JP2013050549A - Negative photosensitive resin composition, partition wall, optical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition from which a partition wall having good ink-repellency of a top face and good ink affinity of a side face can be formed even when the composition is exposed to light in which a light component at a wavelength of 330 nm or shorter is blocked, to provide a partition wall having good ink repellency of a top face and good ink affinity of a side face, formed by curing the above photosensitive composition, even when the composition is exposed to light in which a light component at a wavelength of 330 nm or shorter is blocked, and to provide an optical element having the partition wall.SOLUTION: The negative photosensitive resin composition includes: an alkali-soluble resin; a photopolymerization initiator; an ink repellent agent comprising a polymer having a side chain that contains a fluorine-containing alkyl group optionally having an ether type oxygen atom and/or a siloxane bond; and a solvent in which a solvent having a boiling point of 165°C or higher and a Fedor's solubility parameter of 8.0 to 8.5 occupies 10 to 100 mass% in the whole solvent amount. The partition wall comprises a cured film of the above resin composition, and is formed to partition a substrate surface into a plurality of segments for forming pixels.

Description

  The present invention relates to a negative photosensitive resin composition, a partition using the same, and an optical element having the partition.

  As a partition used for a pixel portion of a color filter or an organic EL (Electro-Luminescence) element which is an optical element, a method is known in which a photosensitive resin composition is applied to a substrate and is formed by a photolithography technique.

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 element.
For example, in the manufacture of a color filter, after the partition walls are formed by photolithography, R (red), G (green), and B (blue) inks are ejected to the openings (dots) surrounded by the partition walls by an inkjet method. , Apply to form pixels.

  In the manufacture of an organic EL element, after a partition wall is formed by photolithography, a hole transport material and a light emitting material solution are sprayed and applied to an opening (dot) surrounded by the partition wall by an ink jet method to form a hole transport layer. A pixel having a light emitting layer or the like is formed.

  In the ink jet method, it is necessary to prevent color mixing of ink between adjacent pixels. Therefore, the partition wall is required to have a property of repelling ink containing water or an organic solvent which is an inkjet discharge 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. It is required to have so-called ink affinity.

  Therefore, in order to make the surface of the partition walls have ink repellency, a technique for adding an ink repellant to the photosensitive resin composition used for forming the partition walls has been developed. For example, when an ink repellent agent having a small surface free energy is added to the photosensitive resin composition, and the solvent evaporates in the drying process of the coating film, the repellent force acts between the ink repellent agent and other solid components. By utilizing the migration, ink repellency is imparted to the surface of the partition wall obtained. In this case, if the surface transferability of the ink repellent agent is insufficient, the ink repellent agent remains inside the film, resulting in poor ink affinity on the side wall of the partition wall or when the film surface is dissolved in the development process. Since the layer where the ink repellent agent has migrated to the surface is thin, all of the layer is removed, resulting in poor ink repellency on the partition wall surface.

  Patent Document 1 describes a technique of a negative photosensitive resin composition that solves such a problem and is used for forming a partition wall to which an ink repellent agent having a sufficiently small surface free energy is added.

  Although exposure of the photosensitive resin composition is performed using an exposure machine, the wavelength irradiated from the exposure machine varies depending on the specifications of the apparatus. Generally, in the proximity exposure method used for color filters, light of 330 nm or less is irradiated. On the other hand, in the projection type mirror projection (MPA) system, light of 330 nm or less is shielded and irradiated. The MPA method has advantages over the proximity exposure method, such as being able to form a sharp partition shape. Recently, the MPA method is sometimes employed to meet the demand for fine partition walls. Therefore, the resist composition is also required to have a composition that can support the MPA system. Further, it may be required to reduce the exposure amount in terms of productivity.

International Publication No. 2008/146855

  According to the knowledge of the present inventors, when exposure is performed with light having a wavelength of 330 nm or less, the surface curing inhibition by oxygen is remarkable, so that the film surface is easily dissolved in the development process, and conventional photosensitivity is achieved. When the resin composition is used, there is a problem that the ink repellency on the partition wall surface is insufficient. Although a method of simply increasing the amount of the ink repellent agent in the photosensitive resin composition is also conceivable, it is conceivable that the ink repellent agent also remains inside the partition wall and the ink is repelled to the side wall.

  The present invention provides a negative photosensitive resin composition capable of forming a partition wall having good ink repellency on the surface and good ink affinity on the side surface even when exposed to light with light of 330 nm or less. Objective. In addition, the present invention has good ink repellency on the surface and good ink affinity on the side surface even when exposed to light with a light of 330 nm or less formed by curing the photosensitive resin composition. An object is to provide a partition and an optical element having the partition.

式（４）中、Ｒ^３は、水素原子、Ｒ^６１またはＯＲ^６２を示し、該Ｒ^６１およびＲ^６２は、それぞれ独立に、炭素原子数１〜２０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、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６〜３０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７〜３０のフェニルアルキル基を示す。
Ｒ^４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６〜３０のフェニル基、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７〜３０のフェニルアルキル基、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、またはシアノ基を示す。
Ｒ^５は、炭素原子数１〜２０のアルキル基、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６〜３０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７〜３０のフェニルアルキル基を示す。
Ｒ^６、Ｒ^７、Ｒ^８およびＲ^９は、それぞれ独立に、水素原子、シアノ基、ハロゲン原子、ニトロ基、Ｒ^６１、ＯＲ^６２、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のアミド基を示す。
Ｒ^０は、Ｒ^６１、ＯＲ^６２、シアノ基またはハロゲン原子を示す。ａは０または１〜３の整数である。
［９］基板表面を画素形成用の複数の区画に仕切る形に形成された隔壁であって、［１］〜［８］のいずれかのネガ型感光性樹脂組成物の硬化膜からなることを特徴とする隔壁。
［１０］基板表面に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光学素子であって、前記隔壁が［９］の隔壁で形成されていることを特徴とする光学素子。 The present invention provides a negative photosensitive resin composition, partition walls, and optical elements having the following configurations [1] to [10].
[1] A negative photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent (C) and a solvent (E), wherein the ink repellent agent (C) is , A polymer having a side chain containing a group represented by the following formula (1) or a group represented by the following formula (2), wherein the solvent (E) has a boiling point of 165 ° C. or higher and the solubility of Fedor: A negative photosensitive resin composition comprising a solvent (E1) having a parameter of 8.0 to 8.5 at a ratio of 10 to 100% by mass with respect to the total amount of the solvent (E).
-CFXR ^f (1)
In the formula (1), X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents the number of carbon atoms in which at least one hydrogen atom optionally having an etheric oxygen atom is substituted with a fluorine atom. 1-20 alkyl groups 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.
[2] The negative photosensitive resin of [1], wherein the ink repellent agent (C) has a side chain containing a group represented by the formula (1) and has a fluorine atom content of 5 to 35% by mass. Resin composition.
[3] The ink repellent agent (C) further has a side chain containing an ethylenic double bond and a side chain containing an acidic group, and a mass average molecular weight (Mw) of 1.2 × 10 ⁴ to 15 × 10. ^4. The negative photosensitive resin composition of [1] or [2], which is ⁴ .
[4] The negative photosensitive resin composition according to any one of [1] to [3], wherein the solvent (E1) is selected from compounds represented by the following formula (3).
R ¹ O (C ₂ H ₄ O) _s R ² (3)
In Formula (3), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents an alkyl group having 2 to 10 carbon atoms, and s represents an integer of 1 to 10.
[5] The negative photosensitive resin composition according to any one of [1] to [4], wherein the solvent (E1) is diethylene glycol ethyl methyl ether.
[6] The solvent (E) further has an aliphatic ring structure, and the solvent (E2) having a Fedor solubility parameter of 9.5 or more is 10% with respect to the total amount of the solvent (E). The negative photosensitive resin composition according to any one of [1] to [5], which is contained at a ratio of ˜40 mass%.
[7] The negative photosensitive resin composition according to any one of [1] to [6], further comprising a black colorant (D).
[8] The negative photosensitive resin composition according to any one of [1] to [7], wherein the photopolymerization initiator (B) is an O-acyloxime compound represented by the following formula (4).

In Formula (4), R ³ represents a hydrogen atom, R ⁶¹ or OR ⁶² , and each of R ⁶¹ and R ⁶² independently represents an alkyl group having 1 to 20 carbon atoms or a hydrogen atom in a cycloalkane ring. Is a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an alkyl group, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group The 6-30 phenyl group or the C7-30 phenylalkyl group which the hydrogen atom in a benzene ring may be substituted by the alkyl group is shown.
R ⁴ is 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 30 in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. A phenyl group of which the hydrogen atom in the benzene ring may be substituted with an alkyl group, a phenylalkyl group of 7 to 30 carbon atoms, an alkanoyl group of 2 to 20 carbon atoms, a hydrogen atom in the benzene ring is an alkyl group A benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a hydrogen atom in the benzene ring which may be substituted with an alkyl group may have 7 to 20 carbon atoms A phenoxycarbonyl group or a cyano group.
R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydrogen group in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring in an alkyl group. An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R ⁶¹ , OR ⁶² , an alkanoyl group having 2 to 20 carbon atoms, or 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 an amide group having 1 to 20 carbon atoms are shown.
R ⁰ represents R ⁶¹ , OR ⁶² , a cyano group or a halogen atom. a is an integer of 0 or 1-3.
[9] A partition wall formed to partition the substrate surface into a plurality of pixel forming sections, and comprising a cured film of the negative photosensitive resin composition according to any one of [1] to [8]. Features a partition wall.
[10] An optical element having a plurality of pixels and a partition located between adjacent pixels on the surface of the substrate, wherein the partition is formed of the partition of [9].

  According to the negative photosensitive resin composition of the present invention, a partition having good surface ink repellency and side ink repellency can be produced even when exposed to light of 330 nm or less. With the negative photosensitive resin composition of the present invention, a partition having good surface ink repellency and side ink repellency and an optical element having the partition can be obtained.

