be provided.

≪Photosensitive resin composition for spacer formation≫
The photosensitive resin composition for forming a spacer according to the present invention (hereinafter also referred to as “photosensitive resin composition”) includes an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C). And at least a compound represented by the above formula (1). Hereinafter, each component contained in the photosensitive resin composition for forming a spacer according to the present invention will be described.

<Alkali-soluble resin (A)>
The alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a 1 μm-thick resin film is formed on the substrate and placed in a 0.05% by mass KOH aqueous solution for 1 minute. When immersed, it means a film that dissolves 0.01 μm or more in thickness.

  As alkali-soluble resin (A), if it is resin conventionally used for the photosensitive resin composition for spacer formation, it will not restrict | limit, It can select suitably and can be used. As a suitable alkali-soluble resin (A), an unsaturated carboxylic acid (a1) and an alicyclic epoxy group-containing unsaturated compound (a2) are used because it is easy to obtain a spacer having excellent breaking strength and adhesion to a substrate. What contains the copolymer (A1) polymerized at least is mentioned.

  As the unsaturated carboxylic acid (a1), monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; anhydrides of these dicarboxylic acids; Etc. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids (a1) can be used alone or in combination of two or more.

  The alicyclic epoxy group-containing unsaturated compound (a2) is not particularly limited as long as it is an unsaturated compound having an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These alicyclic epoxy group-containing unsaturated compounds (a2) can be used alone or in combination of two or more.

  Specifically, examples of the alicyclic epoxy group-containing unsaturated compound (a2) include compounds represented by the following formulas (a2-1) to (a2-16). Among these, in order to moderate developability, compounds represented by the following formulas (a2-1) to (a2-6) are preferable, and the following formulas (a2-1) to (a2-4) are preferable. The compounds represented are more preferred.

In the above formula, R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ¹³ represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and n represents an integer of 0 to 10. R ¹² is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. Examples of R ¹³ include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

The copolymer (A1) comprises an alicyclic group-containing unsaturated compound (a3) having no epoxy group, together with the unsaturated carboxylic acid (a1) and the alicyclic epoxy group-containing unsaturated compound (a2). It may be polymerized.
The alicyclic group-containing unsaturated compound (a3) is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These alicyclic group-containing unsaturated compounds (a3) can be used alone or in combination of two or more.

  Specifically, examples of the alicyclic group-containing unsaturated compound (a3) include compounds represented by the following formulas (a3-1) to (a3-7). Among these, in order to moderate developability, compounds represented by the following formulas (a3-3) to (a3-8) are preferable, and in the following formulas (a3-3) and (a3-4) The compounds represented are more preferred.

In the above formula, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ²³ represents a hydrogen atom or 1 to 5 carbon atoms. Represents an alkyl group. R ²² is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. R ²³ is preferably, for example, a methyl group or an ethyl group.

In addition, the copolymer (A1) comprises the unsaturated carboxylic acid (a1), the alicyclic epoxy group-containing unsaturated compound (a2), and the alicyclic group-containing unsaturated compound (a3). It may be obtained by polymerizing an epoxy group-containing unsaturated compound (a4) having no cyclic group.
Examples of the epoxy group-containing unsaturated compound (a4) include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate. (Meth) acrylic acid epoxy alkyl esters; α-ethyl glycidyl acrylate, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, etc. And alkylacrylic acid epoxy alkyl esters. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable from the viewpoint of copolymerization reactivity and the strength of the cured resin. These epoxy group-containing unsaturated compounds (a4) can be used alone or in combination of two or more.

  Further, the copolymer (A1) may be obtained by further polymerizing other compounds than the above. Examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used alone or in combination of two or more.

  As (meth) acrylic acid esters, linear or branched chain such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc. Alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; etc. are mentioned.

  (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N -Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  As vinyl ethers, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether , Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl vinyl. Examples include enyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

  Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

The proportion of the structural unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A1) is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.
Moreover, the sum total of the ratio of the structural unit derived from the said alicyclic epoxy group containing unsaturated compound (a2) to the copolymer (A1) and the ratio of the structural unit derived from the said epoxy group containing unsaturated compound (a4) is 71 mass% or more is preferable, 71 to 95 mass% is more preferable, and 75 to 90 mass% is further more preferable. In particular, the proportion of the structural unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) in the copolymer (A1) is preferably 71% by mass or more, and preferably 71 to 80% by mass. Is more preferable. By setting the proportion of the structural unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) within the above range, the temporal stability of the photosensitive resin composition can be further improved.
Moreover, it is preferable that the ratio of the structural unit derived from the said alicyclic group containing unsaturated compound (a3) to a copolymer (A1) is 1-30 mass%, and it is 5-20 mass%. More preferred.

