CN103502888B - Negative light-sensitive resin combination, cured film, partition wall and black matrix" and manufacture method thereof, colour filter and organic EL - Google Patents

Abstract

The present invention provides a negative photosensitive resin composition having good ink repellency and good reproducibility of the line width of a mask, and a homogeneous partition obtained by using the composition. A negative photosensitive resin composition, characterized in that it contains an ink repellent (A), a photopolymerization initiator (B) and an alkali-soluble resin (C), and the ink repellent (A) has -CFXR ^f [X is a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f is a fluoroalkyl group having 20 or less carbon atoms which may have an etheric oxygen atom and at least one of the hydrogen atoms is substituted with a fluorine atom, or a fluorine atom ] or -(SiR ¹ R ² -O) _n -SiR ³ R ⁴ R ⁵ [R ¹ , R ² , R ³ , R ⁴ are hydrogen atom, alkyl, cycloalkyl or aryl group, R ⁵ is hydrogen atom or an organic group with 1 to 10 carbon atoms, n is an integer of 1 to 200] side chain, and the polymerization initiator (B) is an oxime ester compound having a nitro group in one molecule.

Description

Negative photosensitive resin composition, cured film, partition wall, black matrix, manufacturing method thereof, color filter, and organic EL element

technical field

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

Background technique

The resist composition is used as a partition wall between pixels forming a color filter, a partition wall between pixels of an organic EL (Electro-Luminescence) display element, a partition wall between elements of an organic EL lighting device, an organic TFT ( ThinFilmTransistor (Thin Film Transistor: Thin Film Transistor) is attracting attention as a material for permanent films such as the partition walls that separate each TFT in the array, the partition walls of the ITO electrodes of the liquid crystal display element, and the partition walls of the circuit board.

In the manufacture of circuit wiring boards, an inkjet method for spraying and applying a metal dispersion liquid when forming circuit wiring has been proposed. The circuit wiring pattern is formed from a resist composition by photolithography, and a cured product of the coating film of the resist composition is used as a partition wall.

In the inkjet method, it is necessary to prevent ink color mixing between adjacent pixels, and the material jetted from the inkjet machine to solidify and adhere to parts other than the specified area, and a resist composition containing an ink repellent has been proposed (Patent Documents 1 to 3 ).

prior art literature

patent documents

Patent Document 1: International Publication No. 2008/146855

Patent Document 2: International Publication No. 2010/001976

Patent Document 3: International Publication No. 2010/013816

Contents of the invention

The problem to be solved by the invention

The exposure of the resist composition was performed using an exposure machine. The wavelength irradiated by the exposure machine varies depending on the specifications of the device, but generally, in the proximity exposure method used for color filters, light of 330 nm or less is irradiated. In contrast, in the mirror projection (MPA) method, light of 330 nm or less is blocked and irradiated. Therefore, a resist composition may also be required to have a composition compatible with the MPA system. In addition, the projection-type MPA method also has advantages over the proximity exposure method, such as being able to form a sharp partition shape. In the MPA method, it is sometimes required to form a fine pattern.

The object of the present invention is to provide a negative photosensitive resin composition with good ink repellency and good reproducibility of the line width of the mask even if the exposure light of 330 nm or less is blocked, and a homogeneous photosensitive resin composition obtained by using the composition. A cured film, a partition wall, and a black matrix, and methods for manufacturing the same. Another object of the present invention is to provide a color filter and an organic EL element having a partition wall or a black matrix with good performance.

solutions to problems

The present invention is the following [1] to [15].

[1] A negative photosensitive resin composition, characterized in that it contains:

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, and

Alkali-soluble resin (C),

- CFXR ^f (1)

-(SiR ¹ R ² -O) _n -SiR ³ R ⁴ R ⁵ (2)

In formula (1), X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents a fluoroalkyl group having 20 or less carbon atoms, which may have an etheric oxygen atom and at least one of the hydrogen atoms is replaced by a fluorine atom , 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, R ⁵ represents a hydrogen atom or an organic group with 1 to 10 carbon atoms, n Represents an integer from 1 to 200.

[2] The negative photosensitive resin composition according to [1], wherein the aforementioned photopolymerization initiator (B) is a compound composed 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 aralkyl group having 7 to 30 carbon atoms, or a cyano group. R ³² represents R ⁴¹ or OR ⁴² , and R ⁴¹ and R ⁴² represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, respectively. R ³³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl 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 0-3, and c is an integer of 1-3.

[3] The negative photosensitive resin composition according to [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] The negative photosensitive resin composition according to any one of [1] to [4], wherein the ink repellent agent (A) has a group (1) or a group (2) in a side chain , The compound whose main chain is a hydrocarbon chain.

[6] The negative photosensitive resin composition according to [5], wherein the ink repellent agent (A) has an acidic group.

[7] The negative photosensitive resin composition according to any one of [1] to [4], wherein the ink repellent agent (A) has a group (1) in the side chain, and the main chain is an organic polymer Compounds with siloxane chains.

[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 obtained by curing a coating film of the negative photosensitive resin composition according to any one of [1] to [8] formed on a substrate.

[10] A partition formed for providing partitions on a substrate, which is formed from the cured film of [9].

[11] A black matrix formed for providing partitions on a substrate, which is formed of the cured film of [9], the cured film is formed of the negative photosensitive resin composition of [3] .

[12] A method for producing a partition, comprising the steps of applying the negative photosensitive resin composition described in any one of [1] to [8] on a substrate in sequence. A step of forming a coating film; a step of exposing and photocuring only a predetermined portion of the film after heating the aforementioned coating film to form a film; a step of removing the film except for the aforementioned photocured portion; and, In the step of heating the photocured part to obtain the partition wall, the change in film thickness of the photocured part before and after removing the film is 60 nm or less.

[13] A method for producing a black matrix in which the partition wall is obtained as a black matrix using the negative photosensitive resin composition of [3] in the production method of [12].

