JP2014167492A - Negative photosensitive composition, partition wall, black matrix, color filter and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative photosensitive composition that achieves the formation of a partition wall (black matrix) having both a fine line pattern and a fine contact hole, to provide a color filter that can produce a bright BOA type liquid crystal display element with low power consumption, and to provide a liquid crystal display element.SOLUTION: The negative photosensitive composition includes an alkali-soluble resin having both an acidic group and an ethylenic double bond, a black colorant, a photopolymerization initiator (C1) comprising an O-acyloxime compound having a carbazole skeleton and a photopolymerization initiator (C2) comprising an O-acyloxime compound having 4-(phenylthio)benzoyl group. A ratio of the total content of the photopolymerization initiator (C1) and the photopolymerization initiator (C2) to the total solid content is 3.5-7.0 mass% and a ratio of the amount of the photopolymerization initiator (C1) to the total content is 5-15 mass%. The partition wall is produced by using the negative photosensitive composition.

Description

  The present invention relates to a negative photosensitive composition, a partition and a black matrix using the same, and a color filter and a liquid crystal display device having the black matrix.

In recent years, a cost reduction process using an inkjet method has been proposed as a method for manufacturing a pixel portion of a color filter or an organic EL (Electro-Luminescence) display element.
For example, in the manufacture of a color filter, after a partition that is a black matrix is formed by photolithography, R (red), G (green), and B (blue) ink is applied to openings (dots) surrounded by the partition. A pixel is formed by spraying and coating by an ink jet method.

  In the manufacture of an organic EL display element, a partition that is a black matrix is formed by photolithography, and then a hole transport material and a light emitting material solution are sprayed and applied to an opening (dot) surrounded by the partition by an inkjet method. A pixel having a hole transport layer, a light emitting layer, and the like is formed.

  In recent years, a technique of a black matrix on array type (hereinafter also referred to as a BOA type) in which a color filter is manufactured on a TFT (Thin Film Transistor) array substrate side in a liquid crystal display has been proposed (Patent Document 1). ). In this case, the black matrix can be made thin because the accuracy can be ensured without alignment compared to a normal color filter that requires precise alignment of the two substrates, the color filter substrate and the TFT array substrate. Since the rate is improved, a liquid crystal display device having both low power consumption and high luminance is obtained.

  In a BOA type color filter, unlike a color filter produced on a normal counter substrate side, in order to connect a switching element such as a TFT and a pixel electrode, it is necessary to form a through hole called a contact hole in a black matrix. Furthermore, in order to increase the area of the pixel formation portion, that is, the display portion, the black matrix is required to be thinned, and the contact hole formed in the black matrix is also required to be miniaturized.

  In the ink jet method, it is necessary to prevent color mixing of ink between adjacent pixels. Therefore, the partition wall (black matrix) is required to have a property of repelling ink containing water or an organic solvent which is an inkjet coating liquid, so-called ink repellency. On the other hand, since the ink layer formed on the pixel by the inkjet method is required to have high film thickness uniformity, the opening (dot) surrounded by the partition wall has good wettability with respect to the discharge liquid. Therefore, it is required to have so-called ink affinity.

  Patent Document 2 discloses a negative photosensitive resin composition containing an ink repellent agent, a black colorant, a photopolymerization initiator, a photosensitive resin, and a radical crosslinking agent.

JP-A-9-105926 International Publication No. 2008/146855

  According to the knowledge of the present inventors, in order to produce a black matrix having minute contact holes, the photo-curing sensitivity of the negative photosensitive resin composition used in the production is reduced, It is necessary to suppress photocuring due to leaked light. For this purpose, methods such as reducing the amount of exposure during black matrix production, reducing the amount of photopolymerization initiator used in the composition to be used, and using a photopolymerization initiator with low photocuring sensitivity can be considered.

When reducing the amount of photopolymerization initiator used, the black matrix pattern disappears due to development caused by insufficient curing during exposure, and the ink repellency of the black matrix obtained when an ink repellent agent is contained is not good. There was a problem of becoming enough.
In the case of reducing the exposure amount, the ink repellency becomes more remarkably insufficient. When the amount of exposure was increased to accelerate curing, it became difficult to form minute contact holes.
As a photopolymerization initiator having a low photocuring sensitivity, for example, when a large amount of a photopolymerization initiator composed of a compound represented by the following formula (4) is used, a pigment such as a black colorant contained in the composition to be used is used. Dispersibility in an alkaline aqueous solution is deteriorated, and the pigment settles during alkali development, causing clogging of the filter, and there is a problem in mass productivity.

That is, in the manufacture of partition walls, particularly black matrix, formation of minute contact holes, formation of partition walls (black matrix) pattern of desired shape, and sufficient partition walls (black matrix) when containing an ink repellent agent The imparting of ink repellency is in a trade-off relationship, and it is difficult to achieve both.
According to the knowledge of the present inventors, when the above-mentioned means was tried using the composition described in Patent Document 2, it was difficult to form a minute contact hole.

  The present invention provides a negative photosensitive composition capable of coexistence of formation of a fine line pattern barrier rib and formation of a minute contact hole in the barrier rib when the barrier rib is produced using the same. The purpose is to provide a partition wall and a black matrix. Another object of the present invention is to provide a color filter that can produce a bright BOA type liquid crystal display element with low power consumption by having such a black matrix, and a liquid crystal display element having the color filter.

式（３）中、Ｒ^１は、水素原子、炭素原子数１〜１２のアルキル基、炭素原子数３〜８のシクロアルキル基、炭素原子数２〜５のアルケニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６〜２０のフェニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６〜２０のフェノキシ基を示し、
Ｒ^２は、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数３〜８のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６〜２０のフェニル基、炭素原子数２〜２０のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７〜２０のベンゾイル基、炭素原子数２〜１２のアルコキシカルボニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７〜２０のフェノキシカルボニル基を示し、
Ｒ^３は、炭素原子数１〜１２のアルキル基を示し、
Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は、互いに独立して、水素原子、炭素原子数１〜１２のアルキル基、シクロアルカン環中の水素原子がアルキル基に置換されていてもよい炭素原子数３〜８のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６〜２０のフェニル基、炭素原子数２〜２０のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７〜２０のベンゾイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７〜２０のベンジルカルボニル基、炭素原子数２〜１２のアルコキシカルボニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７〜２０のフェノキシカルボニル基、炭素原子数１〜２０のアミド基またはニトロ基を示す。

式（４）中、Ｒ^８は、水素原子、炭素原子数１〜１２のアルキル基、炭素原子数３〜８のシクロアルキル基、炭素原子数２〜５のアルケニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６〜２０のフェニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６〜２０のフェノキシ基を示し、
Ｒ^９は、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数３〜８のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数６〜２０のフェニル基、炭素原子数２〜２０のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７〜２０のベンゾイル基、炭素原子数２〜１２のアルコキシカルボニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数７〜２０のフェノキシカルボニル基を示す。
［２］架橋剤（Ｄ）をさらに含み、該架橋剤（Ｄ）が１分子中に２つ以上のエチレン性二重結合を有し、酸性基を有しない化合物である、［１］のネガ型用感光性組成物。
［３］熱硬化剤（Ｉ）をさらに含み、該熱硬化剤（Ｉ）が１分子中に２つ以上のエポキシ基を有する化合物である、［１］または［２］のネガ型用感光性組成物。
［４］撥インク剤（Ｅ）をさらに含む、［１］〜［３］のいずれかのネガ型用感光性組成物。
［５］前記撥インク剤（Ｅ）が、１分子中に下式（１）で表される基または下式（２）で表される基を有する側鎖と、エチレン性二重結合を有する側鎖とを有する撥インク剤（Ｅ）である、［４］のネガ型用感光性組成物。
−ＣＦＸＲ^ｆ （１）
式（１）中、Ｘは水素原子、フッ素原子、またはトリフルオロメチル基を示し、Ｒ^ｆはエーテル性酸素原子を有していてもよい水素原子の少なくとも１つがフッ素原子に置換された炭素原子数２０以下のアルキル基、またはフッ素原子を示す。
−（ＳｉＲ^１０Ｒ^１１Ｏ）_ｎ−ＳｉＲ^１２Ｒ^１３Ｒ^１４ （２）
式（２）中、Ｒ^１０、Ｒ^１１、Ｒ^１２およびＲ^１３はそれぞれ独立に、水素原子、アルキル基、シクロアルキル基、またはアリール基を示し、Ｒ^１４は水素原子または炭素原子数１〜１０のエーテル性酸素原子または窒素原子を含んでいてもよいアルキル基を示し、ｎは１〜２００の整数を示す。
［６］支持基板上に区画を設けるために形成される隔壁であって、［１］〜［５］のいずれかのネガ型用感光性樹脂組成物の硬化膜からなる隔壁。
［７］前記［６］の隔壁からなるブラックマトリックス。
［８］前記隔壁と同時に形成される該隔壁の膜厚方向に貫通する貫通孔を有し、該貫通孔における水平方向の最大孔径が２０μｍ以下であり、最小孔径が１μｍ以上である［７］のブラックマトリックス。
［９］支持基板上に形成される、複数の画素と、隣接する画素間に位置する隔壁とを有するカラーフィルタであって、前記隔壁が［７］または［８］のブラックマトリックスからなることを特徴とする、カラーフィルタ。
［１０］ＴＦＴアレイ基板上に［９］のカラーフィルタを有する液晶表示素子。 The present invention includes the following [1] to [10].
[1] an alkali-soluble resin (A) having an acidic group and an ethylenic double bond in one molecule;
Black colorant (B),
A photopolymerization initiator (C1) comprising a compound represented by the following formula (3),
And a photopolymerization initiator (C2) comprising a compound represented by the following formula (4):
A negative-type photosensitive composition comprising
The ratio of the total content of the photopolymerization initiator (C1) and the photopolymerization initiator (C2) with respect to the total solid content is 3.5 to 7.0% by mass, and the photopolymerization initiator with respect to the total content The negative photosensitive resin composition, wherein the proportion of (C1) is 5 to 15% by mass.

In Formula (3), R ¹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a hydrogen atom in a benzene ring. Represents a phenyl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, or a phenoxy group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group,
R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a hydrogen atom in the benzene ring in which an alkyl group may be substituted with an alkyl group. Phenyl group, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an alkoxycarbonyl group having 2 to 12 carbon atoms Or a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group,
R ³ represents an alkyl group having 1 to 12 carbon atoms,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom in which a hydrogen atom in the cycloalkane ring may be substituted with an alkyl group. A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a hydrogen atom in the benzene ring A benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group, a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom An alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and 1 to 20 carbon atoms It shows a bromide group or a nitro group.

In the formula (4), R ⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a hydrogen atom in a benzene ring. Represents a phenyl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, or a phenoxy group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group,
R ⁹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a carbon atom number 6 to 20 in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. Phenyl group, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an alkoxycarbonyl group having 2 to 12 carbon atoms Alternatively, it represents a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
[2] The negative of [1], further comprising a crosslinking agent (D), wherein the crosslinking agent (D) is a compound having two or more ethylenic double bonds in one molecule and having no acidic group. Photosensitive composition for molds.
[3] Negative type photosensitivity of [1] or [2], further comprising a thermosetting agent (I), wherein the thermosetting agent (I) is a compound having two or more epoxy groups in one molecule. Composition.
[4] The negative photosensitive resin composition according to any one of [1] to [3], further comprising an ink repellent agent (E).
[5] The ink repellent agent (E) has a side chain having a group represented by the following formula (1) or a group represented by the following formula (2) in one molecule and an ethylenic double bond. The negative photosensitive resin composition according to [4], which is an ink repellent agent (E) having a side chain.
-CFXR ^f (1)
In the formula (1), X represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and R ^f is a carbon atom in which at least one hydrogen atom optionally having an etheric oxygen atom is substituted with a fluorine atom. An alkyl group of several 20 or less, or a fluorine atom is shown.
_{^{- (SiR 10 R 11 O)}} n -SiR 12 R 13 R 14 (2)
In formula (2), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ¹⁴ represents a hydrogen atom or a carbon atom number of 1 to 10 An alkyl group which may contain an etheric oxygen atom or nitrogen atom, and n represents an integer of 1 to 200.
[6] A partition formed to provide a partition on the support substrate, the partition formed of a cured film of the negative photosensitive resin composition according to any one of [1] to [5].
[7] A black matrix comprising the partition walls of [6].
[8] A through hole penetrating in the film thickness direction of the partition wall formed simultaneously with the partition wall has a maximum horizontal hole diameter of 20 μm or less and a minimum hole diameter of 1 μm or more. Black matrix.
[9] A color filter formed on a support substrate having a plurality of pixels and a partition located between adjacent pixels, wherein the partition is made of a black matrix of [7] or [8]. Characteristic color filter.
[10] A liquid crystal display device having the color filter according to [9] on a TFT array substrate.

  According to the negative photosensitive composition of the present invention, a partition and a black matrix having a fine line pattern and a fine contact hole can be produced. Further, according to the present invention, by having such a black matrix, a color filter capable of producing a bright BOA type liquid crystal display element with low power consumption and a liquid crystal display element having the color filter can be provided.

The acid value in the present specification means the number of milligrams of potassium hydroxide necessary for neutralizing resin acid or the like in 1 g of a sample, and is a value that can be measured according to the measurement method of JIS K 0070. . The unit is mgKOH / g.
In this specification, “(meth) acryloyl...” Is a general term for “methacryloyl...” And “acryloyl. The same applies to (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, (meth) allyl ..., (meth) acrylic resin.