The solubility parameter of Fedor in this specification refers to RF Fedors, Polym. Eng. Sci. , 14, 147, (1974). The unit is (cal / cm ³ ) ^1/2 , and a value at 25 ° C. is used as a reference value. Further, the solubility parameter of Fedor may be omitted and referred to as “SP value”.
In this specification, “(meth) acryloyl...” Is a general term for “methacryloyl...” And “acryloyl. The same applies to (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, and (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 and compounds.
In the present specification, the “side chain” is a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting a main chain in a polymer in which a repeating unit constitutes the main chain.
The “total solid content” in this specification refers to a partition-forming component among the components contained in the negative photosensitive resin composition, and the negative photosensitive resin composition is heated at 140 ° C. for 24 hours to remove the solvent. It is a removed residue. Specifically, all components other than the volatile component which volatilizes by heating etc. in the partition formation process such as the solvent (E) are shown. The total solid content can also be calculated from the charged amount.
In the present specification, a film coated with the negative photosensitive resin composition is referred to as a “coating film”, a dried state is referred to as a “film”, and a film obtained by curing the film is referred to as a “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 liquid compositions having, for example, optical and electrical 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 indicate sections having optical and electrical functions, which are partitioned by partition walls.
“Ink repellency” in the present specification 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.

  Further, in the “film” and “cured film” obtained from the negative photosensitive resin composition, a surface layer in which the ink repellent agent is present at a higher concentration than other regions formed by transferring the ink repellent agent to the surface is provided. It is called “ink repellent layer”. The thickness of the ink repellent agent layer can be measured by, for example, a method described later that combines surface layer etching and ink repellency evaluation for the “film”.

  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) in the present invention 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 resin composition is polymerized and cured by radicals generated from the photopolymerization initiator (B). 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, an unexposed portion of the uncured negative photosensitive resin composition 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 ink repellent agent (C) mentioned later has.

Although it does not restrict | limit especially as said acidic group, A carboxy group, a phenolic hydroxyl group, a sulfo 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 vinyloxyalkyl group, is mentioned, These are 1 You may use a seed | species independently or may use 2 or more types together. In addition, some or all of the hydrogen atoms of the ethylenic double bond group 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 monomer having a reactive group other than an acidic group in the side chain, for example, a monomer having a reactive group such as a hydroxyl group or an epoxy group, and a monomer having an acidic group in the side chain are copolymerized and reactive. A copolymer having a side chain having a group 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. Alternatively, after copolymerization of a monomer having an acidic group such as a carboxy 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. Let react.
(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 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.
In addition, it is preferable to implement (i) or (ii) in a solvent.
In the present invention, the method (i) is preferably used. Hereinafter, the method (i) will be specifically described.

  Examples of the monomer having a hydroxyl group as a reactive 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 ( Data) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide.

  In the above (i), when using a monomer having a hydroxyl group as a reactive group, the monomer having an acidic group to be copolymerized is not particularly limited. In addition to the monomer having a carboxy group described later, examples of the monomer having a phosphate group include 2- (meth) acryloyloxyethyl phosphate. 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.

Examples of the compound having an ethylenic double bond and a functional group capable of bonding to a hydroxyl group to be reacted with the obtained copolymer include an acid anhydride having an ethylenic double bond, 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-yl succinic 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 monomer as described in 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.

  Examples of the compound having a functional group capable of bonding to an epoxy group and an ethylenic double bond to be reacted with the obtained copolymer include a compound having a carboxy group and 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 a part of the cyclic structure to introduce a carboxy group into the resin (A1-1).

  Examples of the monomer having a carboxy 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 a monomer having a carboxy group as a reactive group, the monomer is polymerized as described above. Examples of the compound having an ethylenic double bond and a functional group capable of bonding to a carboxy group to be reacted with the obtained polymer include compounds having an epoxy group and an ethylenic double bond. 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 carboxy group and the compound having an ethylenic double bond to be reacted with the polymer having a carboxy group is such that the carboxy group in the polymer becomes an acidic group after the reaction. The amount remaining in the chain.

Resin (A1-2) is synthesized by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond, which will be described later, and then reacting with a polyvalent carboxylic acid or its anhydride. Can do.
Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond. Next, a carboxyl group can be introduced by reacting a polycarboxylic acid or an anhydride thereof with an epoxy resin into which an ethylenic double bond has been introduced.

  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の整数であり、２〜１０の整数が好ましい。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 the formula (A1-2a), v is an integer of 1 to 50 and is preferably an integer of 2 to 10. The hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms or halogen. An atom or a part of 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または１〜１０の整数である。）

(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 or It is an integer from 1 to 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または１〜１０の整数である。）

(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 or an integer of 1 to 10.)

  In the case where the epoxy resin represented by the formulas (A1-2a) to (A1-2c) is reacted with a compound having a carboxy group and an ethylenic double bond, and then reacted with a polyvalent carboxylic acid anhydride. It is preferable to use a mixture of a dicarboxylic acid anhydride and a tetracarboxylic dianhydride as the polyvalent carboxylic acid anhydride. By changing the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride, the molecular weight can be controlled.

  As the compound having a carboxy 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-2001H, ZAR-2002, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H (above, Nipponization) Yakusho), EX1010 (manufactured by Nagase ChemteX) and the like.

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

As alkali-soluble resin (A), the peeling of the cured film during development is suppressed, a high-resolution pattern can be obtained, the line linearity is good, and the appearance after the post-baking process is maintained. It is preferable to use the resin (A1-2) in that a smooth cured film surface is 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 greater than or equal to the lower limit of the above range, the exposed portion is excellent in curability, 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 , and particularly preferably 2 × 10 ^{3 to} 20 × 10 ³ . The number average molecular weight (Mn), preferably from 500 to 20 × 10 ^3, and particularly preferably ^{1 × 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, the curability at the time of exposure is excellent, 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 in the above range, the developability of the negative photosensitive resin composition is improved.

The alkali-soluble resin (A) contained in the negative photosensitive resin composition may be used alone or in combination of two or more.
5-80 mass% is preferable and, as for the content rate of alkali-soluble 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 resin composition is good.

[Photoinitiator (B)]
As the photopolymerization initiator (B) in the present invention, a compound that generates a radical by light is used without particular limitation. Specific examples of such compounds include O-acyl oxime compounds. For example, IRGACURE OXE01 (corresponding to BASF Corporation: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)]), Adekaoptomer N-1919, Adeka Cruz NCI -831, NCI-930 (manufactured by ADEKA) and the like. Among the O-acyloxime compounds, a compound represented by the following formula (4) that can produce a partition having a good shape even with a small exposure amount is preferable. Hereinafter, the compound represented by the formula (4) is referred to as a photopolymerization initiator (4). It is preferable that a photoinitiator (B) contains 1 type, or 2 or more types of a photoinitiator (4), and it is especially preferable to be comprised only with a photoinitiator (4).

式（４）中、Ｒ^３は、水素原子、Ｒ^６１またはＯＲ^６２を示し、該Ｒ^６１およびＲ^６２は、それぞれ独立に、炭素原子数１〜２０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、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６〜３０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７〜３０のフェニルアルキル基を示す。
Ｒ^４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６〜３０のフェニル基、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７〜３０のフェニルアルキル基、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、またはシアノ基を示す。
Ｒ^５は、炭素原子数１〜２０のアルキル基、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６〜３０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７〜３０のフェニルアルキル基を示す。
Ｒ^６、Ｒ^７、Ｒ^８およびＲ^９は、それぞれ独立に、水素原子、シアノ基、ハロゲン原子、ニトロ基、Ｒ^６１、ＯＲ^６２、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のアミド基を示す。
Ｒ^０は、Ｒ^６１、ＯＲ^６２、シアノ基またはハロゲン原子を示す。ａは０または１〜３の整数である。

In Formula (4), R ³ represents a hydrogen atom, R ⁶¹ or OR ⁶² , and each of R ⁶¹ and R ⁶² independently represents an alkyl group having 1 to 20 carbon atoms or a hydrogen atom in a cycloalkane ring. Is a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an alkyl group, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group The 6-30 phenyl group or the C7-30 phenylalkyl group which the hydrogen atom in a benzene ring may be substituted by the alkyl group is shown.
R ⁴ is 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 30 in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. A phenyl group of which the hydrogen atom in the benzene ring may be substituted with an alkyl group, a phenylalkyl group of 7 to 30 carbon atoms, an alkanoyl group of 2 to 20 carbon atoms, a hydrogen atom in the benzene ring is an alkyl group A benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a hydrogen atom in the benzene ring which may be substituted with an alkyl group may have 7 to 20 carbon atoms A phenoxycarbonyl group or a cyano group.
R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydrogen group in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring in an alkyl group. An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R ⁶¹ , OR ⁶² , an alkanoyl group having 2 to 20 carbon atoms, or 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 an amide group having 1 to 20 carbon atoms are shown.
R ⁰ represents R ⁶¹ , OR ⁶² , a cyano group or a halogen atom. a is an integer of 0 or 1-3.

Among the photopolymerization initiators (4), compounds having the following modes are preferred.
In formula (4), R ³ 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 ⁴ 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 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 ⁵ represents an alkyl group having 1 to 12 carbon atoms.
R ⁶ , R ⁷ , R ⁸ and R ⁹ 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 which may be substituted with an alkyl group, a benzylcarbonyl group having 7 to 20 carbon atoms with which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and the number of carbon atoms 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.
“A” indicating the number of R ⁰ is 0.
As the photopolymerization initiator (4), No. described in International Publication No. 2008/078678. 1-71 can also be used.

Among the photopolymerization initiators (4), compounds having the following modes are particularly preferable.
R ³ 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 ⁴ 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 ⁵ 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 ⁶ , R ⁸ and R ⁹ are preferably a hydrogen atom or a nitro group.
R ⁷ is 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 or nitro groups are preferred, benzoyl group, 2-methylbenzoyl group, 2-methyl-4-tetrahydropyranylmethoxybenzoyl group, 2-methyl-5-tetrahydrofuranylmethoxybenzoyl group, 2-methyl A -5-tetrahydropyranylmethoxybenzoyl group, a benzylcarbonyl group, a 1,3,5 trimethylbenzylcarbonyl group and a nitro group are particularly preferred.
“A” indicating the number of R ⁰ is 0.