[14] A color filter comprising: a substrate, a plurality of pixels on the substrate, and a partition between adjacent pixels, the partition consisting of any one of [1] to [8] A cured film of the negative photosensitive resin composition is formed.

[15] An organic EL element, characterized in that it comprises: a substrate, a plurality of pixels on the substrate, and a partition between adjacent pixels, the partition consisting of any one of [1] to [8] A cured film of the negative photosensitive resin composition is formed.

The effect of the invention

According to the present invention, it is possible to provide negative photosensitivity that can produce partitions with good ink repellency and good reproducibility of the line width of the mask even when the exposure amount is reduced or the exposure light of 330 nm or less is blocked for exposure. resin composition. According to the present invention, a homogeneous cured film using the negative photosensitive resin composition of the present invention, a partition wall having good performance, a black matrix, and a method for producing the same can be provided. Furthermore, according to this invention, the color filter and organic electroluminescent element with favorable performance provided with the partition of this invention mentioned above and a black matrix can be obtained.

Description of drawings

FIG. 1 is a schematic cross-sectional view showing a production example of a partition for an optical element using the negative photosensitive resin composition of the present invention.

detailed description

The acid value in this specification means the number of milligrams of potassium hydroxide required to neutralize the resin acid etc. in 1g of samples, and it is the value measurable based on the measuring method of JISK0070. The unit is mgKOH/g.

The total solid content in this specification refers to the partition wall forming component among the components contained in the negative photosensitive resin composition, and represents excluding volatile components such as solvent (H) that volatilize due to heating or the like during the partition wall forming process. total composition.

"(meth)acryloyl..." in this specification means the generic term of "methacryloyl..." and "acryloyl...". The same applies to (meth)acrylate, (meth)acrylamide, (meth)allyl..., (meth)acrylic resins.

The hydrocarbon group in this specification means an organic group composed only of carbon and hydrogen.

In this specification, a film coated with a negative photosensitive resin composition is called a "coating film", a dried state is called a "film", and a film obtained by curing it is called a "coating film". "cured film".

In this specification, the "surface" of a partition is used as a term which shows only the upper surface of a partition. Therefore, the "surface" of the partition wall does not include the sides of the partition wall.

The ink in this specification is a general term for liquids that have optical and electrical functions after drying and curing, and is not limited to conventionally used coloring materials. In addition, the term "pixel" formed by injecting the above-mentioned ink is similarly used to indicate divisions each having an optical function and an electrical function separated by a partition wall.

The ink repellency in this specification means the property which moderately has both water repellency and oil repellency in order to repel the said ink, For example, it can evaluate by the method mentioned later.

Embodiments of the present invention will be described below. However, unless otherwise specified in this specification, % represents mass %.

[Ink repellent (A)]

The ink repellent agent (A) of the present invention has 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 also referred to as Group (2).) side chain compound.

- CFXR ^f (1)

-(SiR ¹ R ² -O) _n -SiR ³ R ⁴ R ⁵ (2)

In formula (1), X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents a fluoroalkyl group having 20 or less carbon atoms, which may have an etheric oxygen atom and at least one of the hydrogen atoms is replaced by a fluorine atom , 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, R ⁵ represents a hydrogen atom or an organic group with 1 to 10 carbon atoms, n Represents an integer from 1 to 200.

The ink repellent (A) has a side chain containing a group (1) or a group (2), so it has surface mobility, and is formed by heating and drying a coating film formed of a negative photosensitive resin composition , it migrates toward the surface of the coating film. As a result, ink repellency is exhibited on the surface of the partition wall formed by the cured film formed by curing the film, and the ink injected by the inkjet method does not flow from the opening between the partition walls called a dot (which becomes a pixel). parts) overflow, and color mixing between adjacent pixels is not easy to occur.

The side chain containing group (1) or group (2) can be formed directly by polymerization reaction, or can be formed by chemical transformation after polymerization reaction.

When R ^f in the formula (1) is a fluoroalkyl group having 20 or less carbon atoms which may have an etheric oxygen atom and at least one of the hydrogen atoms is replaced by a fluorine atom, the hydrogen atom in the fluoroalkyl group may also be Other halogen atoms other than fluorine atoms are substituted. As other halogen atoms, chlorine atoms are preferred. In addition, an etheric oxygen atom may exist between the carbon-carbon bonds of the fluoroalkyl group, or may exist at the terminal of the fluoroalkyl group. In addition, examples of the structure of the fluoroalkyl group include a straight chain structure, a branched structure, a ring structure, and a partially ringed structure, and a straight chain structure is preferable.

The group (1) is preferably a polyfluoroalkyl group containing one perfluoroalkyl group or a hydrogen atom, and particularly preferably a perfluoroalkyl group (including a group having an etheric oxygen atom.). Thereby, the ink repellency of the partition formed from a negative photosensitive resin composition becomes favorable.

The number of carbon atoms in the group (1) is 20 or less, preferably 4-6. At this time, sufficient ink repellency is imparted to the partition wall, and the ink repellent agent (A) has good compatibility with other components constituting the negative photosensitive resin composition, and the negative photosensitive resin composition is applied to form a coating. When forming a film, the ink repellent agents (A) do not aggregate together, and can form a partition wall with a good appearance.

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) are listed below.

-CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ , -(CF ₂ ) ₂ CF ₃ , -(CF ₂ ) ₃ CF ₃ , -(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₅ CF ₃ 、-(CF ₂ ) ₆ CF ₃ 、-(CF ₂ ) ₇ CF ₃ 、-(CF ₂ ) ₈ CF ₃ 、-(CF ₂ ) ₉ CF ₃ 、-(CF ₂ ) ₁₁ CF ₃ 、-(CF ₂ ) ₁₅ CF ₃ , -CF(CF ₃ )O(CF ₂ ) ₅ CF ₃ , -CF ₂ O(CF ₂ CF ₂ O) _p CF ₃ (p is an integer from 1 to 8), -CF(CF ₃ )O(CF ₂ CF(CF ₃ )O) _q C ₆ F ₁₃ (q is an integer from 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).