The group represented by Formula (1) in this specification is called group (1). The same applies to other groups.
The monomer represented by the formula (11) in this specification is referred to as a monomer (11). The same applies to other monomers.
The total solid content in the present specification refers to a partition-forming component among the components contained in the negative photosensitive composition, and other than volatile components that volatilize by heating in the partition-forming process such as solvent (F). All components are shown. The amount of total solids can be calculated from the amount charged. When analyzing, the negative photosensitive resin composition is heated at 160 ° C. for 10 minutes to remove the solvent. The residue is the total solids.
In the present specification, the film coated with the negative photosensitive composition is referred to as “coating film”, the dried state is referred to as “film”, and the film obtained by curing it is referred to as “cured film”. .

In this specification, the “surface” of the partition wall is used as a term indicating only the upper surface of the partition wall. Therefore, the “surface” of the partition does not include the side surface of the partition.
The ink in the present specification is a general term for, for example, liquids having optically and electrically functions after being dried and cured, and is not limited to conventionally used coloring materials. Similarly, “pixels” formed by injecting the ink are also used to represent sections having optical and electrical functions, which are partitioned by the partition walls.
In this specification, the ink repellency refers to a property having moderately both water repellency and oil repellency in order to repel the ink, and can be evaluated by, for example, a method described later.

In this specification, the contact hole refers to a through-hole provided for connecting an element and an electrode in a film thickness direction of a partition wall or a black matrix. “Fine” of a minute contact hole means a size in which the maximum horizontal hole diameter in a through hole constituting the contact hole is approximately 20 μm or less. In addition, the horizontal maximum hole diameter in the through hole refers to the long diameter in the cross section having the maximum area in the horizontal cross section of the through hole, and the minimum hole diameter in the cross section having the minimum area in the horizontal cross section of the through hole. The minor axis.
Embodiments of the present invention will be described below. In addition, unless otherwise indicated in this specification,% represents the mass%.

[Alkali-soluble resin (A)]
The alkali-soluble resin (A) is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. Since the alkali-soluble resin (A) has an ethylenic double bond in the molecule, the exposed portion of the negative photosensitive composition is polymerized and cured by radicals generated from the photopolymerization initiator. The exposed portion thus cured is not removed with an alkaline developer. Moreover, when the alkali-soluble resin (A) has an acidic group in the molecule, the unexposed portion of the negative photosensitive composition that is not cured can be selectively removed with an alkali developer. As a result, a partition wall can be formed. In addition, it is preferable that alkali-soluble resin (A) does not contain substantially the group (1) or group (2) which the compound which preferably comprises the below-mentioned ink repellent agent (E) has.

Although it does not restrict | limit especially as said acidic group, A carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, These may be used individually by 1 type or may use 2 or more types together.
Although it does not restrict | limit especially as said ethylenic double bond, The double bond which has addition polymerizability, such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, and a vinyl ether group, is mentioned, These are 1 type. It may be used alone or in combination of two or more. In addition, a part or all of hydrogen atoms of the double bond group having addition polymerization property may be substituted with an alkyl group, preferably a methyl group.

  Although it does not specifically limit as alkali-soluble resin (A), Resin (A1-1) which has a side chain which has an acidic group, and a side chain which has an ethylenic double bond, An acidic group and ethylenic double are added to an epoxy resin. Examples thereof include a resin (A1-2) having a bond introduced therein, a monomer (A1-3) having a side chain having an acidic group and a side chain having an ethylenic double bond. These may be used alone or in combination of two or more.

Resin (A1-1) can be synthesized, for example, by the following method (i) or (ii).
(I) A side having a reactive group obtained by copolymerizing a monomer having a reactive group other than an acidic group in the side chain, for example, a monomer having a hydroxyl group or an epoxy group, and a monomer having an acidic group in the side chain. A copolymer having a chain and a side chain having an acidic group is obtained. Next, this copolymer is reacted with a compound having a functional group capable of bonding to the reactive group and an ethylenic double bond in a solvent. Alternatively, after copolymerizing a monomer having an acidic group such as a carboxyl group in the side chain, the acidic group remains after the reaction with the functional group capable of bonding to the acidic group and the compound having an ethylenic double bond. The amount is dissolved in a solvent and reacted.
(Ii) having a monomer having a reactive group other than an acidic group in the side chain as in (i) above, a functional group capable of binding to this reactive group, and a protected ethylenic double bond The compound is dissolved in a solvent and reacted. Next, after the monomer and a monomer having an acidic group in the side chain are copolymerized, the protection of the ethylenic double bond is removed. Alternatively, after the monomer having an acidic group in the side chain is copolymerized with the monomer having an ethylenic double bond protected in the side chain, the protection of the ethylenic double bond is removed.
Among these, the method (i) is preferably used in the present invention. Hereinafter, the method (i) will be specifically described.

  As monomers having a hydroxyl group as a reactive group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5 -Hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (Meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl ( Data) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide.

  Although it does not specifically limit as a monomer which has an acidic group copolymerized with the monomer which has a hydroxyl group as a reactive group, In addition to the monomer which has the carboxyl group mentioned later, the monomer which has a phosphate group As 2- (meth) acryloyloxyethanephosphoric acid. Copolymerization of a monomer having a hydroxyl group as a reactive group and a monomer having an acidic group can be carried out by a conventionally known method.

As a compound having a functional group capable of bonding to a hydroxyl group and an ethylenic double bond to be reacted with the copolymer having a side chain having a hydroxyl group and a side chain having an acidic group obtained above, an ethylenic double bond is used. Examples include an acid anhydride having a bond, a compound having an isocyanate group and an ethylenic double bond, and a compound having an acyl chloride group and an ethylenic double bond.
Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthal An acid anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, etc. are mentioned.
Examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.
Examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.

Examples of the monomer having an epoxy group as a reactive group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
As a monomer having an acidic group to be copolymerized with a monomer having an epoxy group as a reactive group, the same monomers as described for the monomer having a hydroxyl group as a reactive group can be used, Copolymerization of a monomer having an epoxy group as a reactive group and a monomer having an acidic group can also be performed by a conventionally known method.

  As a compound having a functional group capable of bonding to an epoxy group and an ethylenic double bond, the carboxyl group is reacted with the copolymer having a side chain having an epoxy group and a side chain having an acidic group obtained above. And a compound having an ethylenic double bond. Specific examples of the compound include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. In addition, the hydroxyl group generated here may be reacted with an acid anhydride in which the dehydration-condensation part of the carboxylic acid forms part of the cyclic structure to introduce a carboxyl group into the resin (A1-1).

  Examples of the monomer having a carboxyl group as a reactive group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. In addition, these monomers are used also as a monomer which has the acidic group mentioned above.

  When using the monomer which has a carboxyl group as a reactive group, as above-mentioned, this is copolymerized independently. A compound having an epoxy group and an ethylenic double bond as a compound having an ethylenic double bond and a functional group capable of bonding to the carboxyl group, which is reacted with a copolymer having the resulting carboxyl group as a reactive group Is mentioned. Examples of the compound include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate. In this case, the amount of the functional group capable of bonding to the carboxyl group and the compound having an ethylenic double bond to be reacted with the copolymer having a carboxyl group is such that the carboxyl group is an acidic group in the copolymer after the reaction. As the amount remaining in the side chain.

The resin (A1-2) is synthesized by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, which will be described later, and then reacting with a polybasic carboxylic acid or its anhydride. be able to.
Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond. Next, a carboxyl group can be introduce | transduced by making polybasic carboxylic acid or its anhydride react with the epoxy resin in which the ethylenic double bond was introduce | transduced.

  The epoxy resin is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, epoxy resin having naphthalene skeleton, Examples include an epoxy resin having a biphenyl skeleton represented by (A1-2a), an epoxy resin represented by the following formula (A1-2b), an epoxy resin having a biphenyl skeleton represented by the following formula (A1-2c), and the like. It is done.

（式（Ａ１−２ａ）中、ｖは、１〜５０であり、２〜１０が好ましい。またベンゼン環の水素原子はそれぞれ独立に、炭素原子数１〜１２のアルキル基、ハロゲン原子、または、一部の水素原子が置換基で置換されていてもよいフェニル基、で置換されていてもよい。）

(In Formula (A1-2a), v is 1 to 50, and preferably 2 to 10. The hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or (Some hydrogen atoms may be substituted with a phenyl group, which may be substituted with a substituent.)

（式（Ａ１−２ｂ）中、Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は、それぞれ独立に、水素原子、塩素原子または炭素原子数が１〜５のアルキル基であり、ｗは、０〜１０である。）

(In formula (A1-2b), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and w is 0 to 0. 10)

（式（Ａ１−２ｃ）中、ベンゼン環の水素原子はそれぞれ独立に炭素原子数１〜１２のアルキル基、ハロゲン原子、または、一部の水素原子が置換基で置換されていてもよいフェニル基、で置換されていてもよい。ｕは、０〜１０である。）

(In Formula (A1-2c), the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group in which some of the hydrogen atoms may be substituted with a substituent. And u is 0-10.)

  In addition, after making the epoxy resin represented by Formula (A1-2a)-(A1-2c) and the compound which has a carboxyl group and an ethylenic double bond react, a polybasic carboxylic acid anhydride is made to react. In this case, it is preferable to use a mixture of dicarboxylic anhydride and tetracarboxylic dianhydride as the polybasic carboxylic anhydride. By changing the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride, the molecular weight can be controlled.

  As the compound having a carboxyl group and an ethylenic double bond, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and salts thereof are preferable, and acrylic acid or Methacrylic acid is particularly preferred.

  A commercial item can be used for resin (A1-2). As a commercial item, all are a brand name, KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR- 1535H, ZAR-2002, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H (above, manufactured by Nippon Kayaku Co., Ltd.) And EX1010 (manufactured by Nagase ChemteX Corporation).

  Examples of the monomer (A1-3) include 2,2,2-triacryloyloxymethylethylphthalic acid (NK ester CBX-1 manufactured by Shin-Nakamura Chemical Co., Ltd.).

As the alkali-soluble resin (A), the peeling of the coating film during development is suppressed, a high-resolution pattern can be obtained, the linearity of the line is good, and the appearance after the post-baking process is maintained. The resin (A1-2) is preferably used because a smooth coating surface can be easily obtained.
As the resin (A1-2), a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin, phenol Resin with acid group and ethylenic double bond introduced into novolac type epoxy resin, resin with acid group and ethylenic double bond introduced into cresol novolac type epoxy resin, acid group and ethylene into trisphenol methane type epoxy resin A resin in which an acidic group and an ethylenic double bond are introduced into an epoxy resin represented by the formulas (A1-2a) to (A1-2c) is particularly preferable.

  The number of the ethylenic double bonds that the alkali-soluble resin (A) has in one molecule is preferably 3 or more on average and particularly preferably 6 or more. When the number of ethylenic double bonds is at least the lower limit of the above range, the alkali solubility between the exposed and unexposed portions is likely to be different, and a fine pattern can be formed with a smaller exposure amount.

The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1.5 × 10 ³ to 30 × 10 ³ , particularly preferably 2 × 10 ³ to 15 × 10 ³ . The number average molecular weight (Mn), preferably from 500 to 20 × 10 ^3, and particularly preferably ^{1.0 × 10 3 ~10 × 10 3} . When the mass average molecular weight (Mw) and the number average molecular weight (Mn) are not less than the lower limit of the above range, curing at the time of exposure is sufficient, and when it is not more than the upper limit of the above range, the developability is good.
The acid value of the alkali-soluble resin (A) is preferably 10 to 300 mgKOH / g, particularly preferably 30 to 150 mgKOH / g. When the acid value is within the above range, the developability of the negative photosensitive composition is improved.

The alkali-soluble resin (A) contained in the negative photosensitive composition may be used alone or in combination of two or more.
5-80 mass% is preferable and, as for the content rate of the photosensitive resin (A) in the total solid in a negative photosensitive resin composition, 10-60 mass% is especially preferable. When the content ratio is in the above range, the developability of the negative photosensitive composition is good.

[Black colorant (B)]
The negative photosensitive composition of the present invention contains a black colorant (B).
Examples of the black colorant (B) include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C.I. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned. As the black colorant (B), organic pigments such as red pigments, blue pigments, green pigments, yellow pigments, and mixtures of inorganic pigments can also be used. Specific examples of organic pigments include C.I. I. And CI Pigment Blue 15: 6, Pigment Red 254, Pigment Green 36, Pigment Yellow 150, and azomethine pigments. As the black colorant (B), an organic pigment is preferable from the viewpoint of electrical characteristics, and carbon black is preferable from the viewpoint of cost and light shielding properties. The carbon black is preferably surface-treated with a resin or the like, and a blue pigment or a violet pigment can be used in combination to adjust the color tone.

The organic pigment preferably has a specific surface area of 50 to 200 m ² / g by the BET method from the viewpoint of the shape of the black matrix. When the specific surface area is 50 m ² / g or more, the black matrix shape is hardly deteriorated. When it is 200 m ² / g or less, the dispersion aid is not excessively adsorbed on the organic pigment, and it is not necessary to add a large amount of dispersion aid in order to develop various physical properties.

  Moreover, it is preferable that the average primary particle diameter by the transmission electron microscope observation of an organic pigment is 20-150 nm. When the average primary particle size is 20 nm or more, the negative photosensitive composition can be dispersed at a high concentration and a negative photosensitive composition having good temporal stability can be easily obtained. When it is 150 nm or less, the black matrix shape is hardly deteriorated. Moreover, as an average secondary particle diameter by transmission electron microscope observation, 80-200 nm is preferable.