  The weight average molecular weight of the copolymer (A1) (Mw: measured value by styrene conversion of gel permeation chromatography (GPC). Same in this specification) is preferably 2000 to 200000, and preferably 5000 to 30000. It is more preferable. By setting it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

  The copolymer (A1) is obtained by polymerizing a compound other than the unsaturated carboxylic acid (a1), the alicyclic epoxy group-containing unsaturated compound (a2), and the epoxy group-containing unsaturated compound (a4). In this case, the copolymer (A1) can be produced by a known radical polymerization method. That is, it can be produced by dissolving each compound and a known radical polymerization initiator in a polymerization solvent and then stirring with heating.

On the other hand, the copolymer (A1) is obtained by polymerizing a compound other than the unsaturated carboxylic acid (a1), the alicyclic epoxy group-containing unsaturated compound (a2), and the epoxy group-containing unsaturated compound (a4). If not, the ordinary radical polymerization method comprises the carboxyl group of the unsaturated carboxylic acid (a1) and the epoxy group of the alicyclic epoxy group-containing unsaturated compound (a2) or the epoxy group-containing unsaturated compound (a4). It may react and gel.
Therefore, in such a case, first, an unsaturated carboxylic acid and a specific reactive compound are reacted to obtain a reaction mixture (reaction process), and then this reaction mixture and the alicyclic epoxy group-containing unsaturated group are obtained. A copolymer (A1) is manufactured by copolymerizing a compound or an epoxy group-containing unsaturated compound (polymerization step). If necessary, purification and washing may be performed last (purification step).

  First, in the reaction step, an unsaturated carboxylic acid and at least one compound selected from the compounds represented by the following formulas (i) to (iii) (reactive compounds) are placed in a suitable reaction vessel such as a flask. The reaction mixture is obtained by charging and heating and stirring.

（式（ｉ）中、Ｒ^３１及びＲ^３２はそれぞれ独立して炭素数１〜４のアルキル基を示し、Ｒ^３３は酸素原子を含んでいてもよい炭素数１〜４の直鎖状又は分岐鎖状の炭化水素基を示す。）

(In formula (i), R ³¹ and R ³² each independently represent an alkyl group having 1 to 4 carbon atoms, and R ³³ is a linear or branched chain having 1 to 4 carbon atoms which may contain an oxygen atom. Indicates a chain hydrocarbon group.)

（式（ｉｉ）中、Ｒ^３４及びＲ^３５はそれぞれ独立して炭素数１〜４のアルキル基を示す。）

(In formula (ii), R ³⁴ and R ³⁵ each independently represents an alkyl group having 1 to 4 carbon atoms.)

（式（ｉｉｉ）中、Ｒ^３６及びＲ^３７はそれぞれ独立して炭素数１〜４のアルキル基を示し、Ｒ^３８は水素原子又は炭素数１〜４のアルキル基を示す。）

(In formula (iii), R ³⁶ and R ³⁷ each independently represent an alkyl group having 1 to 4 carbon atoms, and R ³⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  Examples of the compound represented by the above formula (i) include 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dipropoxyethane, 1,2-dibutoxyethane, diethoxymethane, dipropoxy Methane, dibutoxymethane, 1,1-dimethoxypropane, 1,1-diethoxypropane, 1,1-dipropoxypropane, 1,1-dibutoxypropane, 2,2-dimethoxypropane, 2,2-diethoxy Examples include propane, 2,2-dipropoxypropane, 2,2-dibutoxypropane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether.

  Examples of the compound represented by the above formula (ii) include 2,5-dimethoxytetrahydrofuran, 2,5-diethoxytetrahydrofuran, 2,5-dipropoxytetrahydrofuran, 2,5-dibutoxytetrahydrofuran and the like.

  Examples of the compound represented by the above formula (iii) include 3,4-dimethoxytoluene, 3,4-diethoxytoluene, 3,4-dipropoxytoluene, 3,4-dibutoxytoluene, 1,2-dimethoxybenzene. 1,2-diethoxybenzene, 1,2-dipropoxybenzene, 1,2-dibutoxybenzene and the like.

  Among these reactive compounds, diethoxymethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, 2,5 in terms of reactivity with unsaturated carboxylic acid. -Dimethoxytetrahydrofuran, 1,1-diethoxypropane, and 2,2-diethoxypropane are preferred. These reactive compounds can be used alone or in combination of two or more.

  The molar ratio of the unsaturated carboxylic acid and the reactive compound is not particularly limited, but is preferably 1: 0.5 to 1: 3, and more preferably 1: 0.8 to 1: 2. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours.

  Next, in the polymerization step, the reaction mixture obtained in the reaction step, the alicyclic epoxy group-containing unsaturated compound and the epoxy group-containing unsaturated compound are dissolved in a polymerization solvent together with a known radical polymerization initiator, and then heated and stirred. As a result, a copolymer is obtained.

  Finally, in the purification step, the residue is removed by washing with, for example, a poor solvent.