The group (1) is particularly preferably —(CF ₂ ) ₃ CF ₃ or —(CF ₂ ) ₅ CF ₃ .

In formula (2), R ¹ and R ² may be the same or different in each siloxane unit. From the viewpoint that the partition formed by the negative photosensitive resin composition exhibits excellent ink repellency, R ¹ and R ² are preferably a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, It is more preferably a hydrogen atom, a methyl group or a phenyl group, and it is particularly preferable that R ¹ and R ² in 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 end of the siloxane bond, and R ³ and R ⁴ may be the same as R ¹ and R ² , and the preferred form Also the same. In addition, when R ⁵ is an organic group, it may contain a nitrogen atom, an oxygen atom, etc., and R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. N is preferably an integer of 1-200, particularly preferably an integer of 2-100.

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

It is preferable that the ink repellent agent (A) has an acidic group further. When the ink repellent agent (A) has an acidic group, it is preferable from the viewpoint that the solubility to the developing solution of the negative photosensitive resin composition can be improved.

The acidic group is preferably one or more acidic groups selected from the group consisting of carboxyl groups, phenolic hydroxyl groups, and sulfonic acid groups.

The acidic group is preferably present in the side chain from the viewpoint of ease of synthesis. The side chain having an acidic group may be formed by polymerization of a monomer having an acidic group, or may be formed by chemical conversion after the polymerization.

It is preferable that an ink repellent agent (A) has a polyoxyalkylene group. When the ink repellent agent (A) has a polyoxyalkylene group, ink repellency can be maintained even when pressure is raised in an image development process. Furthermore, it is preferable from a viewpoint of being able to prevent the generation|occurrence|production of the residual film which remains in a dot part without removing completely by image development. In addition, as a polyoxyalkylene group used by this invention, the group represented by following formula (11) (it is also called a group (11) below.) specifically, etc. are mentioned.

-(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 with 2 to 4 carbon atoms, R ²³ represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms that may have a substituent, and m represents 0 An integer of -100, j represents an integer of 0-100, and m+j is an integer of 4-100.

In the group (11), R ²¹ and R ²² each independently represent an alkylene group having 2 to 4 carbon atoms. The structure of the alkylene group may be a linear structure or a branched structure. ^R21 and ^R22 may be the same or different. Among such R ²¹ and R ²² , it is preferable that 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 particularly 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 0-100, j represents an integer of 0-100, m and j are preferably 0-50, particularly preferably 0-30, respectively.

Moreover, m+j is an integer of 4-100, Preferably it is an integer of 6-50, Especially preferably, it is an integer of 8-30. When m+j is more than the lower limit of the said range, when performing the jet rinse process using high-pressure water after an image development process, ink repellency will not fall easily. Furthermore, residual film is less likely to be generated. When m+j is below the upper limit of the above range, the ink repellent (A) does not migrate to the opening during post-baking, and the ink affinity of the opening between the partition walls becomes sufficient. When ink is applied by the inkjet method , the ink is sufficiently wetted and diffused in the opening.

The group (11) represents a group having m (R ²¹ O) units and j (R ²² O) units, and the bonding order of (R ²¹ O) units and (R ²² O) units is not particularly limited . In other words, in the group (11), m (R ²¹ O) units and j (R ²² O) units may, for example, be bonded alternately, or randomly, or in blocks.

In the group (11), when R ²³ is an alkyl group having 1 to 10 carbon atoms which may have a substituent, its structure may be a linear structure, a branched structure, a ring structure, a partially ringed structure, or the like. Moreover, as a substituent, a carboxyl group, a hydroxyl group, an alkoxy group with 1-5 carbon atoms, etc. are mentioned specifically,. In the present invention, R ²³ in the group (11) is preferably a straight-chain, unsubstituted alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group and 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 cyclohexenyl .), -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-, etc. 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 group.

The group (11) may be used alone or in combination of two or more. In addition, regarding the introduction of a side chain having a group (11) into the ink repellent (A), as described later, when the ink repellent (A) is produced by polymerization of raw material monomers, it will have the group (11) The compounding quantity of the monomer with respect to the whole raw material monomer is adjusted suitably to the compounding quantity which can provide the effect of the said developability improvement to an ink repellent agent (A) without impairing the effect of this invention, and performs it.

It is preferable that an ink repellent agent (A) has an ethylenic double bond. When the ink repellent (A) has an ethylenic double bond, the ink repellent (A) migrated to the surface of the film during drying passes through the ink repellent (A) each other or the ink repellent (A) and the alkali-soluble resin (C) It is preferable from the viewpoint that it reacts and is easily fixed on the surface of the partition wall.

Examples of the ethylenic double bond include addition-polymerizable unsaturated groups such as (meth)acryloyl groups, allyl groups, vinyl groups, and vinyl ether groups. The hydrogen atoms of these groups may be partially or completely substituted by hydrocarbon groups. The hydrocarbon group is preferably a methyl group.

The introduction of a side chain having an ethylenic double bond into the ink repellent (A) is carried out by adding, as will be described later, to the raw material monomers at the time of producing the ink repellent (A) while appropriately adjusting the compounding amount. The monomer of the reactive group is copolymerized, and then the resulting copolymer is reacted with a compound having a functional group capable of bonding with the aforementioned reactive group and an ethylenic double bond.

As an ink repellent agent (A), the compound which has a group (1) or a group (2) in a side chain, and a main chain is a hydrocarbon chain is preferable. Hereinafter, the ink repellent agent (A) whose main chain is a hydrocarbon chain is also called "ink repellent agent (A ¹ )".

The ink repellent agent (A ¹ ) is produced by, for example, copolymerizing a raw material monomer containing a monomer (a1) having a group (1) or a monomer (a2) having a group (2) , the monomer (a3) which has an acidic group as needed, and the monomer (a4) which has a polyoxyalkylene group as needed.