  The content of the black colorant (B) in the total solid content in the negative photosensitive composition is preferably 20 to 65% by mass, more preferably 25 to 60% by mass, and particularly preferably 30 to 55% by mass. When the content ratio is equal to or higher than the lower limit of the above range, the optical density, which is a value indicating the light blocking property of the obtained partition wall, is sufficient. When the amount is not more than the upper limit of the above range, the curability of the negative photosensitive composition is improved, a cured film having a good appearance is obtained, and the ink repellency is also improved.

In order to improve the dispersibility of the black colorant (B) in the negative photosensitive composition, it is preferable to contain a polymer dispersant. The polymer dispersant is preferably a compound having a basic functional group from the viewpoint of affinity for the black colorant (B). When the basic functional group has a primary, secondary or tertiary amino group, the dispersibility is particularly excellent.
Polymer dispersing agents include urethane, polyimide, alkyd, epoxy, unsaturated polyester, melamine, phenol, acrylic, vinyl chloride, vinyl chloride vinyl acetate copolymer, polyamide, polycarbonate And the like. Of these, urethane-based and polyester-based compounds are particularly preferable.
The amount of the polymer dispersant used is preferably 5 to 30% by weight, particularly preferably 10 to 25% by weight, based on the black colorant (B). When the amount used is not less than the lower limit of the above range, the dispersion of the black colorant (B) becomes good, and when it is not more than the upper limit of the above range, the developability becomes good.

[Photoinitiator (C)]
The negative photosensitive composition of the present invention is represented by a photopolymerization initiator (C1) comprising a compound represented by the following formula (3) as a photopolymerization initiator (C), and the following formula (4). And a photopolymerization initiator (C2) made of a compound.
The ratio of the total content of the photopolymerization initiator (C1) and the photopolymerization initiator (C2) to the total solid content in the negative photosensitive composition is 3.5 to 7.0% by mass. The ratio of the total content is preferably 3.5 to 6.8% by mass, more preferably 3.6 to 6.0% by mass, and particularly preferably 3.7 to 5.5% by mass. When the ratio of the total content is within the above range, the curable negative photosensitive composition has good curability, and after the coating film is formed, a line pattern or a line in a partition or black matrix obtained through an exposure process and a development process. The width can be formed in a shape close to the mask pattern at the time of exposure, and a minute contact hole can be formed. Further, when the ratio of the total content is within the above range, sufficient ink repellency can be imparted when the negative photosensitive composition contains the ink repellent agent (E). Furthermore, the solubility of the pigment such as the black colorant (B) in the alkaline aqueous solution is not inhibited.

  The ratio of the photopolymerization initiator (C1) to the total content of the photopolymerization initiator (C1) and the photopolymerization initiator (C2) in the negative photosensitive composition is 5 to 15% by mass. The ratio of the photopolymerization initiator (C1) to the total content is preferably 6 to 13% by mass, particularly preferably 7 to 12% by mass. When the ratio of the photopolymerization initiator (C1) to the total content is within the above range, the curability of the negative photosensitive composition is good, and the partition wall obtained through the exposure process and the development process after the coating film is formed. In addition, in the black matrix, the line pattern and the line width can be formed in a shape close to the mask pattern at the time of exposure, and a minute contact hole can be formed. Further, when the ratio of the photopolymerization initiator (C1) to the total content is in the above range, sufficient ink repellency is imparted when the negative photosensitive composition contains the ink repellent (E). Is also possible. Furthermore, the solubility of the pigment such as the black colorant (B) in the alkaline aqueous solution is not inhibited.

  The content ratio of the photopolymerization initiator (C1) in the total solid content in the negative photosensitive composition is preferably 0.1 to 5% by mass, more preferably 0.3 to 0.5% by mass, and 35-0.45 mass% is especially preferable. Moreover, 3-7 mass% is preferable and, as for the content rate of the photoinitiator (C2) in the total solid in a negative photosensitive resin composition, 3-6.5 mass% is especially preferable.

When the negative photosensitive composition of the present invention is used, when the partition (black matrix) is produced, the partition (black matrix) is formed in a fine line close to the mask pattern, and at the same time, the partition (black matrix) is formed. When the negative photosensitive composition contains an ink repellent (E), sufficient ink repellency can be achieved. The reason why such an effect can be obtained is not clear, but the above-described effect is that the photopolymerization initiator (C1) and the photopolymerization initiator (C2) are relatively sensitive among the photopolymerization initiators. (C1) is considered to be due to the characteristic that the sensitivity is higher than that of the photopolymerization initiator (C2).
Here, the black matrix is manufactured by forming a mask pattern on the dried film of the negative-type photosensitive composition as a coating film, exposing and developing, and in the process, forming contact holes in the black matrix and The optional ink repellency is simultaneously given, but the formation of contact holes is influenced by the photoreactivity inside the film, and the ink repellency is affected by the photoreactivity of the film surface. Furthermore, because the film for black matrix production has low light transmittance, when exposed from the film side, the photoreactivity may be insufficient near the substrate rather than near the film surface. Sometimes the pattern dissolves and disappears.

  First, regarding the photoreactivity of the film surface, since there is photoreaction inhibition by oxygen, the difference in reactivity between the photopolymerization initiator (C1) and the photopolymerization initiator (C2) is small. On the other hand, with respect to the photoreactivity within the film, the photopolymerization initiator (C1) is more reactive (sensitivity) than the photopolymerization initiator (C2), so it is better to use the photopolymerization initiator (C2). It is preferable for imparting ink repellency and forming minute contact holes. However, when only the photopolymerization initiator (C2) is used, the pattern disappears during development due to insufficient reactivity inside the film due to insufficient transmitted light amount. In the present invention, for the purpose of preventing the disappearance of the pattern during development, a small amount of the photopolymerization initiator (C1) is added to the photopolymerization initiator (C2) to compensate for the reactivity inside the film, and the fine line Formation of barrier ribs having a pattern and formation of minute contact holes in the barrier ribs. Furthermore, when the negative photosensitive composition contains an ink repellent agent (E), sufficient ink repellency is simultaneously achieved. Made it possible to do.

  In the negative photosensitive composition of the present invention, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,4-butanol bis (3-mercaptobutyrate), tris (2-mercapto) Thiol compounds such as propanoyloxyethyl) isocyanurate and pentaerythritol tetrakis (3-mercaptobutyrate) may be used together with the photopolymerization initiator (C1) and the photopolymerization initiator (C2). As a result, a sensitizing effect may be exhibited.

(Photopolymerization initiator (C1))
The photopolymerization initiator (C1) is composed of an O-acyl oxime compound represented by the following formula (3).

In Formula (3), R ¹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a hydrogen atom in a benzene ring. Represents a phenyl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, or a phenoxy group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group,
R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a hydrogen atom in the benzene ring in which an alkyl group may be substituted with an alkyl group. Phenyl group, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an alkoxycarbonyl group having 2 to 12 carbon atoms Or a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group,
R ³ represents an alkyl group having 1 to 12 carbon atoms,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom in which a hydrogen atom in the cycloalkane ring may be substituted with an alkyl group. A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a hydrogen atom in the benzene ring A benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group, a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom An alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and 1 to 20 carbon atoms It shows a bromide group or a nitro group.

R ¹ is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group having 6 to 12 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, such as a methyl group, Examples include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a phenyl group. An alkyl group having 1 to 4 carbon atoms is more preferable, an alkyl group having 1 to 2 carbon atoms is further preferable, and a methyl group is particularly preferable.
R ² is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group and the like. An alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.

R ³ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. An alkyl group having 2 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
R ⁴ , R ⁶ and R ⁷ are preferably hydrogen atoms.
R ⁵ represents a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. 7-20 benzylcarbonyl groups are preferred, benzoyl group, 2-methylbenzoyl group, 2-methyl-4-tetrahydropyranylmethoxybenzoyl group, 2-methyl-5-tetrahydrofuranylmethoxybenzoyl group, 2-methyl-5- A tetrahydropyranylmethoxybenzoyl group, a benzylcarbonyl group, and a 1,3,5 trimethylbenzylcarbonyl group are particularly preferred.

Specific examples of the photopolymerization initiator (C1) include compounds (3-1) to (3-10) in which R ^{1 to} R ⁷ are the following groups in the formula (3), respectively.
Compound (3-1) wherein R ^{1 is a} phenyl group, R ^{2 is an} octyl group, R ^{3 is an} ethyl group, R ⁴ , R ⁶ , R ^{7 is a} hydrogen atom, and R ^{5 is a} benzoyl group,
Compound (3-2) wherein R ^{1 is a} methyl group, R ^{2 is an} octyl group, R ^{3 is an} ethyl group, R ⁴ , R ⁶ , R ^{7 is a} hydrogen atom, and R ^{5 is a} benzoyl group,
A compound (3-3) wherein R ^{1 is a} methyl group, R ^{2 is a} butyl group, R ^{3 is an} ethyl group, R ⁴ , R ⁶ , R ^{7 is a} hydrogen atom, and R ^{5 is a} benzoyl group;
R ¹ : methyl group, R ² : heptyl group, R ³ : ethyl group, R ⁴ , R ⁶ , R ⁷ : hydrogen atom, R ⁵ : compound (3-4) having a benzoyl group,
Compound (3-5), wherein R ¹ : phenyl group, R ² : octyl group, R ³ : ethyl group, R ⁴ , R ⁶ , R ⁷ : hydrogen atom, R ⁵ : 2-methylbenzoyl group,
R ¹ : methyl group, R ² : octyl group, R ³ : ethyl group, R ⁴ , R ⁶ , R ⁷ : hydrogen atom, R ⁵ : compound (3-6) which is 2-methylbenzoyl group,
Compound (3-7) wherein R ^{1 is a} methyl group, R ^{2 is a} methyl group, R ^{3 is an} ethyl group, R ⁴ , R ⁶ , R ^{7 is a} hydrogen atom, and R ^{5 is a} 2-methylbenzoyl group,
R ¹ : methyl group, R ² : methyl group, R ³ : ethyl group, R ⁴ , R ⁶ , R ⁷ : hydrogen atom, R ⁵ : 2-methyl-4-tetrahydropyranylmethoxybenzoyl group (3 -8),
R ¹ : methyl group, R ² : methyl group, R ³ : ethyl group, R ⁴ , R ⁶ , R ⁷ : hydrogen atom, R ⁵ : 2-methyl-5-tetrahydrofuranylmethoxybenzoyl group (3- 9),
R ¹ : methyl group, R ² : methyl group, R ³ : ethyl group, R ⁴ , R ⁶ , R ⁷ : hydrogen atom, R ⁵ : 2-methyl-5-tetrahydropyranylmethoxybenzoyl group (3 -10)

  A commercial item can be used for a photoinitiator (C1). As commercial products, all are trade names and correspond to IRGACURE OXE02 (manufactured by BASF: corresponding to the above compound (3-7)), Adekaoptomer N-1919, Adeka Cruz NCI-831, NCI-930. . As mentioned above, ADEKA company etc.) are mentioned.

(Photopolymerization initiator (C2))
A photoinitiator (C2) consists of a compound represented by the following Formula (4).

In the formula (4), R ⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a hydrogen atom in a benzene ring. Represents a phenyl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, or a phenoxy group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group,
R ⁹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a carbon atom number 6 to 20 in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. Phenyl group, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an alkoxycarbonyl group having 2 to 12 carbon atoms Alternatively, it represents a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.

R ⁸ is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group having 6 to 12 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, such as a methyl group, Examples include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a phenyl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is more preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, and a methyl group is particularly preferable. A phenyl group is likewise preferred.
R ⁹ is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group and the like. An alkyl group having 1 to 6 carbon atoms is more preferable, and a hexyl group and a methyl group are particularly preferable.

A commercial item can be used for a photoinitiator (C2). Examples of commercially available products include IRGACURE OXE01 (trade name, manufactured by BASF: a compound in which R ⁸ is a phenyl group and R ⁹ is a hexyl group in the above formula (4))).

[Crosslinking agent (D)]
The negative photosensitive composition of the present invention may contain a crosslinking agent (D) as an optional component for promoting radical curing. As a crosslinking agent (D), the compound which has two or more ethylenic double bonds in 1 molecule, and does not have an acidic group is preferable. When the negative photosensitive composition contains the crosslinking agent (D), the curability of the negative photosensitive composition at the time of exposure is improved, and a partition can be formed even with a low exposure amount.

  Examples of the crosslinking agent (D) include diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, bi {4- (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide), urethane acrylate and the like. From the viewpoint of photoreactivity, it is preferable to have a large number of ethylenic double bonds. In addition, these may be used individually by 1 type, or may use 2 or more types together.

  A commercial item can be used as a crosslinking agent (D). Commercially available products include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9530 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., dipenta Erythritol pentaacrylate and dipentaerythritol hexaacrylate mixture)), NK Este A-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, new Nakamura Chemical Co., Ltd., ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name, manufactured by Maruzen Petrochemical Co., Ltd., bis {4- (allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimi De) phenyl} methane), BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd., N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide)) and the like. Examples of the urethane acrylate include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D-P20. Etc.

  1-60 mass% is preferable and, as for the content rate of the crosslinking agent (D) in the total solid in a negative photosensitive resin composition, 2-15 mass% is especially preferable. Within the above range, the alkali developability of the negative photosensitive composition is improved.