Specific examples of the photopolymerization initiator (4) include compounds (4-1) to (4) in which R ^{3 to} R ⁹ are each the following groups, and a indicating the number of R ⁰ is 0: (4-10).
Compound (4-1) wherein R ^{3 is a} phenyl group, R ^{4 is an} octyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} benzoyl group.
Compound (4-2) wherein R ^{3 is a} methyl group, R ^{4 is an} octyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} benzoyl group.
Compound (4-3) wherein R ^{3 is a} methyl group, R ^{4 is a} butyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} benzoyl group,
Compound (4-4) wherein R ^{3 is a} methyl group, R ^{4 is a} heptyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} benzoyl group,
Compound (4-5) wherein R ^{3 is a} phenyl group, R ^{4 is an} octyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} 2-methylbenzoyl group.
Compound (4-6) wherein R ^{3 is a} methyl group, R ^{4 is an} octyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} 2-methylbenzoyl group,
Compound (4-7), wherein R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : hydrogen atom, R ⁷ : 2-methylbenzoyl group,
R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : hydrogen atom, R ⁷ : 2-methyl-4-tetrahydropyranylmethoxybenzoyl group (4 -8),
R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : hydrogen atom, R ⁷ : 2-methyl-5-tetrahydrofuranylmethoxybenzoyl group (4- 9),
R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : hydrogen atom, R ⁷ : 2-methyl-5-tetrahydropyranylmethoxybenzoyl group (4 -10)

  A commercial item can be used for a photoinitiator (4). Examples of commercially available products include IRGACURE OXE02 (manufactured by BASF: equivalent to the above compound (4-7)), and the like under the trade name.

  1-15 mass% is preferable, as for the ratio of the photoinitiator (B) in the total solid in a negative photosensitive resin composition, 2-10 mass% is more preferable, and 3-6 mass% is especially preferable. Moreover, 50-100 mass% is preferable, as for the ratio of the photoinitiator (4) in a photoinitiator (B), 75-100 mass% is more preferable, and 100 mass% is especially preferable. When the ratio of the photopolymerization initiator (B) in the total solid content and the ratio of the photopolymerization initiator (4) in the photopolymerization initiator (B) are within the above ranges, the curability of the negative photosensitive resin composition. In the partition walls and black matrix obtained through the exposure process and the development process after forming the coating film, the line pattern and the line width can be formed in a shape close to the mask pattern at the time of exposure. Moreover, the negative photosensitive resin of this invention as the ratio of the photoinitiator (B) in total solid content and the ratio of the photoinitiator (4) in a photoinitiator (B) is the said range. The composition gives a cured film excellent in sufficient ink repellency.

  Examples of the photopolymerization initiator that the photopolymerization initiator (B) may contain together with the photopolymerization initiator (4) in the negative photosensitive resin composition of the present invention include the following photopolymerization initiators.

  Photopolymerization initiators that may be used in combination with the photopolymerization initiator (4) include: α-diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether Acylo ethers such as benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Thioxanthones such as 2,4-diisopropylthioxanthone and thioxanthone-4-sulfonic acid; benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone Benzophenones; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4 Acetophenones such as-(methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; anthraquinone, 2-ethylanthraquinone Quinones such as camphorquinone and 1,4-naphthoquinone; ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate 4-dimethylamino Aminobenzoic acids such as 2-ethylhexyl benzoate; Halogen compounds such as phenacyl chloride and trihalomethylphenylsulfone; Acylphosphine oxides; Peroxides such as di-t-butyl peroxide; 1,2-octanedione, 1 -[4- (phenylthio)-, 2- (O-benzoyloxime) and other O-acyloximes other than the photopolymerization initiator (4), triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N -Aliphatic amines such as methyldiethanolamine and diethylaminoethyl methacrylate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,4-butanolbis (3-mercaptobutyrate), tris (2- Mercaptoethyloleates propanoyloxy ethyl) isocyanurate, pentaerythritol tetrakis (3-mercapto butyrate) thiol compound such as and the like.

[Ink repellent (C)]
The ink repellent agent (C) in the present invention is a polymer that is contained in the negative photosensitive resin composition of the present invention, is unevenly distributed on the surface of the film, and imparts an ink repellent function to the surface of the cured film. A heavy chain having a side chain containing a group represented by the formula (1) (hereinafter also referred to as “group (1)”) or a group represented by the following formula (2) (hereinafter also referred to as group (2)). It is a coalescence.

-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. The alkyl group of number 1-20, 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.

  The ink repellent agent (C) comprises a polymer having a side chain containing the group (1), a polymer having a side chain containing the group (2), and a side chain containing the group (1) and the group (2). The polymer which has a side chain to include may be sufficient, and it may consist of 2 or more types of polymers chosen from these.

  The ink repellent agent (C) has a side chain containing the group (1) or the group (2), so that the surface free energy is small and the surface migration property is sufficient. That is, in the negative photosensitive resin composition of the present invention containing the alkali-soluble resin (A), the photopolymerization initiator (B), the ink repellent agent (C), and the solvent (E) described later, a coating film is used. When they are formed, they are sufficiently mixed to form a uniform composition. In the process of drying the coating film of the composition, the solvent (E) evaporates and the ink repellent agent (C) and Sufficient repulsive force is provided between the other solid components and the ink repellent agent (C) moves to the vicinity of the film surface to form an ink repellent agent layer.

  This ink repellent layer remains sufficiently even after the development process after exposure. Therefore, the partition wall made of a cured film of the composition has an ink repellent layer having an appropriate thickness on the surface thereof. Expresses sex. Further, 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.

  Here, as described above, when exposure is performed by reducing the exposure amount or blocking exposure light of 330 nm or less, the ink repellent agent layer is removed to a certain thickness by development. In the negative photosensitive resin composition of the present invention, it is insufficient by selecting a solvent (E) that can sufficiently exhibit the excellent surface migration property of the ink repellent agent (C) as described below. Even if the ink repellent agent layer removed by development depending on the exposure conditions is thick, the ink repellent agent layer having a sufficient thickness remains after development.

  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.

When R ^f in the group (1) is an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom optionally having an etheric oxygen atom is substituted with a fluorine atom, These hydrogen atoms may be substituted with other halogen atoms other than fluorine atoms, and the other halogen atoms are preferably chlorine atoms. 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). .) The partition formed from the negative photosensitive resin composition is preferable because it has an ink repellent agent layer having a sufficient thickness and good ink repellency. The total number of carbon atoms in the group (1) is preferably 4-6. As a result, sufficient ink repellency is imparted to the partition walls, and the compatibility between the ink repellent agent (C) and other components constituting the negative photosensitive resin composition is good, and the negative photosensitive resin composition When an object is applied to form a coating film, the ink repellent agent (C) 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 resin 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.

The ink repellent agent (C) is preferably a polymer having a side chain having an ethylenic double bond in addition to the side chain containing the group (1) or the group (2). The side chain having an ethylenic double bond can be formed by chemical conversion after the polymerization reaction.
When the ink repellent agent (C) has a side chain containing an ethylenic double bond, a curing reaction of the ink repellent agent (C) occurs during exposure, and is easily immobilized on the partition wall surface. It is difficult for unreacted residual molecules to migrate to the dots and contaminate the dots during post-baking.

  Examples of the ethylenic double bond include double bonds having addition polymerizability such as (meth) acryloyl group, allyl group, vinyl group, vinyloxy group, vinyloxyalkyl group, and these are used alone. Also, two or more of them may be used in combination. 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 (C) is preferably a polymer having a side chain having an acidic group. Some molecules of the ink repellent agent (C) that did not undergo a curing reaction in the exposure process are washed away from the partition wall surface during development because they have a side chain having an acidic group, and are not fixed in the partition wall. The remaining molecules are difficult to remain. 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 improved.

As said acidic group, a carboxy group, a phenolic hydroxyl group, a sulfo group, etc. are mentioned, These may be used individually by 1 type, or may use 2 or more types together.
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 (C) having a side chain containing the group (1) or the group (2) used in the present invention is a raw material composition containing the monomer (a1) and / or the monomer (a2) described later. Can be polymerized by a conventionally known method.
The ink repellent agent (C) having a side chain containing 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) and / or Two or more kinds of monomers including the monomer (a2) and the monomer (a3) having a reactive group can be copolymerized, and then the obtained copolymer and the reactive group can be combined. It can manufacture by making the compound (z1) which has a functional group and an ethylenic double bond react.

The ink repellent agent (C) having a side chain containing the group (1) or group (2) and a side chain having an acidic group used in the present invention is a monomer (a1) and / or a monomer described later. (A2) It can manufacture by copolymerizing the monomer (a4) which has an acidic group.
The ink repellent (C) having a side chain containing the group (1) or the group (2), a side chain having an ethylenic double bond, and a side chain having an acidic group used in the present invention will be described later. Monomer (a1) and / or monomer (a2), monomer (a3) and monomer (a4) are copolymerized, and then the obtained copolymer is reacted with compound (z1) Can be manufactured.

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 the formula (11), R ²¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, Y represents a divalent organic group containing no fluorine atom having 1 to 6 carbon atoms, and R ^f represents an etheric group. An alkyl group in which at least one hydrogen atom having 1 to 20 carbon atoms which may have an oxygen atom is substituted with a fluorine atom, or a fluorine atom is shown.
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, 2- (perfluorobutyl) ethyl (meth) acrylate, and the like. 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 the formula (21), R ²⁵ represents a hydrogen atom or a methyl group, Z represents a divalent organic group having 1 to 6 carbon atoms, and R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently A hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group; R ¹⁴ is a hydrogen atom or an etheric oxygen atom or nitrogen atom having 1 to 10 carbon atoms (—NR ^{41 —;} R ⁴¹ is a hydrogen atom or carbon atom) An alkyl group which may contain 1 to 5), 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, a monomer having an acid anhydride group, a monomer having a carboxy group, and a monomer having an epoxy group Etc. Examples of the reactive group include a hydroxyl group, an acid anhydride group, a carboxy 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.

A commercial item can be used as a monomer which has a hydroxyl group. The following are mentioned as a commercial item.
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),
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 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),
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: k is about 13 in the formula).

Specific examples of the monomer having an acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6- Examples thereof include tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, and 2-buten-1-yl succinic anhydride.
Specific examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and 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 group as the reactive group,
(5) A compound having an epoxy group and an ethylenic double bond as the compound (z1) with respect to the carboxy group as the reactive group,
(6) A compound having a carboxy 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 same compounds as those described above for the monomer having an acid anhydride group.
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 carboxy group and an ethylenic double bond as the compound (z1) include the above-described monomers having a carboxy 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 (C) has side chains having two or more ethylenic double bonds per side chain, and the ink repellent agent (C) is immobilized on the partition wall surface. This is because a partition wall excellent in ink repellency can be obtained.