In addition, when the ink repellent agent (A ¹ ) has an ethylenic double bond, it can be produced by copolymerizing a raw material monomer obtained by further adding a monomer (a5) having a reactive group to the above raw material monomer , followed by reacting the resulting copolymer with a compound (z1) having a functional group capable of bonding with the aforementioned reactive group and an ethylenic double bond.

(monomer (a1))

As a monomer (a1) which has a 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 having 1 to 6 carbon atoms not including a fluorine atom, and is preferably an alkylene group having 2 to 4 carbon atoms in terms of ease of acquisition. X and R ^f have the same meanings as those of the group (1), and their preferred forms 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 COCFXR ^f

CH ₂ =CR ⁶ COOCH ₂ CH(OH)R ¹² CFXR ^f

Here, R ⁶ represents the same meaning as above, R ⁷ , R ⁸ and R ¹⁰ represent an alkylene group with 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 ) 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(CH2CH( _CH3 ) ₂ ) _-etc .

Specific examples of R ¹² include -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH ₂ CH ₂ -, -C(CH ₃ ) ₂ -, -CH (CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₂ CH ₂ CH ₃ )-, etc.

Specific examples of the monomer (a11) include 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, and the like.

The monomer (a11) may be used alone or in combination of two or more.

(monomer (a2))

As a monomer (a2) which has a 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, ^R13 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 , R ⁵ , and n represent the same meanings as those of the group (2), and preferred forms are also the same.

Z is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH ₂ CH ₂ -, -C(CH ₃ ) ₂ -, -CH(CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₂ CH ₂ CH ₃ )-, -CH ₂ (CH ₂ ) ₃ CH ₂ -, -CH(CH ₂ CH(CH ₃ ) ₂ ) - etc.

Specific examples of the monomer (a21) include 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 so on. It should be noted that n is about 4, 60, 160.

As a monomer (a21), a commercial item can be used. Examples of commercially available products include the following under any trade names. X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-2475 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The monomer (a21) may be used alone or in combination of two or more.

(monomer (a3))

When the ink repellent agent (A ¹ ) has an acidic group, it is preferable to copolymerize monomers (a1) to (a2) together with the monomer (a3) which has an acidic group.

As a monomer (a3) which has an acidic group, the monomer which has a carboxyl group, the monomer which has a phenolic hydroxyl group, the monomer which has a sulfonic acid group etc. are mentioned.

Acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, these salts, etc. are mentioned as a monomer which has a carboxyl group.

As a monomer which has a phenolic hydroxyl group, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, etc. are mentioned. Or one or more hydrogen atoms of their benzene rings are replaced by alkyl groups such as methyl, ethyl, and n-butyl; alkoxy groups such as methoxy, ethoxy, and n-butoxy; one of halogen atoms and alkyl groups Compounds in which the above hydrogen atoms are substituted by halogen atoms, haloalkyl groups, nitro groups, cyano groups, amido groups, etc.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, 2-hydroxy-3-(methyl)allyloxypropanesulfonic acid, 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropanesulfonic acid, 2-(meth)acrylamide -2-Methylpropanesulfonic acid.

The monomer (a3) is preferably acrylic acid or methacrylic acid from the viewpoint of easy availability.

The monomer (a3) may be used alone or in combination of two or more.

(monomer (a4))

As a monomer having a group (11) used in the manufacture of the ink repellent agent (A ¹ ), it is preferably a compound represented by the following formula (12) (hereinafter also referred to as compound (12).) or represented by (13). The compound shown (hereinafter also referred to as compound (13).). These may be used individually by 1 type, and may use it in combination of 2 or more types.

CH ₂ =CR ²⁴ -COO-W-(R ²¹ O) _m (R ²² O) _j R ²³ (12)

CH ₂ =CR ²⁵ -OW-(R ²¹ O) _m (R ²² O) _j R ²³ (13)

In formulas (12) and (13), R ²⁴ and R ²⁵ are hydrogen atom, chlorine atom, bromine atom, iodine atom, cyano group, alkyl group with 1 to 20 carbon atoms, and alkyl group with 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 1 to 10 carbon atoms and not having a fluorine atom. -(R ²¹ O) _m (R ²² O) _j R ²³ is the group (11), R ²¹ , R ²² , R ²³ , m and j represent the same meanings as the group (11), and the preferred ranges are also the same .

In compound (12) and compound (13), when W is a divalent organic group having 1 to 10 carbon atoms and not having a fluorine atom, examples include those having a straight-chain 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 partially having a ring structure, a single bond, and the like. Specific examples of the oxyalkylene group include CH ₂ C ₆ H ₁₀ CH ₂ O (wherein, C ₆ H ₁₀ is a cyclohexenyl 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, etc. Among them, W in the compounds (12) and (13) is preferably an oxyalkylene group having 2 to 4 carbon atoms from the viewpoint of easy availability.

In compounds (12) and (13), R ²⁴ and R ²⁵ are each preferably hydrogen atom, chlorine atom, methyl, phenyl, benzyl, etc., particularly preferably hydrogen atom, chlorine atom or methyl.

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 meanings as those of the group (11), and the preferred ranges are also the same. C ₆ H ₁₀ is cyclohexenyl. C ₂ H ₄ , C ₃ H ₆ , and C ₄ H ₈ are any of a linear structure or a branched structure. R ²³ represents the same meaning as the group (11), preferably a straight-chain, unsubstituted alkyl group having 1 to 10 carbon atoms, particularly preferably a methyl group.

As compounds (12) and (13), commercially available items can be used. As a commercial item, the following can be mentioned.

