JP5910629B2 - Negative photosensitive resin composition, cured film, partition and black matrix and method for producing the same, color filter and organic EL device - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition, a cured film, partition walls, a black matrix, a method for producing the same, a color filter, and an organic EL device.

The resist composition includes partition walls between pixels of a color filter, partition walls between pixels of an organic EL (Electro-Luminescence) display element, partition walls between elements of an organic EL illumination, and each TFT of an organic TFT (Thin Film Transistor) array. Attention has been focused on as a material for forming permanent films such as partition walls for partitioning electrodes, partition walls for ITO electrodes of liquid crystal display elements, and partition walls for circuit wiring boards.
In the production of circuit wiring boards, an ink jet method has been proposed in which a metal dispersion is sprayed and applied when forming circuit wiring. A circuit wiring pattern is formed from a resist composition by photolithography, and a cured film of the resist composition is used as a partition wall.

  In the ink jet method, it is necessary to prevent ink color mixing between adjacent pixels and the material ejected by the ink jet to a portion other than a predetermined region from clumping, and a resist composition containing an ink repellent agent is proposed. (Patent Documents 1 to 3).

International Publication No. 2008/146855 International Publication No. 2010/001976 International Publication No. 2010/013816

The resist composition is exposed using an exposure machine. Although the wavelength irradiated from the exposure machine varies depending on the specifications of the apparatus, in general, in the proximity exposure method used for the color filter, light of 330 nm or less is irradiated. On the other hand, in the mirror projection (MPA) system, light of 330 nm or less is shielded and irradiated. Therefore, the resist composition may be required to have a composition that can support the MPA method. Further, the projection type MPA method has advantages over the proximity exposure method, such as being able to form a sharp partition shape. In the MPA method, fine patterning may be required.
An object of the present invention is to provide a negative photosensitive resin composition having good ink repellency even when light rays of 330 nm or less are shielded, and having good reproduction of the mask line width, and a homogeneous photosensitive material obtained using the composition. Provided are a cured film, partition walls, a black matrix, and a method for producing the same. Another object of the present invention is to provide a color filter and an organic EL device having a partition wall or a black matrix having good performance.

式（３）中、Ｒ^３１は、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基またはシアノ基を表す。Ｒ^３２は、Ｒ^４１またはＯＲ^４２を表し、該Ｒ^４１およびＲ^４２は、それぞれ炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数７〜３０のアリールアルキル基を表す。Ｒ^３３は、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基または炭素原子数７〜３０のアリールアルキル基を表す。Ｒ^３４およびＲ^３５はそれぞれ独立に、Ｒ^４１、ＯＲ^４２、シアノ基またはハロゲン原子を表す。ａおよびｂはそれぞれ独立に０〜３の整数、ｃは１〜３の整数である。The present invention includes the following [1] to [15].
[1] An ink repellent agent (A) having a side chain containing a group represented by the following formula (1) or a group represented by the following formula (2):
A photopolymerization initiator (B) which is an oxime ester compound having a nitro group in one molecule;
A negative photosensitive resin composition comprising an alkali-soluble resin (C).
-CFXR ^f (1)
_{^{- (SiR 1 R 2 -O)}} n -SiR 3 R 4 R 5 (2)
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. A fluoroalkyl group having a number of 20 or less, or a fluorine atom.
In formula (2), R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ⁵ represents a hydrogen atom or a C 1-10 carbon atom. An organic group is shown, n shows the integer of 1-200.
[2] The negative photosensitive resin composition according to [1], wherein the photopolymerization initiator (B) is a compound comprising the following formula (3).

In formula (3), R ³¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a cyano group. R ³² represents R ⁴¹ or OR ⁴² , and each of R ⁴¹ and R ⁴² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group. R ³³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R ³⁴ and R ³⁵ each independently represent R ⁴¹ , OR ⁴² , a cyano group or a halogen atom. a and b are each independently an integer of 0 to 3, and c is an integer of 1 to 3.

[3] The negative photosensitive resin composition of [1] or [2], further comprising a black colorant (D).
[4] The negative photosensitive resin composition according to any one of [1] to [3], further comprising a crosslinking agent (G).
[5] Any of [1] to [4], wherein the ink repellent agent (A) is a compound having a group (1) or a group (2) in a side chain and a main chain being a hydrocarbon chain. Negative photosensitive resin composition.
[6] The negative photosensitive resin composition according to [5], wherein the ink repellent agent (A) has an acidic group.
[7] The negative photosensitivity of any one of [1] to [4], wherein the ink repellent agent (A) is a compound having a group (1) in the side chain and the main chain being an organopolysiloxane chain. Resin composition.
[8] The negative photosensitive resin composition according to any one of [5] to [7], wherein the ink repellent agent (A) has an ethylenic double bond.
[9] A cured film formed by curing a coating film of the negative photosensitive resin composition according to any one of [1] to [8] formed on the substrate.
[10] A partition formed to provide a partition on the substrate, the partition formed of the cured film of [9].
[11] A black matrix formed of a cured film according to [9], which is formed from a negative photosensitive resin composition according to [3], which is formed to provide a partition on a substrate.

[12] A step of applying the negative photosensitive resin composition of any one of [1] to [8] onto a substrate to form a coating film, heating the coating film to form a film, The method of manufacturing the partition which has the process of exposing and photocuring only the predetermined part of this, the process of removing films other than the said photocured part, and the process of obtaining the partition by heating the said photocured part The change in thickness of the photocured portion before and after removing the film is 60 nm or less.
[13] A method for producing a black matrix, wherein the partition is obtained as a black matrix using the negative photosensitive resin composition of [3] in the method for producing [12].
[14] A substrate, a plurality of pixels on the substrate, and a partition located between adjacent pixels, and the partition is cured of the negative photosensitive resin composition according to any one of [1] to [8] A color filter comprising a film.
[15] A substrate, a plurality of pixels on the substrate, and a partition located between adjacent pixels, and the partition is cured of the negative photosensitive resin composition according to any one of [1] to [8] An organic EL device comprising a film.

  According to the present invention, a partition wall having good ink repellency and good reproducibility of the line width of a mask even when exposed by reducing the exposure amount or shielding exposure light of 330 nm or less. It is possible to provide a negative photosensitive resin composition that can be produced. According to the present invention, it is possible to provide a homogeneous cured film, a partition wall and a black matrix having good performance, and a method for producing the same, using the negative photosensitive resin composition of the present invention. Furthermore, according to the present invention, it is possible to obtain a color filter and an organic EL device having good performance comprising the partition wall and the black matrix of the present invention.

It is sectional drawing which shows typically the manufacture example of the partition for optical elements using the negative photosensitive resin composition of this invention.

The acid value in this specification refers to the number of milligrams of potassium hydroxide required to neutralize resin acid or the like in 1 g of a sample, and is a value that can be measured according to the measurement method of JIS K 0070. . The unit is mgKOH / g.
The total solid content in this specification refers to a partition-forming component among the components contained in the negative photosensitive resin composition, and other than volatile components that volatilize by heating in the partition-forming process such as solvent (H). All components are shown.
In this specification, “(meth) acryloyl...” Is a general term for “methacryloyl...” And “acryloyl. The same applies to (meth) acrylate, (meth) acrylamide, (meth) allyl ..., (meth) acrylic resin.
The hydrocarbon group in this specification refers to an organic group composed of only carbon and hydrogen.
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, for example, liquids having optically and electrically functions after being dried and cured, and is not limited to conventionally used coloring materials. Similarly, “pixels” formed by injecting the ink are also used to represent sections having optical and electrical functions, which are partitioned by the partition walls.
In this specification, the ink repellency refers to a property having moderately both water repellency and oil repellency in order to repel the ink, and can be evaluated by, for example, a method described later.
Embodiments of the present invention will be described below. In addition, unless otherwise indicated in this specification,% represents the mass%.

[Ink repellent (A)]
The ink repellent agent (A) of the present invention is a group represented by the following formula (1) (hereinafter also referred to as group (1)) or a group represented by the following formula (2) (hereinafter referred to as group (2)). It is a compound having a side chain containing.
-CFXR ^f (1)
_{^{- (SiR 1 R 2 -O)}} n -SiR 3 R 4 R 5 (2)
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. A fluoroalkyl group having a number of 20 or less, or a fluorine atom.
In formula (2), R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ⁵ represents a hydrogen atom or a C 1-10 carbon atom. An organic group is shown, n shows the integer of 1-200.

  Since the ink repellent agent (A) has a side chain containing the group (1) or the group (2), it has a surface migration property, and the coating film formed from the negative photosensitive resin composition is heated and dried. When making a film, it moves to the vicinity of the coating surface. As a result, the surface of the partition wall made of a cured film obtained by curing the film exhibits ink repellency, and the ink injected by the ink jet method does not overflow from the opening between the partition walls (the location that becomes the pixel), Color mixing between adjacent pixels is difficult to occur.

  The side chain containing the group (1) or the group (2) may be formed directly by a polymerization reaction or may be formed by chemical conversion after the polymerization reaction.

When R ^f in formula (1) is a fluoroalkyl group having 20 or less carbon atoms in which at least one hydrogen atom optionally having an etheric oxygen atom is substituted with a fluorine atom, the fluoroalkyl group The hydrogen atom therein may be substituted with a halogen atom other than the fluorine atom. As another halogen atom, a chlorine atom is preferable. Further, the etheric oxygen atom may be present between the carbon-carbon bonds of the fluoroalkyl group or may be present at the terminal of the fluoroalkyl group. Examples of the structure of the fluoroalkyl 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, a group having an etheric oxygen atom is included). Thereby, the partition formed from the negative photosensitive resin composition has good ink repellency.
The number of carbon atoms of the group (1) is 20 or less, and 4-6 are preferable. In this case, sufficient ink repellency is imparted to the partition walls, and the compatibility between the ink repellent agent (A) and the other components constituting the negative photosensitive resin composition is good, and the negative photosensitive resin. When the composition is applied to form a coating film, the ink repellent agent (A) is not aggregated, and a partition wall having a good appearance can be formed.
The group (1) is preferably a perfluoroalkyl group having 4 to 6 carbon atoms or a perfluoroalkyl group having 4 to 9 carbon atoms having an etheric oxygen atom.

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 of 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 1 to 5).
As the group (1), — (CF ₂ ) ₃ CF ₃ or — (CF ₂ ) ₅ CF ₃ is particularly preferable.

In the formula (2), R ¹ and R 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 ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group. It is preferable that it is a hydrogen atom, a methyl group, or a phenyl group, and it is particularly preferable that R ¹ and R ² of all siloxane units are methyl groups.
In the formula (2), R ³ , R ⁴ and R ⁵ are groups bonded to the silicon atom at the terminal of the siloxane bond, and R ³ and R ⁴ can be the same as R ¹ and R ² , The preferred embodiment is also the same. Further, when R ⁵ is an organic group, nitrogen atom, may also be included such as oxygen atom, R ⁵ is 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.

As the group (2), it is preferable that all of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are methyl groups.

The ink repellent agent (A) preferably further has an acidic group. It is preferable that the ink repellent agent (A) has an acidic group in that the solubility of the negative photosensitive resin composition in the developer can be improved.
As the acidic group, one or more acidic groups selected from the group consisting of a carboxyl group, a phenolic hydroxyl group and a sulfonic acid group are preferable.
The acidic group is preferably present in the side chain from the viewpoint of easy synthesis. 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 (A) preferably has a polyoxyalkylene group. When the ink repellent agent (A) has a polyoxyalkylene group, the ink repellency can be maintained even when the pressure is increased in the development process. Furthermore, it is preferable in that it is possible to prevent generation of a remaining film that cannot be completely removed by development and remains in the dot portion. Specific examples of the polyoxyalkylene group used in the present invention include a group represented by the following formula (11) (hereinafter sometimes referred to as group (11)).
-(R ²¹ O) _m (R ²² O) _j R ²³ (11)
In formula (11), R ²¹ and R ²² each independently represent an alkylene group having 2 to 4 carbon atoms, and R ²³ represents a hydrogen atom or an optionally substituted carbon atom having 1 carbon atom. 10 represents an alkyl group, m represents an integer of 0 to 100, j represents an integer of 0 to 100, and m + j represents an integer of 4 to 100.

In group (11), R ²¹ and R ²² each independently represents an alkylene group having 2 to 4 carbon atoms. The structure of the alkylene group may be a linear structure or a branched structure. R ²¹ and R ²² may be the same or different. Among such R ²¹ and R ²² , 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 the group (11), m represents an integer of 0 to 100, and j represents an integer of 0 to 100. m and j are each preferably 0 to 50, and particularly preferably 0 to 30.
Moreover, although m + j is an integer of 4-100, the integer of 6-50 is preferable and the integer of 8-30 is especially preferable. When m + j is equal to or greater than the lower limit of the above range, ink repellency is unlikely to deteriorate when a jet rinsing process using high-pressure water is performed after the development process. Furthermore, it is difficult to generate a residual film. When m + j is less than or equal to the upper limit of the above range, the ink repellent agent (A) does not migrate to the opening during post-baking, and the ink affinity of the opening between the partition walls is sufficient, so that the ink can be formed using an inkjet method. When the ink is applied, the ink is sufficiently spread in the opening.

Group (11), there is indicating that with m ^{(R 21} O) units and the j ^{(R 22} O) units, the binding of ^{(R 21} O) units and ^{(R 22} O) units There is no particular limitation on the order. That is, in the group (11), m (R ²¹ O) units and j (R ²² O) units may be bonded alternately, randomly, or in blocks.

In the group (11), when R ²³ is an optionally substituted alkyl group having 1 to 10 carbon atoms, the structure is a straight chain structure, a branched structure, a ring structure, or a partial ring. It may have a structure or the like. Specific examples of the substituent include a carboxyl group, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms. In the present invention, R ²³ in the group (11) 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 ²¹ O) and (R ²² O) in the group (11) include —CH ₂ C ₆ H ₁₀ CH ₂ O— (wherein C ₆ H ₁₀ is a cyclohexylene group). _{, -CH 2 O -, - CH} 2 CH 2 O -, - CH 2 CH (CH 3) 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 can be mentioned. As specific examples of the group (11), (R ²¹ O) and (R ²² O) are both selected from the oxyalkylene groups exemplified above, m + j is 4 to 100, and R ²³ is CH ₃ . There are certain groups.

  As the group (11), one type may be used alone, or two or more types may be used in combination. Further, the side chain having the group (11) is introduced into the ink repellent agent (A), as described later, when the ink repellent agent (A) is produced by polymerization of the raw material monomer. The blending amount of the monomer to the whole raw material monomer is appropriately adjusted so as to be a blending amount capable of imparting the effect of improving the developability to the ink repellent agent (A) without impairing the effects of the present invention. Done.