[Ink repellent (E)]
The ink repellent agent (E) is a compound that is contained in the negative photosensitive composition of the present invention as necessary, is unevenly distributed on the surface of the coating film, and imparts an ink repellency function to the surface of the cured film.
As the ink repellent agent (E), a group represented by the following formula (1) (hereinafter also referred to as group (1)) or a group represented by the following formula (2) (hereinafter referred to as group (1)) per molecule. Also referred to as 2), a compound having a side chain having a) and a side chain having an ethylenic double bond is preferred.
-CFXR ^f (1)
In the formula (1), X represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and R ^f is a carbon atom in which at least one hydrogen atom optionally having an etheric oxygen atom is substituted with a fluorine atom. An alkyl group of several 20 or less, or a fluorine atom is shown.
_{^{- (SiR 10 R 11 O)}} n -SiR 12 R 13 R 14 (2)
In formula (2), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ¹⁴ represents a hydrogen atom or a carbon atom number of 1 to 10 An alkyl group which may contain an etheric oxygen atom or nitrogen atom, and n represents an integer of 1 to 200.

Since the ink repellent agent (E) has a side chain having the group (1) or the group (2), it has surface migration, and the surface of the coating film when the coating film of the negative photosensitive composition is dried by heating. Move to the neighborhood. Therefore, the surface of the partition wall made of a cured film exhibits ink repellency, and the ink injected by the ink jet method does not overflow from the dots (locations that become pixels), and color mixing between adjacent pixels hardly occurs. In addition, since the ink repellent agent (E) has a side chain having an ethylenic double bond, a curing reaction of the ink repellent agent (E) occurs at the time of exposure and is easily immobilized on the partition wall surface. Therefore, it is unlikely that unreacted residual molecules migrate to the dots and contaminate the dots during post-baking after exposure and development.
The side chain is a branched portion in a chain-like high molecular weight product obtained by polymerization of a low molecular weight product.

  The side chain having the group (1) or the group (2) may be directly formed by a polymerization reaction or may be formed by chemical conversion after the polymerization reaction. Further, the side chain having an ethylenic double bond can be formed by chemical conversion after the polymerization reaction.

When R ^f in the group (1) is an alkyl group having 20 or less carbon atoms in which at least one of hydrogen atoms optionally having an etheric oxygen atom is substituted with a fluorine atom, The hydrogen atom may be substituted with a halogen atom other than the fluorine atom, and the chlorine atom is preferred as the other halogen atom. The etheric oxygen atom may be present between the carbon-carbon bonds of the alkyl group or may be present at the terminal of the alkyl group. Examples of the structure of the alkyl group include a linear structure, a branched structure, a ring structure, or a structure having a partial ring, and a linear structure is preferable.

  The group (1) is preferably a perfluoroalkyl group or a polyfluoroalkyl group containing one hydrogen atom, and particularly preferably a perfluoroalkyl group (however, the alkyl group includes those having an etheric oxygen atom). .) Thereby, the partition formed from the negative photosensitive composition has good ink repellency. The total number of carbon atoms in the group (1) is preferably 4-6. Thus, sufficient ink repellency is imparted to the partition walls, and the compatibility between the ink repellent agent (E) and the other components constituting the negative photosensitive composition is good, and the negative photosensitive composition. When an object is applied to form a coating film, the ink repellent agent (E) is not aggregated, and a partition wall having a good appearance can be formed. As the group (1), a perfluoroalkyl group having 4 to 6 carbon atoms in total is particularly preferable.

Specific examples of the group (1) include the following.
_{-CF 3, -CF 2 CF 3,} -CF 2 CHF 2, - (CF 2) 2 CF 3, - (CF 2) 3 CF 3, - (CF 2) 4 CF 3, - (CF 2) 5 CF ₃ ,-(CF ₂ ) ₆ CF ₃ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₈ CF ₃ ,-(CF ₂ ) ₉ CF ₃ ,-(CF ₂ ) ₁₁ CF ₃ ,-(CF ₂ ) ₁₅ CF ₃ ,
_{-CF (CF 3) O (CF} 2) 5 CF 3,
_{-CF 2 O (CF 2 CF 2} O) p CF 3 (p is an integer from 1 to 8),
_{-CF (CF 3) O (CF} 2 CF (CF 3) O) q C 6 F 13 (q is an integer of 1 to 4),
_{-CF (CF 3) O (CF} 2 CF (CF 3) O) r C 3 F 7 (r is an integer of from 1 to 5).

R ¹⁰ and R ¹¹ in the group (2) may be the same or different for each siloxane unit. Since the partition formed from the negative photosensitive composition exhibits excellent ink repellency, R ¹⁰ and R ¹¹ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group. It is preferably a hydrogen atom, a methyl group, or a phenyl group, and R ¹⁰ and R ¹¹ of all siloxane units are particularly preferably methyl groups.
In the group (2), R ¹² , R ¹³ and R ¹⁴ are groups bonded to the silicon atom at the terminal of the siloxane bond, and R ¹² and R ¹³ can be the same as R ¹⁰ and R ¹¹ , The preferred embodiment is also the same. R ¹⁴ is an etheric oxygen atom having 1 to 10 carbon atoms (—O—) or a nitrogen atom (—NR ^{40 —.} R ⁴⁰ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). Is preferably an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms containing one etheric oxygen atom, and the like. R ¹⁴ is particularly preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n is preferably an integer of 1 to 200, particularly preferably an integer of 2 to 100.

Specific examples of the group (2) include the following.
_{- (Si (CH 3) 2} O) n -Si (CH 3) 2 H, - (Si (CH 3) 2 O) n -Si (CH 3) 2 CH 3, - (Si (CH 3) 2 O _{) n -Si (CH 3) 2} C 2 H 5, - (Si (CH 3) 2 O) n -Si (CH 3) 2 C 3 H 7, - (Si (CH 3) 2 O) n -Si _{(CH 3) 2 C 4 H} 9, - (Si (CH 3) 2 O) n -Si (CH 3) 2 C 5 H 10, - (Si (CH 3) 2 O) n -Si (CH 3) _{2 OH, - (Si (CH} 3) 2 O) n -Si (CH 3) 2 OCH 3, - (Si (CH 3) 2 O) n -Si (CH 3) 2 OC 2 H 5, - (Si _{(C 2 H 5) 2 O} ) n -Si (CH 3) 2 H, - (Si (C 2 H 5) 2 O) n -Si (C 2 H 5) _{2 H, - (Si (C} 2 H 5) 2 O) n -Si (C 2 H 5) 2 H, - (Si (C 2 H 5) 2 O) n -Si (C 2 H 5) 3, _{- (Si (C 2 H 5} ) (CH 3) O) n -Si (C 2 H 5) 2 H.

  Examples of the ethylenic double bond include double bonds having an addition polymerization property such as (meth) acryloyl group, allyl group, vinyl group, vinyl ether group, etc. These may be used alone or in combination of two or more. You may use together. In addition, part or all of the hydrogen atoms of the addition polymerizable group may be substituted with an alkyl group, preferably a methyl group.

  The ink repellent agent (E) is preferably a polymer having a side chain having an acidic group. Some molecules of the ink repellent agent (E) that did not undergo a curing reaction in the exposure process are washed away from the partition wall surface during development because they have side chains having acidic groups, and are not fixed in the partition walls. The remaining molecules are difficult to remain. Therefore, the number of molecules that can migrate to dots in the previous stage of the post-baking process can be further reduced, and the ink affinity of the dots can be further increased.

Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group, and these may be used alone or in combination of two or more.
The side chain having an acidic group may be formed by a polymerization reaction of a monomer having an acidic group, or may be formed by a chemical conversion after the polymerization reaction.

  The ink repellent agent (E) having a side chain having the group (1) or the group (2) and a side chain having an ethylenic double bond used in the present invention is a monomer (a1) or a single monomer described later. Two or more kinds of monomers including a monomer (a2) and a monomer (a3) having a reactive group are copolymerized, and then the obtained copolymer and a functional group capable of binding to the reactive group It can manufacture by making the compound (z1) which has a group and an ethylenic double bond react.

The monomer (a1) is a monomer having the group (1), and the monomer (11) represented by the following formula (11) is preferable.
^{_{CH 2 = CR 21 COO-Y}} -CFXR f (11)
In formula (11), R ²¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, Y represents a single bond or a divalent organic group that does not contain a fluorine atom having 1 to 6 carbon atoms, and R ^f Represents an alkyl group in which at least one hydrogen atom having 20 or less carbon atoms which may have an etheric oxygen atom is substituted with a fluorine atom, or a fluorine atom.
In the monomer (11), the preferred embodiment of -CFXR ^{f is the same as} the preferred embodiment of the group (1). In the monomer (11), Y is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability.

Examples of the monomer (11) include the following.
CH ₂ = CR ²¹ COOR ²² CFXR ^f
CH ₂ = CR ²¹ COOR ²² NR ²³ SO ₂ CFXR ^f
CH ₂ = CR ²¹ COOR ²² NR ²³ COCFRXR ^f
CH ₂ = CR ²¹ COOCH ₂ CH (OH) R ²⁴ CFXR ^f
Here, R ²¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, R ²² represents an alkylene group having 1 to 6 carbon atoms, R ²³ represents a hydrogen atom or a methyl group, and R ²⁴ represents a single atom. A bond or an alkylene group having 1 to 4 carbon atoms is shown, and R ^f has the same meaning as described above.

Specific examples of R ²² include —CH ₂ —, —CH ₂ CH ₂ —, —CH (CH ₃ ) —,
_{-CH 2 CH 2 CH 2 -,} - C (CH 3) 2 -, - CH (CH 2 CH 3) -,
_{-CH 2 CH 2 CH 2 CH 2} -, - CH (CH 2 CH 2 CH 3) -, - CH 2 (CH 2) 3 CH 2 -, - CH (CH 2 CH (CH 3) 2) -, etc. Is mentioned.

Specific examples of R ²⁴ _{are, -CH 2 -, - CH 2} CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH _{2 CH 3) -, - CH} 2 CH 2 CH 2 CH 2 -, - CH (CH 2 CH 2 CH 3) -, and the like.

  Specific examples of the monomer (11) include 2- (perfluorohexyl) ethyl (meth) acrylate and 2- (perfluorobutyl) ethyl (meth) acrylate. Monomer (11) may use 1 type and may use 2 or more types together.

The monomer (a2) is a monomer having the group (2), and the monomer (21) represented by the following formula (21) is preferable.
_{^{CH 2 = CR 25 COO-Z-}} (SiR 10 R 11 O) n -SiR 12 R 13 R 14 (21)
In formula (21), R ²⁵ represents a hydrogen atom or a methyl group, Z represents a single bond or a divalent organic group having 1 to 6 carbon atoms, and R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each Independently, it represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, R ¹⁴ represents a hydrogen atom, an etheric oxygen atom having 1 to 10 carbon atoms, or a nitrogen atom (—NR ^{41 —.} R ⁴¹ represents a hydrogen atom. Or an alkyl group having 1 to 5 carbon atoms.), And n represents an integer of 1 to 200.
In the monomer (21), preferred embodiments of R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and n are the same as the preferred embodiment of the group (2).

Z is preferably a divalent alkyl group having 1 to 6 carbon atoms. Specific examples include the following.
_{-CH 2 -, - CH 2 CH} 2 -, - CH (CH 3) -,
_{-CH 2 CH 2 CH 2 -,} - C (CH 3) 2 -, - CH (CH 2 CH 3) -,
_{-CH 2 CH 2 CH 2 CH 2} -, - CH (CH 2 CH 2 CH 3) -,
_{-CH 2 (CH 2) 3 CH} 2 -, - CH (CH 2 CH (CH 3) 2) - and the like.
The said monomer (21) may use 1 type and may use 2 or more types together.

  The monomer (a3) is a monomer having a reactive group, a monomer having a hydroxyl group, an acid anhydride monomer having an ethylenic double bond, a monomer having a carboxyl group, and an epoxy group. And the like. Examples of the reactive group include a hydroxyl group, an ethylenic double bond, a carboxyl group, and an epoxy group. In addition, it is preferable that a monomer (a3) does not contain group (1) and group (2) substantially.

  Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5- Hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono ( (Meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) Acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide.

Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For _{example, CH 2 = CHOCH 2 C 6} H 10 CH 2 O (C 2 H 4 O) h H ( where, h is 1 to 100 integer, hereinafter the _{same.), CH 2 = CHOC 4} H 8 O (C _{2 H 4 O) h H,} CH 2 = CHCOOC 2 H 4 O (C 2 H 4 O) h H, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) h H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _i (C ₃ H ₆ O) _g H (where i is an integer from 0 to 100, g is an integer from 1 to 100, and m + j is 1 to 100. hereinafter the _{same.), CH 2 = C (} CH 3) COOC 2 H 4 O (C 2 H 4 O) i (C 3 H 6 O) g H , and the like.

Specific examples of the acid anhydride monomer having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4, anhydrous 5,6-tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, and the like can be given.
Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, or salts thereof.
Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

  As the monomer (a3), a compound having a hydroxyl group at the terminal is preferable, (meth) acrylate having a hydroxyl group at the terminal is more preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable.

The compound (z1) is selected according to the reactive group possessed by the monomer (a3). Examples of the combination of the reactive group and the compound (z1) include the following.
(1) An acid anhydride having an ethylenic double bond as the compound (z1) with respect to a hydroxyl group as a reactive group,
(2) A compound having an isocyanate group and an ethylenic double bond as the compound (z1) with respect to the hydroxyl group as the reactive group,
(3) A compound having an acyl chloride group and an ethylenic double bond as the compound (z1) with respect to the hydroxyl group as the reactive group,
(4) A compound having a hydroxyl group and an ethylenic double bond as the compound (z1) with respect to the acid anhydride as the reactive group,
(5) A compound having an epoxy group and an ethylenic double bond as the compound (z1) with respect to the carboxyl group as the reactive group,
(6) A compound having a carboxyl group and an ethylenic double bond as the compound (z1) with respect to the epoxy group as the reactive group.