BLEMMERPME-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 the average value between molecules, and the value of k is about 9 In the following, k, m, and j in the molecular formula of each commercially available product all represent the average value between molecules.), BLEMMERPME-1000 (trade name, manufactured by NOF Corporation, CH ₂ =C(CH ₃ )COO(CH ₂ CH ₂ O) _k CH ₃ . The k in the formula represents the average value between molecules, and the value of k is 23.), NKESTERM-230G: (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., CH ₂ =C(CH ₃ ) COO(CH ₂ CH ₂ O) _k CH ₃ . In the formula, k is about 9.), NewFrontierNFBisomerPEM6E (trade name, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., CH ₂ =C(CH ₃ )COO(CH ₂ CH ₂ O ) _k H: In the formula, k is about 6.), LIGHTESTER130A (trade name, manufactured by Kyoeisha Chemical Co., Ltd., CH ₂ =CHCOO(CH ₂ CH ₂ O) _k CH ₃ . In the formula, k is about 9. ), BLEMMERAE-400 (trade name, manufactured by NOF Corporation, CH ₂ =CHCOO (CH ₂ CH ₂ O) _k H: where k is about 10.), BLEMMERPP-800 (trade name, NOF Corporation CH ₂ =C(CH ₃ )COO(C ₃ H ₆ O) _k H. In the formula, k is about 13.), BLEMMERAP-800 (trade name, manufactured by NOF Corporation, CH ₂ =CHCOO(C ₃ H ₆ O) _k H. In the formula, k is about 13.), BLEMMER70PEP-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. In the formula, m is about 5 and j is about 2.), BLEMMER55PET-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. In the formula, m is about 10 and j is about 5.).

(monomer (a5))

As a monomer (a5) which has a reactive group, the monomer which has a hydroxyl group, the acid anhydride monomer which has an ethylenic double bond, the monomer which has a carboxyl group, the monomer which has an epoxy group etc. are mentioned. It should be noted that the monomer (a5) preferably does not substantially contain the group (1) and the group (2).

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 having a reactive group (a5), the ethylenic double bond is not finally introduced and A monomer remaining as a carboxyl group was regarded as a monomer (a3).

The reactive group of the copolymerized monomer (a5) reacts with the compound (z1) having a functional group that can be bonded to the reactive group and an ethylenic double bond, thereby forming a compound (z1) having an ethylenic double bond. The ink repellent agent (A ¹ ) of the side chain of the bond.

Specific examples of monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, ( 4-Hydroxybutyl Methacrylate, 5-Hydroxypentyl (Meth)acrylate, 6-Hydroxyhexyl (Meth)acrylate, 4-Hydroxycyclohexyl (Meth)acrylate, Neopentyl Glycol mono(meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether , Cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-methylol(meth)acrylamide, N,N-bis(hydroxymethyl)(meth)acrylamide, etc.

Furthermore, as a monomer which has a hydroxyl group, the monomer which has a polyoxyalkylene group whose terminal is a hydroxyl group may be sufficient. For example, CH ₂ =CHOCH ₂ C ₆ H ₁₀ CH ₂ O(C ₂ H ₄ O) _h H (here, h is an integer of 1 to 100, the same applies hereinafter), 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 (here, i is an integer from 0 to 100, g is an integer from 1 to 100, i+g is 1 to 100. Same below.), CH ₂ =C(CH ₃ )COOC ₂ H ₄ O(C ₂ H ₄ O) _i (C ₃ H ₆ O) _g H, etc.

Specific examples of acid anhydride monomers having ethylenic double bonds include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5 , 6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, etc.

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))

Among the monomers used in the polymerization of the present invention, monomers (a3) containing a monomer (a1) having a group (1) or a monomer (a2) having a group (2), and optionally an acidic group ), a monomer (a4) having a polyoxyalkylene group as needed, and when the ink repellent agent (A ¹ ) has an ethylenic double bond, a monomer (a5) having a reactive group may be included, and other than these Monomers other than monomers (a6).

Examples of the monomer (a6) include hydrocarbon-based olefins, vinyl ethers, isopropylene ethers, allyl ethers, vinyl esters, allyl esters, (meth)acrylates, (meth)acrylates, base) acrylamides, aromatic vinyl compounds, chloroolefins, conjugated dienes. These compounds may contain functional groups, and examples of the functional groups include carbonyl groups, alkoxy groups, and the like. In particular, (meth)acrylates or (meth)acrylamides are preferable because the heat resistance of the partition is excellent.

It should be noted that the epoxy group-containing monomers listed as the above-mentioned reactive group-containing monomer (a5), such as glycidyl (meth)acrylate, 3,4-epoxy methacrylate Cyclohexyl ester and the like can also be used as the monomer (a6). In other words, when these epoxy group-containing monomers are used in the polymerization of the present invention, when no ethylenic double bond is introduced after copolymerization, these epoxy group-containing monomers are classified as other monomers (a6). Moreover, even when an ethylenic double bond is introduced, the monomer which does not introduce an ethylenic double bond but remains as an epoxy group is regarded as another monomer (a6).

(Manufacture of ink repellent (A ¹ ))

The ink repellent agent (A ¹ ) can be synthesized by the following method, for example. First, monomers are dissolved in a solvent, heated, and a polymerization initiator is added to carry out copolymerization. In the copolymerization reaction, it is preferable that a chain transfer agent exists as needed. Monomers, polymerization initiators, solvents and chain transfer agents can also be added continuously.

Examples of the solvent include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; and ketones such as acetone, 2-butanone, methyl isobutyl ketone, and cyclohexanone. class; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol and other cellosolves; 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxy Ethoxy) ethanol, 2-(2-butoxyethoxy) ethanol and other carbitols; 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, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Ester, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, butyl lactate, γ-butyrolactone, 3 -Methyl-3-methoxybutyl acetate, ethyl lactate, n-butyl lactate, gamma-butyrolactone, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl 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 Methyl Ether, etc.

As a polymerization initiator, a well-known organic peroxide, an inorganic peroxide, an azo compound, etc. are mentioned. Organic peroxides and inorganic peroxides may be used in combination with a reducing agent as a redox catalyst.

Examples of organic peroxides 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. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4 -Dimethylvaleronitrile), 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-Dimethyl azobisisobutyrate, 2 , 2'-Azobis(2-amidinopropane) dihydrochloride, etc.