Examples of the monomer (a4) include a monomer having a carboxy group, a monomer having a phenolic hydroxyl group, and a monomer having a sulfo group.
Examples of the monomer having a carboxy group include the same monomers as exemplified in the above monomer (a3). When a monomer having a carboxy group is used as the monomer (a4) having an acidic group, and a monomer having a carboxy 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 carboxy 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.

  As the monomer having a sulfo group, vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid, (meth) acrylic acid-2-sulfoethyl, (Meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 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 (51) represented by the following formula (51) having a polyoxyalkylene group or a compound (52) represented by the following formula (52). 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 ... (51)
^{_{CH 2 = CR 26 -O-W-}} (R 27 O) m (R 28 O) j R 29 ... (52).

In Formula (51) and Formula (52), 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, and R ²⁹ represents an alkyl group having 1 to 10 carbon atoms in which a part of hydrogen atoms may be substituted with a substituent. , M is an integer from 0 to 100, j is an integer from 0 to 100, and m + j is an integer from 4 to 100.

In the formula (51) and the formula (52), R ²⁷ and R ²⁸ are each independently an alkylene group having 2 to 4 carbon atoms, and the structure of the alkylene group is a branched structure even if it is a linear structure. 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 (51) and formula (52), m and j each preferably represent an integer of 0 to 50, and particularly preferably an integer of 0 to 30.
Further, m + j is preferably an integer of 6 to 50, particularly preferably an integer of 8 to 30. 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 (C) 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 (51) and Formula (52) indicate that Compound (51) and Compound (52) 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 (51) and the compound (52), m (R ²⁷ O) units and j (R ²⁸ O) units are bonded alternately, randomly, or in blocks, for example. Also good.

In Formula (51) and Formula (52), R ²⁹ is an alkyl group having 1 to 10 carbon atoms in which some hydrogen atoms may be substituted with substituents. The structure of the alkyl chain may be a straight chain structure, a branched structure, a ring structure, a structure having a partial ring, or the like. Specific examples of the substituent include a carboxy group, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms. In the present invention, R ²⁹ in the formulas (51) and (52) 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 (51) and formula (52) include —CH ₂ C ₆ H ₁₀ CH ₂ O— (wherein 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 (51) and (52), among the groups represented by W, W, which is a divalent organic group having no fluorine atom having 1 to 10 carbon atoms, is 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 (51) and (52) is preferably an oxyalkylene group having 2 to 4 carbon atoms from the viewpoint of availability.

In the compound (51) and the compound (52), among the groups in which the R ²⁶ represents a hydrogen atom, a chlorine atom, a methyl group, a phenyl group, a benzyl group, more preferably a hydrogen atom, a chlorine atom or a methyl group, More preferred.

As the compound (51),
_{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.
As the compound (52),
_{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 (51). The following are mentioned as a commercial item of a compound (51).
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).
Light Ester 130A (trade name, manufactured by Kyoeisha Chemical Co., _{Ltd., CH 2 = CHCOO (CH 2} CH 2 O) k CH 3: wherein, k is about 9.).

  The ink repellent agent (C) 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 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 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, γ-butyrolactone, Esters such as 3-methyl-3-methoxybutyl acetate and glycerol triacetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, di Examples include butyl ether and diethylene glycol methyl ethyl ether.

  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 (C) 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 By the reaction, monomer (a1) and / or monomer (a2) and monomer (a3) having a reactive group are copolymerized.
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) and / 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 such a range, the fixing of the ink repellent agent (C) to the partition walls by the introduction of the ethylenic double bond and the developability are good.

In the case of the ink repellent agent (C) having a side chain containing the group (1) or the group (2) and a side chain having an acidic group, the ratio of the monomer (a1) and / or the monomer (a2) is 20-80 mass% is preferable and 30-60 mass% is especially preferable. 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.
20-80 mass% is preferable and, as for the ratio of the monomer (a4) which has an acidic group, 40-70 mass% is especially preferable. 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 ink repellent agent (C) has both a side chain having an ethylenic double bond and a side chain having an acidic group, first, the monomer (a1) and / or the monomer (a2), a single amount The body (a3) and the monomer (a4) having an acidic group are copolymerized.
Next, an ink repellent agent (C) is obtained by making the obtained copolymer and compound (z1) react.
The ratio of the monomer (a1) and / or the monomer (a2) is preferably 20 to 80% by mass and particularly preferably 30 to 60% by mass as described above. The proportion of the monomer (a3) is preferably 20 to 70 mass%, particularly preferably 30 to 50 mass%, as described above. The proportion of the monomer (a4) is preferably 1 to 20% by mass, particularly preferably 1 to 10% 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 using another monomer (a5), the ratio is preferably 5 to 45% by mass, particularly preferably 15 to 35% by mass or less. Within this range, alkali solubility and developability are good.
Preferred combinations of monomers are as follows.
Monomer (a1) and / or monomer (a2): monomer (a3): monomer (a4): monomer (a5) = 30-60 mass%: 30-30 mass%: 1 -10 mass%: 9-35 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 equivalence ratio is not less than the lower limit of the above range, the ink repellent agent (C) can be fixed to the partition walls. 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 carboxy group as both a monomer (a3) and a monomer (a4), it is common so that the acid value of an ink repellent agent (C) may become the range mentioned later. What is necessary is just to adjust the preparation amount of a polymer and a compound (z1).

  When the ink repellent agent (C) has the group (1), the content of fluorine atoms in the ink repellent agent (C) is preferably 5 to 35 mass%, particularly preferably 10 to 30 mass%. When the content is at least the lower limit of the above range, the surface tension of the partition formed from the negative photosensitive resin composition 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 (C) has the group (2), the content of silicon atoms in the ink repellent agent (C) 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 photosensitive resin composition 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 (C) has 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} 3 0.0 × 10 ⁻³ mol / g is particularly preferable. Within the above range, the fixing of the ink repellent agent (C) to the partition and the developability are good.

  When the ink repellent agent (C) 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 (C) is preferably from 1,500 to 50,000, particularly preferably from 10,000 to 50,000. Further, the weight average molecular weight of the ink repellent (C) (Mw) is preferably ^{1.2 × 10 4 ~15 × 10 4} , 5 × 10 4 ~15 × 10 4 is particularly preferable. When the number average molecular weight (Mn) and the mass average molecular weight (Mw) are in the above ranges, alkali solubility and developability are good.

  The content ratio of the ink repellent agent (C) in the total solid content in the negative photosensitive resin 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 photosensitive resin composition 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.

  As described above, the ink repellent agent (C) may have both a side chain having the group (1) and a side chain having the group (2) in one molecule. The negative photosensitive resin composition of the present invention comprises both an ink repellent agent (C) having a side chain having a group (1) and an ink repellent agent (C) having a side chain having a group (2). May be included. The partition wall obtained from the negative photosensitive resin composition can exhibit high ink repellency and ink drop-off property to dots (display portions).

[Black colorant (D)]
The negative photosensitive resin composition in the present invention preferably contains a black colorant (D) as necessary.
Examples of the black colorant (D) 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 (D), a mixture of organic pigments such as red pigments, blue pigments, green pigments, yellow pigments, and 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 (D), 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 diameter is 20 nm or more, the negative photosensitive resin composition can be dispersed at a high concentration with the negative photosensitive resin composition, and a negative photosensitive resin composition with 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 (D) in the total solid content in the negative photosensitive resin composition is preferably 20 to 65 mass%, particularly preferably 25 to 60 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 resin 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 (D) in the negative photosensitive resin 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 (D). 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 (D). When the amount used is not less than the lower limit of the above range, the dispersion of the black colorant (D) becomes good, and when it is not more than the upper limit of the above range, the developability becomes good.

[Solvent (E)]
The negative photosensitive resin composition in the present invention contains a solvent (E). In addition, the solvent (E) has a boiling point of 165 ° C. or higher and the solubility parameter of Fedor is 8.0 to 8.5 with respect to the total amount of the solvent (E). It contains in the ratio.
The solvent (E) reacts with the alkali-soluble resin (A) contained in the negative photosensitive resin composition, the photopolymerization initiator (B), the ink repellent agent (C), and optional components contained as necessary. And has a function of uniformly and simply applying the negative photosensitive resin composition to the base material on which the partition walls are formed by uniformly dissolving or dispersing these solid components. . In addition, in the process of evaporating the solvent (E) in the drying step of the coating film of the composition, it acts so that sufficient repulsive force acts between the ink repellent agent (C) and other solid components in the composition. Thus, the ink repellent agent (C) has a function of facilitating transfer to the film surface.

  Here, regarding the solubility parameter (SP value) of Fedor, the compounds cited as the alkali-soluble resin (A), the photopolymerization initiator (B) and the like are about 10 on average, and the ink repellent (C) Becomes a value near 8.7. In the present invention, the solvent (E) contains a solvent (E1) having an SP value slightly lower than that of the ink repellent agent (C) of 8.0 to 8.5 so that each component can be added at the time of coating. It was made possible to obtain a state in which a sufficient repulsive force acts between the ink repellent agent (C) and other solid components in the coating film drying step while maintaining a uniformly compatible state.

  In addition, as described above, the ink repellent agent (C) is a compound having a small surface free energy by having the group (1) and / or the group (2), and has a high surface migration ability. When the surface transferability is different, high surface transferability is expressed by using the solvent (E) containing the solvent (E1). In addition, by adjusting the boiling point of the solvent (E1) to 165 ° C. or higher, the time required for the ink repellent agent (C) to move to the film surface is adjusted so that the drying rate of the negative photosensitive composition is sufficiently slow. Was able to be secured.

  Thereby, in the film in which the coating film of the negative photosensitive resin composition is dried, most of the ink repellent agent (C) moves to the surface of the film, and the ink repellent agent layer on the film surface is sufficiently thick. With such a film having an ink repellent agent layer, the ink repellent agent layer is removed to a certain extent by development when exposure is reduced or exposure light of 330 nm or less is shielded. However, a partition having an ink repellent layer having a sufficient thickness after development can be obtained. In addition, since the amount of ink repellent agent (C) present in the film after drying is small, the ink repellent agent (C) migrates to the side wall of the partition during post-baking in a cured film that has become a partition shape by exposure and development. There is almost no hindrance to the ink affinity on the side.

