TWI551948B - A photosensitive resin composition for forming a spacer, a spacer, a display device, and a method for forming a spacer - Google Patents

Description

Photosensitive resin composition for spacer formation, spacer, display device, and method for forming spacer

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

In a display device such as a liquid crystal display device or 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, in the liquid crystal panel, since the liquid crystal material is sandwiched by a transparent substrate such as two glass substrates, it is necessary to form a spacer between the two substrates in order to fill the liquid crystal material.

In the past, the formation of a spacer was a method of dispersing ball beads which were spacers on the entire surface of the substrate. However, this method makes it difficult to form spacers with high positional accuracy, and since the pixel display portion also adheres to the beads, there is a problem that the contrast of the portraits or the display image quality is lowered. Therefore, various methods for forming such a spacer by a photosensitive resin composition have been proposed in recent years (refer to Patent Documents 1, 2, etc.). In this method, a photosensitive resin composition is applied onto a substrate, exposed to light through a predetermined mask, and then developed to form a spacer such as a dot, or may be used only in the pixel display portion. The predetermined portion forms a spacer.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2006-184841

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-308961

A display device such as a liquid crystal display device increases the number of pixels in order to obtain a high-definition image, and accordingly, the diameter of the spacer formed on the substrate must be reduced in diameter. However, the photosensitive resin composition used for forming spacers in the past has a problem that it is difficult to form a small-diameter spacer.

Further, in recent years, it has been desired to reduce the price of various display devices, and it is strongly desired to reduce the cost in the complicated manufacturing steps of the display device.

From the viewpoint of cost reduction, in the step of forming a spacer using the photosensitive resin composition, it is preferable to use a proximity exposure device in the exposure apparatus. Because the proximity exposure device is relatively cheap, it can reduce equipment investment. However, when a proximity exposure apparatus is used, an exposure gap is generated between the photomask and the substrate, and in particular, it is difficult to form a spacer having a small diameter.

The present invention has been made in view of the facts of the past, and provides a photosensitive resin for spacer formation which can easily form a spacer having a small diameter even when a spacer is formed using a proximity exposure apparatus in an exposure apparatus. A composition, a spacer formed of the photosensitive resin composition, a display device including the spacer, and a method of forming a spacer using the photosensitive resin composition are intended.

The present inventors have carefully studied in order to solve the above problems. As a result, it has been found that a compound having a specific structure can be prepared by combining a photosensitive resin composition for forming a spacer containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C). The above problems have further completed the present invention. In particular, the present invention provides the following.

The first aspect of the present invention is a photosensitive resin composition for forming a spacer, which comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and the following formula (1) The compound represented.

(Wherein, R ¹ is and R ² each independently represent a hydrogen atom or an organic group. However, R ¹ and R ² is at least one of the .R ¹ represents an organic group and R ² may be bonded to form their ring structure, It may also contain a bond of a hetero atom. R ³ represents a single bond or an organic group. R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a sulfide group, a thiol group, a decyl group, a nitro group, nitroso group, sulfinic acid group, a sulfonic acid group, a sulfonate, a phosphino group, a phosphinyl group, acyl phosphine, phosphonate, or an organic group ^{.R 6, R 7, R 8} , and R ⁹ are each independently Represents hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, mercapto group, decyl group, nitro group, nitroso group, sulfinic acid group, sulfonic acid group, sulfonate group, phosphino group, phosphinyl group, phosphine a mercapto group, a phosphonate group, an amine group, an ammonium group or an organic group. However, R ⁶ and R ⁷ do not form a hydroxyl group. R ⁶ , R ⁷ , R ⁸ and R ^{9 are} bonded to each other to form a ring. The structure may also include a bond of a hetero atom. R ¹⁰ represents a hydrogen atom or an organic group.

A second aspect of the present invention is a spacer formed by forming a spacer resin composition of a first aspect.

A third aspect of the invention is a display device having a second aspect spacer.

A fourth aspect of the present invention provides a method for forming a spacer, comprising: applying a photosensitive resin composition for forming a spacer of a first aspect on a substrate to form a photosensitive resin layer, and applying a predetermined spacer; In the pattern, the exposure step of exposing the photosensitive resin layer, and the exposure of the exposed photosensitive resin layer to form a spacer pattern are developed.

According to the present invention, it is possible to provide a photosensitive resin composition for spacer formation which can easily form a spacer having a small diameter even when a spacer is formed by a proximity exposure apparatus, and the photosensitive resin composition is used. A spacer formed, a display device including the spacer, and a method of forming a spacer using the photosensitive resin composition.

Photosensitive resin composition for forming spacers≫

The photosensitive resin composition for forming a spacer of the present invention (hereinafter also referred to as "photosensitive resin composition") contains at least an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator ( C), and a compound represented by the above formula (1). Hereinafter, each component contained in the photosensitive resin composition for forming a spacer of the present invention will be described in detail.

<alkali soluble resin (A)>

The alkali-soluble resin is a resin film having a film thickness of 1 μm formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and is immersed in a KOH aqueous solution having a concentration of 0.05% by mass. After 1 minute, the film thickness was 0.01 μm or more.

The alkali-soluble resin (A) is not particularly limited as long as it is a resin used for the photosensitive resin composition for forming a spacer, and can be suitably used. The alkali-soluble resin (A) is preferably a material containing at least an unsaturated carboxylic acid (a1) and an alicyclic ring, from the viewpoint of easily obtaining a separator having excellent breaking strength or adhesion to a substrate. The copolymer (A1) in which the oxy unsaturated compound (a2) is polymerized.

The unsaturated carboxylic acid (a1) may, for example, be a monocarboxylic acid such as (meth)acrylic acid or crotonic acid; or a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid. Such anhydrides of dicarboxylic acids and the like. Among these, (meth)acrylic acid and anhydrous maleic acid are also preferable from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, ease of availability, and the like. These unsaturated carboxylic acids (a1) may be used alone or in combination of two or more.

The alicyclic epoxy group-containing unsaturated compound (a2) is as long as it has a fat The cyclic epoxy group-unsaturated compound is not particularly limited. The alicyclic group constituting the alicyclic epoxy group may be a single ring or a polycyclic ring. The monocyclic alicyclic group may, for example, be a cyclopentyl group or a cyclohexyl group. Further, examples of the polycyclic alicyclic group include a thiol group, an isodecyl group, a tricyclic fluorenyl group, a tricyclic fluorenyl group, a tetracyclic decyl group, and the like. These alicyclic epoxy group-containing unsaturated compounds (a2) may be used singly or in combination of two or more.