Examples of the chain transfer agent include mercaptans such as n-butylmercaptan, n-dodecylmercaptan, tert-butylmercaptan, ethyl mercaptoacetate, 2-ethylhexyl mercaptoacetate, and 2-mercaptoethanol. class; chloroform, carbon tetrachloride, carbon tetrabromide and other halogenated alkanes.

In addition, when the ink repellent agent (A ¹ ) has an ethylenic double bond, the copolymer obtained as described above is reacted with a compound (z1) having a functional group capable of bonding with a reactive group and an ethylenic double bond. , thus obtaining the ink repellent agent (A ¹ ).

Examples of the combination with the compound (z1) having a functional group capable of bonding with the reactive group and an ethylenic double bond with respect to the reactive group include the following combinations.

(1) Anhydrides having ethylenic double bonds with respect to hydroxyl groups,

(2) Compounds having an isocyanate group and an ethylenic double bond with respect to a hydroxyl group,

(3) Compounds having an acid chloride group and an ethylenic double bond with respect to a hydroxyl group,

(4) Compounds having hydroxyl groups and ethylenic double bonds with respect to acid anhydrides,

(5) Compounds having an epoxy group and an ethylenic double bond with respect to a carboxyl group,

(6) A compound having a carboxyl group and an ethylenic double bond with respect to an epoxy group.

It can also be introduced into the ink repellent agent (A ¹ ) by reacting an epoxy group with a compound having a carboxyl group and an ethylenic double bond, and reacting the generated hydroxyl group with an acid anhydride of a compound having two or more carboxyl groups in one molecule. Acidic group.

As a specific example of the acid anhydride which has an ethylenic double bond, the above-mentioned example is mentioned. Specific examples of compounds having an isocyanate group and an ethylenic double bond include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl base isocyanate. (Meth)acryloyl chloride is mentioned as a specific example of the compound which has an acid chloride group and an ethylenic double bond. As a specific example of the compound which has a hydroxyl group and an ethylenic double bond, the example of the monomer which has a hydroxyl group mentioned above is mentioned. As a specific example of the compound which has an epoxy group and an ethylenic double bond, the example of the monomer which has an epoxy group mentioned above is mentioned. As a specific example of the compound which has a carboxyl group and an ethylenic double bond, the example of the above-mentioned monomer which has a carboxyl group is mentioned. Moreover, the example of the acid anhydride which has an ethylenic double bond represented by the said monomer (a5) as a specific example of the acid anhydride of the compound which has 2 or more carboxyl groups in 1 molecule is mentioned.

When the copolymer is reacted with the compound (z1) having a functional group capable of bonding with a reactive group and an ethylenic double bond, as the solvent used in the reaction, the solvents exemplified in the above-mentioned synthesis of the copolymer can be used .

Moreover, it is preferable to mix|blend a polymerization inhibitor. As a polymerization inhibitor, 2, 6- di-t-butyl-p-cresol and a t-butyl-p-benzoquinone are mentioned, for example.

In addition, a catalyst and a neutralizing agent may also be added. For example, when reacting a copolymer having a hydroxyl group with a compound having an isocyanate group and an ethylenic double bond, tin compounds such as dibutyltin dilaurate can be used. When reacting the copolymer having a hydroxyl group and the compound having an acid chloride group and an ethylenic double bond, a basic catalyst can be used.

A preferable ratio of each monomer 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 this ratio is more than the lower limit of the said range, ^an ink repellent agent (A1) can reduce the surface tension of the partition which consists of the cured film formed, and can provide high ink repellency to a partition. The adhesiveness of a partition and a base material becomes favorable that this ratio is below the upper limit of the said range.

When the monomer (a3) is included, the ratio thereof is preferably 2 to 20% by mass, particularly preferably 4 to 12% by mass. The developability of a negative photosensitive resin composition becomes favorable as it is the said range.

When the monomer (a4) is contained, the ratio thereof is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, particularly preferably 15 to 50% by mass. Liquid repellency can be maintained even when pressure is raised in an image development process as it is the said range. Furthermore, generation of residual film can be prevented.

When the monomer (a5) is contained, the ratio thereof is preferably 20 to 70% by mass, particularly preferably 30 to 50% by mass. When an ethylenic double bond is introduced via the polymerized unit derived from the monomer (a5) contained in the said range, the immobilization and developability of the ink repellent agent (A1) to the surface of ^a partition become favorable.

When other monomers (a6) are included, the ratio thereof is preferably 70% by mass or less, particularly preferably 50% by mass or less. When it is the said range, alkali solubility and developability are favorable.

The preferable combination of the monomer in manufacture of ^an ink repellent agent (A1) is shown below.

(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 BLEMMERPME-400 and BLEMMERPME-1000,

Monomer (a5): 2-hydroxyethyl (meth)acrylate.

After copolymerizing the above monomers to obtain a copolymer, it is mixed with a compound selected from 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate At least one compound in the group reacted and introduced 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 BLEMMERPME-400 and BLEMMERPME-1000,

Monomer (a6) as required: selected from glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methacrylate, methyl (meth)acrylate, isobornyl (meth)acrylate and at least one selected from the group consisting of cyclohexyl (meth)acrylate.

(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 BLEMMERPME-400 and BLEMMERPME-1000,

Monomer (a5): Glycidyl (meth)acrylate

Monomer (a6): selected from 3,4-epoxycyclohexyl methacrylate, methyl (meth)acrylate, isobornyl (meth)acrylate and cyclohexyl (meth)acrylate At least 1 species in the group.

After copolymerizing the above-mentioned monomers to obtain a copolymer, it is reacted with at least one selected from the group consisting of acrylic acid and methacrylic acid, and then reacted with 3,4,5,6-tetrahydrophthalic anhydride and cis A compound in which at least one of the group consisting of formula-1,2,3,6-tetrahydrophthalic anhydride reacts and introduces 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 BLEMMERPME-400 and BLEMMERPME-1000,

Monomer (a5): 2-hydroxyethyl (meth)acrylate.