  Moreover, as alkali-soluble resin (A), the copolymer which has at least the structural unit derived from the said unsaturated carboxylic acid (a1), and the structural unit which has a superposition | polymerization site | part with the photopolymerizable monomer (B) mentioned later. Polymerization of unit (A2) or structural unit derived from unsaturated carboxylic acid (a1), structural unit derived from epoxy group-containing unsaturated compound (a4), and photopolymerizable monomer (B) described later A resin containing a copolymer (A3) having at least a structural unit having a possible site can also be suitably used. When alkali-soluble resin (A) contains a copolymer (A2) or (A3), the adhesive strength to the board | substrate of the photosensitive resin composition and the fracture strength after hardening of the photosensitive resin composition can be improved. .

  Copolymer (A2) and copolymer (A3) are described as other compounds for copolymer (A1), (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers , Vinyl esters, styrenes and the like may be further copolymerized.

  The structural unit having a site polymerizable with the photopolymerizable monomer (B) preferably has an ethylenically unsaturated group as a polymerizable site with the photopolymerizable monomer (B). For the copolymer (A2), a part of the carboxyl group contained in the homopolymer of the unsaturated carboxylic acid (a1) and the alicyclic epoxy group are used for the copolymerization having such a structural unit. It can be prepared by reacting an unsaturated compound (a2) containing an epoxy group-containing unsaturated compound selected from an alicyclic group-containing unsaturated compound (a3) having no epoxy group. The copolymer (A3) is an epoxy group in a copolymer having a structural unit derived from the unsaturated carboxylic acid (a1) and a structural unit derived from the epoxy group-containing unsaturated compound (a4). It can be prepared by reacting a part with the unsaturated carboxylic acid (a1).

  The mass average molecular weight of the copolymer (A2) and the copolymer (A3) is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

The alkali-soluble resin (A) may contain other conventionally known alkali-soluble resins in addition to the resin selected from the copolymers (A1), (A2), and (A3). However, the proportion of the resin selected from the copolymers (A1), (A2), and (A3) in the alkali-soluble resin (A) is preferably 80% by mass or more, and 90% by mass or more. It is more preferable that the content is 100% by mass.
Moreover, it is preferable that it is 40-85 mass% with respect to solid content of the photosensitive resin composition, and, as for content of alkali-soluble resin (A), it is more preferable that it is 45-75 mass%. By setting it as the above range, there is a tendency that developability is easily balanced.

<Photopolymerizable monomer (B)>
As the photopolymerizable monomer (B) (hereinafter also referred to as “component (B)”) contained in the photosensitive resin composition for forming a spacer according to the present invention, a monomer having an ethylenically unsaturated group is preferably used. be able to. Monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (that is, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-bidoxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

  Among these monomers having an ethylenically unsaturated group, a polyfunctional trifunctional or higher functional group from the viewpoint of increasing the adhesion of the photosensitive resin composition for forming a spacer to the substrate and the breaking strength after curing of the photosensitive resin composition. Monomers are preferred, and polyfunctional monomers having 6 or more functionalities are more preferred.

  The content of the component (B) is preferably 5 to 50% by mass and more preferably 10 to 40% by mass with respect to the solid content of the spacer-forming photosensitive resin composition. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

<Photopolymerization initiator (C)>
It does not specifically limit as a photoinitiator (C) (henceforth "(C) component") contained in the photosensitive resin composition for spacer formation which concerns on this invention, A conventionally well-known photopolymerization start An agent can be used.

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio)- , 2- (O-benzoyloxime)], 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4 -Ethyl dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1 -Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxy Shim, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4- Diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene Peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl Benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloro Acetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butylto Chloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6 -Tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6 -Bis (trichloromethyl) -s-triazine, 2- [2- (furan 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl)- s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-butyl) Lomo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-Bromo-4-methoxy) styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. Among oxime-based photopolymerization initiators, particularly preferred are ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyl). Oxime), and 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)].

  The content of the component (C) is preferably 0.5 to 30% by mass and more preferably 1 to 20% by mass with respect to the solid content of the spacer-forming photosensitive resin composition. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.

  Moreover, you may combine a photoinitiator adjuvant with this (C) component. Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid 2- Ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, pentaerythritol tetra-mercapto acetate, thiol compounds such as 3-mercapto propionate. These photoinitiation assistants can be used alone or in combination of two or more.

<Compound represented by Formula (1)>
The spacer-forming photosensitive resin composition according to the present invention contains a compound represented by the following formula (1). When this compound is contained in the photosensitive resin composition for forming a spacer, even when a spacer is formed using a proximity exposure apparatus as an exposure apparatus, it becomes easy to form a small-diameter spacer. In addition, the compound represented by the formula (1) hardly affects the halftone characteristics and sensitivity of the photosensitive resin composition and the breaking strength of the obtained spacer, and the photosensitive resin composition for forming a spacer according to the present invention is used. The product has the same characteristics as those of the conventional photosensitive resin composition not containing the compound represented by the formula (1).