Specific examples of the acid anhydride having an ethylenic double bond as the compound (z1) include the above-described examples.
Specific examples of the compound having an isocyanate group and an ethylenic double bond as the compound (z1) include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate. It is done.
Specific examples of the compound having an acyl chloride group and an ethylenic double bond as the compound (z1) include (meth) acryloyl chloride.
Specific examples of the compound having a hydroxyl group and an ethylenic double bond as the compound (z1) include the above-described monomer examples having a hydroxyl group.
Specific examples of the compound having an epoxy group and an ethylenic double bond as the compound (z1) include the above-described monomers having an epoxy group.
Specific examples of the compound having a carboxyl group and an ethylenic double bond as the compound (z1) include the above examples of the monomer having a carboxyl group.
As the above combination, the combination of (2) is preferable, and it is particularly preferable to use 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate as the compound (z1). By using this combination, the ink repellent agent (E) has side chains having two or more ethylenic double bonds per side chain, and the ink repellent agent (E) is immobilized on the partition wall surface. This is because a partition wall excellent in ink repellency can be obtained.

When the ink repellent agent (E) has a side chain having an acidic group, it is preferable to copolymerize the monomer (a4) having an acidic group together with the monomers (a1) to (a3).
Examples of the monomer (a4) having an acidic group include a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, and a monomer having a sulfonic acid group.
Examples of the monomer having a carboxyl group include the same monomers as exemplified in the monomer (a3). When a monomer having a carboxyl group is used as the monomer (a4) having an acidic group, and a monomer having a carboxyl group is also used as the monomer (a3) having the reactive group, finally, What is not introduced with an ethylenic double bond and remains as a carboxyl group is regarded as a monomer (a4).

  Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. In addition, one or more hydrogen atoms of these benzene rings are an alkyl group such as a methyl group, an ethyl group or an n-butyl group, an alkoxy group such as a methoxy group, an ethoxy group or an n-butoxy group, a halogen atom or an alkyl group. Examples thereof include compounds in which one or more hydrogen atoms are substituted with a halogen atom, a haloalkyl group, a nitro group, a cyano group, or an amide group.

  Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, and (meth) acrylic acid-2-sulfoethyl. , (Meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, and 2- (meth) acrylamido-2-methylpropanesulfonic acid.

  As a monomer used for the polymerization in the present invention, other monomers (a5) other than the monomers (a1) to (a4) may be used.

The other monomer (a5) is preferably a compound (12) represented by the following formula (12) having a polyoxyalkylene group or a compound (13) represented by the following formula (13). These may be used alone or in combination of two or more.
^{_{CH 2 = CR 26 -COO-W-}} (R 27 O) m (R 28 O) j R 29 ... (12)
^{_{CH 2 = CR 26 -O-W-}} (R 27 O) m (R 28 O) j R 29 ... (13).

In formula (12) and formula (13), R ²⁶ represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms. A substituted alkyl group, an aryl group having 6 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. W is a single bond or a divalent organic group having no fluorine atom having 1 to 10 carbon atoms. R ²⁷ and R ²⁸ each independently represent an alkylene group having 2 to 4 carbon atoms, R ²⁹ represents a hydrogen atom or a part of hydrogen atoms in which a part of the hydrogen atoms may be substituted with a substituent. -10 alkyl groups, m is 0 to 100, j is an integer of 0 to 100, and m + j is 4 to 100.

In the formula (12) and the formula (13), R ²⁷ and R ²⁸ are each independently an alkylene group having 2 to 4 carbon atoms. It may be. R ²⁷ and R ²⁸ may be the same or different. Among such R ²⁷ and R ²⁸ , both are independently —CH ₂ CH ₂ — or —C ₃ H ₆ —, or a combination of —CH ₂ CH ₂ — and —C ₄ H ₈ —. It is preferable that both are —CH ₂ CH ₂ — or a combination of —CH ₂ CH ₂ — and —CH ₂ CH (CH ₃ ) —.

In formula (12) and formula (13), m is an integer from 0 to 100 and j is an integer from 0 to 100. m and j are each preferably from 0 to 50, particularly preferably from 0 to 30. preferable.
Moreover, although m + j is an integer of 4-100, the integer of 6-50 is preferable and the integer of 8-30 is especially preferable. When m + j is equal to or greater than the lower limit of the above range, ink repellency is unlikely to deteriorate when a jet rinsing process using high-pressure water is performed after the development process. Furthermore, it is difficult to generate a residual film. When m + j is less than or equal to the upper limit of the above range, the ink repellent agent (E) does not migrate to the opening during post-baking, and the ink affinity of the opening between the partition walls is sufficient. When the ink is applied, the ink is sufficiently spread in the opening.

Formula (12) and Formula (13) indicate that Compound (12) and Compound (13) have m (R ²⁷ O) units and j (R ²⁸ O) units, The order of bonding of the (R ²⁷ O) unit and the (R ²⁸ O) unit is not particularly limited. That is, in the compound (12) and the compound (13), m (R ²⁷ O) units and j (R ²⁸ O) units are, for example, bonded alternately or randomly or in blocks. Also good.

In Formula (12) and Formula (13), when R ²⁹ is an alkyl group having 1 to 10 carbon atoms in which some of the hydrogen atoms may be substituted with substituents, the structure is a straight chain structure , A branched structure, a ring structure, a structure partially having a ring, or the like may be used. Specific examples of the substituent include a carboxyl group, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms. In the present invention, R ²⁹ in formula (12) and formula (13) is preferably a linear or unsubstituted alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group or an ethyl group.

Specific examples of (R ²⁷ O) and (R ²⁸ O) in formula (12) and formula (13) include —CH ₂ C ₆ H ₁₀ CH ₂ O— (where C ₆ H ₁₀ is cyclohexylene) a _{group), -. CH 2 O -} , - CH 2 CH 2 O -, - CH (CH 3) O -, - CH 2 CH 2 CH 2 O -, - C (CH 3) 2 O -, - _{CH (CH 2 CH 3) O} -, - CH 2 CH 2 CH 2 CH 2 O -, - CH (CH 2 CH 2 CH 3) O -, - CH 2 (CH 2) 3 CH 2 O -, - CH _{(CH 2 CH (CH 3)} 2) O- , and the like. - Specific examples of _{^{(R 27 O) m (R}} 28 O) j R 29 is, ^{(R 27} O) and ^{(R 28} O) are both selected from oxyalkylene groups exemplified above, m + j is 4 And a group in which R ²⁹ is CH ₃ .

In the above formulas (12) and (13), among the groups represented by W, W, which is a divalent organic group having no fluorine atom having 1 to 10 carbon atoms, is represented by R ²⁷ O, R ²⁸ O. Other examples include a straight chain structure, a branched structure, a ring structure, an oxyalkylene group having 1 to 10 carbon atoms, and a single bond. Specific examples of the oxyalkylene group include CH ₂ C ₆ H ₁₀ CH ₂ O (where C ₆ H ₁₀ is a cyclohexylene group), CH ₂ O, CH ₂ CH ₂ O, and CH (CH ₃ ). _{O, CH 2 CH 2 CH 2} O, C (CH 3) 2 O, CH (CH 2 CH 3) O, CH 2 CH 2 CH 2 CH 2 O, CH (CH 2 CH 2 CH 3) O, CH 2 _{(CH 2) 3 CH 2 O} , CH (CH 2 CH (CH 3) 2) O , and the like. Among these, W in the compounds (12) and (13) is preferably an oxyalkylene group having 2 to 4 carbon atoms from the viewpoint of availability.

In the compound (12) and the compound (13), among the groups represented by the above R ²⁶ , a hydrogen atom, a chlorine atom, a methyl group, a phenyl group, a benzyl group and the like are preferable, and a hydrogen atom, a chlorine atom, or a methyl group is preferable. More preferred.

As the compound (12),
_{CH 2 = CHCOO (CH 2 CH} 2 O) m R 29,
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) m R 29,
_{CH 2 = CHCOO (CH 2 CH} 2 O) m (C 3 H 6 O) j R 29,
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) m (C 3 H 6 O) j R 29,
_{CH 2 = CHCOO (C 2 H} 4 O) m (C 4 H 8 O) j R 29
Is preferred.
In addition, as the compound (13),
_{CH 2 = CHOCH 2 C 6 H} 10 CH 2 O (CH 2 CH 2 O) m R 29,
_{CH 2 = CHO (CH 2)} 4 O (CH 2 CH 2 O) m R 29
Is preferred.
In the formula, m and j have the same meaning as described above, and preferred ranges are also the same. C ₆ H ₁₀ is a cyclohexylene group. C ₂ H ₄ , C ₃ H ₆ , and C ₄ H ₈ are either a linear structure or a branched structure. R ²⁹ in the formula represents the same meaning as described above, and a preferred range is a linear or unsubstituted alkyl group having 1 to 10 carbon atoms, such as a methyl group or a hydrogen atom.

A commercial item can be used as a compound (12). The following are mentioned as a commercial item of a compound (12).
Blemmer PME-400 (trade name, manufactured by NOF _{Corporation, CH 2 = C (CH 3} ) COO (CH 2 CH 2 O) k CH 3: k in the formula represents the average value between the molecules, the value of k In the following, k, m, and j in the molecular formula of each commercially available product are all average values between molecules).
Blemmer PME-1000 (trade name, manufactured by NOF Corporation, CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ : k in the formula represents an average value between molecules, and the value of k is About 23.)
NK ester M-230G :( trade name, manufactured by Shin-Nakamura Chemical Co., _{Ltd., CH 2 = C (CH 3} ) COO (CH 2 CH 2 O) k CH 3: wherein, k is about 9).
New Frontier NF biisomer PEM6E (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) _k H: where k is about 6),
Light ester 130A (trade name, manufactured by Kyoeisha Chemical Co., Ltd., CH ₂ ═CHCOO (CH ₂ CH ₂ O) _k CH ₃ : where k is about 9),
Blemmer AE-400:, (trade name, manufactured by NOF _{Corporation, CH 2 = CHCOO (CH 2} CH 2 O) k H wherein, k is about 10.)
Blemmer PP-800:, (trade name, manufactured by NOF _{Corporation, CH 2 = C (CH 3} ) COO (C 3 H 6 O) k H wherein, k is about 13.)
Blemmer AP-800:, (trade name, manufactured by NOF _{Corporation, CH 2 = CHCOO (C 3} H 6 O) k H wherein, k is about 13.)
Blemmer 70PEP-350B (trade name, manufactured by NOF _{Corporation, CH 2 = C (CH 3} ) COO (C 2 H 4 O) m (C 3 H 6 O) j H: wherein, m is from about 5, j is About 2),
Blemmer 55PET-800 (trade name, manufactured by NOF _{Corporation, CH 2 = C (CH 3} ) COO (C 2 H 4 O) m (C 4 H 8 O) j H: wherein, m is about 10, j is About 5).

  The ink repellent agent (E) can be synthesized, for example, by the following method. First, a monomer for obtaining a desired copolymer is dissolved in a solvent and heated, and a polymerization initiator is added for copolymerization to obtain a copolymer. In the copolymerization reaction, it is preferable that a chain transfer agent is present if necessary. The monomer, polymerization initiator, solvent and chain transfer agent may be added continuously.

  Examples of the solvent include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; ketones such as acetone, 2-butanone, methyl isobutyl ketone, and cyclohexanone; 2-methoxyethanol, 2-ethoxy Cellsolves such as ethanol and 2-butoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol; methyl acetate, ethyl Acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, di Tylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, butyl lactate, γ -Esters such as butyrolactone, 3-methyl-3-methoxybutyl acetate, glycerin triacetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl Examples include ether, dibutyl ether, and diethylene glycol methyl ethyl ether.

  Examples of the polymerization initiator include known organic peroxides, inorganic peroxides, azo compounds and the like. Organic peroxides and inorganic peroxides can also be used as redox catalysts in combination with a reducing agent.

  Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl-α-cumyl peroxide and the like. Examples of inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, percarbonate and the like. As the azo compound, 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, Examples include 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (2-amidinopropane) dihydrochloride, and the like. Moreover, it is also possible to use a commercial product V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) or the like as the azo polymerization initiator.

  Examples of chain transfer agents include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate and 2-mercaptoethanol; chloroform, carbon tetrachloride, tetraodor And alkyl halides such as carbon halides.

When the ink repellent agent (E) is a compound having a side chain having a group (1) or a group (2) in one molecule and a side chain having an ethylenic double bond, first, the above copolymerization The monomer (a1) or monomer (a2) and the monomer (a3) having a reactive group are copolymerized by the reaction.
Next, the obtained copolymer is reacted with the compound (z1).
It is preferable to use a solvent for the reaction. As the solvent, the solvent used in the above copolymerization reaction is used.
Moreover, it is preferable to mix | blend a polymerization inhibitor. Examples of the polymerization inhibitor include 2,6-di-t-butyl-p-cresol.
Further, a catalyst or a neutralizing agent may be added. For example, when a copolymer having a hydroxyl group is reacted with a compound having an isocyanate group and an ethylenic double bond, a tin compound such as dibutyltin dilaurate can be used. When the copolymer having a hydroxyl group is reacted with a compound having an acyl chloride group and an ethylenic double bond, a basic catalyst can be used.