Specifically, the alicyclic epoxy group-containing unsaturated compound (a2) may, for example, be a compound represented by the following formulas (a2-1) to (a2-16). Among these, in order to obtain suitable imaging properties, compounds represented by the following formulas (a2-1) to (a2-6) are preferred, and the following formulas (a2-1) to (a2-4) are preferred. The compound represented is preferred.

In the above formula, R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ¹³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. R ¹² that extends straight or branched chain alkyl group of, for example, methylene, ethyl stretching, stretch propyl, tetramethylene, ethyl extending ethyl, pentamethylene, hexamethylene preferred. R ^{13 is,} for example, methylene, ethyl, propyl, tetramethylene, ethylethyl, pentamethylene, hexamethylene, phenyl, cyclohexyl, -CH ₂ -Ph- CH ₂ - (Ph represents a phenylene group) is preferred.

The copolymer (A1) may be an unsaturated compound containing the above unsaturated carboxylic acid (a1) and the above alicyclic epoxy group-containing unsaturated compound (a2) together with an alicyclic group-free unsaturated compound having no epoxy group. (a3) Polymerization.

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 a single ring or a polycyclic ring. The monocyclic alicyclic group may, for example, be a cyclopentyl group or a cyclohexyl group. Further, examples of the polycyclic alicyclic group include an adamantyl group, a decyl group, an isodecyl group, a tricyclodecanyl group, a tricyclic fluorenyl group, and a tetracyclic decyl group. These alicyclic group-containing unsaturated compounds (a3) may be used singly 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 obtain suitable imaging properties, compounds represented by the following formulas (a3-3) to (a3-8) are preferred, and the following formulas (a3-3) and (a3-4) are preferred. The compound represented is preferred.

In the above formula, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ²³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ²² extends to line a single bond, a linear or branched alkyl chain of, for example, methylene, ethyl stretching, stretch propyl, tetramethylene, ethyl extending ethyl, pentamethylene, hexamethylene The base is good. R ²³ is preferably, for example, a methyl group or an ethyl group.

Further, the copolymer (A1) is also an unsaturated compound (a2) which can make the above unsaturated carboxylic acid (a1) and the above alicyclic epoxy group-containing unsaturated compound (a3), and the above alicyclic group-containing unsaturated compound (a3) And the polymerization of the epoxy group-containing unsaturated compound (a4) having no alicyclic group.

The epoxy group-containing unsaturated compound (a4) may, for example, be epoxypropyl (meth)acrylate, 2-methylepoxypropyl (meth)acrylate or 3,4-epoxybutyl ( Methyl) acrylate, 6,7-epoxyheptyl (methyl) Epoxyalkyl (meth)acrylates such as acrylate; glycyl propyl α-ethyl acrylate, glycyl propyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α An α-alkyl acrylate alkylene carbonate or the like such as 6,7-epoxyheptyl ethacrylate. Among these, epoxypropyl (meth)acrylate, 2-methylepoxypropyl (meth)acrylate, and 6 are used from the viewpoints of copolymerization reactivity, strength of the resin after curing, and the like. , 7-epoxyheptyl (meth) acrylate is preferred. These epoxy group-containing unsaturated compounds (a4) may be used singly or in combination of two or more.

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

Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, and t-octyl. a linear or branched alkyl (meth) acrylate such as a (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethyl hydroxy propyl (methyl) Acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, decyl (meth) acrylate, and the like.

Examples of the (meth) acrylamide include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dioxane. (meth)acrylamide, N,N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, and the like.

The allyl compound may, for example, be allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, B. Allyl esters such as allyl acetate, allyl lactate, etc.; allyloxyethanol and the like.

Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl vinyl ether. Chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, Alkylethylene such as dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether or tetrahydrofurfuryl vinyl ether Vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl decyl ether, etc. Aryl ether and the like.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, and vinyl hexanoate. , vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetonitrile acetate, Vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl laurate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthate, and the like.

Examples of the styrene include styrene; methyl styrene and dimethyl benzene. Alkene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, mercaptostyrene, benzylstyrene, chlorine Alkyl styrene such as methyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ethoxymethyl methyl styrene; methoxy styrene, 4-methoxy-3-methyl Alkoxystyrenes such as styrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene And halogenated styrene such as iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, and the like.

The proportion of the constituent unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A1) is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

Further, the proportion of the constituent unit derived from the above-mentioned alicyclic epoxy group-containing unsaturated compound (a2) in the copolymer (A1) and the composition derived from the above epoxy group-containing unsaturated compound (a4) The total ratio of the units is preferably 71% by mass or more, 71 to 95% by mass, and more preferably 75 to 90% by mass. In particular, the proportion of the constituent unit derived from the above-mentioned alicyclic epoxy group-containing unsaturated compound (a2) in the copolymer (A1) is preferably 71% by mass or more, and 71 to 80% by mass. It is better. When the ratio of the constituent unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) is within the above range, the temporal stability of the photosensitive resin composition can be further improved.

Further, the proportion of the constituent unit derived from the alicyclic group-containing unsaturated compound (a3) in the copolymer (A1) is preferably from 1 to 30% by mass. 5 to 20% by mass is preferred.

The mass average molecular weight of the copolymer (A1) (Mw: the measured value obtained by gel permeation chromatography (GPC) in terms of styrene. The same applies in the present specification.) It is preferably from 2,000 to 200,000, and from 5,000 to 30,000. It is better. By setting it in the said range, it is easy to acquire the balance of the film formation energy of the photosensitive resin composition, and the imaging property after exposure.

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

On the other hand, the copolymer (A1) is not other than the unsaturated carboxylic acid (a1), the alicyclic epoxy group-containing unsaturated compound (a2), and the epoxy group-containing unsaturated compound (a4). When the compound is polymerized, the carboxyl group of the unsaturated carboxylic acid (a1) and the above-mentioned alicyclic epoxy group-containing unsaturated compound (a2) or the above epoxy group-containing one are not usually used in the radical polymerization method. The epoxy group of the saturated compound (a4) is reacted to cause gelation.

Therefore, in this case, the unsaturated carboxylic acid is first reacted with a specific reactive compound to obtain a reaction mixture (reaction step), and secondly, by reacting the reaction mixture with an alicyclic epoxy group-containing unsaturated compound Or the epoxy group-containing unsaturated compound is subjected to copolymerization (polymerization step) to produce a copolymer (A1). Purified and washed at the end if necessary (Purification step).