  From the above viewpoint, the boiling point of the solvent (E1) is 165 ° C. or higher, and preferably 170 ° C. to 220 ° C. If it is at least the lower limit of the above range, it is possible to sufficiently secure the time for the ink repellent agent (C) to migrate to the surface as described above, so the thickness of the ink repellent agent layer in the film of the negative photosensitive resin composition is increased. And the ink repellency of the partition wall surface is improved. When the amount is not more than the upper limit of the above range, productivity is hardly lowered due to the occurrence of sticking and the time required for the drying process.

  From the above viewpoint, the SP value of the solvent (E1) is 8.0 to 8.5, and 8.2 to 8.5 is particularly preferable. Within the above range, the repulsive force acting between the ink repellent agent (C) and other solid components is good. Further, the ink repellent agent (C) is not aggregated inside the film, the surface transferability is improved, and the ink repellency on the partition wall surface and the ink affinity on the side surface of the partition wall are improved.

  Content in the solvent (E) of a solvent (E1) is 10-100 mass%, 20-100 mass% is preferable and 30-90 mass% is especially preferable. When the content is in the above range, it is possible to ensure a long time in which a repulsive force is acting between the ink repellent agent (C) and other solid components in the drying process of the coating film of the negative photosensitive resin composition. Therefore, the surface of the ink repellent agent (C) can be sufficiently transferred. The thickness of the ink repellent agent layer can be increased, and the ink repellency of the resulting partition is improved.

As the solvent (E1), specifically, a compound represented by the following formula (3) is preferable. Since the compound (3) contains polar etheric oxygen, it has a high ability to dissolve the alkali-soluble resin (A) and is excellent in storage stability. Moreover, what is called re-dissolution property which melt | dissolves the dried material of a negative photosensitive resin composition again with the same composition can be improved. Re-solubility is a property that it is preferable to have, particularly when a negative photosensitive resin composition is applied by a slit coating method. In the slit coating method, the negative photosensitive resin composition adhering to or remaining on the slit nozzle during repeated use becomes projections of the dried product, and streaks occur in the direction of nozzle movement during coating, or the dried product Has fallen and foreign matter is mixed into the coating film. In order to prevent this, the negative photosensitive resin composition is required to have re-solubility.
R ¹ O (C ₂ H ₄ O) _s R ² (3)
In Formula (3), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents an alkyl group having 2 to 10 carbon atoms, and s represents an integer of 1 to 10.

In the compound (3), R ¹ is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 carbon atom. R ² is preferably an alkyl group having 2 to 4 carbon atoms, and particularly preferably an alkyl group having 2 carbon atoms. Further, s is preferably 1 to 3, and 2 is particularly preferable.

Specific examples of compound (3) are shown below together with abbreviations, boiling points and SP values.
Diethylene glycol ethyl methyl ether (EDM, boiling point: 176 ° C, SP value: 8.2), diethylene glycol diethyl ether (EDE, boiling point: 189 ° C, SP value: 8.2), diethylene glycol isopropyl methyl ether (IPDM, boiling point: 179 ° C) , SP value: 8.0), diethylene glycol ethyl isopropyl ether (EDIP, SP value: 8.1), diethylene glycol butyl methyl ether (BDM, boiling point: 212 ° C., SP value: 8.2), diethylene glycol butyl ethyl ether (BDE) , SP value: 8.2) and the like. These may be used alone or in combination of two or more.

  Among these, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and diethylene glycol butyl methyl ether are preferable, and diethylene glycol ethyl methyl ether is particularly preferable.

In the negative photosensitive resin composition of the present invention, it is preferable to use the solvent (E2) together with the solvent (E1) as the solvent (E). The solvent (E2) is a compound having an aliphatic ring structure and a Fedor solubility parameter of 9.5 or more. 10-40 mass% is preferable and, as for the ratio of the solvent (E2) with respect to the whole quantity of a solvent (E), 15-30 mass% is especially preferable.
In the present invention, the re-solubility is further improved because the solvent (E) contains the solvent (E2).

  In the negative photosensitive resin composition of the present invention, when the solvent (E) contains the solvent (E2) together with the solvent (E1), in addition to the thickening of the ink repellent agent layer, re-solubility is achieved. Thus, coating by the slit coating method can be supported. Here, in order not to inhibit the effect of the solvent (E1), the boiling point of the solvent (E2) is preferably less than the boiling point of the solvent (E1), and particularly preferably 10 ° C. or lower than the boiling point of the solvent (E1). preferable. When the coating film of the negative photosensitive resin composition is dried, the repulsive force acting between the ink repellent agent (C) and other solid components is suppressed by the presence of the solvent (E2) in the film for a long time. . By setting the boiling point of the solvent (E2) to be lower than the boiling point of the solvent (E1), the solvent (E2) evaporates first in the drying step and is not present in the composition, and the surface migration of the ink repellent agent (C) Does not disturb.

In the solvent (E2), from the above viewpoint, the boiling point is preferably from 100 to 210 ° C, particularly preferably from 100 to 200 ° C. The SP value of the solvent (E2) is 9.5 or more as described above. Although the upper limit of SP value of a solvent (E2) is not specifically limited, 12.0 is mentioned as an upper limit from the point which suppresses aggregation of an ink repellent agent (C) in a negative photosensitive resin composition.
Specific examples of the solvent (E2) include cyclohexanone (boiling point: 155 ° C., SP value: 9.8) and γ-butyrolactone (boiling point: 204 ° C., SP value: 10.5).

  Moreover, the negative photosensitive resin composition of this invention may contain solvent (E3) other than the above-mentioned solvent (E1) and solvent (E2) as needed as a solvent (E). As the solvent (E3), the solvent used for the synthesis of the alkali-soluble resin (A) or the ink repellent agent (C) is the negative photosensitive resin composition together with the alkali-soluble resin (A) or the ink repellent agent (C). Examples of the solvent used when blended with products.

  In addition, as a solvent used for the synthesis | combination of the said alkali-soluble resin (A) or an ink repellent agent (C), the said solvent (E1) and a solvent (E2) may be used. When the negative photosensitive resin composition contains the solvent (E1) or the solvent (E2) derived from these compounding components, it is calculated by the total amount of the solvent (E1) and the solvent (E2) containing them. What is necessary is just to adjust so that content of the solvent (E1) and the solvent (E2) in a solvent (E) may become said range, respectively.

  The solvent (E3) is not particularly limited as long as it does not inhibit the above function as the solvent (E). Although the boiling point of the solvent (E3) depends on the SP value, it is preferably less than the boiling point of the solvent (E1) in order not to inhibit the effect of the solvent (E1), and is 10 ° C. or higher than the boiling point of the solvent (E1). A low value is particularly preferred. In the solvent (E3), from the above viewpoint, the boiling point is preferably 70 to 210 ° C, particularly preferably 80 to 200 ° C. The SP value of the solvent (E3) is based on the compatibility with the solvent (E1) and the solvent (E2) used as necessary, and the solubility and dispersibility of the solid component used in the negative photosensitive resin composition Therefore, 7.8 to 12.0 is preferable.

  Therefore, when the alkali-soluble resin (A) or the ink repellent agent (C) is blended in the negative photosensitive resin composition together with the solvent used for the synthesis, such a boiling point or SP value is used as the solvent used in the synthesis. It is preferable to select the solvent to have.

  Specific examples of the solvent (E3) include propylene glycol 1-monomethyl ether 2-acetate (PGMEA, boiling point: 146 ° C., SP value: 8.7), diethylene glycol dimethyl ether (MDM, boiling point: 162 ° C., SP value: 8. 1), dipropylene glycol dimethyl ether (DMM, boiling point: 171 ° C., SP value: 7.9), cyclohexyl acetate (CHXA, boiling point: 173 ° C., SP value: 9.2), isopropyl alcohol (IPA, boiling point: 82 ° C.) , SP value: 11.6), butyl acetate (BA, boiling point: 126 ° C., SP value: 8.7) and the like.

  The content of the solvent (E3) in the solvent (E) is an amount obtained by subtracting the amounts of the solvent (E1) and the solvent (E2) from the total amount of the solvent (E), specifically, the total amount of the solvent (E). The ratio of 1 to 90% by mass is preferable, and 20 to 80% by mass is particularly preferable.

  In addition, as a specific aspect of a solvent (E), the aspect comprised with the solvent (E1), the solvent (E2), and / or the solvent (E3) comprised only with a solvent (E1) is mentioned. As a preferable blending ratio (mass ratio) when the solvent (E) is composed of the solvent (E1) and the solvent (E2), solvent (E1): solvent (E2) = 85: 15 to 70:30 can be mentioned. A preferable blending ratio (mass ratio) when the solvent (E) is composed of the solvent (E1) and the solvent (E3) includes solvent (E1): solvent (E3) = 90: 10 to 30:70. As a preferable blending ratio (mass ratio) when the solvent (E) is composed of the solvent (E1), the solvent (E2), and the solvent (E3), solvent (E1): solvent (E2): solvent (E3 ) = 30-75: 15-30: 10-55.

  Although the content rate of the solvent (E) in a negative photosensitive resin composition changes with compositions, uses, etc. of a negative photosensitive resin composition, it is a ratio of 50-99 mass% in a negative photosensitive resin composition. It is preferable to mix | blend, 60-95 mass% is more preferable, and 65-90 mass% is especially preferable.

[Crosslinking agent (F)]
The negative photosensitive resin composition in the present invention may contain a crosslinking agent (F) as an optional component for promoting radical curing. As a crosslinking agent (F), 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 resin composition contains the crosslinking agent (F), the curability of the negative photosensitive resin composition at the time of exposure is improved, and the partition can be formed even with a low exposure amount.

  As the crosslinking agent (F), 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 (F). 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.

  3-50 mass% is preferable and, as for the content rate of the crosslinking agent (F) in the total solid in a negative photosensitive resin composition, 5-40 mass% is especially preferable. Within the above range, the alkali developability of the negative photosensitive resin composition is improved.

[Fine particles (G)]
The negative photosensitive resin composition in the present invention may contain fine particles (G) as necessary. When the negative photosensitive resin composition contains the fine particles (G), the partition obtained from the negative photosensitive resin 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 resin 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.