The ink repellent agent (A) preferably has an ethylenic double bond. When the ink repellent agent (A) has an ethylenic double bond, the ink repellent agent (A) that has migrated to the film surface during drying may cause the ink repellent agent (A) or the ink repellent agent (A ) And the alkali-soluble resin (C) are preferable in that they are easily immobilized on the surface of the partition wall.
Examples of the ethylenic double bond include addition polymerizable unsaturated groups such as a (meth) acryloyl group, an allyl group, a vinyl group, and a vinyl ether group. Some or all of the hydrogen atoms of these groups may be substituted with a hydrocarbon group. As the hydrocarbon group, a methyl group is preferable.

  As described later, the introduction of the side chain having an ethylenic double bond into the ink repellent agent (A) reacts with the raw material monomer for producing the ink repellent agent (A) while appropriately adjusting the blending amount. Copolymerization is carried out by adding a monomer having a reactive group, and then the obtained copolymer is reacted with a compound having a functional group capable of binding to the reactive group and an ethylenic double bond. Is called.

As the ink repellent agent (A), a compound having the group (1) or the group (2) in the side chain and the main chain being a hydrocarbon chain is preferable. Hereinafter, the ink repellent agent (A) whose main chain is a hydrocarbon chain is also referred to as “ink repellent agent (A ¹ )”.
The ink repellent agent (A ¹ ) includes, for example, a monomer (a1) having a group (1) or a monomer (a2) having a group (2), and a monomer having an acidic group if necessary ( a3) If necessary, it can be produced by copolymerizing a raw material monomer containing a monomer (a4) having a polyoxyalkylene group.
Further, when the ink repellent agent (A ¹ ) has an ethylenic double bond, a raw material monomer obtained by adding a monomer (a5) having a reactive group to the raw material monomer is copolymerized, Subsequently, it can manufacture by making the compound (z1) which has the functional group which can couple | bond with the obtained copolymer, the said reactive group, and an ethylenic double bond react.

(Monomer (a1))
As the monomer (a1) having the group (1), the following monomer (a11) is preferable.
_{^{CH 2 = CR 6 COO-Y}} -CFXR f (a11)
In the formula, R ⁶ represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, or a trifluoromethyl group. Y represents a single bond or a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms, and is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability. X and R ^f have the same meaning as the group (1), and preferred embodiments are also the same.

Examples of the monomer (a11) include the following.
CH ₂ = CR ⁶ COOR ⁷ CFXR ^f
CH ₂ = CR ⁶ COOR ⁸ NR ⁹ SO ₂ CFXR ^f
CH ₂ = CR ⁶ COOR ¹⁰ NR ¹¹ COCFRXR ^f
CH ₂ = CR ⁶ COOCH ₂ CH (OH) R ¹² CFXR ^f
Here, R ⁶ represents the same meaning as described above, R ⁷ , R ⁸ and R ¹⁰ represent an alkylene group having 1 to 6 carbon atoms, R ⁹ and R ¹¹ represent a hydrogen atom or a methyl group, and R ¹² Represents a single bond or an alkylene group having 1 to 4 carbon atoms.

Specific examples of R ⁷ , R ⁸ and R ¹⁰ include —CH ₂ —, —CH ₂ CH ₂ —, —CH (CH ₃ ) —, —CH ₂ CH ₂ CH ₂ —, —C (CH _{3, respectively.} ) _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.
Specific examples of R ¹² _{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 (a11) include 2- (perfluorohexyl) ethyl (meth) acrylate and 2- (perfluorobutyl) ethyl (meth) acrylate.
As the monomer (a11), one type may be used, or two or more types may be used in combination.

(Monomer (a2))
As the monomer (a2) having the group (2), the following monomer (a21) is preferable.
_{^{CH 2 = CR 13 COO-Z-}} (SiR 1 R 2 -O) n -SiR 3 R 4 R 5 (a21)
In the formula, R ¹³ represents a hydrogen atom or a methyl group, and Z represents a single bond or a divalent organic group having 1 to 6 carbon atoms. R ¹ , R ² , R ³ , R ⁴ , and R ⁵ and n have the same meaning as in the group (2), and preferred embodiments are also the same.

Z is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific _{examples, -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. are mentioned.

Specific examples of the monomer _{(a21), CH 2 = CHCOO} -CH 2 CH 2 - (Si (CH 3) 2 -O) n -Si (CH 3) 3, CH 2 = CCH 3 COO-CH 2 _{CH 2 - (Si (CH 3} ) 2 -O) n -Si (CH 3) 3, CH 2 = CHCOO-CH 2 CH 2 CH 2 - (Si (CH 3) 2 -O) n -Si (CH 3 ) ₃ , CH ₂ ═CCH ₃ COO—CH ₂ CH ₂ CH ₂ — (Si (CH ₃ ) ₂ —O) _n —Si (CH ₃ ) _{3 and the} like. Note that n is approximately 4, 60, 160.
A commercially available product can be used as the monomer (a21). As commercial products, the following are listed as trade names. X-22-174DX (made by Shin-Etsu Chemical), X-22-2426 (made by Shin-Etsu Chemical), X-22-2475 (made by Shin-Etsu Chemical).
As the monomer (a21), one type may be used, or two or more types may be used in combination.

(Monomer (a3))
When the ink repellent agent (A ¹ ) has an acidic group, it is preferable to copolymerize the monomer (a3) having an acidic group together with the monomers (a1) to (a2).
Examples of the monomer (a3) having an acidic group include a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, and a monomer having a sulfonic acid group.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.
Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. In addition, one or more hydrogen atoms of these benzene rings are an alkyl group such as a methyl group, an ethyl group or an n-butyl group, an alkoxy group such as a methoxy group, an ethoxy group or an n-butoxy group, a halogen atom or an alkyl group. Examples thereof include compounds in which one or more hydrogen atoms are substituted with a halogen atom, a haloalkyl group, a nitro group, a cyano group, or an amide group.
Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, and (meth) acrylic acid-2-sulfoethyl. , (Meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, and 2- (meth) acrylamido-2-methylpropanesulfonic acid.

As the monomer (a3), acrylic acid or methacrylic acid is preferable from the viewpoint of easy availability.
As the monomer (a3), one type may be used, or two or more types may be used in combination.

(Monomer (a4))
The monomer having the group (11) used for the production of the ink repellent agent (A ¹ ) is represented by the compound represented by the following formula (12) (hereinafter also referred to as the compound (12)) or (13). It is preferable that it is a compound (henceforth a compound (13)). These may be used alone or in combination of two or more.
_{^{CH 2 = CR 24 -COO-W-}} (R 21 O) m (R 22 O) j R 23 (12)
_{^{CH 2 = CR 25 -O-W-}} (R 21 O) m (R 22 O) j R 23 (13)
In formulas (12) and (13), R ²⁴ and R ²⁵ are each 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 alkyl group having 7 to 20 carbon atoms. An alkyl group substituted with an aryl 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 ²¹ O) _m (R ²² O) _j R ²³ is the group (11), R ²¹ , R ²² , R ²³ , m and j have the same meaning as the group (11), and the preferred ranges are also the same. It is.

In the compounds (12) and (13), when W is a divalent organic group having no fluorine atom having 1 to 10 carbon atoms, a linear structure other than R ²¹ O and R ²² O, a branched structure , A ring structure, an oxyalkylene group having 1 to 10 carbon atoms in a structure partially having a ring, a single bond, and the like. Specifically, as the oxyalkylene group, CH ₂ C ₆ H ₁₀ CH ₂ O (wherein C ₆ H ₁₀ is a cyclohexylene group), CH ₂ O, CH ₂ CH ₂ O, CH ₂ CH (CH _{3) 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. Among these, W in the compounds (12) and (13) is preferably an oxyalkylene group having 2 to 4 carbon atoms because of availability.

In the compounds (12) and (13), each of R ²⁴ and R ²⁵ is preferably a hydrogen atom, a chlorine atom, a methyl group, a phenyl group, or a benzyl group, and particularly preferably a hydrogen atom, a chlorine atom, or a methyl group.

Examples of the compound represented by the compound (12) include the following.
_{CH 2 = CHOCH 2 C 6 H} 10 CH 2 O (CH 2 CH 2 O) m R 23,
_{CH 2 = CHO (CH 2)} 4 O (CH 2 CH 2 O) m R 23.
Examples of the compound represented by the compound (13) include the following.
_{CH 2 = CHCOO (CH 2 CH} 2 O) m R 23,
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) m R 23,
_{CH 2 = CHCOO (CH 2 CH} 2 O) m (C 3 H 6 O) j R 23,
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) m (C 3 H 6 O) j R 23,
_{CH 2 = CHCOO (C 2 H} 4 O) m (C 4 H 8 O) j R 23.
In the formula, m and j have the same meaning as in the group (11), 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 ²³ has the same meaning as the group (11), and a preferable range is a linear or unsubstituted alkyl group having 1 to 10 carbon atoms, and a methyl group is particularly preferable.

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

(Monomer (a5))
As the monomer (a5) having a reactive group, a monomer having a hydroxyl group, an acid anhydride monomer having an ethylenic double bond, a monomer having a carboxyl group, a monomer having an epoxy group Etc. In addition, it is preferable that a monomer (a5) does not contain group (1) and group (2) substantially.
When a monomer having a carboxyl group is used as the monomer (a3) having an acidic group and a monomer having a carboxyl group is also used as the monomer (a5) having the reactive group, finally, What is not introduced with an ethylenic double bond and remains as a carboxyl group is regarded as a monomer (a3).

By reacting the reactive group of the monomer (a5) after copolymerization with the compound (z1) having a functional group capable of binding to the reactive group and an ethylenic double bond, the An ink repellent agent (A ¹ ) having a side chain having a heavy bond is formed.

  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 group 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 i + g is 1 to 100. hereinafter the _{same.), CH 2 = C (} CH 3) COOC 2 H 4 O (C 2 H 4 O) i (C 3 H 6 O) g H , and the like.

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

(Monomer (a6))
The monomer used for the polymerization in the present invention includes the monomer (a1) having the group (1) or the monomer (a2) having the group (2), and a monomer having an acidic group as necessary. (A3) a monomer (a4) having a polyoxyalkylene group, if necessary, and a monomer having a reactive group when the ink repellent (A ¹ ) has an ethylenic double bond ( a5) is included, but other monomers (a6) other than these monomers may be included.

As the monomer (a6), hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic acid esters, (meth) acrylamides, aromatic Group vinyl compounds, chloroolefins, and conjugated dienes. These compounds may contain a functional group, and examples of the functional group include a carbonyl group and an alkoxy group. In particular, (meth) acrylic acid esters or (meth) acrylamides are preferable because of excellent heat resistance of the partition walls.
In addition, the monomer which has the epoxy group mentioned as the monomer (a5) which has the said reactive group, for example, glycidyl (meth) acrylate, 3, 4- epoxy cyclohexyl methyl acrylate, etc., monomer (a6) Can also be used. That is, when these monomers having an epoxy group are used in the polymerization in the present invention, when no ethylenic double bond is introduced after copolymerization, these monomers having an epoxy group are other monomers ( a6). In addition, even when an ethylenic double bond is introduced, an ethylenic double bond is not finally introduced and what remains as an epoxy group is regarded as another monomer (a6).

(Manufacture of ink repellent agent (A ¹ ))
The ink repellent agent (A ¹ ) can be synthesized, for example, by the following method. First, the monomer is dissolved in a solvent and heated, and a polymerization initiator is added for copolymerization. In the copolymerization reaction, it is preferable that a chain transfer agent is present if necessary. The monomer, polymerization initiator, solvent and chain transfer agent may be added continuously.

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

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

  Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl-α-cumyl peroxide and the like. Examples of inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, percarbonate and the like. As the azo compound, 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, Examples include 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (2-amidinopropane) dihydrochloride, and the like.

  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.

In addition, when the ink repellent agent (A ¹ ) has an ethylenic double bond, the copolymer obtained as described above, a functional group capable of binding to a reactive group, and an ethylenic double bond are combined. The ink repellent agent (A ¹ ) is obtained by reacting with the compound (z1) it has.
Examples of the combination of the reactive group and the compound (z1) having a functional group capable of binding to the reactive group and an ethylenic double bond include the following combinations.
(1) An acid anhydride having an ethylenic double bond with respect to the hydroxyl group,
(2) A compound having an isocyanate group and an ethylenic double bond with respect to the hydroxyl group,
(3) A compound having an acyl chloride group and an ethylenic double bond with respect to the hydroxyl group,
(4) A compound having a hydroxyl group and an ethylenic double bond with respect to the acid anhydride,
(5) A compound having an epoxy group and an ethylenic double bond with respect to the carboxyl group,
(6) A compound having a carboxyl group and an ethylenic double bond with respect to the epoxy group.
After reacting a compound having a carboxyl group and an ethylenic double bond with an epoxy group, the resulting hydroxyl group is reacted with an acid anhydride of a compound having two or more carboxyl groups in one molecule, and ink repellent An acidic group can also be introduced into the agent (A ¹ ).

  Specific examples of the acid anhydride having an ethylenic double bond include those described above. Specific 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. Specific examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride. Specific examples of the compound having a hydroxyl group and an ethylenic double bond include the above-described monomers having a hydroxyl group. Specific examples of the compound having an epoxy group and an ethylenic double bond include the above-described monomers having an epoxy group. Specific examples of the compound having a carboxyl group and an ethylenic double bond include the above-described examples of the monomer having a carboxyl group. Specific examples of the acid anhydride of a compound having two or more carboxyl groups in one molecule include the acid anhydrides having an ethylenic double bond shown for the monomer (a5). .

When the copolymer is reacted with the compound (z1) having a functional group capable of binding to a reactive group and an ethylenic double bond, the solvent exemplified in the synthesis of the copolymer is used as a solvent for the reaction. Can be used.
Moreover, it is preferable to mix | blend a polymerization inhibitor. Examples of the polymerization inhibitor include 2,6-di-t-butyl-p-cresol and t-butyl-p-benzoquinone.
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.