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

[7] of the ^{R 31 -OR 33 -OR 32 (i} ) ( formula (i), R ³¹ and R ³² each independently represent an alkyl group having 1 to 4 carbon atoms of, R ³³ represents an oxygen atom may also contain a carbon number of a linear or branched chain hydrocarbon group of 1 to 4.

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

(In the 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.)

The compound represented by the above formula (i) may, for example, be 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dipropoxyethane, 1,2- Dibutoxyethane, diethoxymethane, dipropoxymethane, dibutoxymethane, 1,1-dimethoxypropane, 1,1-diethoxypropane, 1,1-di Propoxypropane, 1,1-dibutoxypropane, 2,2-dimethoxypropane, 2,2-diethoxy Propane, 2,2-dipropoxypropane, 2,2-dibutoxypropane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and the like.

The compound represented by the above formula (ii) may, for example, be 2,5-dimethoxytetrahydrofuran, 2,5-diethoxytetrahydrofuran, 2,5-dipropoxytetrahydrofuran or 2,5-dibutoxy Tetrahydrofuran and the like.

The compound represented by the above formula (iii) may, for example, be 3,4-dimethoxytoluene, 3,4-diethoxytoluene, 3,4-dipropoxytoluene or 3,4-dibutoxy Toluene, 1,2-dimethoxybenzene, 1,2-diethoxybenzene, 1,2-dipropoxybenzene, 1,2-dibutoxybenzene, and the like.

Among these reactive compounds, from the viewpoint of reactivity with an unsaturated carboxylic acid, diethoxymethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, 2,5-dimethoxytetrahydrofuran, 1,1-diethoxypropane, and 2,2-diethoxypropane are good. These reactive compounds may be used singly or in combination of two or more.

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

Next, the polymerization step is such that the reaction mixture obtained in the reaction step and the unsaturated compound containing an alicyclic epoxy group or the unsaturated compound containing an epoxy group are dissolved together with a known radical polymerization initiator in a polymerization solvent. The copolymer was obtained by heating and stirring.

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

In addition, as the alkali-soluble resin (A), a copolymer comprising the above-mentioned constituent unit derived from the unsaturated carboxylic acid (a1) and at least a constituent unit having a polymerization site of the photopolymerizable monomer (B) described later (for example) can be suitably used ( A2) or the constituent unit derived from the unsaturated carboxylic acid (a1), the constituent unit derived from the epoxy group-containing unsaturated compound (a4), and at least the photopolymerizable monomer (B) described later. A resin of a copolymer (A3) which is a constituent unit of a polymerization site. When the alkali-soluble resin (A) contains the copolymer (A2) or (A3), the adhesion of the photosensitive resin composition to the substrate and the breaking strength of the photosensitive resin composition after curing can be improved.

The copolymer (A2) and the copolymer (A3) may be further described as (meth) acrylates, (meth) acrylamides, olefins described as other compounds in the copolymer (A1). A compound obtained by copolymerization of a base compound, a vinyl ether, a vinyl ester, or a styrene.

Among the constituent units having a polymerizable portion capable of reacting with the photopolymerizable monomer (B), it is preferred that the polymerizable portion of the photopolymerizable monomer (B) has an ethylenically unsaturated group. When the copolymer (A2) has a copolymerization unit, the copolymer (A2) may be a part of a carboxyl group contained in the homopolymer of the unsaturated carboxylic acid (a1), and an alicyclic epoxy group selected from the above The ethylenically unsaturated compound (a2) and an epoxy group-containing unsaturated compound having an alicyclic group-containing unsaturated compound (a3) having no epoxy group are reacted and prepared. Further, the copolymer (A3) can be obtained by having the above-mentioned constituent unit derived from the unsaturated carboxylic acid (a1) and the above-mentioned unsaturated compound derived from an epoxy group-containing compound. A part of the epoxy group in the copolymer of the constituent unit (a4) is prepared by reacting with the unsaturated carboxylic acid (a1).

The mass average molecular weight of the copolymer (A2) and the copolymer (A3) is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. When it is set in the said range, it is easy to acquire the balance of the film formation energy of the photosensitive resin composition, and the imaging property after exposure.

Further, the alkali-soluble resin (A) may contain, in addition to the resins of the copolymers (A1), (A2) and (A3), other alkali-soluble resins which have been conventionally known. However, the ratio of the resin selected from the copolymers (A1), (A2) and (A3) in the alkali-soluble resin (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass. % is the best.

Further, the content of the alkali-soluble resin (A) is preferably from 40 to 85% by mass, and preferably from 45 to 75% by mass, based on the solid content of the photosensitive resin composition. By setting it in the said range, it is easy to acquire the imaging balance.

<Photopolymerizable monomer (B)>

The photopolymerizable monomer (B) (hereinafter also referred to as "(B) component") contained in the photosensitive resin composition for spacer formation of the present invention is preferably a monomer having an ethylenically unsaturated group. . The monomer having an ethylenically unsaturated group has a monofunctional monomer and a polyfunctional monomer.

The monofunctional monomer may, for example, be (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) propylene. Guanamine, propoxymethyl (meth) acrylamide, butyl Oxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid , maleic acid, anhydrous maleic acid, itaconic acid, anhydrous itaconic acid, citraconic acid, anhydrous citraconic acid, crotonic acid, 2-propenylamine-2-methylpropane sulfonic acid, tert-butyl Acrylamine sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (methyl Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropane Base (meth) acrylate, 2-(meth) propylene oxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, tetrahydroindenyl (meth) acrylate, Dimethylamino (meth) acrylate, epoxy propyl (meth) acrylate, 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoro A propyl (meth) acrylate, a half (meth) acrylate of a decanoic acid derivative, or the like. These monofunctional monomers may be used singly or in combination of two or more.

On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di( Methyl) acrylate, polypropylene glycol di(meth) acrylate, butane diol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 1,6-hexanediol di(methyl) Acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, season Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2 , 2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane, 2 -hydroxy-3-(methyl)propenyloxypropyl (meth) acrylate, ethylene glycol diepoxypropyl ether di(meth) acrylate, diethylene glycol diepoxy propyl ether (Meth) acrylate, diepoxypropyl phthalate di(meth) acrylate, glycerol triacrylate, glycerol polyepoxypropyl ether poly(meth) acrylate, amine group A Reaction of acid ester (meth) acrylate (ie, methyl phenyl diisocyanate), trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate a polyfunctional monomer such as a condensate of methylene bis(meth) acrylamide, (meth) acrylamide dimethylamine ether, a polyol and N-methylol (meth) acrylamide , or 1,3,5-tripropylene decyl hexahydro-1,3,5-three Triacrylformal and the like. These polyfunctional single systems may be used singly or in combination of two or more.