Silica is preferable as the fine particles (G). As silica, colloidal silica is preferable. In general, colloidal silica includes silica hydrosol dispersed in water and organosilica sol in which water is replaced with an organic solvent, and organosilica sol using an organic solvent as a dispersion medium is preferable.
As such an organosilica sol, commercially available products can be used, and as commercially available products, PMA-ST (silica particle diameter: 10 to 20 nm, silica solid content is a product name manufactured by Nissan Chemical Industries, Ltd. : 30% by mass, propylene glycol monomethyl ether acetate: 70% by mass), NPC-ST (silica particle diameter: 10 to 20 nm, silica solid content: 30% by mass, n-propyl cellosolve: 70% by mass), IPA- ST (silica particle diameter: 10 to 20 nm, silica solid content: 30% by mass, isopropyl alcohol (2-propanol): 70% by mass) and the like.

  5-35 mass% is preferable and, as for the content rate of microparticles | fine-particles (G) in the total solid in a negative photosensitive resin composition, 10-30 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 storage stability of the negative photosensitive resin composition is good. Become.

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

  A commercial item can be used as a silane coupling agent (H). Examples of commercially available products include KBM5013 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloyloxypropyltrimethoxysilane).

  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 resin 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 resin composition in the present invention may contain a thermosetting agent (I) as necessary. When the negative photosensitive resin composition contains the thermosetting agent (I), 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.

  0.1-20 mass% is preferable and, as for the content rate of the thermosetting agent (I) in the total solid in a negative photosensitive resin composition, 1-20 mass% is especially preferable. Within the above range, the developability of the obtained negative photosensitive resin composition becomes good.

[Phosphate compound (J)]
The negative photosensitive resin composition in this invention may contain the phosphoric acid compound (J) as needed. 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, 0.1-1 mass% is especially preferable. Adhesiveness with the base material of the cured film formed from the negative photosensitive resin composition obtained as it is the said range becomes favorable.

[Other additives]
The negative photosensitive resin composition in the present invention can further use a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber, and the like as necessary. .

[Negative photosensitive resin composition]
The negative photosensitive resin composition of the present invention contains an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent (C), and a solvent (E). Furthermore, a black coloring agent (D) and a crosslinking agent (F) are contained as needed. Furthermore, you may contain said fine particle (G), a silane coupling agent (H), a thermosetting agent (I), a phosphoric acid compound (J), and another additive.
It does not restrict | limit especially as a method of manufacturing the negative photosensitive resin composition of this invention, It can manufacture by weighing predetermined amount of said each component and mixing with a general method.

  The negative photosensitive resin composition of the present invention is used as a material such as photolithography in the same manner as an ordinary negative photosensitive resin composition, and the obtained cured film is used as an ordinary negative photosensitive resin as a partition or the like. It can be used as a member of an optical element in which a cured film of the composition is used. Negative photosensitive resin of the present invention in which the specific ink repellent agent (C) and other solid components are combined with a solvent (E) containing a compound (solvent (E1)) having characteristics such as a boiling point and a solubility parameter of Fedor. When the composition is used, as described above, a partition wall having a surface with good ink repellency and a side surface with good ink affinity can be formed even when exposed to light with a light of 330 nm or less.

(Preferred combination of negative photosensitive resin composition)
In the negative photosensitive resin composition of the present invention, it is preferable to appropriately select the composition and the mixing ratio in accordance with the application and required characteristics.
The preferable composition of the various compounding components in the negative photosensitive resin composition of the present invention is shown below.

<Combination 1>
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,

Photopolymerization initiator (B): O-acyloxime compound, 3 to 6% by mass in the total solid content in the negative photosensitive resin composition
Ink repellent agent (C): selected from a compound having a side chain having a group represented by the formula (1) in a molecule, a side chain having an ethylenic double bond, and a side chain having an acidic group. At least one ink repellent agent, 0.05 to 20% by mass in the total solid content of the negative photosensitive resin composition,

Black colorant (D): at least one colorant selected from carbon black and organic pigments, 20.95-60 mass% in the total solid content in the negative photosensitive resin composition,
Solvent (E): 30 to 90% by mass of a solvent (E1) having a boiling point of 165 ° C. or higher and a Fedor solubility parameter of 8.0 to 8.5 with respect to the total amount of the solvent (E), E3) PGMEA is contained in 10 to 70% by mass, and the solvent (E) is 65 to 90% by mass in the negative photosensitive resin composition,
Crosslinking agent (F): a compound having two or more ethylenic double bonds in the molecule and no acidic group, and 5 to 40 mass in the total solid content in the negative photosensitive resin composition %,

Fine particles (G): silica fine particles having an average particle size of 200 nm or less and negatively charged, and 10 to 30% by mass in the total solid content in the negative photosensitive composition,
Silane coupling agent (H): tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -At least one compound selected from mercaptopropyltrimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and imidazolesilane, in the total solid content in the negative photosensitive resin composition 1 to 10% by mass,

<Combination 2>
Alkali-soluble resin (A), photopolymerization initiator (B), ink repellent agent (C), black colorant (D), crosslinking agent (F), fine particles (G) and silane coupling agent (H) are combined 1 And the solvent (E) is as follows.
Solvent (E): 30 to 75% by mass of a solvent (E1) having a boiling point of 165 ° C. or higher and a Fedor solubility parameter of 8.0 to 8.5 with respect to the total amount of the solvent (E), aliphatic The solvent (E2) has a ring structure, the Fedor solubility parameter is 9.5 or more, and the boiling point is less than the boiling point of the solvent (E1). % Of the solvent (E) containing 65% to 90% by mass in the negative photosensitive resin composition.

<Combination 3>
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,

Photopolymerization initiator (B): O-acyloxime compound, 3 to 6% by mass in the total solid content in the negative photosensitive resin composition
Ink repellent agent (C): selected from a compound having a side chain having a group represented by the formula (1) in a molecule, a side chain having an ethylenic double bond, and a side chain having an acidic group. At least one ink repellent agent, 0.05 to 20% by mass in the total solid content of the negative photosensitive resin composition,

Black colorant (D): at least one colorant selected from carbon black and organic pigments, 20.95-60 mass% in the total solid content in the negative photosensitive resin composition,
Solvent (E): 30 to 75% by mass of a solvent (E1) having a boiling point of 165 ° C. or higher and a Fedor solubility parameter of 8.0 to 8.5 with respect to the total amount of the solvent (E), aliphatic 15-30% by mass of solvent (E2) having a ring structure, a Fedor solubility parameter of 9.5 or more and a boiling point less than that of solvent (E1), and PGMEA of 10-55% by weight as solvent (E3) % Of the solvent (E), 65 to 90% by mass in the negative photosensitive resin composition,
Crosslinking agent (F): a compound having two or more ethylenic double bonds in the molecule and having no acidic group, and 4 to 40 mass in the total solid content in the negative photosensitive resin composition %,

Fine particles (G): silica fine particles having an average particle size of 200 nm or less and negatively charged, and 10 to 30% by mass in the total solid content in the negative photosensitive composition,
Silane coupling agent (H): tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -At least one compound selected from mercaptopropyltrimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and imidazolesilane, in the total solid content in the negative photosensitive resin composition 1 to 10% by mass,
Thermosetting agent (I): at least one compound selected from an amino resin, a compound having two or more epoxy groups, and a compound having two or more oxazoline groups, and the total solid in the negative photosensitive resin composition 1-20% by weight in minutes.

[Partition and manufacturing method thereof]
The partition of this invention is a partition formed in order to provide a division on the substrate surface, Comprising: It consists of a cured film of the said negative photosensitive resin composition of this invention. The partition of the present invention is suitably used for an optical element, and when the negative photosensitive resin composition contains a black colorant (D), the resulting partition can be applied as a black matrix. is there. 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 substrate surface.

  Examples of the method for producing the partition for the optical element of the present invention using the negative photosensitive resin composition of the present invention include the following methods.

  The negative photosensitive resin composition of the present invention is applied to the substrate surface to form a coating film (coating film forming process), then the coating film is dried to form a film (drying process), and then the film Then, only the part to be the partition wall is exposed and photocured (exposure process), and then the film other than the photocured part is removed to form the partition wall made of the photocured part of the film (development process), and then The partition walls for the optical element of the present invention can be produced by further thermally curing the formed partition walls and the like as necessary (post-baking step). 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 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. Thermoplastic plastic sheet; Cured sheet of 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.
It is preferable to clean the application surface of the negative photosensitive resin composition on the substrate by alcohol cleaning, ultraviolet / ozone cleaning or the like before application.

(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. In particular, a slit coating method that can be applied to a large area at once is preferable. When the negative photosensitive resin composition of the present invention contains the solvent (E2) as a part of the solvent (E), the composition is excellent in re-solubility and is a defect caused by a dried product around the slit nozzle. This is particularly advantageous in the slit coating method.
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 resin 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 substrate surface in the coating film forming step is dried to obtain a film. By drying, the volatile components including the solvent contained in the negative photosensitive resin composition constituting the coating film are volatilized and removed, and a non-sticky film is obtained. At this time, the ink repellent agent (C) moves to the vicinity of the film surface.
The negative photosensitive resin composition of the present invention adopts the above composition so that the transfer of the ink repellent agent (C) to the film surface in the drying step is promoted, and the film surface obtained here The thickness of the ink repellent agent layer is such that it remains sufficiently even after the following exposure process and development process.

As a drying method, vacuum drying or heat drying (pre-baking) is preferable. 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 10 to 500 Pa for 10 to 300 seconds.
Heat drying is preferably performed at 50 to 120 ° C. for 10 to 2,000 seconds using a heating device such as a hot plate or oven together with the substrate.

  The drying temperature and time are selected so that the transfer of the ink repellent agent (C) to the coating film surface is promoted by the composition of the solvent (E) used in the negative photosensitive resin composition. For example, when a solvent containing diethylene glycol ethyl methyl ether is used as the solvent (E), the drying temperature is preferably 75 to 100 ° C., and the drying time is preferably 30 to 300 seconds.

  Here, the thickness of the ink-repellent agent layer after the drying step is determined as follows on the surface of the cured film (partition) that is slightly removed together with the unexposed portion in the normal development process after forming a cured film by the following exposure process. It is calculated | required that it is more than thickness. In the exposure process, when exposure is performed by blocking light of 330 nm or less, the thickness of the surface of the cured film (partition) removed by development is assumed to increase. Even when the exposure is performed by shielding light of 330 nm or less, if the thickness of the ink repellent agent layer after the drying step is approximately 60 nm or more, the cured film even after the development step after the exposure step (Partition wall) The ink repellency on the surface is secured. Therefore, the thickness of the ink repellent agent layer in the drying step is preferably 60 nm or more, and is preferably 300 nm or less from the viewpoint of making the side surface ink-philic.