After copolymerizing the above monomers to obtain a copolymer, it is mixed with a compound selected from 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate At least one compound in the group reacted and introduced 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 BLEMMERPME-400 and BLEMMERPME-1000,

Monomer (a5): 2-hydroxyethyl (meth)acrylate.

After copolymerizing the above monomers to obtain a copolymer, it is mixed with a compound selected from 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate At least one compound in the group reacted and introduced an ethylenic double bond.

When the ink repellent (A ¹ ) has an ethylenic double bond, the copolymer and the compound (z1) preferably have an equivalent ratio of [functional group of the compound (z1)]/[reactive group of the copolymer] of 0.5 to 2.0 The way input, especially preferably 0.8 ~ 1.5. The immobilization of the ink repellent agent (A ¹ ) with respect to the partition becomes favorable as it is more than the lower limit of the said range. When it is below the upper limit of the said range, the impurity which is an unreacted compound (z1) will increase and the external appearance of a coating film will deteriorate. In addition, when using a monomer having a carboxyl group as both the monomer (a3) and the monomer (a4), adjust the input amount of the copolymer and the compound (z1) so that the acid of the ink repellent agent (A ¹ ) The value reaches the specified value.

When the ink repellent (A ¹ ) has a group (1), the content of fluorine atoms in the ink repellent (A ¹ ) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, particularly preferably 20% by mass. ~35% by mass. The ink repellent agent (A ¹ ) is excellent in the effect of reducing the surface tension of a partition as it is more than the lower limit of the said range, and the partition excellent in ink repellency can be obtained. The adhesiveness of a partition and a base material becomes favorable that it is below the upper limit of the said range.

When the ink repellent (A ¹ ) has a group (2), the content of silicon atoms in the ink repellent (A ¹ ) is preferably 0.1 to 25% by mass, particularly preferably 0.5 to 10% by mass. The ink repellent agent (A ¹ ) provides the effect of reducing the surface tension of the formed partition and the effect of improving ink releasability as it is more than the lower limit of the said range. The adhesiveness of a partition and a base material becomes 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. When it is the said range, both the solubility in the developing solution of a negative photosensitive resin composition, and the development of ink repellency can be compatible.

When the ink repellent agent (A1) contains an ethylenic double bond, the amount is preferably 0.5×10 ^-3 to 5×10 ^-3 mol/g, particularly preferably 1×10 ^-3 to 4.5×10 ^-3 mol/g. Fixation of the ink repellent agent (A ¹ ) to a partition and developability become favorable in the said range.

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 , particularly preferably 1×10 ⁴ to 7×10 ⁴ . When it is the said range, alkali solubility and developability are favorable.

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 , particularly preferably 3×10 ⁴ to 12×10 ⁴ . When it is the said range, alkali solubility and developability are favorable.

As an ink repellent agent (A), it is also preferable to have a group (1) in a side chain and the compound whose main chain is an organopolysiloxane chain. Hereinafter, the ink repellent agent (A) whose main chain is an organopolysiloxane chain is also called "ink repellent agent (A2 ⁾ ".

As the ink repellent agent (A ² ), it is preferably formed from a hydrolyzable silane compound mixture or a partially hydrolyzed condensate of the mixture, and the hydrolyzable silane compound mixture contains a hydrolyzable silane compound represented by the following formula (14) (hereinafter , also known as silane compound (a7).) or its partial hydrolysis condensate, and the hydrolyzable silane compound represented by the following formula (15) (hereinafter also referred to as silane compound (a8).) or its partial hydrolysis condensate .

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 the same as above,

Q ¹ : a divalent organic group with 1 to 10 carbon atoms not including a fluorine atom,

R ^H1 : a hydrocarbon group with 1 to 6 carbon atoms,

X ¹ , X ² : hydrolyzable groups,

p: 0, 1 or 2,

Among them, the three X ¹ in the formula (14), the (4-p) X ² in the formula (15), and the p R ^H1 may be different 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. When the content of fluorine atoms is within the above range, Excellent ink repellency and ink repellent ultraviolet resistance/ozone resistance can be provided to the partition obtained from the negative photosensitive resin composition.

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 per silicon atom, more preferably 0.2 to 2, and particularly preferably 0.5 to 1.5. When it is more than the lower limit of the said range, when forming a partition using a negative photosensitive resin composition, it can prevent that an ink repellent agent (A2) ^leaves from a board|substrate surface. The ink repellent agent (A ² ) is excellent in compatibility with a solvent and other components in the negative photosensitive resin composition as it is below the upper limit of the above-mentioned range.

It should be noted that the number of silanol groups in the ink repellent agent (A ² ) can be determined by the ratio of the peak areas of Si groups having silanol groups and Si groups not having silanol groups measured by ²⁹ Si-NMR. figured out.

The said hydrolyzable silane compound mixture contains a silane compound (a7) or its partial hydrolysis condensate, and a silane compound (a8) or its partial hydrolysis condensate.

The partially hydrolyzed condensate of a hydrolyzable silane compound refers to a high-molecular-weight polymer that is soluble in a solvent among oligomers (polymers) produced by hydrolyzing a polyfunctional hydrolyzable silane compound, followed by dehydration condensation . In addition, relatively low molecular weight polymers such as 2- to 4-mers of hydrolyzable silane compounds are also partial hydrolysis-condensation products in the present invention. The partially hydrolyzed condensate may have a silanol group formed by hydrolysis of a hydrolyzable group and an unreacted hydrolyzable group. A partially hydrolyzed condensate having a high molecular weight mainly has a silanol group, and a partially hydrolyzed condensate having a low molecular weight may also have a hydrolyzable group.

The partially hydrolyzed condensate has the property of being further condensed and hydrolyzed to finally become a high-molecular-weight cured product insoluble in a solvent. The partially hydrolyzed condensate may be a mixture of oligomers with different degrees of multimerization.

The partially hydrolyzed condensate can be produced, for example, by stirring a hydrolyzable silane compound under a predetermined reaction temperature condition for a predetermined time in the presence of an acid catalyst and water. The degree of multimerization of the obtained partially hydrolyzed condensate can be appropriately adjusted by acid concentration, reaction temperature, reaction time, and the like.