Among the monomers having an ethylenically unsaturated group, the adhesion of the photosensitive resin composition for forming a spacer to the substrate and the breaking strength of the photosensitive resin composition after curing are more than three or more A functional monomer is preferred, and a polyfunctional monomer having 6 or more functional groups is preferred.

The content of the component (B) is preferably 5 to 50% by mass, and preferably 10 to 40% by mass, based on the solid content of the photosensitive resin composition for spacer formation. By setting it within the above range, it is easy to obtain sensitivity and imaging. The tendency to balance sex and resolution.

<Photopolymerization initiator (C)>

The photopolymerization initiator (C) (hereinafter also referred to as "(C) component)) contained in the photosensitive resin composition for spacer formation of the present invention is not particularly limited, and conventionally known photopolymerization can be used. Starting agent.

The photopolymerization initiator may specifically be, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxyl) 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-diphenylethan-1-one, bis (4 -Dimethylaminophenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- 3-yl], 1-(O-acetamidine), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylindenyl)], 2,4 ,6-trimethylbenzylidenediphenylphosphine oxide, 4-benzylindolyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethylamino Methyl benzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethyl Amino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethylketal, 1-phenyl-1 , 2-propanedione-2-(O-ethoxycarbonyl) fluorene, methyl o-benzyl benzoate, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4 - dimethyl thioxanthone, 1-chloro-4-propoxythene thioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylhydrazine, octamethylguanidine, 1,2-benzophenone Bismuth, 2,3-diphenylanthracene, azobisisobutyronitrile, benzamidine peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2- Mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, 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, dichloroacetophenone, trichloroacetophenone, p- Tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, alpha, alpha-dichloro- 4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2 - Isopropylthioxanthone, dibenzocycloheptenone, pentyl-4-dimethylaminobenzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl) Heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-para (trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl) Vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s -Triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2 -(3,4-dimethoxyphenyl)vinyl]-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(trichloro) Methyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethane 6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styryl Phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, and the like. These photopolymerization initiators may be used singly or in combination of two or more.

Among these, it is particularly preferable to use a lanthanide photopolymerization initiator from the viewpoint of sensitivity. Among the oxime-based photopolymerization initiators, for example, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazol-3-yl, 1-(O-acetamidine), and 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylindenyl).

The content of the component (C) is preferably from 0.5 to 30% by mass, and preferably from 1 to 20% by mass, based on the solid content of the photosensitive resin composition for spacer formation. By setting it in the said range, sufficient heat resistance and chemical-resistance are acquired, and formation of a coating film can be improved, and hardening failure can be suppressed.

Further, a photoinitiator may be combined with the component (C). The photoinitiating aid may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Isoamyl methylamino benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4 , 4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxy Bismuth, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2- Thiol compounds such as mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetradecyl acetate, 3-mercaptopropionate Wait. These photoinitiating aids may be used singly or in combination of two or more.

<Compound represented by formula (1)>

The photosensitive resin composition for forming a spacer of the present invention contains a compound represented by the following formula (1). When the photosensitive resin composition for forming a spacer contains such a compound, even when a spacer is formed by using a proximity exposure apparatus in an exposure apparatus, a spacer having a small diameter can be easily formed. Further, the compound represented by the formula (1) is less likely to adversely affect the halftone characteristics and sensitivity of the photosensitive resin composition or the fracture strength of the obtained spacer, and the photosensitive resin composition for spacer formation of the present invention is These characteristics are inferior to those of the conventional photosensitive resin composition which does not contain 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.

The organic group in R ¹ and R ² may, for example, be an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group. The organic group may further contain a bond or a substituent other than the hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a ring. The organic group is usually monovalent, but when it forms a cyclic structure, it can be an organic group having two or more valences.

R ¹ and R ² may be bonded to each other to form a cyclic structure, and may further contain a bond of a hetero atom. The cyclic structure may, for example, be a heterocycloalkyl group or a heteroaryl group, or may be a condensed ring.

The bonding other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include bonding of hetero atoms including an oxygen atom, a nitrogen atom, and a ruthenium atom. . Specific examples thereof include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, a guanamine bond, a urethane bond, and an imido bond (-N=C(-R)-, - C(=NR)-: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinium bond, an azo bond, or 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 is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, a guanamine bond, or a urethane bond. , an imido bond (-N=C(-R)-, -C(=NR)-: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond good.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, and an isocyano group. , cyanooxy, isocyanooxy, thiocyanooxy, isothiocyanooxy, decyl, decyl, alkoxy, alkoxycarbonyl, aminemethanyl, thiamine, nitro , nitroso, carboxyl, carboxylate, sulfhydryl, decyloxy, sulfinate, sulfonate, sulfonate, phosphino, phosphinyl, phosphonium, phosphonate, hydroxyimido , alkyl ether group, alkenyl ether group, alkyl sulfide group, alkenyl sulfide group, aryl ether group, aryl sulfide group, amine group (-NH ₂ , -NHR, -NRR': R and R' each independently represents a hydrocarbon group) and the like. The hydrogen atom contained in the above substituent may be substituted by a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of a linear chain, a branched chain, and a cyclic group.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is a halogen atom, a hydroxyl group, a thiol group, a sulfide group, a cyano group, an isocyano group, a cyanooxy group, an isocyanato group, a thiocyanoxy group, or a different one. Thiocyanate, sulfhydryl, decyl, alkoxy, alkoxycarbonyl, aminemethanyl, thiamine, nitro, nitroso, carboxyl, carboxylate, sulfhydryl, hydrazine Base, sulfinate, sulfonate, sulfonate, phosphino, phosphinyl, phosphonium, phosphonate, hydroxyimino, alkyl ether, alkenyl ether, alkyl sulfide An alkenyl sulfide group, an aryl ether group or an aryl sulfide group is preferred.

In the above, R ¹ and R ^{2 are} at least one of an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or bonded to each other to form a heterocycloalkyl group having 2 to 20 carbon atoms or Heteroaryl is preferred. Examples of the heterocycloalkyl group include a piperidinyl group and a morpholinyl 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.

The organic group in R ³ may, for example, be a group in which one hydrogen atom is removed from an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group. The organic group may further contain a substituent in the organic group. The substituents are exemplified as in R ¹ and R ² . Further, the organic group may be either a linear chain or a branched chain.

Among the above, 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 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, silicon based, silanol groups, a nitro group, a nitroso group, a sulfinic acid group, a sulfonic acid a base, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate group, or an organic group.