In this case, the preferable ratio of each monomer with respect to the total mass of monomers to be copolymerized is as follows.
The ratio of the monomer (a1) or the monomer (a2) is preferably 20 to 80% by mass, particularly preferably 30 to 60% by mass. When the ratio is not less than the lower limit of the above range, the surface tension of the partition made of a cured film can be reduced, and high ink repellency can be imparted to the partition. Adhesiveness of a partition and a base material becomes it favorable that it is below the upper limit of the said range.
The proportion of the monomer (a3) is preferably 20 to 70 mass%, particularly preferably 30 to 50 mass%. Within this range, the fixing of the ink repellent agent (E) to the partition walls by the introduction of the ethylenic double bond and the developability are good.

When the ink repellent agent (E) has a side chain having an acidic group, the ink repellent agent (E) is obtained by copolymerizing the monomer (a4) having an acidic group together with the monomers (a1) to (a3). ) Is obtained.
The proportion of the monomer (a4) is preferably 2 to 20% by mass, particularly preferably 4 to 12% by mass. Within this range, residual molecules that have not been immobilized in the exposure step are easily washed away from the partition walls in the development step.
When the other monomer (a5) is used, the proportion is preferably 70% by mass or less, particularly preferably 50% by mass or less. Within this range, alkali solubility and developability are good.

Preferred combinations of monomers are as follows.
Monomer (a1): Monomer (a3): Monomer (a4): Monomer (a5) = 40-50 mass%: 20-70 mass%: 1-10 mass%: 15-25 mass %.

The copolymer and the compound (z1) are preferably charged so that the value of the equivalent ratio of [functional group of the compound (z1)] / [reactive group of the copolymer] is 0.5 to 2, 0.8 to 1.5 is particularly preferable. When the equivalent ratio is not less than the lower limit of the above range, the ink repellent agent (E) can be fixed to the partition wall. When the amount is not more than the upper limit of the above range, the amount of the unreacted compound (z1) present as an impurity can be kept low, and the coating film appearance can be maintained well.
In addition, when using the monomer which has a carboxyl group as both a monomer (a3) and a monomer (a4), it is common so that the acid value of an ink repellent agent (E) may become the range mentioned later. What is necessary is just to adjust the preparation amount of a polymer and a compound (z1).

  When ink repellent agent (E) has group (1), 5-35 mass% is preferable, and, as for the content rate of the fluorine atom in ink repellent agent (E), 10-35 mass% is especially preferable. When the content is at least the lower limit of the above range, the surface tension of the partition formed from the negative compound can be reduced, and a partition excellent in ink repellency can be obtained. Adhesiveness of a partition and a base material becomes it favorable that it is below the upper limit of the said range.

  When the ink repellent agent (E) has the group (2), the content of silicon atoms in the ink repellent agent (E) is preferably from 0.1 to 25 mass%, particularly preferably from 0.5 to 10 mass%. When the content is equal to or higher than the lower limit of the above range, the surface tension of the partition formed from the negative compound can be reduced and the ink falling property to dots (display portions) can be improved. Adhesiveness of a partition and a base material becomes it favorable that it is below the upper limit of the said range.

When the ink repellent agent (E) contains an ethylenic double bond, the amount is preferably 1.0 × 10 ^{−3 to} 5.0 × 10 ⁻³ mol / g, and 1.5 × 10 ⁻³ to 4 0.5 × 10 ⁻³ mol / g is particularly preferable. Within the above range, the immobilization of the ink repellent agent (E) to the partition and the developability are good.

  When the ink repellent agent (E) has an acidic group, the acid value is preferably 100 mgKOH / g or less, particularly preferably 10 to 50 mgKOH / g. Within the above range, residual molecules that are not immobilized in the exposure process are easily washed away from the partition walls in the development process.

  The number average molecular weight (Mn) of the ink repellent agent (E) is preferably from 1,500 to 50,000, particularly preferably from 3,000 to 50,000. Alkali solubility and developability are favorable in the said range.

  The content ratio of the ink repellent agent (E) in the total solid content in the negative photosensitive composition is preferably 0.01 to 30% by mass, and particularly preferably 0.05 to 20% by mass. When the content ratio is at least the lower limit of the above range, the surface tension of the partition formed from the negative compound can be reduced, and a partition excellent in ink repellency can be obtained. Adhesiveness of a partition and a base material becomes it favorable that it is below the upper limit of the said range.

  The ink repellent agent (E) in the present invention may have both a side chain having a group (1) and a side chain having a group (2) in one molecule. The negative photosensitive composition of the present invention comprises both an ink repellent agent (E) having a side chain having a group (1) and an ink repellent agent (E) having a side chain having a group (2). May be included. In these cases, the partition walls obtained from the negative photosensitive composition can exhibit high ink repellency and ink drop-off properties to dots (display portions).

[Solvent (F)]
The negative photosensitive composition of the present invention contains a solvent (F) as necessary. When the negative photosensitive composition contains a solvent (F), the viscosity of the negative photosensitive composition is reduced, and therefore the negative photosensitive composition is easily applied onto a substrate. Therefore, a uniform coating film of the negative photosensitive resin composition can be formed. In addition, when a negative photosensitive composition does not contain a solvent (F), the coating film of a negative photosensitive composition becomes the same as the film | membrane of a negative photosensitive composition.

  The solvent (F) contained in the negative photosensitive composition of the present invention is the alkali-soluble resin (A), black colorant (B), photopolymerization initiator (C1) contained in the negative photosensitive composition. ) And a photopolymerization initiator (C2), and if necessary, a crosslinking agent (D), an ink repellent agent (E), a thermosetting agent (I) described later, and an optional component described later are uniformly dissolved or dispersed. There is no particular limitation as long as it has a function of uniformly and easily applying the negative photosensitive composition to the base material on which the partition walls are formed, and has no reactivity with these components. The same solvent as that used in the synthesis of the ink repellent agent (E) can be used. Other examples include chain hydrocarbons such as n-butane and n-hexane, cyclic saturated hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene, xylene, and benzyl alcohol. These may be used alone or in combination of two or more.

  The content ratio of the solvent (F) contained in the negative photosensitive composition varies depending on the composition and use of the negative photosensitive composition, but is 50 to 99% by mass in the negative photosensitive composition. It is preferable to mix | blend, 60-95 mass% is more preferable, and 65-90 mass% is especially preferable.

[Fine particles (G)]
The negative photosensitive composition may contain fine particles (G) as necessary. When the negative photosensitive composition contains the fine particles (G), the partition obtained from the negative photosensitive composition becomes a partition excellent in heat resistance in which thermal sagging is prevented.
As the fine particles (G), various inorganic and organic fine particles can be used, and those in which the basic polymer dispersant is negatively charged from the viewpoint of adsorption ability are preferably used.

Examples of inorganic materials include silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO). Examples of the organic system include polyethylene and polymethyl methacrylate (PMMA). In consideration of heat resistance, inorganic fine particles are preferable, and in view of availability and dispersion stability, silica or zirconia is particularly preferable. Furthermore, considering the exposure sensitivity of the negative photosensitive composition, it is preferable that the fine particles (G) do not absorb the light irradiated at the time of exposure, i-line (365 nm), which is the main emission wavelength of the ultra-high pressure mercury lamp, It is particularly preferable not to absorb h-line (405 nm) and g-line (436 nm).
The particle diameter of the fine particles (G) is preferably 1 μm or less, and particularly preferably 200 nm or less, because the surface smoothness of the partition walls is improved.

  3-20 mass% is preferable, as for the content rate of the microparticles | fine-particles (G) in the total solid in a negative photosensitive resin composition, 5-15 mass% is more preferable, and 7-10 mass% is especially preferable. When the content ratio is not less than the lower limit of the above range, there is an effect of suppressing the decrease in ink repellency due to post-baking, and when it is not more than the upper limit of the above range, the stability of the liquid of the negative photosensitive composition is good. become.

[Silane coupling agent (H)]
The negative photosensitive composition may contain a silane coupling agent (H) as necessary. When the negative photosensitive composition contains the silane coupling agent (H), the substrate adhesion of the cured film formed from the negative photosensitive composition can be improved.
Specific examples of the silane coupling agent (H) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloropropyl. Examples include trimethoxysilane, 3-mercaptopropyltrimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and imidazolesilane. These may be used alone or in combination of two or more.

  0.1-20 mass% is preferable and, as for the content rate of the silane coupling agent (H) in the total solid in a negative photosensitive resin composition, 1-10 mass% is especially preferable. When it is at least the lower limit of the above range, the substrate adhesion of the cured film formed from the negative photosensitive composition is improved, and when it is at most the upper limit of the above range, the ink repellency is good.

[Thermosetting agent (I)]
The negative photosensitive composition may contain a thermosetting agent (I) as necessary. By including the thermosetting agent (I) in the negative photosensitive composition, the heat resistance and water permeability of the partition walls can be improved.
The thermosetting agent (I) includes an amino resin, a compound having two or more epoxy groups, a compound having two or more hydrazino groups, a polycarbodiimide compound, a compound having two or more oxazoline groups, two or more Examples thereof include compounds having an aziridine group, polyvalent metals, compounds having two or more mercapto groups, and polyisocyanate compounds. Among these, an amino resin, a compound having two or more epoxy groups, or a compound having two or more oxazoline groups is particularly preferable from the viewpoint of improving chemical resistance of the formed partition wall.

  1-50 mass% is preferable and, as for the content rate of the thermosetting agent (I) in the total solid in a negative photosensitive resin composition, 1-30 mass% is especially preferable. Within the above range, the developability of the obtained negative photosensitive composition is improved.

[Phosphate compound (J)]
The negative photosensitive composition may contain a phosphoric acid compound (J) as necessary. Adhesiveness with a base material can be improved because a negative photosensitive resin composition contains a phosphoric acid compound (J).
Examples of the phosphoric acid compound include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.

  0.1-10 mass% is preferable and, as for the content rate of the phosphoric acid compound (J) in the total solid in a negative photosensitive resin composition, 0.3-1 mass% is especially preferable. Adhesiveness with the base material of the cured film formed from the negative photosensitive composition obtained as it is the said range becomes favorable.

[Other additives]
In the negative photosensitive composition, a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber, and the like can be used as necessary.

[Negative photosensitive composition]
The negative photosensitive composition of the present invention contains an alkali-soluble resin (A), a black colorant (B), a photopolymerization initiator (C1), and a photopolymerization initiator (C2). Furthermore, a crosslinking agent (D), an ink repellent agent (E), a solvent (F), and a thermosetting agent (I) are contained as needed. Furthermore, you may contain said fine particle (G), a silane coupling agent (H), a phosphoric acid compound (J), and another additive.
The negative photosensitive composition is used as a material such as photolithography in the same manner as an ordinary negative photosensitive composition, and the cured film obtained is a cured film of an ordinary negative photosensitive composition. It can be used as a member of the optical element used.

(Preferred combination of negative photosensitive composition)
In the negative photosensitive composition of the present invention, it is preferable to select a composition and a blending ratio in accordance with applications and required characteristics.
The preferable composition of the various compounding components in the negative photosensitive resin composition of the present invention is shown below.
Alkali-soluble resin (A): a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol A type epoxy resin, a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol F type epoxy resin, phenol novolac type Resin with an acidic group and ethylenic double bond introduced into an epoxy resin, a resin with an acidic group and ethylenic double bond introduced into a cresol novolac type epoxy resin, an acidic group and an ethylenic double group into a trisphenolmethane type epoxy resin A resin having a double bond introduced therein, or at least one resin selected from resins having an acidic group and an ethylenic double bond introduced into the epoxy resins represented by the above formulas (A1-2a) to (A1-2c). 10 to 60% by mass in the total solid content in the negative photosensitive resin composition,

Black colorant (B): at least one colorant selected from carbon black and organic pigments, 20 to 65% by mass in the total solid content in the negative photosensitive composition,
Photopolymerization initiator (C1): an O-acyloxime compound represented by the formula (3), wherein 0.1 to 5% by mass in the total solid content in the negative photosensitive composition,
Photopolymerization initiator (C2): an O-acyloxime compound represented by formula (4), wherein 3 to 7% by mass (light relative to the total solid content) in the total solid content in the negative photosensitive composition The ratio of the total content of the polymerization initiator (C1) and the photopolymerization initiator (C2) is 3.5 to 7.0% by mass, and the ratio of the photopolymerization initiator (C1) to the total content is 5 to 15% by mass),
Crosslinking agent (D): a compound having two or more ethylenic double bonds in the molecule and no acidic group, and 2 to 15 mass in the total solid content in the negative photosensitive composition %,
Ink repellent agent (E): at least one ink repellent agent selected from a compound having a side chain having a group represented by the formula (1) in a molecule and a side chain having an ethylenic double bond. In the total solid content in the negative photosensitive resin composition, 0.01 to 30% by mass,

Solvent (F): at least one solvent selected from water, 2-propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol ethyl methyl ether, butyl acetate, 4-butyrolactone, and cyclohexanone. In the negative photosensitive composition, 50 to 99% by mass,
Thermosetting agent (I): a compound having two or more epoxy groups in a molecule, and 1 to 30% by mass in the total solid content in the negative photosensitive composition.

[Optical Element Partitions and Manufacturing Method Thereof]
The partition of this invention is a partition formed in order to provide a division on a support substrate, Comprising: It consists of a cured film of the said negative photosensitive resin composition of this invention. The partition of this invention is used suitably for the use of an optical element, and since the said negative photosensitive composition contains a black coloring agent (B), the partition obtained can be applied as a black matrix. . The partition of the present invention is applied to a partition for an optical element having, for example, a plurality of pixels and a partition located between adjacent pixels on a support substrate.