  The thickness of the ink repellent layer can be measured, for example, by the following method. For a film having an ink repellent agent layer on the sample surface, that is, a film obtained by drying a coating film of a negative photosensitive resin composition, after measuring the initial film thickness, the developer used for the following development By changing the concentration and the processing time, a plurality of samples having different thicknesses of films removed by etching from the surface layer (hereinafter also referred to as “etching thickness”) are manufactured. Here, the etching thickness is obtained as a value obtained by subtracting the film thickness measured for the film samples after these etching processes from the initial film thickness. Next, after the heat treatment is performed on the film sample after the etching treatment, the presence or absence of ink repellency is confirmed, for example, when the contact angle of PGMEA is 40 degrees or more, ink repellency is “present”, and less than 40 degrees is “no”. . The thickness of the ink repellent agent layer is determined from the relationship between the presence or absence of the ink repellency and the etching thickness.

(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 portion is cured, and the negative photosensitive resin composition in the unexposed portion is not cured.
As the irradiation light, visible light; ultraviolet light; far ultraviolet light; excimer laser such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, KrAr excimer laser, Ar ₂ excimer laser; X-ray; Etc. The irradiation light is preferably light having a wavelength of 100 to 600 nm, more preferably light having a distribution in the range of 300 to 500 nm, and particularly preferably i-line (365 nm), h-line (405 nm) and g-line (436 nm). . When an exposure method using a mirror projection (MPA) method is used, exposure light is irradiated while blocking light of 330 nm or less.

A well-known super high pressure mercury lamp etc. can be used as an irradiation apparatus. Exposure dose, i-line basis, preferably ^{5~1,000mJ / cm 2, 10~200mJ / cm} 2 is particularly preferred. Further, when the cut following electromagnetic wave 330nm by cut filter or the like, in an i-line standard, preferably 5~1,000mJ / cm ^2, more preferably ^{5~200mJ / cm 2, 10~100mJ / cm} 2 is Further preferred is 15-50 mJ / cm ² . When the exposure amount is at least the lower limit of the above range, the negative photosensitive resin composition serving as the partition is sufficiently cured, and subsequent development does not easily cause dissolution or peeling from the substrate. A high resolution is obtained when it is not more than the upper limit of the above range. The surface of the cured film obtained from the negative photosensitive resin composition of the present invention has particularly good ink repellency even when electromagnetic waves of 330 nm or less are cut by a cut filter or the like.

(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 the development, water on the substrate surface can be removed by washing with high pressure water or running water and 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. Exposure is preferably 50 mJ / cm ² or more, more preferably 200 mJ / cm ² or more, 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. 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.

  In the pattern formed from the negative photosensitive resin composition of the present invention, the average width of the partition walls is preferably 100 μm or less, and particularly preferably 20 μm or less. The average distance between adjacent barrier ribs (dot width) is preferably 300 μm or less, and particularly preferably 100 μm or less. The average height of the partition walls is preferably 0.05 to 50 μm, and particularly preferably 0.2 to 10 μm.

  The ink repellency of the cured film formed from the negative photosensitive resin composition can be estimated by the contact angle of PGMEA, and the contact angle of PGMEA is preferably 40 degrees or more, particularly preferably 45 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 of the present invention is applied include a color filter and an organic EL element.

[Color filter manufacturing method]
After forming a partition, for example, a black matrix on the substrate surface as described above, a pixel is formed by injecting ink into the region partitioned by the black matrix by using an ink jet apparatus using an ink jet method. Can be manufactured. Hereinafter, a case where the partition walls are a black matrix will be described as an example.

  In addition, in the substrate on which the black matrix is formed, before injecting ink into the region (dots) partitioned by the black matrix, the substrate surface exposed in the dots is washed with, for example, an alkaline aqueous solution, The ink-repellent treatment may be performed by a method such as ultraviolet cleaning, ultraviolet / 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.

The ink used for the ink jet method mainly includes 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 elution from the black matrix or the ink in 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 black matrix 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 black matrix include plasma ashing and light ashing.
Further, if necessary, it is preferable to form a photo spacer on the black matrix in order to improve the quality of a liquid crystal panel or the like manufactured using a color filter.

[Method of manufacturing organic EL 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 resin composition of the present invention, and after the dot is made into an ink-inking treatment, a solution of a hole transport material and a light emitting material is sequentially applied to the dot using an ink jet method and dried. Thus, a hole transport layer and a light emitting layer are formed. Thereafter, an electrode of aluminum or the like is formed by a vapor deposition method or the like, thereby obtaining a pixel of the organic EL element.

  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 11 are examples, and examples 21 to 24 are comparative examples.

[Evaluation method]
Each measurement was performed by the following method.
(Number average molecular weight (Mn), mass average molecular weight (Mw))
Polystyrene was measured as a standard substance by gel permeation chromatography (GPC method).
(Content of fluorine atom in ink repellent agent (C), amount of ethylenic double bond, acid value)
The fluorine atom content in the ink repellent agent (C) was calculated by ¹⁹ F NMR measurement using 1,4-ditrifluoromethylbenzene as a standard substance.
The amount of ethylenic double bond in the ink repellent agent (C) was calculated by ¹ H NMR measurement using 1,4-ditrifluoromethylbenzene as a standard substance.
The acid value (mgKOH / g) of the ink repellent agent (C) is a theoretical value calculated from the blending ratio of monomers as raw materials.
(Film thickness)
The film thickness of the “film” and “cured film” was measured using a high-precision fine shape measuring device SURFCORDER ET4000A (manufactured by Kosaka Laboratory).

[Abbreviations for compounds]
Abbreviations of the compounds used in Synthesis Examples and Examples are as follows.
(Alkali-soluble resin (A))
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 mg KOH / g, solid content: 70% by mass, PGMEA: 30% by mass).
ZAR2001: Resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a bisphenol A skeleton (manufactured by Nippon Kayaku, trade name: ZAR2001H, mass average molecular weight (Mw): 16,200, acid value: 100 mgKOH / g, solid content: 70% by mass, PGMEA: 30% by mass).

(Photopolymerization initiator (B))
OXE02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (in the compound represented by the formula (4), R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : hydrogen atom, R ⁷ : 2-methylbenzoyl group, manufactured by BASF, trade name: OXE02. ).
NCI831 (manufactured by ADEKA, trade name: Adeka Cruz NCI-831).

(Compound used for synthesis of ink repellent agent (C))
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)).
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.

(Black colorant (D) + polymer dispersant)
CB: carbon black dispersion (average secondary particle size: 120 nm, carbon black: 20% by mass, polyurethane polymer dispersant having an amine value of 18 mgKOH / g: 5% by mass, PGMEA: 75% by mass).
Mixed organic pigment: C.I. I. Pigment blue 15: 6, C.I. I. Pigment red 254, C.I. I. Pigment Yellow 139 and a polymeric dispersant in a 10: 5: 5: 5 mixture (solid content: 25 mass%, PGMEA: 75 mass%).

(Solvent (E))
(I) Solvent (E1)
EDM: Diethylene glycol ethyl methyl ether (boiling point: 176 ° C., SP value: 8.2).
EDE: Diethylene glycol diethyl ether (boiling point: 189 ° C., SP value: 8.2).
BDM: Diethylene glycol butyl methyl ether (boiling point: 212 ° C., SP value: 8.2).
(ii) Solvent (E2)
CHN: cyclohexanone (boiling point: 155 ° C., SP value: 9.8).

(iii) Solvent (E3)
PGMEA: Propylene glycol 1-monomethyl ether 2-acetate (boiling point: 146 ° C., SP value: 8.7).
MDM: Diethylene glycol dimethyl ether (boiling point: 162 ° C., SP value: 8.1).
DMM: Dipropylene glycol dimethyl ether (boiling point: 171 ° C., SP value: 7.9).
CHXA: cyclohexyl acetate (boiling point: 173 ° C., SP value: 9.2).
IPA: isopropyl alcohol (boiling point: 82 ° C., SP value: 11.6).
BA: butyl acetate (boiling point: 126 ° C., SP value: 8.7).

(Crosslinking agent (F))
UX5002: polyfunctional urethane acrylate oligomer (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD UX-5002D-P20, solid content: 80% by mass, PGMEA: 20% by mass).
(Fine particles (G))
PMA-ST: trade name (manufactured by Nissan Chemical Industries, organosilica sol, solid content: 30% by mass, PGMEA: 70% by mass).
(Silane coupling agent (H))
KBM5103: trade name (manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloyloxypropyltrimethoxysilane).
(Thermosetting agent (I))
XD1000: Multifunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: XD1000)

[Synthesis Example 1: Synthesis of ink repellent agent (C-1)]
(Synthesis of copolymer 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, the mixture was reacted at 40 ° C. for 24 hours to obtain a solution of the ink repellent agent (C-1). The MEK solution of the obtained ink repellent agent (C-1) was added to heptane for purification by reprecipitation, followed by vacuum drying to obtain ink repellent agent (C-1) (41 g). The number average molecular weight (Mn) was 38,000, and the mass average molecular weight (Mw) was 105,000. As a result of infrared spectroscopic analysis of the ink repellent agent (C-1), absorption band (1,635 cm ⁻¹ ) derived from C═C stretching vibration of acryloyl group, and CH _{2 in-} plane bending vibration of 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 (C-1).
Number average molecular weight (Mn), mass average molecular weight (Mw, × 10 ⁴ ), fluorine atom content, ethylenic double bond amount (× 10 ⁻³ mol / min) of the obtained ink repellent agent (C-1) g) and acid value (mgKOH / g) are shown in Table 1.

[Examples 1-11, 21-24]
(Preparation of negative photosensitive resin composition)
In the proportions shown in Table 2 and Table 3, the alkali-soluble resin (A) (containing 30% by mass of PGMEA as a solvent), a photopolymerization initiator (B), and an ink repellent agent (C) (90% by mass of PGMEA as a solvent) ), A mixture of a black colorant (D) and a polymer dispersant (75% by weight of PGMEA is included as a solvent), a solvent (E), and a crosslinking agent (F) (20% by weight of PGMEA is included as a solvent). Fine particles (G) (containing 70 mass% of PGMEA as a solvent), silane coupling agent (H) and thermosetting agent (I) were blended to obtain a negative photosensitive resin composition. The compositions in Tables 2 and 3 are preparation amounts. In Example 1, when the negative photosensitive resin composition was heated at 140 ° C. for 24 hours, the total solid content was the negative photosensitive resin composition. It was 13 mass% in the inside, and it was confirmed that it was consistent with the charged amount.