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of R ¹ and R ² represents an organic group.

Examples of the organic group in R ¹ and R ² include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic. This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.

R ¹ and R ² may be bonded to each other to form a cyclic structure, and may further include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired, and includes a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. It is done. Specific examples include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (—N═C (—R) —, —C (═NR) —: R is A hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.

From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group of R ¹ and R ² includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond ( -N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group. , Cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy Group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, alkyl ether group, alkenyl ether group, alkyl thioether group, alkenyl thioether group, aryl ether group, aryl thioether Group, an amino group _{(-NH 2, -NHR, -NRR '} : R and R' each independently represent a hydrocarbon group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

Substituents other than hydrocarbon groups in the organic groups of R ¹ and R ² include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups. Group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, A phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an alkyl thioether group, an alkenyl thioether group, an aryl ether group, and an aryl thioether group are preferred.

Among the above, as R ¹ and R ² , at least one of them is an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or a heterocycloalkyl group having 2 to 20 carbon atoms bonded to each other. Alternatively, it preferably forms a heteroaryl group. Examples of the heterocycloalkyl group include a piperidino group and a morpholino group, and examples of the heteroaryl group include an imidazolyl group and a pyrazolyl group.

In the above formula (1), R ³ represents a single bond or an organic group.

Examples of the organic group for R ³ include groups in which one hydrogen atom has been removed from an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, aralkyl group, and the like. This organic group may contain a substituent in the organic group. Examples of the substituent include those exemplified for R ¹ and R ² . Further, this organic group may be either linear or branched.

Among these, R ³ is preferably a single bond, or a group in which one hydrogen atom is removed from an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms.

In the above formula (1), R ⁴ and R ⁵ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group. A group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group;

Examples of the organic group for R ⁴ and R ⁵ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

Among these, R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, or 7 carbon atoms. -16 aryloxyalkyl group, C7-20 aralkyl group, C2-C11 alkyl group having a cyano group, C1-C10 alkyl group having a hydroxyl group, C1-C10 alkoxy group , An amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group. ), An aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted with an aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted benzyl group , Amino group is preferably a methylthio group. More preferably, both R ⁴ and R ⁵ are hydrogen atoms, or R ⁴ is a methyl group and R ⁵ is a hydrogen atom.

In the above formula (1), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, A sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group is shown.
Examples of the organic group for R ⁶ , R ⁷ , R ⁸ , and R ⁹ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

In the above formula (1), R ⁶ and R ⁷ do not become a hydroxyl group.

Two or more of R ⁶ , R ⁷ , R ⁸ , and R ⁹ may be bonded to form a cyclic structure, and may include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring. For ^{example, R 6, R 7, R} 8, and ^{R 9} may combine two or more of ^{them, R 6, R 7, R} 8, and share an atom of the benzene ring ^{to which R 9} is attached A condensed ring such as naphthalene, anthracene, phenanthrene, and indene may be formed.

Among these, R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, or a group having 4 to 13 carbon atoms. A cycloalkenyl group, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, carbon C1-C10 alkoxy group, C2-C11 amide group, C1-C10 alkylthio group, C1-C10 acyl group, C2-C11 ester group, C6-C20 Aryl group, electron donating group and / or electron withdrawing group substituted aryl group having 6 to 20 carbon atoms, electron donating group and / or electron withdrawing group substituted benzyl group, cyano group, methylthio group, nitro On the basis Preferably there is.

In addition, as R ⁶ , R ⁷ , R ⁸ , and R ⁹ , two or more of them are bonded to share a benzene ring atom to which R ⁶ , R ⁷ , R ⁸ , and R ⁹ are bonded. In the case where condensed rings such as naphthalene, anthracene, phenanthrene, and indene are formed, it is preferable from the viewpoint that the absorption wavelength becomes longer.

More preferably, all of R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen atoms, or any one of R ⁶ , R ⁷ , R ⁸ , and R ⁹ is a nitro group, and the remaining 3 One is a hydrogen atom.

In the formula ^{(1), R 10} represents a hydrogen atom or an organic group.

Examples of the organic group for R ¹⁰ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

Since the compound represented by the above formula (1) has an —OR ¹⁰ group at the para-position of the benzene ring, the solubility in a solvent is good.

Among these, R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.

  Among the compounds represented by the above formula (1), particularly preferred specific examples include compounds represented by the following formulas.

  The method for synthesizing the compound represented by the above formula (1) is not particularly limited, but it can be synthesized according to the method described in Examples described later.

  The content of the compound represented by the above formula (1) in the photosensitive resin composition for forming a spacer is not particularly limited as long as the object of the present invention is not impaired. The content of the compound represented by the formula (1) is typically 0.01 to 2 with respect to 100 parts by mass of the total amount of the alkali-soluble resin (A) and the photopolymerizable monomer (B). 0.5 mass part is preferable, and 0.01-0.5 mass part is more preferable. When the content of the compound represented by the above formula (1) in the photosensitive resin composition for forming a spacer is within such a range, it is easy to form a spacer having excellent adhesion to the substrate.