The organic group in R ⁴ and R ⁵ may be exemplified as in R ¹ and R ² . Similarly to the case of R ¹ and R ² , the organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a ring.

In the above, R ⁴ and R ⁵ each independently represent 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, and a carbon number of 7 to 16 An aryloxyalkyl group, 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 and a alkoxy group having 1 to 10 carbon atoms a thiol group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a fluorenyl group having 1 to 10 carbon atoms, and 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 aryl group having 6 to 20 carbon atoms substituted by an electron-donating group and/or an electron-attracting group, a benzyl group or a cyanogen substituted with an electron-donating group and/or an electron-attracting group; The base and methylthio group are preferred. More preferably, both of R ⁴ and R ⁵ are a hydrogen atom, or R ⁴ is a methyl group and R ⁵ is a hydrogen atom.

The above-described formula ^{(1), R 6, R 7, R} 8, and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, silicon based, silanol groups, nitro, nitroso, A sulfinic acid group, a sulfonic acid group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate group, an amine group, an ammonium group, or an organic group.

The organic group in R ⁶ , R ⁷ , R ⁸ and R ⁹ may be exemplified as in R ¹ and R ² . Similarly to the case of R ¹ and R ² , the organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a ring.

Further, in the above formula (1), R ⁶ and R ^{7 are} not 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 also contain a bond of a hetero atom. The cyclic structure may, for example, be a heterocycloalkyl group or a heteroaryl group, or may be a condensed ring. For example, R ⁶ , R ⁷ , R ⁸ , and R ^{9 are} bonded to each other by two or more atoms, and the atoms of the benzene ring bonded by R ⁶ , R ⁷ , R ⁸ and R ⁹ are bonded to form naphthalene, anthracene, phenanthrene, A condensed ring such as hydrazine may also be used.

In the above, 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, and a cycloolefin having 4 to 13 carbon atoms. Base, aryloxyalkyl group having 7 to 16 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkyl group having 2 to 11 carbon atoms having a cyano group, alkyl group having 1 to 10 carbon atoms having a hydroxyl group, carbon Alkoxy groups of 1 to 10, amidino groups having 2 to 11 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, fluorenyl groups having 1 to 10 carbon atoms, ester groups having 2 to 11 carbon atoms, and carbon number 6 An aryl group of ~20, an aryl group having 6 to 20 carbon atoms substituted by an electron-donating group and/or an electron-attracting group, a benzyl group substituted with an electron-donating group and/or an electron-attracting group, a cyano group, and a group Sulfur-based and nitro are preferred.

Further, R ⁶ , R ⁷ , R ⁸ and R ^{9 are} bonded to each other by two or more atoms, and the atoms of the benzene ring bonded to R ⁶ , R ⁷ , R ⁸ and R ⁹ form a naphthalene, an anthracene or a phenanthrene. In the case of a condensed ring such as hydrazine, it is preferred that the absorption wavelength is long-wavelength.

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

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

The organic group in R ¹⁰ can be exemplified as in R ¹ and R ² . Similarly to the case of R ¹ and R ² , the organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a ring.

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

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

Among the compounds represented by the above formula (1), a specific example of the compound represented by the following formula is exemplified.

The method for synthesizing the compound represented by the above formula (1) is not particularly limited, and it can be synthesized in accordance with the method described in the examples below.

The content of the compound represented by the above formula (1) in the photosensitive resin composition for spacer formation is not particularly limited as long as it does not inhibit the object of the present invention. The content of the compound represented by the above formula (1) is preferably 0.01 to 2.5 parts by mass based on 100 parts by mass of the total of the alkali-soluble resin (A) and the photopolymerizable monomer (B). 0.01 to 0.5 parts by mass is preferred. The above-mentioned photosensitive resin composition for spacer formation When the content of the compound represented by the formula (1) is within this range, it is easy to form a spacer excellent in adhesion to the substrate.

<Colorant (D)>

The photosensitive resin composition for forming a spacer of the present invention may further contain a coloring agent (D). In particular, when the photosensitive resin composition for forming a spacer contains a light-shielding agent as a colorant, it can be suitably used for the formation of a black spacer. By the black spacer, light leakage from the spacer portion in the display device can be suppressed, and a display device capable of displaying a high contrast and suitable image can be manufactured.

The coloring agent (D) contained in the photosensitive resin composition for spacer formation of the present invention is not particularly limited, and is, for example, a pigment classified in a color index (CI; issued by The Society of Dyers and Colourists). The compound, specifically, is preferably numbered with the color index (CI) number described below.

Examples of the yellow pigment which can be suitably used include, for example, CI Pigment Yellow 1 (hereinafter, similarly, "CI Pigment Yellow", but 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.

An example of an orange pigment which can be suitably used is, for example, C.I. Pigment Orange 1 (Hereinafter, it is also "CI Pigment Orange", but only the numbers), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61 , 63, 64, 71, and 73.

Examples of the purple pigment which can be suitably used include CI Pigment Violet 1 (hereinafter, similarly, "CI Pigment Violet", but only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50.

Examples of the red pigment which can be suitably used include CI Pigment Red 1 (hereinafter, similarly, "CI Pigment Red", but 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, 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, 178, 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 the blue pigment which can be suitably used include, for example, CI Pigment Blue 1 (hereinafter, similarly, "CI Pigment Blue", but only the number is described), 2, 15, 15:3, 15:4, 15:6 , 16, 22, 60, 64, and 66.

Examples of the pigments of the above other hue which can be suitably used include green pigments such as C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, and the like. Black pigments such as C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment Brown 28, etc., C.I. Pigment Black 1, C.I. Pigment Black 7, etc.

Moreover, when a coloring agent is used as an opacifier, it is preferable to use a black pigment as an opacifier. Examples of the black pigment include metal oxides such as carbon black, black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, composite oxides, metal sulfides, and metal sulfates. Metal carbonates and the like, regardless of various pigments of organic matter and inorganic matter. Among these, carbon black having high light blocking property is also preferred.

As the carbon black, a known carbon black such as channel black, furnace black, hot carbon black, or lamp black can be used, but it is preferable to use a groove black having excellent light shielding properties. Further, carbon black coated with a resin can also be used.

Further, in order to adjust the color tone of carbon black, the above organic pigment may be suitably added as an auxiliary pigment.

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

Further, the inorganic pigment and the organic pigment may be used singly or in combination of two or more kinds, and in combination, in the range of 10 to 80 parts by mass based on 100 parts by mass of the total of the inorganic pigment and the organic pigment. It is preferred to use an organic pigment in the range, and it is preferably used in the range of 20 to 40 parts by mass.