The preferable ratio of each monomer with respect to the total mass of monomers to be copolymerized is as follows. The ratio of the monomer (a1) or the monomer (a2) is preferably 20 to 80% by mass, particularly preferably 30 to 60% by mass. When the ratio is not less than the lower limit of the above range, the ink repellent agent (A ¹ ) can reduce the surface tension of the partition wall formed of the cured film to be formed, and can impart high ink repellency to the partition wall. Adhesiveness of a partition and a base material becomes it favorable that it is below the upper limit of the said range.
When the monomer (a3) is included, the proportion is preferably 2 to 20% by mass, particularly preferably 4 to 12% by mass. Within the above range, the developability of the negative photosensitive resin composition becomes good.
When the monomer (a4) is included, the proportion is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 15 to 50% by mass. Within the above range, liquid repellency can be maintained even when the pressure is increased in the development step. Furthermore, the generation of a residual film can be prevented.
When the monomer (a5) is included, the proportion is preferably 20 to 70 mass%, particularly preferably 30 to 50 mass%. When the ethylenic double bond is introduced through the polymerization unit derived from the monomer (a5) included in the above range, the immobilization of the ink repellent agent (A ¹ ) to the partition wall surface and the developability are improved.
When the other monomer (a6) is included, the proportion is preferably 70% by mass or less, and particularly preferably 50% by mass or less. Within the above range, alkali solubility and developability are good.

Preferred combinations of monomers in the production of the ink repellent agent (A ¹ ) are as follows.
(Combination 1)
Monomer (a1): at least one selected from the group consisting of 2- (perfluorobutyl) ethyl (meth) acrylate and 2- (perfluorohexyl) ethyl (meth) acrylate,
Monomer (a3): at least one selected from the group consisting of acrylic acid and methacrylic acid,
Monomer (a4): at least one selected from the group consisting of Blemmer PME-400 and Blemmer PME-1000,
Monomer (a5): 2-hydroxyethyl (meth) acrylate.
After copolymerizing the above monomers to obtain a copolymer, at least one selected from the group consisting of 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate A compound in which a seed is reacted to introduce an ethylenic double bond.

(Combination 2)
Monomer (a1): at least one selected from the group consisting of 2- (perfluorobutyl) ethyl (meth) acrylate and 2- (perfluorohexyl) ethyl (meth) acrylate,
Monomer (a3): at least one selected from the group consisting of acrylic acid and methacrylic acid,
Monomer (a4): at least one selected from the group consisting of Blemmer PME-400 and Blemmer PME-1000,
As necessary, the monomer (a6) is selected from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate, methyl (meth) acrylate, isobornyl (meth) acrylate and cyclohexyl (meth) acrylate. At least one.

(Combination 3)
Monomer (a1): at least one selected from the group consisting of 2- (perfluorobutyl) ethyl (meth) acrylate and 2- (perfluorohexyl) ethyl (meth) acrylate,
Monomer (a4): at least one selected from the group consisting of Blemmer PME-400 and Blemmer PME-1000,
Monomer (a5): Glycidyl (meth) acrylate Monomer (a6): 3,4-epoxycyclohexylmethyl acrylate, methyl (meth) acrylate, isobornyl (meth) acrylate, and cyclohexyl (meth) acrylate At least one selected.
After the copolymer is obtained by copolymerizing the above monomers, at least one selected from the group consisting of acrylic acid and methacrylic acid is reacted, followed by anhydrous 3,4,5,6-tetrahydrophthalic acid And a compound in which at least one selected from the group consisting of cis-1,2,3,6-tetrahydrophthalic anhydride is reacted to introduce an acidic group and an ethylenic double bond.

(Combination 4)
Monomer (a1): at least one selected from the group consisting of 2- (perfluorobutyl) ethyl (meth) acrylate and 2- (perfluorohexyl) ethyl (meth) acrylate,
Monomer (a2): at least one selected from the group consisting of X-22-174DX, X-22-2426 and X-22-247;
Monomer (a3): at least one selected from the group consisting of acrylic acid and methacrylic acid,
Monomer (a4): at least one selected from the group consisting of Blemmer PME-400 and Blemmer PME-1000,
Monomer (a5): 2-hydroxyethyl (meth) acrylate.
After copolymerizing the above monomers to obtain a copolymer, at least one selected from the group consisting of 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate A compound in which a seed is reacted to introduce an ethylenic double bond.

(Combination 5)
Monomer (a2): at least one selected from the group consisting of X-22-174DX, X-22-2426 and X-22-247;
Monomer (a3): at least one selected from the group consisting of acrylic acid and methacrylic acid,
Monomer (a4): at least one selected from the group consisting of Blemmer PME-400 and Blemmer PME-1000,
Monomer (a5): 2-hydroxyethyl (meth) acrylate.
After copolymerizing the above monomers to obtain a copolymer, at least one selected from the group consisting of 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate A compound in which a seed is reacted to introduce an ethylenic double bond.

When the ink repellent agent (A ¹ ) has an ethylenic double bond, the copolymer and the compound (z1) have an equivalent ratio of [functional group of the compound (z1)] / [reactive group of the copolymer]. It is preferable to prepare such that the value of 0.5 to 2.0 is preferable, and 0.8 to 1.5 is particularly preferable. When it is at least the lower limit of the above range, the ink repellent agent (A ¹ ) can be fixed on the partition wall. When the amount is not more than the upper limit of the above range, the amount of impurities which are unreacted compound (z1) increases, and the appearance of the coating film deteriorates. In addition, when using a monomer having a carboxyl group as both the monomer (a3) and the monomer (a4), the acid value of the ink repellent agent (A ¹ ) is set to a predetermined value. What is necessary is just to adjust the preparation amount of a copolymer and a compound (z1).

If the ink repellent ^{(A 1)} has a group (1), the content of fluorine atoms in the ink repellent ^{(A 1)} is preferably from 5 to 50 mass%, more preferably from 10 to 40 wt%, 20 to 35 Mass% is particularly preferred. When it is at least the lower limit of the above range, the ink repellent agent (A ¹ ) is excellent in the effect of lowering the surface tension of the partition wall, and a partition wall 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 (A ¹ ) has the group (2), the content of silicon atoms in the ink repellent agent (A ¹ ) is preferably 0.1 to 25% by mass, and particularly preferably 0.5 to 10% by mass. . When it is at least the lower limit of the above range, the ink repellent agent (A ¹ ) imparts the effect of lowering the surface tension of the partition wall to be formed and the effect of increasing the ink falling property. Adhesiveness of a partition and a base material becomes it favorable that it is below the upper limit of the said range.

The acid value of the ink repellent agent (A ¹ ) is preferably 150 mgKOH / g or less, particularly preferably 10 to 100 mgKOH / g. Within the above range, both the solubility of the negative photosensitive resin composition in the developer and the expression of ink repellency can be achieved.

When the ink repellent agent (A ¹ ) contains an ethylenic double bond, the amount is preferably 0.5 × 10 ^{−3 to} 5 × 10 ⁻³ mol / g, and 1 × 10 ^{−3 to} 4.5 × 10. ^-3 mol / g is particularly preferred. Within the above range, the immobilization of the ink repellent agent (A ¹ ) to the partition and the developability are good.

The number average molecular weight (Mn) of the ink repellent agent (A ¹ ) is preferably 5 × 10 ³ to 10 × 10 ^4, more preferably 8 × 10 ^{3 to} 9 × 10 ⁴ , and 1 × 10 ^{4 to} 7 × 10 ^4. Is particularly preferred. Within the above range, alkali solubility and developability are good.
The mass average molecular weight (Mw) of the ink repellent agent (A ¹ ) is preferably 1.2 × 10 ^{4 to} 20 × 10 ^4, more preferably 2 × 10 ⁴ to 15 × 10 ⁴ , and 3 × 10 ^{4 to} 12 × 10. ⁴ is particularly preferred. Within the above range, alkali solubility and developability are good.

As the ink repellent agent (A), a compound having the group (1) in the side chain and the main chain being an organopolysiloxane chain is also preferable. Hereinafter, the ink repellent agent (A) whose main chain is an organopolysiloxane chain is also referred to as “ink repellent agent (A ² )”.
Examples of the ink repellent agent (A ² ) include a hydrolyzable silane compound represented by the following formula (14) (hereinafter also referred to as silane compound (a7)) or a partially hydrolyzed condensate thereof, and the following formula (15). A hydrolyzable silane compound (hereinafter also referred to as silane compound (a8)) or a partially hydrolyzed condensate thereof, or a partially hydrolyzed condensate of the mixture. It is preferable.
R ^f —CFX—Q ¹ —SiX ¹ ₃ (14)
R ^H1 _p -SiX ² _(4-p) (15)
(The symbols in formulas (14) and (15) are as follows.
X and R ^f are as described above,
Q ¹ : a divalent organic group not containing a fluorine atom having 1 to 10 carbon atoms,
R ^H1 : a hydrocarbon group having 1 to 6 carbon atoms,
X ¹ , X ² : hydrolyzable group,
p: 0, 1 or 2,
However, three X ^{1 in} the formula (14), (4-p) X ² in the formula (15), and p R ^H1 may be different from each other or the same. )

The content of fluorine atoms in the ink repellent agent (A ² ) is preferably 10 to 55% by mass, more preferably 12 to 40% by mass, and particularly preferably 15 to 30% by mass, and the content of fluorine atoms is in the above range. In addition, excellent ink repellency and ink repellency UV / ozone resistance can be imparted to the partition obtained from the negative photosensitive resin assembly.

The ink repellent agent (A ² ) preferably has a silanol group (that is, a hydroxyl group bonded to a silicon atom). The number of silanol groups is preferably 0.2 to 3.5, more preferably 0.2 to 2, and particularly preferably 0.5 to 1.5 per silicon atom. When it is at least the lower limit of the above range, it is possible to prevent detachment of the ink repellent agent (A ² ) from the substrate surface when the partition is formed using the negative photosensitive resin composition. When the amount is not more than the upper limit of the above range, the ink repellent agent (A ² ) is excellent in compatibility with the solvent and other components in the negative photosensitive resin composition.
The number of silanol groups in the ink repellent agent (A ² ) is calculated from the ratio of peak areas of Si groups having silanol groups and Si groups having no silanol groups, as measured by ²⁹ Si-NMR.

The hydrolyzable silane compound mixture includes a silane compound (a7) or a partial hydrolysis condensate thereof, and a silane compound (a8) or a partial hydrolysis condensate thereof.
A partially hydrolyzed condensate of a hydrolyzable silane compound is an oligomer (multimer) produced by hydrolyzing a polyfunctional hydrolyzable silane compound and then dehydrating and condensing it in a solvent. Of high molecular weight. A relatively low molecular weight multimer such as a dimer or tetramer of a hydrolyzable silane compound is also a partial hydrolysis condensate in the present invention. The partially hydrolyzed condensate has a silanol group generated by hydrolysis of a hydrolyzable group, and may have an unreacted hydrolyzable group. The relatively high molecular weight partially hydrolyzed condensate mainly has silanol groups, and the relatively low molecular weight partially hydrolyzed condensate may further have hydrolyzable groups.
The partially hydrolyzed condensate has the property of finally becoming a high molecular weight cured product that does not dissolve in the solvent as a result of further condensation or hydrolysis. The partial hydrolysis-condensation product may be a mixture of oligomers having different degrees of multimerization.
The partially hydrolyzed condensate can be produced, for example, by stirring the hydrolyzable silane compound in the presence of an acid catalyst and water for a predetermined time under a predetermined reaction temperature condition. The degree of multimerization of the resulting partially hydrolyzed condensate can be appropriately adjusted depending on the acid concentration, reaction temperature, reaction time, and the like.
In addition, the molar ratio indicating the ratio of the following hydrolyzable silane compound is such that when at least one of the following hydrolyzable silane compounds is a partial hydrolysis condensate, the above molar ratio is determined for each hydrolyzable silane compound. It is the ratio of the number of derived silicon atoms.

(Hydrolyzable silane compound represented by formula (14))
As shown by the formula (14), the silane compound (a7) is a hydrolyzable silane compound having a group (1). In the formula (14), Q ¹ is a divalent organic group that links the group (1) and the hydrolyzable silyl group (—SiX ¹ ₃ ), and includes a fluorine atom having 1 to 10 carbon atoms. There are no divalent organic groups. When Q ¹ is represented as Si bonded to the right bond and R ^f —CFX— bonded to the left bond, specifically, — (CH ₂ ) _i1 — (where i1 is 1 to 5) ), —CH ₂ O (CH ₂ ) _i2 — (i2 is an integer of 1 to 4), —SO ₂ NR ¹ — (CH ₂ ) _i3 — (R ¹ is a hydrogen atom, a methyl group, or ethyl. Group, i3 is 1 or more, and an integer of 4 or less in total with the number of carbon atoms of R ¹ ), — (C═O) —NR ¹ — (CH ₂ ) _i4 — (R ¹ is the same as above. , I4 is 1 or more, and a group represented by a total of 4 or less in total with the number of carbon atoms of R ¹ is preferable. As Q ¹ , — (CH ₂ ) _i1 — in which i1 is 2 or 3 is more preferable, and — (CH ₂ ) ₂ — is particularly preferable.

When the group (1) is a perfluoroalkyl group having 1 to 6 carbon atoms, examples of the ^{_{Q 1, - (CH 2)}} i1 - (i1 is the same) the group represented by the formula. i1 is preferably an integer of 2 to 4, and i ( ₂ ) is particularly preferably — (CH ₂ ) ₂ —.
In the case where the group (1) is a C 4-9 perfluoroalkyl group containing an etheric oxygen atom, as Q ¹ , — (CH ₂ ) _i1 —, —CH ₂ O (CH ₂ ) _i2 —, A group represented by —SO ₂ NR ¹ — (CH ₂ ) _i3 — or — (C═O) —NR ¹ — (CH ₂ ) _i4 — (i1 to _i4 and R ¹ are the same as described above) is preferable. In this case, - _{(CH 2) 2} - is particularly preferred.

In formula (14), X ¹ represents a hydrolyzable group bonded to a silicon atom. Examples of X ¹ include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, and a group in which hydrogen of the amino group is substituted with an alkyl group. An alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferable, and a methoxy group, an ethoxy group, or a chlorine atom is particularly preferable. The group becomes a hydroxyl group (silanol group) by a hydrolysis reaction, and further, a reaction for forming a Si—O—Si bond through a condensation reaction between molecules easily proceeds smoothly.

Specific examples of the silane compound (a7) include the following compounds.
F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , F (CF ₂ ) ₄ CH ₂ CH ₂ SiCl ₃ , F _{(CF 2) 6 CH 2 CH} 2 Si (OCH 3) 3, F (CF 2) 6 CH 2 CH 2 Si (OCH 2 CH 3) 3, F (CF 2) 6 CH 2 CH 2 SiCl 3.
_{CF 3 OCF 3 CF 2 CF 2} CH 2 CH 2 Si (OCH 3) 3, F (CF 2) 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CH 2 CH 2 Si (OCH 2 CH 3) ₃ , CF ₃ OCF (CF ₃ ) CF ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .
F (CF ₂ ) ₂ OCF ₂ CF ₂ OCF ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₂ O (CF ₂ ) ₂ O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .
_{F (CF 2) 3 OCF 2} CF 2 CH 2 CH 2 SiCl 3, F (CF 2) 3 OCF (CF 3) CF 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3.