<Colorant (D)>
The photosensitive resin composition for forming a spacer according to the present invention may further contain a colorant (D). In particular, when the photosensitive resin composition for forming a spacer contains a light-shielding agent as a colorant, it is suitably used for forming a black spacer. According to the black spacer, it is possible to suppress light leakage from the spacer portion in the display device, and it is possible to manufacture a display device capable of displaying a suitable image with high contrast.

  Although it does not specifically limit as a coloring agent (D) contained in the photosensitive resin composition for spacer formation which concerns on this invention, For example, in a color index (CI; The Society of Dyers and Colorists company publication), It is preferable to use compounds classified as “Pigment”, specifically those having the following color index (CI) numbers.

  Examples of yellow pigments that can be suitably used include C.I. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 , And 185.

  Examples of orange pigments that can be suitably used include C.I. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, and 73.

  Examples of purple pigments that can be suitably used include C.I. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50 Can be mentioned.

  Examples of red pigments that can be suitably used include C.I. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57: 1, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 1 8, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

  Examples of blue pigments that can be suitably used include C.I. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , And 66.

  Examples of pigments of other hues that can be suitably used include C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment Green 37 and other green pigments, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigments such as CI Pigment Brown 28, C.I. I. Pigment black 1, C.I. I. And black pigments such as CI Pigment Black 7.

  Moreover, when using a colorant as a light shielding agent, it is preferable to use a black pigment as the light shielding agent. Black pigments include carbon black, perylene black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides, metal sulfates or metals Various pigments can be mentioned regardless of organic substances and inorganic substances such as carbonates. Among these, it is preferable to use carbon black having high light shielding properties.

  As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

  Moreover, in order to adjust the color tone of carbon black, you may add said organic pigment suitably as an auxiliary pigment.

  In order to uniformly disperse the colorant in the photosensitive resin composition for forming a spacer, a dispersant may be further used. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

  In addition, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, but when used in combination, the organic pigment is used in an amount of 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. Preferably, it is used in the range of 20 to 40 parts by mass.

  The amount of the colorant used in the photosensitive resin composition for forming a spacer can be appropriately selected within the range that does not impair the object of the present invention. Typically, the total solid content of the photosensitive resin composition for forming a spacer is 100 parts by mass. The amount is preferably 5 to 70 parts by mass, and more preferably 25 to 60 parts by mass. By setting the above range, it is easy to form a spacer having a desired shape.

  In particular, when forming a black spacer using the spacer-forming photosensitive resin composition, the spacer-forming photosensitive resin composition has an OD value of 0.5 or more per 1 μm of the black spacer coating. It is preferable to adjust the amount of the light shielding agent. If the OD value per 1 μm of the coating on the black spacer is 0.5 or more, light leakage from the spacer portion of the display device can be easily suppressed and sufficient display contrast can be obtained.

  The colorant is preferably added to the spacer-forming photosensitive resin composition after making it into a dispersion liquid dispersed at an appropriate concentration using a dispersant.

<Light absorber (E)>
The photosensitive resin composition for forming a spacer according to the present invention may contain a light absorber (E) (hereinafter also referred to as “component (E)”) as necessary. The light absorber (E) is not particularly limited, and those that can absorb exposure light can be used, and those that absorb light in the wavelength region of 200 to 450 nm are particularly preferable. Examples thereof include naphthalene compounds, dinaphthalene compounds, anthracene compounds, phenanthroline compounds, and dyes.

  Specifically, α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5- Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, anthracene, 9,10 -Naphthalene derivatives such as dihydroxyanthracene or anthracene or derivatives thereof; azo dyes, benzophenone dyes, amino ketone dyes, quinoline dyes, anthraquinone dyes, diphenyl cyanoacrylate dyes, triazines Fee, dyes such as p- aminobenzoic acid dyes; and the like. Among these, naphthalene derivatives are preferably used, and naphthalene derivatives having a hydroxyl group are particularly preferable. These light absorbers can be used alone or in combination of two or more.

  The content of the component (D) is preferably 0.01 to 10 parts by mass, and 0.05 to 7 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). More preferably, it is 0.1-5 mass parts. By setting it as said range, the ratio of the film thickness change of the resin pattern when changing exposure amount can be enlarged, keeping the fracture strength after hardening favorable.

<Organic solvent (S)>
The spacer-forming photosensitive resin composition according to the present invention preferably contains an organic solvent (S) (hereinafter also referred to as “component (S)”) for improving coating properties and adjusting viscosity.

  Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether, (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Diethylene Other ethers such as recall dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl 2-lactic acid esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-butyrate Other esters such as -propyl, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; toluene, xylene Aromatic hydrocarbons such as N-methylpyrrolidone, N, N-dimethylformamide, amides such as N, N-dimethylacetamide, and the like. Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, alkyl lactate esters, and other esters described above are preferable, alkylene glycol monoalkyl ether acetates described above. Other ethers and other esters described above are more preferred. These solvents can be used alone or in combination of two or more.

  The content of the component (S) is not particularly limited, and is a concentration that can be applied to a substrate or the like and is appropriately set according to the coating film thickness. The viscosity of the photosensitive resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and still more preferably 20 to 30 cp. Moreover, it is preferable that solid content concentration is 5-100 mass%, and it is more preferable that it is 20-50 mass%.

<Other ingredients>
The photosensitive resin composition according to the present invention may contain additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, and an antifoaming agent as necessary. Any additive can be used as the additive. Examples of the surfactant include anionic, cationic, and nonionic compounds, examples of the adhesion improver include conventionally known silane coupling agents, and examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone mono Examples of the antifoaming agent include silicone-based and fluorine-based compounds.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition according to the present invention is prepared by mixing (dispersing and kneading) each of the above components with a stirrer such as a three-roll mill, a ball mill, or a sand mill and, if necessary, filtering with a filter such as a 5 μm membrane filter. can do.

≪Spacer and display device≫
The spacer according to the present invention is the same as the conventional spacer formed using the photosensitive resin composition except that the above-described photosensitive resin composition for forming a spacer is used. The display device according to the present invention is the same as the conventional display device except that the display device includes a spacer formed of the above-described photosensitive resin composition for forming a spacer. Only the method for forming the spacer will be described below.

  The method for forming the spacer using the above-described photosensitive resin composition for forming a spacer is not particularly limited, and can be appropriately selected from conventionally used methods for forming a spacer for a display device. As a suitable spacer forming method, the above-described photosensitive resin composition for forming a spacer is applied on a substrate to form a photosensitive resin layer, and the photosensitive resin layer is formed according to a predetermined spacer pattern. There is a method including an exposure step of exposing and a developing step of developing the exposed photosensitive resin layer to form a spacer pattern.

  First, in the coating process, a contact transfer type coating device such as a roll coater, reverse coater or bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is formed on a substrate on which a spacer is to be formed. The photosensitive resin composition which concerns on this invention is apply | coated using, and a photosensitive resin layer is formed by removing a solvent by drying as needed.

  The spacer in the display device is used to form a space of a predetermined height between two types of substrates arranged opposite to each other, and the photosensitive resin layer is formed on any surface of the two types of substrates. Also good. Specifically, for example, when the display device uses a TFT liquid crystal panel, the photosensitive resin layer may be formed on the TFT substrate or the color filter substrate.

Next, the substrate having the photosensitive resin layer formed on the surface is subjected to an exposure process. In the exposure step, the photosensitive resin layer is irradiated with active energy rays such as ultraviolet rays and excimer laser light through a negative mask, and the photosensitive resin layer is partially exposed according to a predetermined spacer pattern. For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The amount of exposure varies depending on the composition of the photosensitive resin composition, but is preferably about 10 to 600 mJ / cm ² , for example.

  The exposure apparatus used in the exposure step is not particularly limited, and a mirror projection type exposure apparatus, a proximity exposure apparatus, or the like can be used. Specific examples of the mirror projection type exposure apparatus include MPA-7800CF (manufactured by Canon Inc.). According to the mirror projection type exposure apparatus, since there is no exposure gap between the photomask and the substrate, it is easy to form a spacer having a minute diameter. Specific examples of the proximity exposure apparatus include TME-150 RTO (manufactured by Topcon Corporation). Since the proximity exposure apparatus is inexpensive, it can reduce the manufacturing cost of the display device. On the other hand, since an exposure gap is formed between the photomask and the substrate during exposure, the diameter of the spacer tends to increase. However, if the above-described photosensitive resin composition for forming a spacer is used, it is easy to form a small-diameter spacer even when exposure is performed using a proximity exposure apparatus.

  When the substrate is an element formed on a substrate such as a TFT substrate, it is necessary to form a spacer on the element or at a location facing the element on the substrate that is paired with the substrate on which the element is formed. There is. In such a case, it is preferable to perform exposure through a halftone mask because it is necessary to change the height of the spacer between the part where the element is formed and other parts in consideration of the height of the element. By using the above-described photosensitive resin composition for forming a spacer, spacers having different heights can be easily formed by performing exposure through a halftone mask.

  In the development step, the spacer is formed by developing the exposed photosensitive resin layer with a developer. The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Since the photosensitive resin composition according to the present invention exhibits appropriate developability, proper development is possible.