The amount of the coloring agent used in the photosensitive resin composition for spacer formation The range of the solid content of the photosensitive resin composition for spacer formation is preferably from 5 to 70 parts by mass, preferably from 25 to 60 parts by mass, based on 100 parts by mass of the solid content of the photosensitive resin composition for spacer formation. It is better. By being set within the above range, a spacer of a desired shape can be easily formed.

In particular, when a black spacer is formed using the photosensitive resin composition for spacer formation, the amount of the light-shielding agent in the photosensitive resin composition for spacer formation is adjusted so that the OD value per 1 μm of the film of the black spacer becomes 0.5 or more. It is better. When the OD value per 1 μm of the film of 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 coloring agent is preferably added to the negative photosensitive resin composition after being dispersed in a suitable concentration to form a dispersion using a dispersing agent.

<Light Absorber (E)>

The photosensitive resin composition for forming a spacer of the present invention may contain a light absorbing agent (E) (hereinafter also referred to as "(E) component)" as necessary. The light absorbing agent (E) is not particularly limited, and those which can absorb light for exposure can be used, and in particular, those which absorb light in the wavelength range of 200 to 450 nm are preferable. For example, a naphthalene compound, a dinaphthyl compound, an anthraquinone compound, a phenanthroline compound, a dye, etc. are mentioned.

Specific examples thereof include 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-di Hydroxynaphthalene, 2,7-dihydroxynaphthalene, a naphthalene derivative such as ruthenium, 9,10-dihydroxyindole or an anthracene or a derivative thereof; an azo dye, a benzophenone dye, an aminoketone dye, a quinoline dye, an anthraquinone dye, A dye such as a phenyl cyanoacrylate dye, a triazine dye, or a p-amino benzoic acid dye. Among these, a naphthalene derivative is preferably used, and a naphthalene derivative having a hydroxyl group is particularly preferred. These light absorbers may be used singly or in combination of two or more.

The content of the component (D) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and 0.1 to 5 parts by mass based on 100 parts by mass of the total of the components (A) and (B). The serving is better. By setting it within the above range, the breaking strength after hardening can be favorably maintained at the same time, and the ratio of the film thickness change of the resin pattern at the time of changing the exposure amount can be increased.

<Organic Solvent(S)>

The photosensitive resin composition for forming a spacer of the present invention preferably contains an organic solvent (S) (hereinafter also referred to as "(S) component") in order to improve coatability and adjust 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, and diethylene glycol single Methyl 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, dipropylene glycol monoethyl ether, two Propylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether (poly)alkylene glycol monoalkyl ether acetates such as acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, etc.; diethylene glycol dimethyl ether, two Other ethers such as ethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; - alkyl lactate such as methyl hydroxypropionate or ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, acetic acid n- Propyl ester, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, butyl Acid n-propyl ester, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2 Other esters such as ethyl acetobutanoate; aromatic hydrocarbons such as toluene and hydrazine; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethyl B Amidoxime, such as guanamine. Among these, alkanediol monoalkyl ethers, alkanediol monoalkyl ether acetates, the above other ethers, alkyl lactates, and the other esters described above are preferred. The alcohol monoalkyl ether acetates, the above other ethers, and the other esters described above are preferred. These solvents may be used singly or in combination of two or more.

The content of the (S) component is not particularly limited, and may be applied to a substrate or the like. The concentration of the cloth is appropriately set depending on the thickness of the coating film. The viscosity of the photosensitive resin composition is preferably 5 to 500 cp, preferably 10 to 50 cp, and more preferably 20 to 30 cp. Further, the solid content concentration is preferably 5 to 100% by mass, and more preferably 20 to 50% by mass.

<Other ingredients>

The photosensitive resin composition of the present invention may contain an additive such as a surfactant, an adhesion-promoting agent, a thermal polymerization inhibiting agent, or an antifoaming agent, if necessary. Any of the additives can be used in the past. Examples of the surfactant include compounds such as anionic, cationic, and nonionic. Examples of the adhesion-promoting agent include a conventionally known decane coupling agent, and examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone. Examples of the antifoaming agent such as ethyl ether include a polyfluorene-based compound and a fluorine-based compound.

<Modulation Method of Photosensitive Resin Composition>

In the photosensitive resin composition of the present invention, the above components may be mixed (dispersed, kneaded) in a mixer such as a three-roll mill, a ball mill, or a sand mill, and may be prepared by filtration using a filter such as a 5 μm membrane filter.

≪ spacers, and display devices≫

The spacer of 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 spacer formation is used. Moreover, the display device of the present invention includes a spacer formed of the photosensitive resin composition for forming a spacer described above. In addition, the other systems are the same as the previous display devices. The following list only describes the method of forming the spacer.

The method of forming the spacer by using the above-described spacer-forming photosensitive resin composition is not particularly limited, and may be suitably selected from a method of forming a spacer for a display device which has been used in the past. The method of forming a suitable spacer includes a coating step of applying a photosensitive resin composition for forming a spacer onto a substrate to form a photosensitive resin layer, and exposing the photosensitive resin layer to a predetermined spacer pattern. The exposure step and the method of developing the photosensitive resin layer which has been exposed to form a pattern of the spacer pattern.

First, the coating step is performed on a substrate on which spacers are to be formed, and a contact transfer type coating device or a spin coater (rotary coating device) using a roll coater, a reverse coater, a bar coater, or the like, and a curtain coating flow In the non-contact type coating device such as an applicator, the photosensitive resin composition of the present invention is applied, and it is necessary to form a photosensitive resin layer by drying and removing the solvent.

The spacer in the display device is a user who can form a space of a predetermined height between the two substrates arranged in the opposite direction, and the photosensitive resin layer can be formed on either surface of the two types of substrates. Specifically, for example, when a TFT liquid crystal panel is used as the display device, the photosensitive resin layer may be formed on the TFT substrate or may be formed on the color filter substrate.

Next, the substrate on which the photosensitive resin layer is formed on the surface is supplied to the exposure step. In the exposure step, the photosensitive resin layer is irradiated with an active energy ray such as ultraviolet rays or excimer laser light through a negative mask, and the photosensitive resin layer is partially exposed in accordance with a pattern of a predetermined spacer. The exposure may use a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like that emits ultraviolet light. The amount of exposure differs depending on the composition of the photosensitive resin composition, and is preferably, for example, about 10 to 600 mJ/cm ² .