As the silane compound (a7), among others, F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , F (CF ₂₎ ) ₆ CH ₂ CH ₂ SiCl ₃ , F (CF ₂ ) ₃ OCF (CF ₃ ) CF ₂ O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) _{3 and the} like are particularly preferable.
As the hydrolyzable silane compound contained in the hydrolyzable silane compound mixture, the silane compound (a7) may be used alone or in combination of two or more.
The hydrolyzable silane compound mixture may contain a partial hydrolysis condensate of the silane compound (a7). However, it is preferable that it is a silane compound (a7) simple substance rather than a partial hydrolysis-condensation product.

(Hydrolyzable silane compound represented by formula (15))
The silane compound (a8) represented by the formula (15) is used as a hydrolyzable silane compound contained in the hydrolyzable silane compound mixture together with the silane compound (a7).
In the formula (15), R ^H1 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Examples of ^RH1 other than an alkyl group include alkenyl groups such as vinyl groups and allyl groups, and hydrocarbon groups having rings such as phenyl groups and cycloalkyl groups.
X ² is a hydrolyzable group, and is the same as X ¹ in the above formula (15), including preferred embodiments. p is 0, 1 or 2. However, two R ^{H1 s} when p is 2 and (4-p) X ^{2 s} may be different from each other or the same.
The silane compound (a8) is preferably a tetrafunctional compound in which p is 0 or a trifunctional compound in which p is 1.

Ink repellent agent in (A ^2), water repellency is expressed by a silane compound (a7) from the group (1) and the silane compound (a8) from the R ^H1, oil repellency is expressed mainly by group (1) . In order for the cured product of the ink repellent agent (A ² ) to exhibit sufficient oil repellency, the group (1) with respect to the sum of the group (1) and R ^{H1 in the} ink repellent agent (A ² ). It is preferable that the ratio of is high. When p = 0, the ratio of the group (1) in the ink repellent agent (A ² ) is increased, the oil repellency is improved, and the film forming property is excellent. In the case of p = 1 or 2, the presence of R ^H1 to some extent makes the ink repellent agent (A ² ) easily dissolved in a hydrocarbon solvent, and the coating film of the negative photosensitive resin composition on the surface of the substrate. A relatively inexpensive solvent can be selected when forming the film.

As the silane compound (a8), the following compounds are preferable. Moreover, the partial hydrolysis-condensation product of a silane compound (a8) can be used instead of a silane compound (a8). The partially hydrolyzed condensate is preferably a relatively low molecular weight compound. Examples of the partially hydrolyzed condensate include the following.
Si (OCH ₃ ) ₄ , Si (OCH ₂ CH ₃ ) ₄ , CH ₃ Si (OCH ₃ ) ₃ ,
CH ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ CH ₂ Si (OCH ₃ ) ₃ ,
CH ₃ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₃ ) ₂ ,
(CH ₃ ) ₂ Si (OCH ₂ CH ₃ ) ₂ , (C ₆ H ₅ ) Si (OCH ₂ CH ₃ ) ₃ ,
A partially hydrolyzed condensate of Si (OCH ₃ ) ₄ (for example, methyl silicate 51 (trade name) manufactured by Colcoat Co.),
Partially hydrolyzed condensate of Si (OCH ₂ CH ₃ ) ₄ (for example, ethyl silicate 40 and ethyl silicate 48 (both trade names) manufactured by Colcoat).

As the hydrolyzable silane compound contained in the hydrolyzable silane compound mixture of the present invention, the silane compound (a8) may be used alone or in combination of two or more. When using 2 or more types together, a bifunctional compound can also be used together with a tetrafunctional compound and / or a trifunctional compound.
The content of the silane compound (a8) in the hydrolyzable silane compound mixture is preferably 0.1 to 9 mol of the silane compound (a8) with respect to 1 mol of the silane compound (a7), and preferably 0.5 to 9 mol. Is particularly preferred. Furthermore, hydrolyzable silane compounds other than the silane compound (a7) and the silane compound (a8) (hereinafter also referred to as silane compound (a9)) and a partial hydrolysis condensate of the silane compound (a9) may be included. .

(Silane compound (a9))
The silane compound (a9) is a difunctional or trifunctional silane compound having a hydrolyzable group and is a known silane as long as it is a compound that co-condenses with the silane compound (a7) and the silane compound (a8). Compounds can be used.
The silane compound (a9) is preferably a silane compound having a structure having a hydrocarbon group substituted with a hydrocarbon group having 7 or more carbon atoms or a reactive group in place of R ^{H1 in} the formula (15). . However, when p is 2 in the formula (15), one of the two ^{R H1} may be ^{R H1.} As the reactive group, a (meth) acryloyloxy group, an amino group, a hydrocarbon-substituted amino group, an epoxy group, and the like are preferable. In particular, a reactive group having an ethylenic double bond such as a (meth) acryloyloxy group is preferred.
A preferred silane compound (a9) is a hydrolyzable silane compound having a reactive group having an ethylenic double bond, and trialkoxysilane or dialkoxysilane having a (meth) acryloyloxy group-substituted alkyl group is particularly preferred. By using the silane compound (a9) having an ethylenic double bond, an ink repellent agent (A ² ) having an ethylenic double bond can be obtained.
Specific examples of the particularly preferred compound silane compound (a9) include the following.
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OCH 2 CH 3) 3,
_{CH 2 = CHCOO (CH 2)} 3 Si (OCH 3) 3,
_{CH 2 = CHCOO (CH 2)} 3 Si (OCH 2 CH 3) 3,
_{[CH 2 = C (CH 3} ) COO (CH 2) 3] CH 3 Si (OCH 3) 2,
_{[CH 2 = C (CH 3} ) COO (CH 2) 3] CH 3 Si (OCH 2 CH 3) 2,
_{(C 6 H 5) NH (} CH 2) 3 Si (OCH 3) 3.
As the hydrolyzable silane compound contained in the hydrolyzable silane compound mixture of the present invention, the silane compound (a9) may be used alone or in combination of two or more.
The compounding amount of the silane compound (a9) in the hydrolyzable silane compound mixture of the present invention is preferably 5 mol or less, preferably 4 mol or less with respect to 1 mol of the total amount of the silane compound (a7) and the silane compound (a8). Is particularly preferred.

A monofunctional silane compound can be mix | blended with a hydrolysable silane compound mixture as a hydrolysable silane compound. The monofunctional silane compound functions as a molecular weight regulator when hydrolyzing and condensing a hydrolyzable silane compound mixture to form a partially hydrolyzed condensate. That is, it is used for the purpose of producing a partially hydrolyzed condensate having a relatively low molecular weight or for the purpose of preventing the partially hydrolyzed condensate from becoming too high in molecular weight and becoming insoluble in a solvent. It is preferable to appropriately adjust the amount used depending on the molecular weight of the target partial hydrolysis-condensation product.
As the monofunctional silane compound, a compound having a structure in which p is 3 or hexaalkyldisiloxane in the formula (15) is preferable. The alkyl group in these compounds preferably has 4 or less carbon atoms, and particularly preferably a methyl group or an ethyl group.

The ink repellent agent (A ² ) used in the negative photosensitive resin composition of the present invention is a hydrolyzable silane compound mixture of the raw materials or a partial hydrolysis condensate thereof, and a plurality of condensates having different degrees of polymerization. It is preferable that the mixture is a mixture of partially hydrolyzed condensates. That is, the ink repellent agent (A ² ) is a partially hydrolyzed condensate produced using the silane compound (a7) and the silane compound (a8) as essential components and optionally using the silane compound (a9). preferable. The partial hydrolysis-condensation product is preferably a product produced by mixing the silane compound (a7), the silane compound (a8), and optionally the silane compound (a9), and then subjecting the mixture to partial hydrolysis-condensation. In addition, instead of the silane compound (a7), the silane compound (a8), and the silane compound (a9), partial hydrolysis condensates thereof may be used.

  The partial hydrolysis-condensation product produced using the silane compound (a7) and the silane compound (a8) has a structure having an average composition formula represented by the following formula (16). However, since it is actually a product (partially hydrolyzed condensate) in which a hydrolyzable group or silanol group remains, it is difficult to express this product by a chemical formula. In the average composition formula represented by the formula (16), in the partially hydrolyzed condensate produced as described above, all of the hydrolyzable groups or silanol groups were completely hydrolyzed and condensed to form siloxane bonds. The chemical formula of the case.

式（１６）中、Ｒ^ｆ、Ｒ^Ｈ１、Ｑ^１およびｐの好ましい範囲は上述したものと同様である。ｓ、ｔは、重合度の異なる複数の部分加水分解縮合物における各単位の平均存在モル数である。

In formula (16), the preferred ranges of R ^f , R ^H1 , Q ¹ and p are the same as those described above. s and t are the average number of moles of each unit in a plurality of partial hydrolysis-condensation products having different degrees of polymerization.

In the partial hydrolysis-condensation product having the structure of the average composition formula represented by the formula (16), it is assumed that the units derived from the silane compound (a7) and the silane compound (a8) are randomly arranged. The In addition, s / t (molar ratio) in the average composition formula (16) when using the silane compound (a7) and the silane compound (a8) is hydrolyzable as an average value of the entire ink repellent agent (A ² ). The range described above as the content of the silane compound (a7) with respect to the silane compound (a8) in the silane compound mixture, that is, 10/1 to 90 (molar ratio) is preferable, and 10/5 to 90 (molar ratio) is particularly preferable.

When the ink repellent agent (A ² ) is produced using the silane compound (a7), the silane compound (a8) and the silane compound (a9), the unit derived from the silane compound (a9) is further added to the formula (16). It has the structure of the average composition formula co-condensed.

As the ink repellent agent (A ² ), a partial hydrolysis-condensation product of a mixture of the following silane compounds is preferable.
(Combination 6)
Silane compound (a7): at least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane,
Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane.
(Combination 7)
Silane compound (a7): at least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane,
Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane,
Monofunctional silane compound: hexamethyldisiloxane or trimethylmethoxysilane.
(Combination 8)
Silane compound (a7): at least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane,
Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane,
Silane compound (a9): 3-acryloyloxypropyltrimethoxysilane or 3-methacryloyloxypropyltrimethoxysilane.
(Combination 9)
Silane compound (a7): at least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane,
Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane,
Silane compound (a9): 3-acryloyloxypropyltrimethoxysilane or 3-methacryloyloxypropyltrimethoxysilane,
Monofunctional silane compound: hexamethyldisiloxane or trimethylmethoxysilane.
(Combination 10)
Silane compound (a7): at least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane,
Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane,
Silane compound (a9): 3-glycidyloxypropyltrimethoxysilane,
Monofunctional silane compound: hexamethyldisiloxane or trimethylmethoxysilane.

The ink repellent agent (A ² ) in the negative photosensitive resin composition of the present invention has excellent ink repellent properties even in the process of exposure, curing, and the like, in which silanol groups contained are further condensed, and ultraviolet / ozone irradiation is performed. It is considered that a partition wall exhibiting properties is formed.

The number average molecular weight (Mn) of the ink repellent agent (A ² ) in the negative photosensitive resin composition of the present invention is preferably 500 or more, preferably less than 1,000,000, and particularly preferably less than 10,000. When the number average molecular weight (Mn) is not less than the lower limit of the above range, detachment from the substrate surface can be prevented when the partition is formed using the negative photosensitive resin composition. When the number average molecular weight (Mn) is less than the upper limit of the above range, the solubility in a solvent is good and the workability is excellent. The number average molecular weight (Mn) of the ink repellent agent (A ² ) can be adjusted by selecting reaction conditions and the like.

(Manufacture of ink repellent agent (A ² ))
When the ink repellent agent (A ² ) in the negative photosensitive resin composition of the present invention is a partially hydrolyzed condensate, the hydrolyzable silane compound mixture described above is hydrolyzed and partially condensed (hereinafter referred to as reaction). It is also called a process.) Hydrolysis and partial condensation are reactions in which a silanol group is generated by a hydrolysis reaction of a hydrolyzable group and a siloxane bond is formed by a dehydration condensation reaction between silanol groups as described above. In the reaction step, the reaction conditions usually used for the reaction of hydrolyzing and condensing the hydrolyzable silane compound can be applied without particular limitation, and for example, water, a catalyst, an organic solvent and the like can be used.

When water is used in the reaction step, the amount is preferably 25 to 9,900 parts by weight, particularly preferably 100 to 1,900 parts by weight, based on 100 parts by weight of the hydrolyzable silane compound mixture. By controlling the amount of water within the above range, the hydrolysis and condensation reaction can be easily controlled.
As the catalyst used in the reaction step, it is preferable to use inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as acetic acid, oxalic acid and maleic acid. The amount of the catalyst to be used is preferably 0.01 to 10 parts by mass, particularly preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the hydrolyzable silane compound mixture.

An organic solvent may be used in the reaction step. As the organic solvent, the organic solvent usually used for hydrolyzing and condensing the hydrolyzable silane compound, specifically, the organic solvents mentioned in (Production of ink repellent agent (A ¹ )) are used. it can. An organic solvent may be used individually by 1 type, or may use 2 or more types together.
In the reaction step, the amount of the organic solvent is preferably 25 to 9,900 parts by weight, particularly preferably 100 to 1,900 parts by weight, based on 100 parts by weight of the hydrolyzable silane compound mixture.

The obtained partial hydrolysis-condensation product is blended into the negative photosensitive resin composition together with the solvent used in the reaction step. Therefore, it is preferable to use a solvent that stabilizes the silanol group in the ink repellent agent (A ² ) as the solvent used in the reaction step. Examples of the solvent that stabilizes the silanol group include compounds having a hydroxyl group and a relative dielectric constant (ε) in the range of 5 to 20 at 25 ° C.

  Specific examples include glycol-based monoalkyl ether acetate solvents having 2 to 8 carbon atoms, glycol-based monoalkyl ether solvents, glyme solvents, and hydrocarbon alcohols having 2 to 4 carbon atoms. . More specifically, propylene glycol monomethyl ether acetate (ε: 8.3) as a glycol-based monoalkyl ether acetate solvent, propylene glycol monomethyl ether (ε: 12.3) as a glycol-based monoalkyl ether solvent, carbonization Examples of the hydrogen alcohol include 2-propanol (ε: 19.92). Propylene glycol monomethyl ether is particularly preferred because of its high silanol group stabilizing effect.

The reaction step is preferably carried out at a temperature from room temperature to the boiling point of the solvent under suitable stirring conditions. The reaction time is generally 0.5 to 24 hours, preferably 1 to 10 hours, although it depends on the amount of raw material components to be used, reaction temperature, stirring conditions and the like. After completion of the reaction, the obtained ink repellent agent (A ² ) can be contained in the negative photosensitive resin composition of the present invention without removing the organic solvent. After removing the organic solvent by a usual method, the ink repellent agent (A ² ) may be isolated and then contained in the negative photosensitive resin composition.