  Then, if necessary, post-baking is performed on the spacer after development, and it is cured by heating. The post-baking temperature is preferably 150 to 250 ° C.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<Examples 1-15, Comparative Examples 1-5>
The components shown in Table 1 below were mixed and dissolved in a solvent so that the solid content was 37% by mass to prepare a photosensitive resin composition. As the solvent, a mixed solvent composed of 10% by mass of propylene glycol monomethyl ether acetate (PM) and 90% by mass of diethylene glycol methyl ether (MEDG) was used.

  In Table 1, each abbreviation indicates the following, and the numerical value in parentheses is the blending amount (part by mass).

(Alkali-soluble resin (A))
A: Methacrylic acid: 2,3-epoxycyclohexan-1-ylmethyl methacrylate: tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate = 12: 71: 17 (mass ratio) Resin (mass average molecular weight 12000)
B: Methacrylic acid: 2,3-epoxycyclohex-1-ylmethyl methacrylate: tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate = 14: 71: 15 (mass ratio) Resin (mass average molecular weight 8000)

(Photopolymerizable monomer (B))
DPHA: Dipentaerythritol hexaacrylate

(Photopolymerization initiator (C))
OXE01: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (“IRGACURE OXE01” manufactured by BASF)
OXE02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) ("IRGACURE OXE02" manufactured by BASF)
C-1: 3-mercaptopropionic acid (photoinitiator aid)

(Additive compound)
In the examples and comparative examples, the compound represented by the formula (1) used in the examples and the compound having a structure similar to the compound represented by the formula (1) used in the comparative examples are referred to as “additive compounds”. Called.
In Examples and Comparative Examples, the following compounds were used as additive compounds. Among the additive compounds, a method for synthesizing MCIMA and MCDEA, which are compounds represented by the formula (1), is described below.

[Synthesis of MCIMA]
3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, and triethylamine 4.59 ml (equivalent ratio 1.1) and imidazole 2.25 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain MCIMA (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis of MCDEA]
3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, triethylamine 4.59 ml (equivalent ratio 1.1), diethylamine 2.41 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain MCDEA (4.65 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

(Light absorber (E))
1,5DON: 1,5-dihydroxynaphthalene

<Evaluation>
[Developability evaluation]
The photosensitive resin composition prepared in each of the above Examples and Comparative Examples was applied on a 6-inch glass substrate (1737 glass manufactured by Dow Corning), then dried at 80 ° C. for 5 minutes, and 3.8 μm. The photosensitive resin layer which has the film thickness of was obtained. Next, using a proximity exposure apparatus (product name: TME-150 RTO (manufactured by Topcon Co., Ltd.)), the photosensitive resin layer is selectively irradiated with ultraviolet rays through a negative mask having a mask size of 9 μm to obtain a concentration as a developer. A dot-like pattern was formed by spray development at 23 ° C. using a 0.05 mass% KOH aqueous solution. And developability was evaluated by measuring time (BP: break point) until an unexposed part is melt | dissolved completely. The results are shown in Table 2 below.

The photosensitive resin composition prepared in each of the above Examples and Comparative Examples was applied on a 6-inch glass substrate (1737 glass manufactured by Dow Corning), then dried at 80 ° C. for 5 minutes, and 3.8 μm. The photosensitive resin layer which has the film thickness of was obtained. Next, using a proximity exposure apparatus (product name: TME-150 RTO (manufactured by Topcon Co., Ltd.)), UV light is selectively irradiated with an exposure amount of 50 mJ / cm ² through a negative mask with a mask size of 9 μm, and a developer. As a result, a dot-like pattern was formed by spray development at 23 ° C. using an aqueous KOH solution having a concentration of 0.05% by mass. Thereafter, post-baking was performed on a hot plate at 100 ° C. for 10 minutes, then at 220 ° C. for 40 minutes, and the diameter of the spacer formed after the post-baking was measured.
Then, the minimum spacer diameter that remained in close contact was evaluated according to the following evaluation criteria. The results are shown in Table 2 below.
○: Spacer diameter is less than 10 μm.
X: Spacer diameter is 10 μm or more.

[Thin dot adhesion evaluation]
A dot-like pattern was formed in the same manner as in the above “development evaluation”. The development time was about 1.5 times the BP with the breakpoint (BP) as a reference. Then, it wash | cleaned with the pure water, and the dot-like pattern was formed by performing a post-baking with respect to the formed pattern at 100 degreeC for 10 minutes, and then at 220 degreeC for 40 minutes.
The developable dot pattern dimensions were examined at an exposure amount of 50 mJ / cm ² to evaluate adhesion. The criteria for determining adhesion are as follows. The results are shown in Table 2 below.
(Double-circle): The minimum mask dimension which was closely_contact | adhered is 5 micrometers or less.
(Circle): The minimum mask dimension which was closely_contact | adhered is 7 micrometers or less.
(Triangle | delta): The minimum mask dimension which was closely_contact | adhered is 10 micrometers or less.
X: The minimum mask dimension which adhered was 15 micrometers or less.