The exposure device used in the exposure step is not particularly limited, and a mirror projection type exposure device, a proximity exposure device, or the like can be used. Specific examples of the mirror-projection type exposure apparatus include, for example, MPA-7800CF (manufactured by Canon Inc.). Since the exposure apparatus of the mirror projection method has no exposure gap between the photomask and the substrate, a spacer having a small diameter can be easily formed. Specific examples of the proximity exposure apparatus include TME-150RTO (manufactured by TOPCON Co., Ltd.). The proximity exposure apparatus can reduce the manufacturing cost of the display device because of the parity, but the exposure gap is formed between the photomask and the substrate during exposure, so that the diameter of the spacer tends to become large. However, when the above-described photosensitive resin composition for spacer formation is used, even when exposure is performed using a proximity exposure apparatus, a spacer having a small diameter can be easily formed.

When the substrate is a TFT substrate or the like, and a component is formed on the substrate, it is necessary to form a spacer on the component or on a substrate facing the substrate on which the component is formed. In this case, considering the height of the element, it is preferable to perform exposure by a halftone mask because it is necessary to change the height of the spacer at a place where the element is formed and at another place. When the photosensitive resin composition for forming a spacer described above is used, it is possible to easily form spacers having different heights by exposure through a halftone mask.

In the developing step, a spacer is formed by developing the exposed photosensitive resin layer as a developing liquid. The development method is not particularly limited, and a dipping method, a spray method, or the like can be used. Specific examples of the developing liquid include, for example, monoethanolamine and An organic system such as ethanolamine or triethanolamine, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or a quaternary ammonium salt. Since the photosensitive resin composition of the present invention exhibits moderate developability, it can be appropriately developed.

Moreover, it is necessary to heat-harden the spacer after the development after the application. The post-baking temperature is preferably 150 to 250 °C.

[Examples]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples.

<Examples 1 to 15 and Comparative Examples 1 to 5>

Each component shown in the following Table 1 was mixed and dissolved in a solvent to have a solid content of 37% by mass to prepare a photosensitive resin composition. Further, 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 abbreviated number represents the following, and the values in parentheses are The amount of blending (parts by mass).

(alkali soluble resin (A))

A: methacrylic acid: 2,3-epoxycyclohex-1-ylmethyl methacrylate: tricyclo[5.2.1.0 ^2,6 ]癸-8-yl methacrylate = 12:71:17 (mass ratio) resin (mass average molecular weight 12000)

B: methacrylate: 2,3-epoxy-1-yl methacrylate: tricyclo [5.2.1.0 ^2,6] deca-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-benzylindenyl)] ("IRGACURE OXE01", manufactured by BASF Corporation)

OXE02: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-indazol-3-yl], 1-(O-acetamidine) (IRGACURE, manufactured by BASF Corporation) OXE02")

C-1: 3-mercaptopropionic acid (photoinitiator)

(additive compound)

In the examples and comparative examples, the compounds represented by the formula (1) used in the examples and the compounds represented by the formula (1) used in the comparative examples are similar. The compound of the structure is referred to as "additive compound".

In the examples and comparative examples, the following compounds were used as the additive compounds. Among the additive compounds, the synthesis method of MCIMA and MCDEA of the compound represented by the formula (1) is as follows.

[Synthesis of MCIMA]

5.90 g (30 mmol) of 3-(4-methoxyphenyl)acrylic acid chloride was dissolved in 50 ml of the dried ether, and 4.59 ml (equivalent ratio of 1.1) of triethylamine and 2.25 ml of imidazole (equivalent ratio of 1.1) were added. ), stirred at room temperature for 1 hour. After washing with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, the mixture was dried over magnesium sulfate and concentrated under reduced pressure. The hexane-ethyl acetate was used as a developing solvent, and the silica gel was used as a support carrier and purified by column chromatography to obtain MCIMA (3.41 g, 15 mmol). The yield based on chlorinated acrylic acid was 50%.

[Synthesis of MCDEA]

5.90 g (30 mmol) of 3-(4-methoxyphenyl)acrylic acid chloride was dissolved in 50 ml of the dried ether, and 4.59 ml (equivalent ratio of 1.1) of triethylamine and 2.41 ml of diethylamine were added. The equivalent ratio was 1.1) and the mixture was stirred at room temperature for 1 hour. After washing with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, the mixture was dried over magnesium sulfate and concentrated under reduced pressure. The hexane-ethyl acetate was used as a developing solvent, and the silica gel was used as a support carrier and purified by column chromatography to obtain MCDEA (4.65 g, 20 mmol). The yield based on chlorinated acrylic acid was 67%.

(light absorber (E))

1,5DON: 1,5-dihydroxynaphthalene

<evaluation> [Density evaluation]

The photosensitive resin composition prepared in each of the above Examples and Comparative Examples was applied onto a 6-inch glass substrate (manufactured by Dow Corning Co., Ltd., 1737 glass), and then dried at 80 ° C for 5 minutes to obtain a photosensitive film having a film thickness of 3.8 μm. Resin layer. Next, using a proximity exposure apparatus (product name: TME-150RTO (manufactured by TOPCON Co., Ltd.)), the photosensitive resin layer was selectively irradiated with ultraviolet rays via a negative mask having a mask size of 9 μm, and the use concentration was 0.05% by mass. The KOH aqueous solution was used as a developing solution, and a dot pattern was obtained by performing spray development at 23 °C. Thereafter, the development performance was evaluated by measuring the time (BP: Break Point, demarcation point) until the unexposed portion was completely dissolved. The results are shown in Table 2 below.

The photosensitive resin composition prepared in each of the above Examples and Comparative Examples was applied onto a 6-inch glass substrate (manufactured by Dow Corning Co., Ltd., 1737 glass), and then dried at 80 ° C for 5 minutes to obtain a photosensitive film having a film thickness of 3.8 μm. Resin layer. Next, using a proximity exposure apparatus (product name: TME-150RTO (manufactured by TOPCON Co., Ltd.)), a negative-type mask having a mask size of 9 μm was used, and ultraviolet rays were selectively irradiated at an exposure amount of 50 mJ/cm ² using a concentration of 0.05. A mass% KOH aqueous solution was used as a developing solution to form a dot pattern by performing spray development at 23 °C. Thereafter, post-baking was carried out on a hot plate at 100 ° C for 10 minutes, followed by 220 ° C for 40 minutes, and the diameter of the spacer formed after post-baking was measured.

Further, the minimum spacer diameter remaining in the adhesion was evaluated using the following evaluation criteria. The results are shown in Table 2 below.