(Formation of partition walls)
A negative photosensitive resin composition was applied to the glass substrate surface using a spinner to form a coating film (coating film forming step). Next, it dried on the hotplate for 2 minutes at 100 degreeC, and obtained the glass substrate (1) in which the film | membrane with a film thickness of 2.0 micrometers was formed (drying process). Next, through a photomask having a linear opening of 10 μm × 10 mm, an ultrahigh pressure mercury lamp (light of 330 nm or less is shielded by a cut filter. A mixed line mainly composed of i-line, h-line, and g-line) is used. Then, the exposure amount was irradiated with light of 50 mJ / cm ^{2 on} the basis of i-line (365 nm) to obtain a glass substrate (1-2) (exposure process).

Next, the glass substrate (1-2) was developed by being immersed in an inorganic alkali type developer (manufactured by Yokohama Yushi Kogyo Co., Ltd., trade name: 10 times diluted aqueous solution of semi-clean DL-A4), and the unexposed area was washed away 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).

  Further, the glass substrate (1) was immersed in an inorganic alkali type developer (manufactured by Yokohama Yushi Kogyo Co., Ltd., trade name: dilute aqueous solution of semi-clean DL-A4) and developed so as to have an etching thickness of 300 nm. Subsequently, the glass substrate (3) with which the cured film was formed was obtained by heating on a hotplate at 220 degreeC for 1 hour.

(Evaluation)
Using the glass substrates (1) to (3), the ink repellency on the partition wall surface, the ink repellency on the side surface of the partition wall, and the thickness of the ink repellent agent layer were measured and evaluated by the following methods. The evaluation results are shown in Table 2 and Table 3.

(1) Ink repellency on partition wall surface The ink repellency on the partition wall surface was evaluated by the contact angle (degree) of PGMEA on the partition wall surface 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 on the partition wall surface. A PGMEA contact angle of 40 ° or more was evaluated as ◯ (good), and a contact angle of less than 40 ° was evaluated as x (defective).

(2) Ink affinity on the side wall of the partition wall The ink affinity on the side surface of the partition wall was evaluated by measuring the contact angle (degree) of PGMEA of the cured film on the surface of the glass substrate (3). It is to be noted that the smaller this angle, the better the ink affinity on the side wall of the partition wall. A contact angle of PGMEA of less than 10 degrees was evaluated as ◯ (good) and 10 degrees or more as x (defective).

(3) Thickness of ink repellent agent layer Prepare a plurality of the above glass substrates (1), and use an inorganic alkali type developer (Yokohama Yushi Kogyo Co., Ltd., trade name: semi-clean DL-A4 diluted aqueous solution). A plurality of glass substrates having different etching thicknesses from 0 to 300 nm were prepared by changing the concentration and immersion time and developing and drying. These were heated on a hot plate at 220 ° C. for 1 hour to obtain a glass substrate on which a cured film having an etched film surface was formed. The contact angle of PGMEA of the cured film on the obtained multiple glass substrates was measured. Of the cured films on glass substrates having different etching thicknesses, the etching thickness of the largest etching thickness among those having a PGMEA contact angle of 40 degrees or more was defined as the thickness of the ink repellent layer.

  It can be presumed that the greater the thickness of the ink repellent agent layer, the better the ink repellency of the partition wall surface. In order to impart good ink repellency to the surface of the partition wall produced by shading and exposing light of 330 nm or less, this value is preferably 60 nm or more.

(4) Re-solubility About the said glass substrate (1), the dried product of the negative photosensitive resin composition coated is made into the mixed solution equivalent to the solvent except the solid content of each negative photosensitive resin composition. After dissolution, this was filtered with a polyethylene 2.5 μm pore membrane filter, and the precipitate adhered to the membrane filter was observed visually or with an optical microscope. Those in which no precipitate was observed were described as ◎ (good), those in which the precipitate was not observed but colored on the membrane filter were marked as ◯ (good), and those in which the precipitate was observed were marked as x (bad).

As can be seen from Table 2, the partition formed using the negative photosensitive resin composition of the present invention had an ink repellency on the surface, an ink repellency on the side, and a large thickness of the ink repellent agent layer. In particular, Examples 4 to 8 and 10 to 11 using the negative photosensitive resin composition containing the solvent (E2) had good resolubility.
On the other hand, in Table 3, in Examples 21 and 22 using a negative photosensitive resin composition containing no solvent having a Fedor solubility parameter of 8.0 to 8.5, the ink repellency of the partition wall surface, the partition wall side surface The ink affinity and ink repellent layer thickness was insufficient. The thickness of the ink repellent agent layer is described as less than 56 nm and less than 33 nm, respectively, which indicates that the contact angle of the cured film PGMEA was less than 40 degrees when the etching was 56 nm and 33 nm, respectively. ing. Although the exact thickness of the ink repellent agent layer has not been evaluated, it can be seen that it is smaller than 60 nm, which is the thickness of the ink repellent agent layer necessary for imparting good ink repellency to the partition wall surface. When a solvent having a Fedor solubility parameter greater than 8.5 is used, the repelling force of the ink repellent agent acting on other solid components is suppressed, resulting in a decrease in surface migration and a Fedor solubility parameter of 8. If it is less than 0, it is presumed that the repelling force is too strong, and as a result, the ink repellent agent aggregates inside the film and the surface transferability of the ink repellent agent is reduced.

In Example 23 using a negative photosensitive resin composition containing a solvent having a Fedor solubility parameter of 8.1 and a boiling point of 162 ° C., the ink repellency on the partition wall surface was poor and the thickness of the ink repellent agent layer was not good. It was enough. If the boiling point is less than 165 ° C., the drying speed of the coating film in the drying process is high, and it is estimated that the solvent repels before the ink repellent agent sufficiently migrates to the surface and the ink repellent agent cannot migrate to the surface. Is done.
In Example 24 using the negative photosensitive resin composition in which the ratio of the solvent (E1) to the total amount of the solvent (E) was 5% by mass, the ink repellency on the partition wall surface was poor and the thickness of the ink repellent agent layer was It was insufficient at 60 nm or less. It is presumed that because the content of the solvent (E1) is small, the solvent evaporates before the ink repellent agent sufficiently migrates to the surface so that the ink repellent agent cannot migrate to the surface.

The negative photosensitive resin composition of the present invention can produce a partition having good surface ink repellency and side ink affinity even when exposed to light of 330 nm or less.
The negative photosensitive resin composition of the present invention is suitably used for forming barrier ribs for the production of optical elements utilizing the ink jet recording technique.

Claims (10)

A negative photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent (C) and a solvent (E), wherein the ink repellent agent (C) is represented by the following formula: A polymer having a side chain containing a group represented by (1) or a group represented by the following formula (2), wherein the solvent (E) has a boiling point of 165 ° C. or higher and a Fedor solubility parameter of 8 A negative photosensitive resin composition comprising a solvent (E1) of 0.0 to 8.5 in a proportion of 10 to 100% by mass with respect to the total amount of the solvent (E).
-CFXR ^f (1)
In the formula (1), X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents the number of carbon atoms in which at least one hydrogen atom optionally having an etheric oxygen atom is substituted with a fluorine atom. 1-20 alkyl groups 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.   The negative photosensitive resin according to claim 1, wherein the ink repellent agent (C) has a side chain containing a group represented by the formula (1) and has a fluorine atom content of 5 to 35 mass%. Resin composition. The ink repellent agent (C) further has a side chain containing an ethylenic double bond and a side chain containing an acidic group, and the mass average molecular weight (Mw) is 1.2 × 10 ⁴ to 15 × 10 ⁴ . The negative photosensitive resin composition of Claim 1 or 2. The negative photosensitive resin composition as described in any one of Claims 1-3 in which the said solvent (E1) is chosen from the compound represented by the following Formula (3).
R ¹ O (C ₂ H ₄ O) _s R ² (3)
In Formula (3), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents an alkyl group having 2 to 10 carbon atoms, and s represents an integer of 1 to 10.   The negative photosensitive resin composition as described in any one of Claims 1-4 whose said solvent (E1) is diethylene glycol ethyl methyl ether.   The solvent (E) further has an aliphatic ring structure, and the solvent (E2) having a Fedor solubility parameter of 9.5 or more is 10 to 40 masses based on the total amount of the solvent (E). The negative photosensitive resin composition according to claim 1, which is contained at a ratio of%.   Furthermore, the negative photosensitive resin composition as described in any one of Claims 1-6 containing a black coloring agent (D). The negative photosensitive resin composition as described in any one of Claims 1-7 whose said photoinitiator (B) is an O-acyl oxime compound represented by the following Formula (4).

In Formula (4), R ³ represents a hydrogen atom, R ⁶¹ or OR ⁶² , and each of R ⁶¹ and R ⁶² independently represents an alkyl group having 1 to 20 carbon atoms or a hydrogen atom in a cycloalkane ring. Is a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an alkyl group, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group The 6-30 phenyl group or the C7-30 phenylalkyl group which the hydrogen atom in a benzene ring may be substituted by the alkyl group is shown.
R ⁴ is 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 30 in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. A phenyl group of which the hydrogen atom in the benzene ring may be substituted with an alkyl group, a phenylalkyl group of 7 to 30 carbon atoms, an alkanoyl group of 2 to 20 carbon atoms, a hydrogen atom in the benzene ring is an alkyl group A benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a hydrogen atom in the benzene ring which may be substituted with an alkyl group may have 7 to 20 carbon atoms A phenoxycarbonyl group or a cyano group.
R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydrogen group in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring in an alkyl group. An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R ⁶¹ , OR ⁶² , an alkanoyl group having 2 to 20 carbon atoms, or 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 an amide group having 1 to 20 carbon atoms are shown.
R ⁰ represents R ⁶¹ , OR ⁶² , a cyano group or a halogen atom. a is an integer of 0 or 1-3.   It is a partition formed in the shape which partitions the board | substrate surface into several division for pixel formation, Comprising: It consists of a cured film of the negative photosensitive resin composition as described in any one of Claims 1-8. A partition wall.   An optical element having a plurality of pixels and a partition located between adjacent pixels on the surface of the substrate, wherein the partition is formed by the partition according to claim 9.