The content ratio of the ink repellent agent (A) in the negative photosensitive resin composition of the present invention is preferably 0.01 to 10% by mass in the total solid content in the negative photosensitive resin composition.
When the ink repellent agent (A ¹ ) is used as the ink repellent agent (A), the content is more preferably 0.05 to 5% by mass, and particularly preferably 0.2 to 1% by mass. When the content ratio of the ink repellent agent (A) is not less than the lower limit of the above range, a partition wall excellent in the effect of lowering the surface tension of the formed partition wall and 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 (A ² ) is used as the ink repellent agent (A), the content is more preferably 0.1 to 6% by mass, and particularly preferably 0.2 to 3% by mass. When the content of the ink repellent agent (A ² ) is in the above range, the negative photosensitive resin composition is excellent in storage stability, and the partition walls of the optical element obtained from the negative photosensitive resin composition have ink repellent properties. Excellent in properties and has a smooth surface.

  The ink repellent agent (A) in the present invention may have both a side chain having a group (1) and a side chain having a group (2) in one molecule. The negative photosensitive resin composition of the present invention comprises both an ink repellent agent (A) having a side chain having a group (1) and an ink repellent agent (A) having a side chain having a group (2). May be included. In these cases, the negative photosensitive resin composition can exhibit high ink repellency and ink falling properties.

[Photoinitiator (B)]
The negative photosensitive resin composition of this invention contains the photoinitiator (B) which is an oxime ester compound which has a nitro group in 1 molecule.
The photopolymerization initiator (B) is preferably a compound represented by the following formula (3).

In formula (3), R ³¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a cyano group. R ³² represents R ⁴¹ or OR ⁴² , and each of R ⁴¹ and R ⁴² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group. R ³³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R ³⁴ and R ³⁵ each independently represent R ⁴¹ , OR ⁴² , a cyano group or a halogen atom. R ⁴¹ and R ⁴² are the same as described above. a and b are each independently an integer of 0 to 3, and c is an integer of 1 to 3.

As R ³¹ , a hydrogen atom of an alkyl group, an aryl group, and an arylalkyl group is further OR ⁴³ , COR ⁴⁴ , SR ⁴⁵ , NR ⁴⁶ R ⁴⁷ , —NCOR ⁴⁸ —OCOR ⁴⁹ , a cyano group, a halogen atom, —CR ^50. ═CR ⁵¹ R ⁵² or —CO—CR ⁵³ ═CR ⁵⁴ R ⁵⁵ may be substituted, R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group or a heterocyclic group having 2 to 20 carbon atoms.

As R ³² , the hydrogen atom of the alkyl group, aryl group and arylalkyl group may be further substituted with a halogen atom.
The methylene group of the alkylene moiety of the substituent represented by R ³¹ , R ³³ , R ^{43 to} R ⁵⁵ is 1 to 1 by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. The alkyl moiety of the substituent may have a branched side chain, may be a cyclic alkyl, or the alkyl terminal of the substituent may be an unsaturated bond. R ³ may form a ring together with the adjacent benzene ring.
The oxime ester compound in the present invention has geometric isomers due to the double bond of oxime, but these are not distinguished from each other, and the formula (3) and the exemplified compound described below represent a mixture of both or one of them. However, it is not limited to the structure showing the isomer.

Examples of the alkyl group represented by R ^{41 to} R ⁵⁵ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxy Ethyl, propoxyethyl, pentyloxyethyl, octyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, 2-methoxy-1-methyl Ruechiru, and the like.
Examples of the aryl group represented by R ^{41 to} R ⁵⁵ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, phenyl, biphenylyl, naphthyl, anthryl, etc. substituted with one or more of the above alkyl groups. Can be mentioned.
Examples of the arylalkyl group represented by R ^{41 to} R ⁵⁵ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like.

Examples of the heterocyclic group represented by R ^{43 to} R ⁵⁵ include pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl , Is preferably a 5- to 7-membered heterocyclic ring such as isoxazolidyl, piperidyl, piperazyl, morpholinyl.
Examples of the ring that R ³³ can form together with the adjacent benzene ring include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring. Is mentioned.
Examples of the halogen atom that may substitute R ^{41 to} R ⁵⁵ and the halogen atom represented by R ³⁴ and R ³⁵ include fluorine, chlorine, bromine, and iodine.

  The methylene group of the alkylene part of the above substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. May be one or more groups, and in the case of a group that can be interrupted continuously, two or more groups may be interrupted continuously. The alkyl part of the substituent may have a branched side chain, may be a cyclic alkyl, and the alkyl terminal of the substituent may be an unsaturated bond.

Among the oxime ester compounds of the present invention, in the formula (3), R ³¹ is an alkyl group having 11 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. Or R ³³ is an alkyl group having 1 to 12 carbon atoms or an alkyl group having 13 to 20 carbon atoms interrupted 1 to 5 times by an ether bond or an ester bond, in particular, R ³¹ is An alkyl group having 11 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, or R ³³ is interrupted 1 to 5 times by an ether bond or an ester bond in the methylene group of the alkylene portion of the alkyl group. A branched alkyl group having 8 or more carbon atoms, the methylene group of the alkylene part of the alkyl group is interrupted 1 to 5 times by an ether bond or an ester bond What is carbon atoms which may be atoms have 13 or more alkyl groups; those R ³³ is an alkyl group which is interrupted 1 to 5 times by ether linkage; R ³³ is interrupted 1 to 5 times by an ester bond The alkyl group used is preferred because it is easy to synthesize and has high sensitivity, and when used as a photopolymerization initiator, it dissolves 1% by mass or more in a solvent and satisfies the requirements as a photopolymerization initiator. This solubility measurement is preferably performed at 20 to 30 ° C. As the solvent, propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone is preferable.

The oxime ester compound of the present invention can be dimerized via R ³¹ or R ³² as shown in the following formulas (4) and (5).

  Specific examples of the oxime ester compound represented by the formula (3) include the following compound Nos. The compound shown by 1-71 is mentioned.

  The oxime ester compound represented by the formula (3) can be produced, for example, by the following method according to the reaction formula of the following formula (6). First, acyl body 3 is obtained by reacting nitrocarbazole compound 1 and acid chloride 2 in the presence of zinc chloride. Next, the oxime compound 4 is obtained by reacting the acyl compound 3 with hydroxylamine hydrochloride in the presence of DMF. Subsequently, the oxime compound 4 and the acid anhydride 5 or the acid chloride 5 'are reacted to obtain an oxime ester compound represented by the formula (3).

  The content ratio of the photopolymerization initiator (B) in the negative photosensitive resin composition of the present invention is preferably 1 to 15% by mass in the total solid content in the negative photosensitive resin composition, and is preferably 2 to 10% by mass. Is more preferable, and 3 to 6% by mass is particularly preferable. Curability is good when it is in the above range, and a pattern or line width close to a mask pattern can be formed in the exposure process and the development process. In particular, the surface of the cured film has good ink repellency even when exposure light of 330 nm or less is shielded by a cut filter or the like, and even at a low exposure amount.

In the negative photosensitive resin composition of the present invention, a photopolymerization initiator other than the photopolymerization initiator (B) may be used in combination.
Photopolymerization initiators that can be used in combination include α-diketones such as benzyl, diacetyl, methylphenylglyoxylate, and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl Acyloin ethers such as ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone Thioxanthones such as thioxanthone-4-sulfonic acid; benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, etc. Nzophenones; 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-Dimethylaminobenzoic acid Aminobenzoic acids such as 2-ethylhexyl acid; halogen compounds such as phenacyl chloride and trihalomethylphenyl sulfone; acylphosphine oxides; peroxides such as di-t-butyl peroxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime ) Oxime esters, triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, aliphatic amines such as diethylaminoethyl methacrylate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2 -Merca DOO benzothiazole, 1,4-butanol-bis (3-mercapto butyrate), tris (2-mercapto-propanoyl oxyethyl) isocyanurate, pentaerythritol tetrakis (3-mercapto butyrate) thiol compound such as and the like.
Of these, benzophenones, aminobenzoic acids, aliphatic amines, and thiol compounds are preferred when used together with other photopolymerization initiators because they may exhibit a sensitizing effect.

  When the photopolymerization initiator other than the photopolymerization initiator (B) in the negative photosensitive resin composition is contained, the content ratio is 20% by mass or less in the total solid content in the negative photosensitive resin composition. Preferably, 1-15 mass% is more preferable, and 2-10 mass% is especially preferable.

[Alkali-soluble resin (C)]
Although it does not specifically limit as alkali-soluble resin (C), Resin (C1-1) 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 (C1-2) introduced with a bond, a monomer (C1-3) 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 (C1-1) is a side chain having a reactive group obtained by copolymerizing a monomer having a reactive group such as a hydroxyl group, a carboxyl group, and an epoxy group and a monomer having an acidic group; It can be synthesized by dissolving a copolymer having a side chain having an acidic group, a compound having a functional group capable of bonding to the reactive group and an ethylenic double bond in a solvent and reacting them.

  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) acryl Bromide, N, N-bis (hydroxymethyl) (meth) acrylamide.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. These monomers are also used as monomers having an acidic group.
Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
Although it does not specifically limit as a monomer which has an acidic group, 2- (meth) acryloyloxyethane phosphoric acid etc. are mentioned as a monomer which has a phosphate group other than the monomer which has the said carboxyl group. It is done.

The copolymerization of the monomer having a reactive group and the monomer having an acidic group can be performed by a conventionally known method.
Examples of the monomer having a hydroxyl group as a reactive group include an acid anhydride having an ethylenic double bond, a compound having an isocyanate group and an ethylenic double bond, and a compound having an acyl chloride group and an ethylenic double bond. Can be mentioned.
Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthal An acid anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, etc. are mentioned.
Examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.
Examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.

  Examples of the monomer having a carboxyl group as a reactive group include compounds having an epoxy group and an ethylenic double bond. Examples of the compound include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate. 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 carboxyl group into the resin (C1-1).

  Examples of the monomer having an epoxy group as a reactive group include compounds having a carboxyl 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. 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 carboxyl group into the resin (C1-1).

Resin (C1-2) can be synthesized by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond and then reacting with a polybasic carboxylic acid or its anhydride. .
Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond. Next, a carboxyl group can be introduce | transduced by making polybasic carboxylic acid or its anhydride react with the epoxy resin in which the ethylenic double bond was introduce | transduced.

  The epoxy resin is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, epoxy resin having naphthalene skeleton, An epoxy resin having a biphenyl skeleton represented by (C1-2a), an epoxy resin represented by the following formula (C1-2b), an epoxy resin having a biphenyl skeleton represented by the following formula (C1-2c), etc. It is done.

（式（Ｃ１−２ａ）中、ｖは、１〜５０であり、２〜１０が好ましい。またベンゼン環の水素原子はそれぞれ独立に、炭素原子数１〜１２のアルキル基、ハロゲン原子、または、置換基を有してもよいフェニル基で置換されていてもよい。）

(In Formula (C1-2a), v is 1 to 50, and preferably 2 to 10. The hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or (It may be substituted with a phenyl group which may have a substituent.)

（式（Ｃ１−２ｂ）中、Ｒ^６１、Ｒ^６２、Ｒ^６３およびＲ^６４は、それぞれ独立に、水素原子、塩素原子または炭素原子数が１〜５のアルキル基であり、ｗは、０〜１０である。）

(In the formula (C1-2b), R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and w is 0 to 0. 10)

（式（Ｃ１−２ｃ）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、置換基を有してもよいフェニル基で置換されていてもよい。ｕは、０〜１０である。）

(In Formula (C1-2c), each hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an optionally substituted phenyl group. U is 0-10.)

  In addition, after making the epoxy resin represented by Formula (C1-2a)-(C1-2c) and the compound which has a carboxyl group and an ethylenic double bond react, a polybasic carboxylic acid anhydride is made to react. In this case, it is preferable to use a mixture of dicarboxylic anhydride and tetracarboxylic dianhydride as the polybasic carboxylic anhydride. By changing the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride, the molecular weight can be controlled.

  A commercial item can be used for resin (C1-2). 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-2002H, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H, ZCR-1761H, ZAR-2001H ( As mentioned above, Nippon Kayaku Co., Ltd.), EX1010 (manufactured by Nagase ChemteX Corporation) and the like can be mentioned.

  Examples of the monomer (C1-3) include 2,2,2-triacryloyloxymethylethylphthalic acid (trade name: NK ester CBX-1, manufactured by Shin-Nakamura Chemical Co., Ltd.).

As the alkali-soluble resin (C), peeling of the coating film during development is suppressed, a high-resolution pattern can be obtained, the linearity of the line is good, and the appearance after the post-baking process is maintained. The resin (C1-2) is preferably used in that a smooth coating surface can be easily obtained.
As the resin (C1-2), 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 into which an acidic group and an ethylenic double bond are introduced into an epoxy resin represented by the formulas (C1-2a) to (C1-2c) is particularly preferable.

The mass average molecular weight (Mw) of the alkali-soluble resin (C) is preferably 1.5 × 10 ³ to 30 × 10 ³ , particularly preferably 2 × 10 ³ to 15 × 10 ³ . The number average molecular weight (Mn) of preferably from 500 to 20 × 10 ^3, and particularly preferably ^{1.0 × 10 3 ~10 × 10 3} . When the mass average molecular weight (Mw) and the mass average molecular weight (Mn) are not less than the lower limit of the above range, curing at the time of exposure is sufficient, and when the mass average molecular weight (Mw) is not more than the upper limit of the above range, the developability is good.

The number of ethylenic double bonds that the alkali-soluble resin (C) has in one molecule is preferably 3 or more on average, and more preferably 6 or more. When the number of ethylenic double bonds is at least the lower limit of the above range, the alkali solubility between the exposed and unexposed portions is likely to be different, and a fine pattern can be formed with a smaller exposure amount.
The acid value of the alkali-soluble resin (C) is preferably 10 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g. When the acid value is in the above range, the negative photosensitive resin composition has good storage stability and developability.

The alkali-soluble resin (C) contained in the negative photosensitive resin composition may be one type or a mixture of two or more types.
As for the content rate of alkali-soluble resin (C) in the negative photosensitive resin composition of this invention, 10-50 mass% is preferable in the total solid in a negative photosensitive resin composition, and 12-40 mass% is preferable. More preferably, 15 to 30% by mass is particularly preferable. When the content ratio is in the above range, the developability is good.