[Evaluation of halftone (HT) characteristics]
The photosensitive resin composition prepared in each of the above Examples and Comparative Examples was applied on a 6-inch glass substrate (manufactured by Dow Corning, 1737 glass), then dried at 100 ° C. for 2 minutes, and 3.8 μm. The photosensitive resin layer which has the film thickness of was obtained. Subsequently, this photosensitive resin layer was exposed with a ghi mixed light source using a proximity exposure apparatus (product name: TME-150 RTO, manufactured by Topcon Corporation). The exposure amount was 10, 20, 30, 40, 50 mJ / cm ² . Next, paddle development was performed at 23 ° C. for 60 seconds using a 0.05% by weight aqueous KOH solution as the developer. Thereafter, post-baking was performed on a hot plate at 100 ° C. for 10 minutes, then at 220 ° C. for 40 minutes, and the film thickness after post-baking was measured.
And the halftone characteristic (HT characteristic) of the photosensitive resin composition was evaluated on the following evaluation criteria. The results are shown in Table 2 below.
○: The difference in film thickness after post-baking is 0.5 μm or more between the exposure amount of 10 mJ / cm ^{2 and} the case of 50 mJ / cm ² .
X: The difference in film thickness after post-baking is less than 0.5 μm between the exposure amount of 10 mJ / cm ^{2 and} the case of 50 mJ / cm ² .

[Evaluation of fracture strength]
A dot-like resin pattern was formed in the same manner as in the above “Evaluation of halftone (HT) characteristics” except that the photosensitive resin layer was exposed at an exposure amount of 50 mJ / cm ² through a 15 μm diameter mask.
Then, pressurization was performed at an additional speed of 14.2 mN / sec, the force required until the pattern was broken was examined, and the breaking strength of the resin pattern was evaluated according to the following evaluation criteria. The results are shown in Table 2 below.
○: The force required to be destroyed is 150 mN or more.
X: The force required to be destroyed is less than 150 mN.

  According to Examples 1-15, the photosensitive resin for spacer formation containing alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and the compound represented by Formula (1). It can be seen that a small-diameter spacer can be easily formed even when a proximity exposure apparatus is used with a conductive resin composition. On the other hand, according to Comparative Examples 1-4, when the photosensitive resin composition for spacer formation does not contain the compound represented by Formula (1), it turns out that it is difficult to form a small diameter spacer. Further, according to Comparative Example 5, even when the photosensitive resin composition for forming a spacer contains a compound having a structure similar to the compound represented by the formula (1), it is still difficult to form a spacer having a small diameter. I understand.

  Furthermore, according to the comparison between Examples 1 to 15 and Comparative Examples 1 to 4, even if the compound represented by the formula (1) is added to the spacer-forming photosensitive resin composition, halftone identification and destruction It turns out that characteristics, such as intensity | strength, are not inferior to these characteristics of the photosensitive resin composition for spacer formation which does not contain the compound represented by Formula (1).

  Moreover, according to Examples 1-11, since content of the compound represented by Formula (1) in the photosensitive resin composition for spacer formation is excellent in the adhesiveness to the board | substrate of a spacer, it is alkali-soluble resin. It turns out that 0.01-2.5 mass parts is preferable with respect to 100 mass parts of total amounts of (A) and a photopolymerizable monomer (B), and 0.01-0.5 mass part is more preferable.

Claims (7)

The photosensitive resin composition for spacer formation containing alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and the compound represented by following formula (1).

(Wherein, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2} are they are attached may form a cyclic structure, optionally .R ³ also contain binding heteroatoms, .R ⁴ and R ⁵ represents a single binding are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto Group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group , Sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, or organic group, provided that R ⁶ and R ⁷ do not become a hydroxyl group R ⁶ and / or R ⁷ Is an organic group, the organic group may be an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a cycloalkyl group that may have a substituent, or a substituent. A cycloalkenyl group which may have, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an aryloxyalkyl group having 7 to 16 carbon atoms, an amide group having 2 to 11 carbon atoms , An alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, and a cyano group , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are those 2 Two or more combined to form a ring May form a granulation may .R ¹⁰ also include binding heteroatom is a hydrogen atom or an organic group.)   Furthermore, the photosensitive resin composition for spacer formation of Claim 1 containing a coloring agent (D).   The spacer formed from the photosensitive resin composition for spacer formation of Claim 1 or 2.   A display device comprising the spacer according to claim 3. Applying the photosensitive resin composition for forming a spacer according to claim 1 or 2 on a substrate to form a photosensitive resin layer; and
An exposure step of exposing the photosensitive resin layer according to a pattern of a predetermined spacer;
A development step of developing the exposed photosensitive resin layer to form a spacer pattern.   The spacer forming method according to claim 5, wherein the exposure in the exposure step is performed by a proximity exposure apparatus.   The spacer forming method according to claim 5, wherein exposure is performed through a halftone mask in the exposure step.