By using the negative photosensitive composition of the present invention, partition walls can be formed on fine lines close to the mask pattern. At the same time, if contact holes are required on the partition walls, minute contact holes can be formed. It is. Furthermore, when the negative photosensitive composition contains the ink repellent agent (E), sufficient ink repellency can be imparted at the same time.
Examples of the method for producing the barrier rib (black matrix) for the optical element of the present invention using the negative photosensitive composition of the present invention include the following methods.

  The negative photosensitive composition of the present invention is applied onto the support substrate to form a coating film (coating film forming process), and then the coating film is dried to form a film (drying process). Only the part which becomes the partition of the film is exposed and photocured (exposure process), and then the coating film other than the photocured part is removed to form the partition consisting of the photocured part of the coating film (development process) Then, if necessary, the partition walls formed as described above are further thermally cured (post-baking step), whereby the partition walls (black matrix) for the optical element of the present invention can be produced. Moreover, you may put further the photocuring (post exposure process) of the said formed partition etc. between a image development process and a post-baking process.

The material of the support substrate is not particularly limited, but various glass plates; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, poly (meth) acrylic resin, etc. A thermoplastic plastic sheet; a cured sheet of a thermosetting resin such as epoxy resin and unsaturated polyester can be used. In particular, a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance. Moreover, since a post exposure may be performed from the back surface (board | substrate side) in which the partition is not formed, it is preferable that it is a transparent substrate.
The coating surface of the negative photosensitive resin composition of the support substrate is preferably cleaned in advance by alcohol cleaning, ultraviolet / ozone cleaning or the like before coating.
Further, when the partition (black matrix) is formed on the TFT array substrate like a BOA type color filter, it is only necessary to prepare a support member on which a predetermined member such as a TFT array is formed in advance.

(Coating film formation process)
The coating method is not particularly limited as long as a coating film having a uniform film thickness is formed. Usually, spin coating, spraying, slit coating, roll coating, spin coating, bar coating, etc. The method used for the coating film formation of this is mentioned.
The film thickness of the coating film is determined in consideration of the height of the partition wall finally obtained and the solid content concentration of the negative photosensitive composition. The film thickness of the coating film is preferably from 500 to 2,000%, particularly preferably from 550 to 1,000%, of the height of the partition wall finally obtained. The thickness of the coating film is preferably from 0.3 to 100 μm, particularly preferably from 1 to 50 μm.

(Drying process)
The coating film formed on the support substrate in the coating film forming step is dried to obtain a film. By drying, volatile components including the solvent contained in the negative photosensitive composition constituting the coating film are volatilized and removed, and a non-sticky film is obtained. Further, when the negative photosensitive composition contains the ink repellent agent (E), the ink repellent agent (E) moves to the vicinity of the coating film surface.
Drying is preferably performed by vacuum drying or heat drying (pre-baking). Moreover, it is more preferable to use vacuum drying and heat drying together in order to efficiently dry the coating film without causing unevenness of the coating film appearance.
The vacuum drying conditions vary depending on the type of each component, the blending ratio, and the like, but it is preferable to perform the drying at 500 to 10 Pa for 10 to 300 seconds.
Heat drying is preferably performed at 50 to 120 ° C. for 10 to 2,000 seconds with a heating device such as a hot plate or oven together with the support substrate.

(Exposure process)
A part of the obtained film is exposed through a mask having a predetermined pattern. The negative photosensitive resin composition in the exposed area is cured, and the negative photosensitive resin composition in the unexposed area is not cured. Examples of the irradiation light include excimer lasers such as visible light, ultraviolet light, far ultraviolet light, KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, KrAr excimer laser, Ar ₂ excimer laser, X-rays, and electron beams Etc. Light having a wavelength of 100 to 600 nm is preferable, electromagnetic waves having a distribution in the range of 300 to 500 nm are more preferable, and i-line (365 nm), h-line (405 nm), and g-line (436 nm) are particularly preferable.
As the irradiation device, a known ultra-high pressure mercury lamp or the like can be used. Exposure is preferably ^{5~1,000mJ / cm 2, 50~400mJ / cm} 2 is particularly preferred. When the exposure amount is not less than the lower limit of the above range, the partition walls are sufficiently cured. A high resolution is obtained when it is not more than the upper limit of the above range.

(Development process)
It develops with a developing solution and the negative photosensitive resin composition of an unexposed part is removed. As the developing solution, an alkaline aqueous solution containing alkalis such as inorganic alkalis, amines, alcohol amines, and quaternary ammonium salts can be used. Further, an organic solvent such as a surfactant or alcohol can be added to the developer in order to improve solubility and remove residues.
The development time (time for contacting with the developer) is preferably 5 to 180 seconds. Examples of the developing method include a liquid piling method, a dipping method, and a shower method. After development, water on the support substrate can be removed by washing with high pressure water or running water and air-drying with compressed air or compressed nitrogen.

(Post exposure process)
Next, you may perform post exposure as needed. The post-exposure may be performed from either the front surface where the partition walls are formed or the back surface (substrate side) where the partition walls are not formed. Moreover, you may expose from both front and back. Preferred exposure is at 50 mJ / cm ² or more, good 200 mJ / cm ² or more, and more preferably 1,000 mJ / cm ² or more, 2,000 mJ / cm ² or more is particularly preferable.

  The light to be irradiated is preferably ultraviolet light, and a known ultrahigh pressure mercury lamp or high pressure mercury lamp can be used as the light source. These light sources are preferably used because they emit light having a wavelength of 600 nm or less that contributes to the hardening of the barrier ribs, and emit less light having a wavelength of 200 nm or less that causes oxidative decomposition of the barrier ribs. Furthermore, it is preferable that the quartz tube glass used for the mercury lamp has an optical filter function for cutting light of 200 nm or less.

A low pressure mercury lamp can also be used as the light source. However, a low-pressure mercury lamp has a high emission intensity at a wavelength of 200 nm or less, and oxidative decomposition of the partition walls is likely to occur due to the generation of ozone. The exposure amount is preferably 500 mJ / cm ² or less, particularly preferably 300 mJ / cm ² or less.

(Post bake process)
Subsequently, it is preferable to heat the partition wall. By performing heat treatment for 5 to 90 minutes with a heating device such as a hot plate or an oven, a pattern composed of the partition walls and the regions (dots) divided by the partition walls is formed.
The heating temperature is preferably 150 to 250 ° C, particularly preferably 180 to 250 ° C. When the heating temperature is equal to or higher than the lower limit of the above range, the partition walls are sufficiently cured, and sufficient chemical resistance is obtained. When the ink is applied in the subsequent inkjet coating process, the solvent is contained in the ink. The partition wall does not swell and the ink does not ooze. When it is below the upper limit of the above range, thermal decomposition of the partition wall is difficult to occur.

  The pattern formed from the negative photosensitive composition of the present invention preferably has an average partition wall width of 100 μm or less, particularly preferably 20 μm or less. In addition, the average distance between adjacent partition walls (dot width) is preferably 300 μm or less, and particularly preferably 100 μm or less. Moreover, it is preferable that the average of the height of a partition is 0.05-50 micrometers, and it is especially preferable that it is 0.2-10 micrometers.

  When the partition wall (black matrix) of the present invention is applied to a so-called BOA color filter in which a color filter is disposed on a TFT array substrate, the partition wall (black matrix) is used to connect a switching element such as a TFT and a pixel electrode. It is necessary to form a through-hole penetrating in the film thickness direction as a contact hole in the matrix. The contact hole is formed by forming a mask having a predetermined pattern used in the above exposure process into a pattern capable of forming a contact hole. The size of the contact hole depends on the type and design of the optical element to be used, but if the negative photosensitive composition of the present invention is used, the major axis of the cross section having the largest horizontal cross-sectional area in the through hole serving as the contact hole, that is, A minute contact hole having a maximum hole diameter of 20 μm or less can be formed. Therefore, the partition wall (black matrix) of the present invention is suitable as a partition wall (black matrix) for optical elements that require such minute contact holes.

  Here, in order for the through hole in the film thickness direction to function as a contact hole, the minimum horizontal hole diameter in the through hole is preferably 1 μm or more, and particularly preferably 2 μm or more. In order to make the contact hole sufficiently small in size, the maximum hole diameter in the horizontal direction of the through hole is preferably 20 μm or less, and particularly preferably 15 μm or less.

  The ink repellency of the cured film formed from the negative photosensitive composition can be estimated by the contact angle of PGMEA, and the contact angle of PGMEA is preferably 30 degrees or more, particularly preferably 35 degrees or more. Within the above range, ink repellency is sufficient to prevent color mixing due to overflow of the inkjet coating liquid into adjacent pixels.

Examples of the optical element to which the partition wall (black matrix) of the present invention is applied include a color filter and an organic EL display element. In particular, since the partition wall can be formed in a fine line pattern close to the mask pattern to be used, and at the same time, a minute contact hole can be formed in the fine partition wall, the black matrix of the present invention has the BOA. It is suitably used for a type of color filter.
Furthermore, the present invention provides a liquid crystal display element in which the color filter of the present invention is formed on a TFT array substrate. Since the color filter of the present invention employs a black matrix in which minute contact holes are formed in a minute line pattern, if a liquid crystal display element having this color filter on a TFT array substrate is used, low power consumption is achieved. A liquid crystal display device compatible with high luminance can be obtained.

[Color filter manufacturing method]
After the partition (black matrix) is formed as described above, a color filter can be manufactured by injecting ink into the region divided by the partition using an inkjet method using an inkjet apparatus to form pixels.

  When the color filter of the present invention is formed on a TFT array substrate, a support substrate having a TFT array previously formed on the substrate as described above is used, and the above-described color filter of the present invention is placed at a predetermined position on the substrate. After forming the black matrix by the manufacturing method, the pixels may be formed by injecting ink into the region partitioned by the black matrix on the substrate by an ink jet method.

  In addition, in the support substrate having or without the TFT array in which the black matrix is formed, before injecting ink into the region (dot) partitioned by the black matrix, the substrate surface exposed in the dot is For example, the ink-repellent treatment may be performed by a method such as cleaning with an alkaline aqueous solution, UV cleaning, UV ozone cleaning, excimer cleaning, corona discharge, or oxygen plasma.

The ink jet device is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, a method in which ink is ejected intermittently using a piezoelectric element, and ink is heated to foam. An apparatus using various methods such as a method of intermittent injection by use can be used.
The pixel shape may be any known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type. When the color filter of the present invention is formed on the TFT array substrate, the black matrix has a predetermined position set in consideration of the shape of the pixel and the positional relationship of the TFT array on the TFT array substrate. Formed in a predetermined shape.

The ink mainly contains a coloring component, a binder resin component, and a solvent. As the coloring component, it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like.
As the binder resin component, a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin. The water-based ink contains water and, if necessary, a water-soluble organic solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary. The oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.
In the ink jet method, after ink is injected into the dots by the ink jet device, the ink layer formed in the dots is subjected to treatment such as drying, heat curing, and ultraviolet curing as necessary. Pixels are formed.

After the pixel formation, a protective film layer is formed as necessary. The protective film layer is preferably formed for the purpose of increasing the surface flatness and for blocking the eluate from the ink in the partition walls and the pixel portion from reaching the liquid crystal layer. When forming the protective film layer, it is preferable to remove the ink repellency of the partition wall in advance. If the ink repellency is not removed, the overcoat coating solution is repelled, and a uniform film thickness cannot be obtained. Examples of the method for removing the ink repellency of the partition include plasma ashing and optical ashing.
Further, if necessary, it is preferable to form a photo spacer on the partition wall in order to improve the quality of a liquid crystal panel or the like manufactured using a color filter.

[Method of manufacturing organic EL display element]
Before forming the partition walls, a transparent electrode such as tin-doped indium tin oxide (ITO) is formed on a transparent substrate such as glass by sputtering or the like, and the transparent electrode is etched into a desired pattern as necessary. Next, a barrier rib is formed using the negative photosensitive composition of the present invention, and after a dot is made into an ink, a solution of a hole transport material and a light emitting material is sequentially applied to the dot using an inkjet method and dried. Thus, a hole transport layer and a light emitting layer are formed. Then, an organic EL display element pixel is obtained by forming an electrode such as aluminum by vapor deposition or the like.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Examples 1 to 7 are examples, and examples 11 to 17 are comparative examples.

Each measurement was performed by the following method.
[Number average molecular weight (Mn)]
Polystyrene was measured as a standard substance by gel permeation chromatography.
[Content of fluorine atom in ink repellent agent (E), amount of ethylenic double bond, acid value]
The fluorine atom content in the ink repellent agent (E) was calculated by ¹⁹ F NMR measurement using 1,4-ditrifluoromethylbenzene as a standard substance.
The amount of ethylenic double bonds in the ink repellent agent (E) was calculated by ¹ H NMR measurement using 1,4-ditrifluoromethylbenzene as a standard substance.
The acid value (mgKOH / g) in the ink repellent agent (E) and the number of ethylenic double bonds in one molecule are theoretical values calculated from the blending ratio of the monomer as a raw material.

Abbreviations of the compounds used in Synthesis Examples and Examples are as follows.
(Alkali-soluble resin (A))
EX1010: a resin in which an ethylenic double bond and an acidic group are introduced into the epoxy resin represented by the above formula (A1-2b) (manufactured by Nagase ChemteX Corporation, trade name: EX-1010, mass average molecular weight (Mw): 3,300, acid value: 60 mg KOH / g, solid content: 70% by mass).
ZCR1642: Resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the above formula (A1-2a) (trade name: ZCR-1642H, mass average molecular weight, manufactured by Nippon Kayaku Co., Ltd.) (Mw): 5,800, acid value: 100 mgKOH / g, solid content: 70% by mass).
(Black colorant (B))
DINA: PGMEA dispersion of organic pigment (manufactured by DIC Corporation, trade name: DINA mixed color BM, solid content: 19.5% by mass).