[Negative photosensitive resin composition]
The negative photosensitive resin composition of the present invention comprises an ink repellent agent (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a black colorant (D) if necessary, a polymer dispersant ( E), a dispersion aid (F), a crosslinking agent (G) and a solvent (H). Furthermore, you may contain the following thermal crosslinking agents (I), a silane coupling agent (J), microparticles | fine-particles (K), a phosphoric acid compound (L), and another additive.

By using the negative photosensitive resin composition of the present invention, the negative photosensitive resin composition having good ink repellency and good reproducibility of the mask line width even when an exposure light beam of 330 nm or less is shielded, and the composition Homogeneous partition walls obtained using the product can be produced. Therefore, it is possible to cope with a case where fine patterning is required. The reason is considered as follows.
As the photopolymerization initiator, a highly sensitive compound that is efficiently activated by absorbing exposure light exceeding 330 nm is required, and a photopolymerization initiator (B) can be selected.

According to the knowledge of the present inventor, when exposure light having a wavelength of 330 nm or less is shielded, the curability of the surface of the partition wall is extremely lowered, and the ink repellent portion of the surface tends to be scraped, and the ink repellency tends to be lowered. If it is a negative photosensitive resin composition containing a photoinitiator (B), the sclerosis | hardenability of the surface of a partition can be made high. In the negative photosensitive resin composition containing a compound having poor transferability to the partition wall surface as the ink repellent agent, the ink repellent agent has not yet moved to the partition wall surface when the partition surface is cured. Ink repellency is improved by using an ink repellent agent that has good transferability to.
The combination of the ink repellent agent and the photopolymerization initiator (B) is a viscosity that can be applied to the negative photosensitive resin composition in addition to the above-described curability and surface transferability, and a stable combination is required. is there. The inventors have found a combination of an ink repellent agent (A) and a photopolymerization initiator (B).

[Black colorant (D)]
The negative photosensitive resin composition of the present invention may contain a black colorant (D).
When the negative photosensitive resin composition is used for forming a black matrix that is a grid-like black portion surrounding the three color pixels R, G, and B of the color filter of the liquid crystal display element, the black colorant (D) is used. It is preferable to include.
The black colorant (D) is 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. Mixtures of organic pigments such as red pigments, blue pigments, green pigments, yellow pigments, azomethine black pigments, and inorganic pigments can also be used. As the black colorant (D), carbon black is preferable from the viewpoint of cost and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together. For black matrix on array type color filters and organic EL elements, low dielectric constant and high resistance coating films and partition walls are required. In order to obtain a coating film and partition walls as described above, it is preferable to use a mixture of the above organic pigments and an azomethine black pigment.

Carbon black having a specific surface area of 50 to 200 m ² / g by the BET method is preferable 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, it is not necessary to blend a large amount of dispersion aid in order to develop various physical properties without excessively adsorbing the dispersion aid on carbon black.
Moreover, as carbon black, the oil absorption amount of dibutyl phthalate is preferably 120 cc / 100 g or less from the viewpoint of sensitivity, and the smaller one is more preferable.

  Furthermore, it is preferable that the average primary particle diameter of carbon black observed by a transmission electron microscope is 20 to 50 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 50 nm or less, the shape of the black matrix is hardly deteriorated. Moreover, as an average secondary particle diameter by transmission electron microscope observation, 80-200 nm is preferable.

  When the negative photosensitive resin composition of the present invention contains a black colorant (D) and is used for black matrix formation or the like, the content of the black colorant (D) in the negative photosensitive resin composition is negative. 15-80 mass% is preferable in the total solid in a type photosensitive resin composition, 20-70 mass% is more preferable, and 25-65 mass% is especially preferable. The negative photosensitive resin composition obtained when it is in the above range has good sensitivity, and the formed partition has excellent light shielding properties.

[Polymer dispersant (E)]
When the negative photosensitive resin composition contains a dispersible material such as the black colorant (D), it is preferable to contain a polymer dispersant (E) in order to improve the dispersibility. The polymer dispersant (E) is not particularly limited, but is urethane, polyimide, alkyd, epoxy, polyester, melamine, phenol, acrylic, polyether, vinyl chloride, vinyl chloride acetic acid. A vinyl copolymer system, a polyamide system, a polycarbonate system, and the like can be mentioned, and a urethane system or a polyester system is preferable. Moreover, the polymer dispersing agent (E) may have a structural unit derived from ethylene oxide and / or propylene oxide.

When the polymer dispersant (E) is used for dispersing the black colorant (D), the polymer dispersant (E) having a basic group is used in consideration of the affinity for the black colorant (D). It is preferable to use it. Although it does not specifically limit as a basic group, A primary, secondary, or tertiary amino group is mentioned.
A commercially available product may be used as the polymer dispersant (E). As commercial products, Disparon DA-7301 (trade name, manufactured by Enomoto Kasei Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (all trade names, manufactured by BYK-Chemie), Solspurs 5000, Solspers 17000 (all trade names, Zeneca).
The content of the polymer dispersant (E) is preferably 5 to 30% by mass and particularly preferably 10 to 25% by mass with respect to the black colorant (D). When it is at least the lower limit of the above range, the dispersibility of the black colorant (D) is improved, and when it is at most the upper limit of the above range, the developability of the negative photosensitive resin composition is improved.

[Dispersion aid (F)]
The negative photosensitive resin composition may contain a phthalocyanine pigment derivative or a metal phthalocyanine sulfonamide compound as the dispersion aid (F). The dispersion aid (F) is considered to have a function of improving the dispersion stability by adsorbing to the dispersible material such as the black colorant (D) and the polymer dispersant (E).

[Crosslinking agent (G)]
The negative photosensitive resin composition of the present invention may contain a crosslinking agent (G) as an optional component that promotes radical curing. As a crosslinking agent (G), the compound which has two or more ethylenic double bonds in 1 molecule, and does not have an acidic group is preferable. When a negative photosensitive resin composition contains a crosslinking agent (G), the sclerosis | hardenability of the said alkali-soluble resin (C) at the time of exposure improves, and the exposure amount at the time of forming a partition can be reduced.

  The crosslinking agent (G) having two or more ethylenic double bonds in one molecule and having no acidic group is not particularly limited as long as it is a compound having this condition, but diethylene glycol di (meth) acrylate, tetra Ethylene 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, ethoxy Isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl } Methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), urethane acrylate and the like. These may be used alone or in combination of two or more.

  A commercial item can be used as a crosslinking agent (G). 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)), V # 802 (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd., dipentaerythritol acrylate, tripentaerythritol acrylate, tetrapentaerythritol acrylate), NK Este A- 9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, manufactured by Shin-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-dicarboximide) ) 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-di) Carboxyimide)) 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.

  Among these, KAYARAD DPHA and NK ester A-9530 are preferable because they improve the sensitivity of the cured film obtained from the negative photosensitive resin composition. NK ester A-9300, BANI-M and BANI-X are preferable from the viewpoint of imparting hardness to the cured film and suppressing thermal sagging. NK ester A-9300-1CL is preferable from the viewpoint of imparting flexibility to the cured film. Urethane acrylate is preferable because an appropriate development time can be realized and developability is improved.

  The content of the crosslinking agent (G) in the negative photosensitive resin composition of the present invention is preferably 3 to 30% by mass, more preferably 5 to 20% by mass in the total solid content in the negative photosensitive resin composition. 7 to 15% by mass is preferable. The alkali developability of a negative photosensitive resin composition will become favorable as it is the said range.

[Solvent (H)]
The negative photosensitive resin composition of this invention contains a solvent (H) as needed. When the solvent (H) is contained, the viscosity of the negative photosensitive resin composition is reduced, so that the negative photosensitive resin composition can be easily applied on the substrate. A uniform negative photosensitive resin composition coating film can be formed. In addition, when a negative photosensitive resin composition does not contain a solvent (H), the coating film of a negative photosensitive resin composition becomes the same as the film | membrane of a negative photosensitive resin composition.
The solvent (H) contained in the negative photosensitive resin composition of the present invention is the ink repellent agent (A), photopolymerization initiator (B), alkali-soluble resin (C) contained in the negative photosensitive resin composition. ), If necessary, the black colorant (D), the polymer dispersant (E), the dispersion aid (F) and the crosslinking agent (G), as well as the optional components described later, are uniformly dissolved or dispersed to form a partition wall. There is no particular limitation as long as it has a function of uniformly and easily applying the negative photosensitive resin composition to the substrate on which the resin is formed and has no reactivity with these components. The solvent similar to the solvent used at the time of the synthesis | combination of an ink agent (A) can be used.

  Although the content rate of the solvent (H) contained in a negative photosensitive resin composition changes with compositions, uses, etc. of a negative photosensitive resin composition, it is 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.

  The negative photosensitive resin composition of the present invention comprises an ink repellent agent (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a black colorant (D) if necessary, a polymer dispersant ( E), a dispersion aid (F), a crosslinking agent (G) and a solvent (H). Furthermore, you may contain the following thermal crosslinking agents (I), a silane coupling agent (J), microparticles | fine-particles (K), a phosphoric acid compound (L), and another additive.

[Thermal crosslinking agent (I)]
The thermal crosslinking agent (I) is a compound having two or more groups capable of reacting with a carboxyl group and / or a hydroxyl group. When the alkali-soluble resin (B) has a carboxyl group and / or a hydroxyl group, the thermal crosslinking agent (I) reacts with the alkali-soluble resin (B) to increase the crosslinking density of the cured film and improve the heat resistance. Have

  Preferred examples of the thermal crosslinking agent (I) include at least one selected from the group consisting of amino resins, epoxy compounds, oxazoline compounds, polyisocyanate compounds, and polycarbodiimide compounds. These compounds may be used alone or in combination of two or more.

  The content of the thermal crosslinking agent (I) in the negative photosensitive resin composition of the present invention is preferably 1 to 50% by mass, and 5 to 30% by mass in the total solid content in the negative photosensitive resin composition. Particularly preferred. The developability of the negative photosensitive resin composition obtained when it is in the above range becomes good.

[Silane coupling agent (J)]
When the silane coupling agent (J) is used, the substrate adhesion of the cured film formed from the obtained negative photosensitive resin composition is improved.
Specific examples of the silane coupling agent (J) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-methacryloyloxy. Propyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, etc. It is done. These may be used alone or in combination of two or more.
A commercial item can be used as a silane coupling agent (J). Examples of commercially available products include KBM5013 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloyloxypropyltrimethoxysilane).

  The content ratio of the silane coupling agent (J) in the negative photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass in the total solid content in the negative photosensitive resin composition, and preferably 1 to 10%. Mass% is particularly preferred. 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.

[Fine particles (K)]
The negative photosensitive resin composition may contain fine particles (K) as necessary. By mix | blending microparticles | fine-particles (K), it becomes possible to prevent the heat dripping of the partition obtained from a negative photosensitive resin composition.

  The fine particles (K) are not particularly limited, and inorganic fine particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO); organic materials such as polyethylene and polymethyl methacrylate (PMMA) In view of heat resistance, inorganic fine particles are preferable, and in view of availability and dispersion stability, silica or zirconia is particularly preferable. Further, when the negative photosensitive resin composition contains the black colorant (G) and the polymer dispersant (E), the fine particles ( K) is preferably negatively charged. Furthermore, considering the exposure sensitivity of the negative photosensitive resin composition, it is preferable that the fine particles do not absorb the light irradiated at the time of exposure, and i-line (365 nm), h-line ( 405 nm) and g-line (436 nm) are not particularly absorbed.

Silica is preferable as the fine particles (K). 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 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, IPA: 70% by mass) and the like.

  The content ratio of the fine particles (K) in the negative photosensitive resin composition of the present invention is preferably from 3 to 40% by mass, particularly preferably from 5 to 30% by mass, based on the total solid content in the negative photosensitive resin composition. . Most preferably, it is 7 mass% or more and less than 25 mass%. When the content ratio is in the above range, the ink repellency is good and the storage stability of the negative photosensitive resin composition is good.

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

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

[Preferred combination of negative photosensitive resin composition]
In the negative photosensitive resin composition of the present invention, it is preferable to select a composition and a blending ratio in accordance with applications and required characteristics.
The preferable composition of the various compounding components in the negative photosensitive resin composition of the present invention is shown below.

Ink repellent agent (A): A preferred combination 1 to 5 of the ink repellent agent (A ¹ ) or a preferred combination 6 to 10 of the ink repellent agent (A ² ), and the total solid in the negative photosensitive resin composition 0.01 to 10 mass% in a minute,
Photopolymerization initiator (B): Compound No. described in International Publication No. 2008/078678. 1 to 58, 0.01 to 10% by mass in the total solid content in the negative photosensitive resin composition,
Alkali-soluble resin (C): selected from the group consisting of (C1-2a), (C1-2b), (C1-2c) and a resin in which an acidic group and an ethylenic double bond are introduced into a cresol novolac type epoxy resin 12 to 40% by mass in the total solid content of at least one kind of the negative photosensitive resin composition,
Solvent (H): at least one selected from the group consisting of 2-propanol, γ-butyrolactone, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone and butyl lactate 50 to 99% by mass in the negative photosensitive resin composition.

[Method for producing negative photosensitive resin composition]
As a method for producing a negative photosensitive resin composition, an ink repellent agent (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a black colorant (D) if necessary, a polymer dispersant (E), a dispersion assistant (F), a crosslinking agent (G) and a solvent (H) are contained. Furthermore, a method of mixing with the following thermal crosslinking agent (I), silane coupling agent (J), fine particles (K), phosphoric acid compound (L) and other additives is preferable.

  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 a cured film obtained by curing a coating film of the composition is usually It can be used as a member of an optical element in which a cured film of the negative photosensitive resin composition is used.

[Method for producing partition for optical element]
The present invention is applied to the manufacture of a partition for an optical element having a plurality of pixels and a partition located between adjacent pixels on a substrate.
The negative photosensitive resin composition of the present invention is applied onto the substrate to form a coating film (coating film forming step), then the coating film is heated (prebaking step), and then the partition walls of the coating film Then, only the part to be exposed is photocured (exposure process), then the coating film other than the photocured part is removed to form a partition consisting of the photocured part of the coating film (development process), and then By heating the formed partition wall (post-baking step), a partition wall for an optical element can be manufactured.
In addition, when the negative photosensitive resin composition of this invention contains a black coloring agent (D), the partition for optical elements is formed as a black matrix.

  The material of the substrate is not particularly limited. For example, various glass plates; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, poly (meth) acrylic resin Thermosetting plastic sheets such as epoxy resins, and cured sheets of thermosetting resins such as epoxy resins and unsaturated polyesters can be used. In particular, a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance.