○: The spacer diameter is less than 10 μm.

x: The spacer diameter is 10 μm or more.

[fine point adhesion evaluation]

In the same manner as the "development evaluation" described above, a dot pattern is formed. The development time is set to be about 1.5 times BP based on the above-mentioned boundary point (BP). Thereafter, it was washed with pure water, and formed into a dot pattern by baking the formed pattern at 100 ° C for 10 minutes and then at 220 ° C for 40 minutes.

Further, the dot pattern size which can be developed was examined under an exposure amount of 50 mJ/cm ² and evaluated for adhesion. The criteria for determining the adhesion are as follows. The results are shown in Table 2 below.

◎: The minimum mask size of the adhesion is 5 μm or less.

○: The minimum mask size of the adhesion is 7 μm or less.

△: The minimum mask size of the adhesion is 10 μm or less.

×: The minimum mask size of the adhesion is 15 μm or less.

[Evaluation of halftone (HT) characteristics]

The photosensitive resin composition prepared in each of the above Examples and Comparative Examples was applied onto a 6-inch glass substrate (manufactured by Dow Corning Co., Ltd., 1737 glass), and then dried at 100 ° C for 2 minutes to obtain a photosensitive film having a film thickness of 3.8 μm. Resin layer. Next, the photosensitive resin layer was exposed by a ghi mixed light source using a proximity exposure apparatus (product name: TME-150RTO, manufactured by TOPCON Co., Ltd.). The exposure amount was set to 10, 20, 30, 40, and 50 mJ/cm ² . Next, a KOH aqueous solution having a concentration of 0.05% by mass was used as a developing solution, and liquid imaging was carried out at 23 ° C for 60 seconds. Thereafter, post-baking was carried out on a hot plate at 100 ° C for 10 minutes, followed by 220 ° C for 40 minutes, and the film thickness after post-baking was measured.

Further, the halftone characteristics (HT characteristics) of the photosensitive resin composition were evaluated using the following evaluation criteria. The results are shown in Table 2 below.

○: In the case of an exposure amount of 10 mJ/cm ² and 50 mJ/cm ² , the difference in film thickness after post-baking is 0.5 μm or more.

X: In the case of an exposure amount of 10 mJ/cm ² and 50 mJ/cm ² , the difference in film thickness after post-baking was less than 0.5 μm.

[damage strength evaluation]

A dot-like resin pattern was formed in the same manner as the above-mentioned "evaluation of halftone (HT) characteristics" except that the photosensitive resin layer was exposed to a mask having a diameter of 15 μm and an exposure amount of 50 mJ/cm ² .

Further, the pressure was applied at a rate of addition of 14.2 mN/sec, and the force necessary until the pattern was broken was examined, and the breaking strength of the resin pattern was evaluated using the following evaluation criteria. The results are shown in Table 2 below.

○: The force necessary for destruction is 150 mN or more.

×: The force necessary for destruction is less than 150 mN.

According to Examples 1 to 15, it is understood that spacers containing the alkali-soluble resin (A), the photopolymerizable monomer (B), the photopolymerization initiator (C), and the compound represented by the formula (1) are formed. Composition with photosensitive resin However, even when a proximity exposure apparatus is used, a spacer of a small diameter can be easily formed. On the other hand, according to the comparative examples 1 to 4, when the compound represented by the formula (1) for forming a spacer for the spacer is not contained, it is difficult to form a spacer having a small diameter. Further, according to the comparative example 5, it is found that even if a compound having a structure similar to the compound represented by the formula (1) is formed, the photosensitive resin composition for spacer formation is difficult to form a spacer having a small diameter.

In addition, according to the comparison of the examples 1 to 15 and the comparative examples 1 to 4, it is understood that the compound represented by the formula (1) is blended with the photosensitive resin composition for forming a spacer, and the halftone specificity, the breaking strength, and the like are The characteristics are not inferior to those of the photosensitive resin composition for forming a spacer which does not contain the compound represented by the formula (1).

Further, according to Examples 1 to 11, it is understood that the content of the compound represented by the formula (1) in the photosensitive resin composition for spacer formation is superior to the viewpoint of the excellent adhesion of the spacer to the substrate. The 100 parts by mass of the total amount of the alkali-soluble resin (A) and the photopolymerizable monomer (B) is preferably 0.01 to 2.5 parts by mass, more preferably 0.01 to 0.5 parts by mass.

Claims (7)

A photosensitive resin composition for forming a spacer, comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a compound represented by the following formula (1); In the formula, R ¹ and R ² each independently represent a hydrogen atom or an organic group, but R ¹ and R ² represents at least one of an organic group; R ¹ and R ² may be bonded to form their ring structure, may a bond containing a hetero atom; R ³ represents a single bond; and R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a sulfhydryl group, a sulfide group, a fluorenyl group, a decyl group, a nitro group, a nitrous group Base, sulfino, sulfo, sulfonato, phosphino, phosphinyl, phosphono, phosphonato Or an organic group; R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a mercapto group, a decyl group, a nitro group, a nitroso group, a sulfinic acid group. a base, a sulfonate group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate group, an amine group, an ammonium group or an organic group; however, R ⁶ and R ^{7 are} not a hydroxyl group; R ⁶ and/or when R ⁷ is the organic group, the organic group is selected from the group consisting of an optionally substituted alkyl group, an alkenyl group may have a substituent group, the group may have a substituent of the cycloalkyl ring may have a substituent group of a group, 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, a decylamino group having 2 to 11 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms a group having a carbon number of 1 to 10 and a group of a cyano group; two or more of R ⁶ , R ⁷ , R ⁸ and R ⁹ may be bonded to each other to form a cyclic structure, and may also contain a hetero atom. Bonded; R ¹⁰ represents a hydrogen atom or an organic group. The photosensitive resin composition for spacer formation of claim 1 further contains a colorant (D). A spacer formed of the photosensitive resin composition for forming a spacer according to claim 1 or 2. A display device having a spacer as claimed in claim 3. A method for forming a spacer, comprising the steps of applying a photosensitive resin composition for forming a spacer for forming a spacer according to claim 1 or 2 to form a photosensitive resin layer, and forming a spacer according to a predetermined spacer; An exposure step of exposing the photosensitive resin layer, and a developing step of developing a pattern of the spacer by developing the exposed photosensitive resin layer. A method of forming a spacer according to claim 5, wherein the exposure in the exposing step is performed by a proximity exposure device. A method of forming a spacer according to claim 5 or 6, wherein the exposure is performed via a halftone mask in the foregoing exposure step.