(Photopolymerization initiator (C1))
OXE02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (in the compound represented by the formula (3), R ¹ : methyl group, R ² : methyl group, R ³ : ethyl group, R ⁴ , R ⁶ , R ⁷ : hydrogen atom, R ⁵ : 2-methylbenzoyl group, manufactured by BASF, trade name: OXE02. ).
(Photopolymerization initiator (C2))
OXE01: 1.2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (0-benzoyloxime) (in the compound represented by formula (4), R ⁸ : phenyl group, R ⁹ : It is represented by a hexyl group, manufactured by BASF, trade name: OXE01).
(Crosslinking agent (D))
UX5002: polyfunctional urethane acrylate oligomer (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD UX-5002D-P20).

(Compound used for synthesizing ink repellent agent (E))
MEK: 2-butanone.
_{C6FMA: CH 2 = C (CH} 3) COOCH 2 CH 2 (CF 2) 6 F ( corresponding to the monomer (a1).).
MAA: Methacrylic acid (corresponding to monomer (a4)).
PME400: BLEMMER PME-400 (manufactured by NOF Corporation, CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ , _{k in} the formula represents an average value between molecules, and the value of k is about 9) (corresponds to the monomer (a5) compound (12)).
PME1000: Blemmer PME-1000 (manufactured by NOF Corporation, CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ : k in the formula represents an average value between molecules, and the value of k is about (It corresponds to the compound (12) of the monomer (a5).).
2-HEMA: 2-hydroxyethyl methacrylate (corresponds to monomer (a3)).
V-65: an azo polymerization initiator (trade name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.).
AOI: 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz AOI) (corresponds to compound (z1)).
DBTDL: Dibutyltin dilaurate.
BHT: 2,6-di-t-butyl-p-cresol.

(Solvent (F))
PGMEA: Propylene glycol 1-monomethyl ether 2-acetate.
(Thermosetting agent (I))
XD1000: Multifunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: XD1000)

[Synthesis Example 1: Synthesis of ink repellent agent (E-1)]
MEK (700 g), C6FMA (140 g), MAA (15 g), PME400 (60 g), 2-HEMA (85 g) and polymerization initiator V-65 (2 g) are charged into an autoclave having an internal volume of 2 L equipped with a stirrer. While stirring in nitrogen gas, polymerization was carried out at 50 ° C. for 24 hours to synthesize a crude copolymer. The resulting crude copolymer solution was added to hexane for reprecipitation purification, and then vacuum dried to obtain copolymer 1 (242 g).
The copolymer 1 had a number average molecular weight (Mn) of 35,000 and a mass average molecular weight (Mw) of 91,000.

(Introduction of ethylenic double bond)
Into a 300 mL glass flask equipped with a thermometer, stirrer, and heating device, copolymer 1 (40 g), AOI (12 g), DBTDL (0.05 g), BHT (0.2 g) and MEK (130 g) were added. ) And stirred for 24 hours at 40 ° C. to obtain a solution of the ink repellent agent (E-1). The MEK solution of the obtained ink repellent agent (E-1) was added to heptane for purification by reprecipitation, followed by vacuum drying to obtain ink repellent agent (E-1) (65.6 g). The number average molecular weight (Mn) was 38,000. Infrared spectroscopic analysis of the ink repellent agent (E-1) revealed that the absorption band (1,635 cm ⁻¹ ) derived from the C═C stretching vibration of the acryloyl group and the CH _{2 in-} plane bending vibration of the acryloyl group. absorption band derived from (1,409cm ^-1), and CH ₂ faces out bending absorption band derived from the vibration of an acryloyl group (810 cm ^-1) is present, also the absorption band derived from the NCO stretching vibration of AOI ( 2,274 cm ⁻¹ ) had disappeared, confirming the presence of an acryloyl group in the ink repellent agent (E-1).
The number average molecular weight (Mn) of the obtained ink repellent agent (E-1), the content of fluorine atoms, the amount of ethylenic double bonds (C = C amount, × 10 ⁻³ mol / g), acid value ( mgKOH / g) is shown in Table 1.

[Synthesis Example 2: Synthesis of ink repellent agent (E-2)]
Copolymer 2 was obtained by the same copolymerization reaction except that the composition of the raw materials was changed as shown in Table 1 in the synthesis of copolymer 1. Next, in the synthesis of the ink repellent agent (E-1), an ink repellent agent (E-2) was obtained by the same reaction except that the composition of the raw materials was changed as shown in Table 1. The number average molecular weight (Mn) of the obtained ink repellent agent (E-2), the content of fluorine atoms, the amount of ethylenic double bonds (C = C amount, × 10 ⁻³ mol / g), acid value ( mgKOH / g) is shown in Table 1.

[Examples 1 to 7 and 11 to 17: Preparation of negative photosensitive composition, formation and evaluation of partition walls]
In the proportions shown in Tables 2 and 3, the alkali-soluble resin (A) (containing 40% by mass of PGNEA as a solvent), the black colorant (B) (containing 80% by mass of PGMEA as a solvent), and a photopolymerization initiator. (C1), photopolymerization initiator (C2), crosslinking agent (D) (containing 20% by mass of PGMEA as a solvent), ink repellent agent (E) (containing 90% by mass of PGMEA as a solvent), thermosetting agent. PGMEA was blended as (I) and the solvent (F) to obtain a negative photosensitive composition.
A negative photosensitive resin composition was applied onto a glass substrate using a spinner to form a coating film (coating film forming step). Next, it was dried on a hot plate at 100 ° C. for 2 minutes to obtain a glass substrate (1) having a film thickness of 3 μm (drying step). Next, the exposure dose is based on i-line (365 nm) using a super high pressure mercury lamp through a photomask having a linear opening of 10 μm × 10 mm and a light-shielding part having a diameter of 20 μm in the center of the opening of 50 μm × 50 μm. Was irradiated with light of 50 mJ / cm ² (exposure process).

Subsequently, the unexposed portion was developed by being immersed in an inorganic alkali type developer (manufactured by Yokohama Oil & Fats Co., Ltd., trade name: semi-clean DL-A4 10-fold diluted aqueous solution), and the unexposed portion was washed with water and dried. (Development process).
Subsequently, the glass substrate (2) in which the pattern was formed was obtained by heating on a hotplate at 220 degreeC for 1 hour (post-baking process). About these, pattern formation property, developability, and ink repellency were measured and evaluated by the method shown below. The evaluation results are shown in Tables 2 and 3.

(Line resolution)
With respect to the glass substrate (2), the presence or absence of the pattern was evaluated with ○ (good) indicating that a linear pattern having a width of 10 μm and a length of 10 mm remained, and × (defective) not remaining.
(Contact hole resolution)
Regarding the glass substrate (2), a circular hole having a diameter of 20 μm in the upper part of the partition wall was penetrated with a diameter of 1 μm or more without developing a residue or the like at the bottom part by development. The presence / absence of a pattern was evaluated as “bad”.
(Solubility in developer)
About the said glass substrate (1), the coated negative photosensitive composition was melt | dissolved in the developing solution, and the presence or absence of the deposit was observed visually. Those in which no precipitate was observed were described as ◯ (good), and those that were observed as x (bad).

(Ink repellency)
The ink repellency was evaluated by the contact angle (degree) of PGMEA of the cured film on the glass substrate (2). The contact angle is an angle formed by a solid surface and a tangent to the liquid surface at a point where the solid and the liquid are in contact, and is defined as an angle including the liquid. The larger the angle, the better the ink repellency of the cured film. A contact angle of PGMEA of 35 degrees or more was expressed as ◯ (good), and a contact angle of less than 35 degrees was expressed as x (bad).

From Table 2, the negative photosensitive composition of the present invention has good solubility in a developer, and a fine line width pattern can be formed from the negative photosensitive composition. The formation of was also possible. Further, the ink repellency of the cured film formed from the negative photosensitive composition was also good.
On the other hand, in Table 3, the negative type photosensitivity in which the total ratio of the content of the photopolymerization initiator (C1) and the content of the photopolymerization initiator (C2) in the total solid content is 3.5% by mass or less. In Examples 11 and 13 using the composition, the line resolution and ink repellency were insufficient. The photocurability inside the black matrix was insufficient, and the lower part of the pattern dissolved during development, resulting in poor line resolution. Further, since the amount of the photopolymerization initiator used is insufficient, the ink repellent agent on the surface of the structure does not sufficiently photoreact and is eluted during development.
In Table 3, a negative photosensitive composition in which the total ratio of the content of the photopolymerization initiator (C1) and the content of the photopolymerization initiator (C2) in the total solid content is 7% by mass or more is used. In Examples 15, 16 and 17, the contact hole resolution was insufficient. This is because photocuring of the unexposed area occurs because the amount of the photopolymerization initiator used is excessive.

Negative photosensitive resin composition in which the ratio of the content of the photopolymerization initiator (C1) to the total of the content of the photopolymerization initiator (C1) and the content of the photopolymerization initiator (C2) is 5% by mass or less. In Example 12 using the line resolution, the line resolution was insufficient. Further, the solubility of the negative photosensitive composition in the developer was insufficient. This is presumed to be because the photopolymerization initiator (C2) is contained in a large amount so as to adsorb on the pigment dispersant and deteriorate the dispersibility of the pigment in the aqueous alkali solution.
Negative photosensitive resin composition in which the ratio of the content of the photopolymerization initiator (C1) to the total content of the photopolymerization initiator (C1) and the photopolymerization initiator (C2) is 15% by mass or more. In Example 14 using the contact hole, the resolution of the contact hole was insufficient. This is because the photopolymerization initiator (C1) amount relative to the total amount of the initiator is excessive, so that photocuring occurs at the light shielding portion.

  According to the negative photosensitive composition of the present invention, a partition and a black matrix having a fine line pattern and a fine contact hole can be produced. Such a black matrix is suitably used for a color filter, in particular, a BOA type color filter capable of obtaining a high luminance image with low power consumption.

Claims (10)

An alkali-soluble resin (A) having an acidic group and an ethylenic double bond in one molecule;
Black colorant (B),
A photopolymerization initiator (C1) comprising a compound represented by the following formula (3),
And a photopolymerization initiator (C2) comprising a compound represented by the following formula (4):
A negative-type photosensitive composition comprising
The ratio of the total content of the photopolymerization initiator (C1) and the photopolymerization initiator (C2) with respect to the total solid content is 3.5 to 7.0% by mass, and the photopolymerization initiator with respect to the total content The negative photosensitive resin composition, wherein the proportion of (C1) is 5 to 15% by mass.

In Formula (3), R ¹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a hydrogen atom in a benzene ring. Represents a phenyl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, or a phenoxy group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group,
R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a hydrogen atom in the benzene ring in which an alkyl group may be substituted with an alkyl group. Phenyl group, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an alkoxycarbonyl group having 2 to 12 carbon atoms Or a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group,
R ³ represents an alkyl group having 1 to 12 carbon atoms,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom in which a hydrogen atom in the cycloalkane ring may be substituted with an alkyl group. A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a hydrogen atom in the benzene ring A benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group, a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom An alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and 1 to 20 carbon atoms It shows a bromide group or a nitro group.

In the formula (4), R ⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a hydrogen atom in a benzene ring. Represents a phenyl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, or a phenoxy group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group,
R ⁹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a carbon atom number 6 to 20 in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. Phenyl group, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an alkoxycarbonyl group having 2 to 12 carbon atoms Alternatively, it represents a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.   The negative mold according to claim 1, further comprising a crosslinking agent (D), wherein the crosslinking agent (D) is a compound having two or more ethylenic double bonds in one molecule and having no acidic group. Photosensitive composition.   The negative photosensitive composition according to claim 1 or 2, further comprising a thermosetting agent (I), wherein the thermosetting agent (I) is a compound having two or more epoxy groups in one molecule.   The negative photosensitive resin composition as described in any one of Claims 1-3 which further contains an ink repellent agent (E). The ink repellent agent (E) includes a side chain having a group represented by the following formula (1) or a group represented by the following formula (2) in one molecule, and a side chain having an ethylenic double bond. The negative photosensitive resin composition according to claim 4, which is an ink repellent agent (E) containing
-CFXR ^f (1)
In the formula (1), X represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and R ^f is a carbon atom in which at least one hydrogen atom optionally having an etheric oxygen atom is substituted with a fluorine atom. An alkyl group of several 20 or less, or a fluorine atom is shown.
_{^{- (SiR 10 R 11 O)}} n -SiR 12 R 13 R 14 (2)
In formula (2), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ¹⁴ represents a hydrogen atom or a carbon atom number of 1 to 10 An alkyl group which may contain an etheric oxygen atom or nitrogen atom, and n represents an integer of 1 to 200.   It is a partition formed in order to provide a partition on a support substrate, Comprising: The partition which consists of a cured film of the negative photosensitive resin composition as described in any one of Claims 1-5.   A black matrix comprising the partition walls according to claim 6.   The through hole penetrating in the film thickness direction of the partition wall formed simultaneously with the partition wall, the maximum horizontal hole diameter in the through hole being 20 μm or less, and the minimum hole diameter being 1 μm or more. Black matrix.   A color filter having a plurality of pixels formed on a support substrate and a partition located between adjacent pixels, wherein the partition is made of the black matrix according to claim 7 or 8. , Color filter.   A liquid crystal display element having the color filter according to claim 9 on a TFT array substrate.