FIG. 1 is a cross-sectional view schematically showing a production example of an optical element partition using the negative photosensitive resin composition of the present invention. FIG. 1 (I) is a view showing a cross section in a state where a coating film 2 made of the negative photosensitive resin composition of the present invention is formed on a substrate 1. (II) is a figure which shows an exposure process typically. (III) is sectional drawing which shows the board | substrate 1 after the image development process, and the partition 6 formed on the board | substrate.
Hereinafter, the manufacturing method of the partition for optical elements using the negative photosensitive resin composition of this invention is demonstrated concretely using FIG.

(Coating film formation process)
As shown in a cross section in FIG. 1 (I), the negative photosensitive resin composition of the present invention is applied onto a substrate 1 to form a coating film 2 made of the negative photosensitive resin composition. In addition, before forming the coating film 2 of the negative photosensitive resin composition on the board | substrate 1, the application surface of the negative photosensitive resin composition of the board | substrate 1 is wash | cleaned by alcohol washing | cleaning, ultraviolet rays / ozone washing | cleaning, etc. preferable.

The coating method of the negative photosensitive resin composition is not particularly limited as long as a coating film having a uniform film thickness is formed. Spin coating, spraying, slit coating, roll coating, spin coating The method used for normal coating-film formation, such as a method and a bar coating method, is mentioned.
The film thickness of the coating film 2 is determined in consideration of the height of the partition wall finally obtained. The film thickness of the coating film 2 is preferably 100 to 3,000%, particularly preferably 100 to 2,000% of the height of the partition wall finally obtained. The film thickness of the coating film 2 is preferably from 0.3 to 325 μm, particularly preferably from 1.3 to 65 μm.

(Pre-baking process)
The coating film 2 formed on the substrate 1 in the coating film forming step is heated to obtain the film 2. By heating, 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. Further, the ink repellent agent (A) moves to the vicinity of the coating film surface. Examples of the heating method include a method in which the coating film 2 is heat-treated at 50 to 120 ° C. for about 10 to 2,000 seconds with a heating apparatus such as a hot plate and an oven together with the substrate 1.

  In addition, although it is possible to remove volatile components such as a solvent by heating in the pre-baking step as described above, a drying step such as vacuum drying other than heating (drying) is performed in order to remove volatile components such as a solvent. You may provide separately before a prebaking process. Further, in order to efficiently dry the coating film without causing unevenness in the appearance of the coating film, it is more preferable to use heating combined with the drying by the prebaking step and vacuum drying in combination. The conditions for vacuum drying vary depending on the type of each component, the blending ratio, and the like, but preferably 500 to 10 Pa and a wide range of about 10 to 300 seconds.

(Exposure process)
As shown in FIG. 1 (II), the film 2 is irradiated with light 5 through a mask 4 having a predetermined pattern. Only the predetermined pattern portion cut by the mask 4 is transmitted through the light 5, reaches the film on the substrate 1, and only the portion is photocured. Therefore, when forming a partition, the said predetermined pattern is provided in the form suitable for the shape of a partition.
For example, the average partition wall width after the post-baking step is preferably 100 μm or less, and particularly preferably 20 μm or less. Moreover, it is preferable that the average of the distance between adjacent partition walls is 500 micrometers or less, and 300 micrometers or less are especially preferable. It is preferable to use a mask in which a pattern is formed so as to be in the above range.

  In FIG. 1 (II), the exposed portion 3 of the film irradiated with light is composed of a cured film of a negative photosensitive resin composition, while the unexposed portion is a film 2 of an uncured negative photosensitive resin composition. It is a state in which it remains.

The irradiation light 5 is 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; Examples include lines. The irradiation light 5 is preferably an electromagnetic wave having a wavelength of 100 to 600 nm, more preferably a light ray having a distribution in the range of 300 to 500 nm, particularly i-line (365 nm), h-line (405 nm) and g-line (436 nm). preferable. For example, when an exposure method using a mirror projection (MPA) method is used, an exposure light beam is irradiated after cutting an electromagnetic wave of 330 nm or less. Thus, in the manufacturing method of this invention, the exposure which cut | disconnected electromagnetic waves below 330 nm may be performed as needed.

A well-known super high pressure mercury lamp etc. can be used as an irradiation apparatus. Exposure amount in i-line basis in the case of cutting the following electromagnetic wave 330nm by cut filter or the like, 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 a partition is sufficiently cured, and subsequent development does not easily cause dissolution or peeling from the substrate 1. 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.
The exposure time depends on the exposure amount, the composition of the negative photosensitive composition, the thickness of the coating film, etc., but is preferably 1 to 60 seconds, and particularly preferably 5 to 20 seconds.

(Development process)
Development is performed using a developer, and the unexposed portion 2 on the substrate 1 shown in FIG. 1 (II) is removed. Thereby, the structure of the partition 6 formed by the cured film of the negative photosensitive resin composition on the board | substrate 1 and the said board | substrate which a cross-sectional view is shown by FIG.1 (III) is obtained. Further, a portion surrounded by the partition wall 6 and the substrate 1 is a portion called a dot 7 where a pixel is formed by ink injection or the like. The obtained substrate 10 becomes a substrate that can be used for manufacturing an optical element by an ink jet method through a post-bake process described later.

  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 1 and the partition wall 6 can be removed by performing high-pressure water washing or running water washing and air-drying with compressed air or compressed nitrogen.

  Further, the change in the thickness of the cured film at the portion that becomes the partition before and after the development step is preferably 60 nm or less, more preferably 50 nm, and particularly preferably 45 nm or less. When the change in film thickness is 60 nm or less, the ink repellent layer for expressing the ink repellency of the cured film surface layer after exposure remains sufficiently on the surface, and the ink repellency of the cured film after post-baking becomes good. .

(Post bake process)
The partition 6 on the substrate 1 is heated. Examples of the heating method include a method in which the partition wall 6 together with the substrate 1 is heated at 150 to 250 ° C. for 5 to 90 minutes using a heating device such as a hot plate or an oven. By the heat treatment, the partition walls 6 made of a cured film of the negative photosensitive resin composition on the substrate 1 are further cured, and the shape of the dots 7 surrounded by the partition walls 6 and the substrate 1 is further fixed. The heating temperature is particularly preferably 180 ° C. or higher. If the heating temperature is too low, curing of the partition wall 6 is insufficient, so that sufficient chemical resistance cannot be obtained, and when the ink is injected into the dots 7 in the subsequent inkjet coating process, the solvent contained in the ink As a result, the partition wall 6 may swell or ink may ooze. On the other hand, if the heating temperature is too high, thermal decomposition of the partition walls 6 may occur.

In the negative photosensitive composition of the present invention, the average partition wall width is preferably 100 μm or less, particularly preferably 20 μm or less. In addition, the average distance between adjacent barrier ribs (dot width) is preferably 500 μm or less, and particularly preferably 300 μm or less. Moreover, 0.05-50 micrometers is preferable and, as for the average of the height of a partition, 0.2-10 micrometers is especially preferable.
The ink repellency of the cured coating film formed from the negative photosensitive resin composition of the present invention can be estimated by the contact angle of water and propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as PGMEA). The contact angle of water is preferably 90 degrees or more, more preferably 95 degrees or more. Further, the contact angle of PGMEA is preferably 30 degrees or more, more preferably 35 degrees or more, and particularly preferably 40 degrees or more. Regarding the ink repellency of the cured coating film, it is particularly preferable that the contact angle of water is 90 ° or more and the contact angle of PGMEA is 30 ° or more.

[Method for Manufacturing Optical Element]
After the partition wall is formed on the substrate by the above manufacturing method, the substrate surface exposed in the region surrounded by the substrate and the partition wall is subjected to an ink affinity treatment (ink affinity treatment step), and then the ink jet is applied to the region. Ink is injected by the method to form the pixel (ink injection step). In addition, the ink-repellent treatment process is not an essential process in the manufacture of the optical element, and may not be performed depending on the manufactured optical element.

(Ink affinity process)
Examples of the lyophilic process include a cleaning process using an alkaline aqueous solution, an ultraviolet cleaning process, an ultraviolet / ozone cleaning process, an excimer cleaning process, a corona discharge process, and an oxygen plasma process.
The cleaning process using an alkaline aqueous solution is a wet process in which the substrate surface is cleaned using an alkaline aqueous solution (potassium hydroxide, tetramethylammonium hydroxide aqueous solution, or the like).
The ultraviolet cleaning process is a dry process for cleaning the substrate surface using ultraviolet rays.

The ultraviolet / ozone cleaning process is a dry process that cleans the substrate surface using a low-pressure mercury lamp that emits light of 185 nm and 254 nm.
The excimer cleaning process is a dry process for cleaning the substrate surface using a xenon excimer lamp that emits light at 172 nm.
The corona discharge treatment is a dry treatment that uses a high-frequency high voltage to generate corona discharge in the air and cleans the substrate surface.
The oxygen plasma treatment is a dry treatment in which oxygen is excited in a vacuum mainly using a high frequency power source as a trigger to clean the substrate surface using a highly reactive “plasma state”.

  As a method for the ink-philic treatment, a dry treatment method such as an ultraviolet / ozone cleaning treatment is preferable because it is simple. UV / ozone can be generated using commercially available equipment. An ink-repellent treatment can be performed by placing a substrate on which a partition wall is formed inside an ultraviolet / ozone device and performing the treatment in air at room temperature for about 1 to 10 minutes within a range that does not impair the oil repellency of the partition wall. it can. In addition, about processing time, what is necessary is just to adjust to the time used as the range which does not impair the oil repellency of a partition according to each ultraviolet-ray / ozone apparatus.

  With this ink repellency treatment, the removal of impurities remaining on the dots after the formation of the partition walls can be sufficiently performed to make the dot ink fond, and a color display device using the resulting optical element can be used. It is possible to prevent white spots.

(Ink injection process)
This is a step of forming pixels by injecting ink into the dots after the ink affinity treatment step by an ink jet method. This step can be performed in the same manner as a normal method using an ink jet apparatus generally used in the ink jet method. The ink jet device used for forming such pixels is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, and ink is ejected intermittently using a piezoelectric element. An ink jet apparatus using various methods such as a method, a method of heating ink, and intermittently ejecting the ink using the foaming can be used.

  Examples of the optical element produced using the negative photosensitive resin composition of the present invention include a color filter, an organic EL display element, and an organic TFT array.

[Manufacture of color filters]
The formation of partition walls, the process of making dots ink-philic, and ink injection by the inkjet method are as described above. In the color filter, the shape of the pixel to be formed can 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 forming the pixel 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.
Moreover, after injecting ink by the inkjet method, it is preferable to perform drying, heat curing, and ultraviolet curing as necessary.

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

[Manufacture of organic EL display elements]
Before forming the partition walls, a transparent electrode such as tin-doped indium 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. Then, an organic EL display element pixel is obtained by forming an electrode such as aluminum by vapor deposition or the like.

[Manufacture of organic TFT array]
An organic TFT array can be manufactured through the following steps (i) to (iii).
(I) A partition wall is formed on a transparent substrate such as glass using the negative photosensitive resin composition of the present invention. After the dot is made into an ink-philic process, a gate electrode material solution is applied to the dots using an inkjet method to form a gate electrode.
(Ii) After forming the gate electrode, a gate insulating film is formed thereon. A barrier rib is formed on the gate insulating film using the negative photosensitive resin composition of the present invention, and after the dot is made into an ink-philic process, a solution of a source / drain electrode material is applied to the dot using an ink jet method. A drain electrode is formed.
(Iii) After forming the source / drain electrodes, a partition is formed using the negative photosensitive resin composition of the present invention so as to surround a region including the pair of source / drain electrodes, and the ink is made to be ink-insensitive Thereafter, an organic semiconductor solution is applied to the dots using an ink jet method to form an organic semiconductor layer between the source and drain electrodes.
In (i) to (iii), the partition using the negative photosensitive resin composition of the present invention may be used in only one step, or the negative photosensitive resin of the present invention in two or more steps. You may utilize the partition using a conductive resin composition.

[Manufacture of organic EL lighting elements]
It can be produced in the same manner as in the production of the organic EL display element. The light emitting layer may be formed by laminating light emitting bodies that develop colors such as red, green, and blue by ink jetting, or the light emitting bodies may be separately coated on a plane.

  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 21 are examples, and examples 31 to 33 are comparative examples.

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

Abbreviations of the compounds used in Synthesis Examples and Examples are as follows.
(Compound used for synthesis of ink repellent agent (A ¹ ))
MEK: 2-butanone.
_{C6FMA: CH 2 = C (CH} 3) COOCH 2 CH 2 (CF 2) 6 F.
MAA: methacrylic acid.
MMA: methyl methacrylate.
PME400: Blemmer PME-400 (manufactured by NOF Corporation. Α-methyl-ω-methacryloyloxypoly (oxyethylene). CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ : k in the formula Indicates an average value between molecules, and the value of k is about 9.)
PME1000: Blemmer PME-1000 (manufactured by NOF Corporation. Α-methyl-ω-methacryloyloxypoly (oxyethylene). CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ : k in the formula Indicates an average value between molecules, and the value of k is 23).
V-65: Trade name (manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azobis (2,4-dimethylvaleronitrile)).
2-HEMA: 2-hydroxyethyl methacrylate.
GMA: glycidyl methacrylate.
AOI: 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz AOI).
DBTDL: Dibutyltin dilaurate.
TBQ: t-butyl-p-benzoquinone.

(Compound used for synthesis of ink repellent agent (A ² ))
Compound _{(a7-1): CF 3 (CF} 2) 5 CH 2 CH 2 Si (OCH 3) 3 ( manufactured by Asahi Glass Co., Ltd.).
Compound (a8-1): Si (OC ₂ H ₅ ) ₄ (manufactured by Colcoat).
Compound _{(a9-1): CH 2 = CHCOO} (CH 2) 3 Si (OCH 3) 3 ( manufactured by Tokyo Kasei Kogyo Co., Ltd.).
TMMS: Trimethylmethoxysilane [(CH ₃ ) ₃ Si (OCH ₃ )] (manufactured by Tokyo Chemical Industry Co., Ltd.).
PGME: Propylene glycol monomethyl ether.
PGMEA: Propylene glycol monomethyl ether acetate.

(Photopolymerization initiator (B))
In the above compound No. 1-3, compound no. 7, Compound No. 10, compound no. 12, Compound No. 20, compound no. 33, compound no. 45-51 and compound no. The compound shown by 53-58.
(Photopolymerization initiator other than photopolymerization initiator (B))
OXE02: Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime) (trade name: OXE02 manufactured by Ciba Specialty Chemicals).
IR907: Trade name; IRGACURE907, manufactured by BASF, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.
EAB: 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.).
(Alkali-soluble resin (C))
EX1010: Resin in which an ethylenic double bond and an acidic group are introduced into the epoxy resin represented by the above formula (C1-2b) (manufactured by Nagase ChemteX Corporation, trade name: EX-1010. Solid content: 60% by mass, PGMEA: 40% by mass.)
ZCR1761: 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 (C1-2a) (trade name: ZCR-1761H, manufactured by Nippon Kayaku Co., Ltd., solid content: 60 mass%, PGMEA: 40 mass%.).
ZCR1642: Resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the above formula (C1-2a) (Nippon Kayaku Co., Ltd., trade name: ZCR-1642H. Solid content: 60 mass%, PGMEA: 40 mass%.).
C-1: A resin obtained by reacting a cresol novolac type epoxy resin with acrylic acid and then 1,2,3,6-tetrahydrophthalic anhydride, and introducing a resin introduced with acryloyl group and carboxyl group with hexane, solid content 70 %, Acid value 60 mgKOH / g, PGMEA: 30% by mass.
ZAR2002: Trade name: KAYARAD ZAR-2002, manufactured by Nippon Kayaku Co., Ltd., a resin in which a carboxyl group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, solid content 70%, acid value 60 mgKOH / g, PGMEA: 30 mass %.

(Black colorant (D))
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 156, 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%).
(Crosslinking agent (G))
UX5002: Multifunctional urethane acrylate oligomer (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD UX-5002D-P20. Solid content: 80% by mass, PGMEA: 20% by mass).
A9300CL: ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-9300-1CL).
A9530: Mixed product of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-9530).

(Solvent (H))
PGMEA: Propylene glycol 1-monomethyl ether 2-acetate.
IPA: 2-propanol.
(Silane coupling agent (J))
KBM5013: Trade name (manufactured by Shin-Etsu Chemical Co., Ltd. 3-acryloyloxypropyltrimethoxysilane).
(Fine particles (K))
IPA-ST: Trade name (manufactured by Nissan Chemical Industries, Ltd., organosilica sol, solid content: 30% by mass, IPA: 70% by mass).

[Synthesis Example 1: Synthesis of ink repellent agent (A ¹ -1)]
A 1 L autoclave equipped with a stirrer was charged with MEK (420 g), C6FMA (90 g), MAA (9 g), PME1000 (81 g) and polymerization initiator V-65 (0.2 g) in nitrogen gas. While stirring, polymerization was carried out at 50 ° C. for 24 hours to synthesize a crude polymer. Hexane was added to the obtained crude polymer solution for purification by reprecipitation, followed by vacuum drying to obtain an ink repellent agent (A-1) (158.6 g). The ink repellent agent (A ¹ -1) had a number average molecular weight (Mn) of 64,690 and a mass average molecular weight (Mw) of 92,270.

Synthesis Example 2: Synthesis of the ink repellent ^(A 1 -2)]
In an autoclave with an internal volume of 1 L equipped with a stirrer, MEK (420 g), C6FMA (85 g), 2-HEMA (50 g), PME400 (36 g), MAA (9 g) and polymerization initiator V-65 (0.7 g) And polymerized at 50 ° C. for 24 hours with stirring in nitrogen gas to obtain a solution of the polymer (1).

(Introduction of ethylenic double bond)
A solution (500 g) of the above polymer (1), AOI (45.6 g), DBTDL (0.13 g), TBQ (1.6 g) and MEK (17.1 g) in an autoclave having an internal volume of 1 L equipped with a stirrer. And stirred for 24 hours at 40 ° C. to introduce an ethylenic double bond into the polymer (1). To the resulting solution was made by adding hexane re-precipitation, and dried in vacuo to give the ink repellent agent ^{(A 1 -2) (165.0g)} . The ink repellent agent (A ¹ -2) has a number average molecular weight (Mn) of 41,200, a mass average molecular weight (Mw) of 110,800, a fluorine atom content of 20.6% by mass, and an ethylenic double bond (C = C amount, × 10 ⁻³ mol / g) was 1.66 × 10 ⁻³ mol / g, and the acid value was 25.0 mgKOH / g.

Synthesis Example 3-4: Synthesis of the ink repellent ^(A 1 -3) and ^(A 1 -4)]
In the synthesis of the ink repellent agent (A ¹ -1), the ink repellent agents (A ¹ -3) and (A ¹ -4) were prepared by the same copolymerization reaction except that the composition of the raw materials was changed as shown in Table 1. Obtained. The obtained ink repellent ^(A 1 -3) and the number average molecular weight of ^(A 1 -4) (Mn), weight average molecular weight (Mw), the content of fluorine atoms (mass%), acid value (mg KOH / g ) Is shown in Table 1.

Synthesis Example 5: Synthesis of the ink repellent ^(A 1 -5)]
In the synthesis of the polymer (1), a polymer (2) was obtained by the same copolymerization reaction except that the blending of raw materials was changed as shown in Table 1. In the synthesis of the ink repellent (A 1 ^-2), by the exception that the formulation of raw materials as shown in Table 1 is the same reaction, by introducing an ethylenic double bond in the polymer (2), the ink repellent ( was obtained a ¹ -5). The weight average molecular weight of the obtained ink repellent ^(A 1 -5) (Mn), the number average molecular weight (Mw), the content of fluorine atoms (mass%), an acid value (mgKOH / g), ethylenic double bonds Table 1 shows the amount of C (C = C amount, × 10 ⁻³ mol / g).

[Synthesis Example 6: Production of ink repellent agent (A ² -1)]
In a 1,000 cm ³ three-necked flask equipped with a stirrer, 11.8 g of compound (a7-1), 29.4 g of compound (a8-1), 29.4 g of compound (a9-1), 29 of TMMS .4 g was added to obtain a hydrolyzable silane compound mixture. Next, 564.7 g of PGMEA was added to the mixture to prepare a solution (raw material solution).
52.0g of 1.0% hydrochloric acid aqueous solution was dripped at 40 degreeC to the obtained raw material solution, stirring. After completion of the dropwise addition, the mixture was stirred at 40 ° C. for 5 hours, and the ink repellent agent (A ² -1) was changed to a PGMEA solution (ink repellent agent (A ² -1) concentration: 10% by mass. Hereinafter, “(A ² -1)”. Liquid).). The reaction solution was measured using gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit.
The obtained ink repellent number average molecular weight of ^{(A 2 -1) (Mn)} , weight average molecular weight (Mw), the content of fluorine atoms, the charged amount the composition of the ink repellent ^(A 2 -1) ^(mol% ) And in Table 2.

Synthesis Example 7: Production of an ink repellent ^(A 2 -2)]
In a 1,000 cm ³ three-necked flask equipped with a stirrer, 16.7 g of compound (a7-1), 41.7 g of compound (a8-1), and 41.7 g of compound (a9-1) were placed. A hydrolyzable silane compound mixture was obtained. Next, 564.7 g of PGME was added to the mixture to prepare a solution (raw material solution).
To the obtained raw material solution, 65.7 g of 1.0% nitric acid aqueous solution was added dropwise at 40 ° C. with stirring. After completion of the dropwise addition, and stirred for 5 hours at 40 ° C., the ink repellent agent ^(A 2 -2) PGME solution (ink repellent ^(A 2 -2) Concentration:. 10 wt% or less, ^"(A 2 -2) Liquid).). The reaction solution was measured using gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit.
The number average molecular weight of the obtained ink repellent ^{(A 2 -2) (Mn)} , weight average molecular weight (Mw), the fluorine atom content, the charged amounts composition of the ink repellent ^(A 2 -2) (mol%) The results are shown in Table 2.

[Examples 1 to 24 and Examples 31 to 33: Preparation of negative photosensitive resin composition, formation and evaluation of partition walls]
In the proportions (mass%) shown in Table 3 and Table 4, the ink repellent agent (A), photopolymerization initiator (B), alkali-soluble resin (C), black colorant (D), cross-linking agent (G), solvent (H), a silane coupling agent (J), and fine particles (K) were blended to obtain a negative photosensitive resin composition.
After applying a negative photosensitive resin composition on a glass substrate using a spinner, it was dried on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Next, an ultrahigh pressure mercury lamp (with a wavelength of 330 nm or less was shielded from light by a cut filter through the mask (lattice pattern of light shielding part 100 μm × 200 μm, light transmission part 20 μm). Mainly i line, h line and g line The predetermined exposure amount shown in Table 3 and Table 4 was irradiated.

Next, the unexposed portion was developed by being immersed in an inorganic alkali type developer (manufactured by Yokohama Oil & Fats Co., Ltd., trade name Semi Clean DL-A4, 10-fold diluted aqueous solution), and the unexposed portion was washed away with water and dried.
Subsequently, the glass substrate (1) in which the pattern was formed was obtained by heating on a hotplate at 220 degreeC for 1 hour. Moreover, the glass substrate (2) with which the coating-film cured film was formed was obtained similarly to the above except having exposed without using said mask. For the glass substrate (1) or (2), the line width, the film thickness after development, and the ink repellency (PGMEA contact angle) were measured and evaluated by the following methods. The results are shown in Table 3 and Table 4.

(Line width)
About the said glass substrate (1), the line | wire width of the grid | lattice pattern of 20 micrometers of light transmission parts was measured using ultra deep shape measurement microscope VK-8500 (made by Keyence Corporation). The closer the line width is to 20 μm of the light transmission part of the mask, the more the line width of the mask can be reproduced.
(Reduced film after development)
About the glass substrate (1), the film thickness (THK1) before development of the exposed part (cured film) and the film thickness (THK2) after development are measured using a high-precision fine shape measuring instrument SURFCORDER ET4000A (manufactured by Kosaka Laboratory). It was measured. A value obtained by subtracting the film thickness after development from the film thickness before development is defined as film reduction after development. The smaller the value, the better the photocuring of the negative photosensitive resin composition.

(Ink repellency)
It evaluated by the PGMEA contact angle (degree) of the cured film surface of the said glass substrate (2). The contact angle is an angle formed by a solid surface and a tangent to the liquid surface at a point where the solid and the liquid are in contact, and is defined as an angle including the liquid. The larger the angle, the better the ink repellency of the cured film.
In accordance with JIS R 3257 “Test method for wettability of substrate glass surface”, PGMEA droplets were placed on three measurement surfaces on the substrate by the sessile drop method, and each PGMEA droplet was measured. The droplet was 2 μL / droplet, and the measurement was performed at 20 ° C. The contact angle is indicated by an average value of three measured values (n = 3).

The negative photosensitive resin compositions of Examples 1 to 24 all had good photocuring properties. Further, the cured film formed from the composition had good ink repellency and could reproduce the line width of the mask.
On the other hand, since the negative photosensitive resin compositions of Examples 31 to 33 did not use an oxime ester compound having a nitro group in one molecule as a photopolymerization initiator, the exposure doses were 20 mJ / cm ² and 40 mJ / cm ^2. In both cases, the film loss after development was more than 60 nm, and photocuring was insufficient. Further, the formed cured film had insufficient ink repellency, and the line width of the mask could not be reproduced.

The negative photosensitive resin composition of the present invention has good ink repellency and reproduction of the mask line width even when exposed by reducing the exposure amount or shielding exposure light of 330 nm or less. Can produce a good partition.
The negative photosensitive resin composition of the present invention is suitably used for forming partition walls for the production of color filters and the production of organic EL display elements utilizing the ink jet recording technique.
It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2011-102039 filed on April 28, 2011 is cited here as the disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Coating film of negative photosensitive resin composition, 3 ... Coating film exposure part, 4 ... Mask, 5 ... Light, 6 ... Partition, 7 ... Dot, 10 ... Substrate for optical elements used for inkjet system

Claims (15)

An ink repellent (A) having a side chain containing a group represented by the following formula (1) or a group represented by the following formula (2);
A photopolymerization initiator (B) which is an oxime ester compound having a nitro group in one molecule;
A negative photosensitive resin composition comprising an alkali-soluble resin (C).
-CFXR ^f (1)
_{^{- (SiR 1 R 2 -O)}} n -SiR 3 R 4 R 5 (2)
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. A fluoroalkyl group having a number of 20 or less, or a fluorine atom.
In formula (2), R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ⁵ represents a hydrogen atom or a C 1-10 carbon atom. An organic group is shown, n shows the integer of 1-200. The negative photosensitive resin composition of Claim 1 whose said photoinitiator (B) is a compound which consists of the following Formula (3).

In formula (3), R ³¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a cyano group. R ³² represents R ⁴¹ or OR ⁴² , and each of R ⁴¹ and R ⁴² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group. R ³³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R ³⁴ and R ³⁵ each independently represent R ⁴¹ , OR ⁴² , a cyano group or a halogen atom. a and b are each independently an integer of 0 to 3, and c is an integer of 1 to 3.   The negative photosensitive resin composition of Claim 1 or 2 which further contains a black coloring agent (D).   The negative photosensitive resin composition as described in any one of Claims 1-3 which further contains a crosslinking agent (G).   The negative according to any one of claims 1 to 4, wherein the ink repellent agent (A) is a compound having a group (1) or a group (2) in a side chain and a main chain being a hydrocarbon chain. Type photosensitive resin composition.   The negative photosensitive resin composition of Claim 5 in which an ink repellent agent (A) has an acidic group.   The negative photosensitive resin as described in any one of Claims 1-4 whose ink repellent agent (A) is a compound which has group (1) in a side chain, and a principal chain is an organopolysiloxane chain. Composition.   The negative photosensitive resin composition as described in any one of Claims 5-7 in which an ink repellent agent (A) has an ethylenic double bond.   The cured film formed by hardening | curing the coating film of the negative photosensitive resin composition as described in any one of Claims 1-8 formed on the board | substrate.   A partition formed to provide a partition on a substrate, the partition comprising the cured film according to claim 9.   A black matrix comprising a cured film according to claim 9, wherein the black matrix is formed to provide a partition on a substrate, and is formed from the negative photosensitive resin composition according to claim 3.   Applying the negative photosensitive resin composition according to any one of claims 1 to 8 on a substrate to form a coating film, heating the coating film to form a film, and then forming a predetermined film It is a method for manufacturing a partition wall, which includes a step of exposing only a portion to photocuring, a step of removing a film other than the photocured portion, and a step of heating the photocured portion to obtain a partition wall. The method for manufacturing a partition wall is characterized in that a change in film thickness of the photocured portion before and after removing the film is 60 nm or less.   The method for producing a black matrix according to claim 12, wherein the partition walls are obtained as a black matrix using the negative photosensitive resin composition according to claim 3.   A cured film of the negative photosensitive resin composition according to any one of claims 1 to 8, comprising a substrate, a plurality of pixels on the substrate, and a partition located between adjacent pixels. A color filter comprising:   A cured film of the negative photosensitive resin composition according to any one of claims 1 to 8, comprising a substrate, a plurality of pixels on the substrate, and a partition located between adjacent pixels. An organic EL device comprising:

Images