It should be noted that, regarding the molar ratio representing the ratio of the following hydrolyzable silane compounds, when at least one of the following hydrolyzable silane compounds is a partially hydrolyzed condensate, the above molar ratio is derived from each hydrolyzable silane The ratio of the number of silicon atoms in the compound.

(Hydrolyzable silane compound represented by formula (14))

The silane compound (a7) is a hydrolyzable silane compound having a group (1) as shown in the aforementioned formula (14). In the aforementioned formula (14), Q ¹ is a divalent organic group linking the group (1) and the hydrolyzable silyl group (-SiX ¹ ₃ ), and is a divalent organic group with 1 to 10 carbon atoms that does not include a fluorine atom. Organic based. When Q ¹ is expressed in the form that Si is bonded to the atom bond on the right side and R ^f -CFX- is bonded to the atom bond on the left side, specifically, -(CH ₂ ) _i1 - (i1 is 1 to 5.), -CH ₂ O(CH ₂ ) _i2 - (i2 is an integer from 1 to 4.), -SO ₂ NR ¹ -(CH ₂ ) _i3 - (R ¹ is a hydrogen atom, methyl or ethyl group, i3 is 1 or more, and the sum of carbon atoms of R ¹ is an integer of 4 or less.), -(C=O)-NR ¹ -(CH ₂ ) _i4 -(R ¹ is the same as above, i4 is 1 above, and the sum of the number of carbon atoms of R1 is ^an integer of 4 or less.) The group represented. As Q ¹ , -(CH ₂ ) _i1 - in which i1 is 2 or 3 is more preferred, and -(CH ₂ ) ₂ - is particularly preferred.

When the group (1) is a perfluoroalkyl group having 1 to 6 carbon atoms, Q ¹ is preferably a group represented by -(CH ₂ ) _i1 - (i1 is the same as above). i1 is preferably an integer of 2 to 4, and i1 is particularly preferably 2 -(CH ₂ ) ₂ -.

When the group (1) is a perfluoroalkyl group having 4 to 9 carbon atoms including an etheric oxygen atom, Q ¹ is preferably -(CH ₂ ) _i1 -, -CH ₂ O(CH ₂ ) _i2 - A group represented by -SO ₂ NR ¹ -(CH ₂ ) _i3 -, -(C=O)-NR ¹ -(CH ₂ ) _i4 - (i1 to i4 and R ¹ are the same as above). In this case, -(CH ₂ ) ₂ - is particularly preferable.

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. It is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, particularly preferably a methoxy group, an ethoxy group, or a chlorine atom. This group becomes a hydroxyl group (silanol group) through a hydrolysis reaction, and the reaction in which a Si—O—Si bond is formed through an intermolecular condensation reaction proceeds easily and 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 ) 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 them, 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 so on.

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.

Moreover, the said hydrolyzable silane compound mixture may contain the partial hydrolysis condensate of a silane compound (a7). However, the silane compound (a7) monomer is more preferable than the partial hydrolysis condensate.

(Hydrolyzable silane compound represented by formula (15))

The silane compound (a8) represented by the aforementioned formula (15) is used together with the above-mentioned silane compound (a7) as the hydrolyzable silane compound contained in the hydrolyzable silane compound mixture.

In 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 R ^H1 other than the alkyl group include alkenyl groups such as vinyl and allyl; and ring-containing hydrocarbon groups such as phenyl and cycloalkyl.

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, when p is 2, the two R ^H1 and (4-p) X ² may be different from each other or may be 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.

The ink repellent (A ² ) exhibits water repellency through the group (1) derived from the silane compound (a7) and R ^H1 derived from the silane compound (a8), and exhibits oil repellency mainly through the group (1) . In addition, in order to make the cured product of the ink repellent agent (A ² ) exhibit sufficient oil repellency, it is preferable that the group (1) in the ink ^repellent agent (A ² ) is The ratio of the sum is high. When p=0, the ratio of the group (1) in the ink repellent agent (A ² ) increases, oil repellency improves, and film-forming properties are excellent. When p=1 or 2, the ink repellent agent (A ² ) becomes easily soluble in the hydrocarbon solvent due to the presence of a certain amount of R ^H1 , and can be selected when forming a coating film of a negative photosensitive resin composition on the surface of the substrate. less expensive solvents.

As the silane compound (a8), the following compounds are preferable. In addition, instead of the silane compound (a8), a partial hydrolysis condensate of the silane compound (a8) can be used. As the partial hydrolysis condensate, a compound having a relatively low molecular weight is preferable. As a partial hydrolysis-condensation product, the following thing is mentioned, for example.

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 ,

Partially hydrolyzed condensate of Si(OCH ₃ ) ₄ (for example, MethylSilicate 51 (trade name) manufactured by COLCOAT CO., Ltd.),

Partially hydrolyzed condensate of Si(OCH ₂ CH ₃ ) ₄ (for example, EthylSilicate 40 and EthylSilicate 48 (both trade names) manufactured by COLCOAT CO., Ltd.).

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 in combination of 2 or more types, you may use a quaternary functional compound and/or a trifunctional compound and a bifunctional compound in combination.

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) relative to 1 mol of the silane compound (a7), particularly preferably 0.5 to 9 mol. Furthermore, hydrolyzable silane compounds other than silane compounds (a7) and silane compounds (a8) (hereinafter also referred to as silane compounds (a9)) and partial hydrolysis condensates of silane compounds (a9) may also be included.

(silane compound (a9))

As the silane compound (a9), any known silane can be used as long as it is a difunctional or trifunctional silane compound having a hydrolyzable group and co-condenses with the silane compound (a7) and the silane compound (a8). compound.

The silane compound (a9) is preferably a silane compound having a structure in which R ^H1 is replaced by a hydrocarbon group having 7 or more carbon atoms or a hydrocarbon group substituted with a reactive group in the formula (15). Wherein, when p in formula (15) is 2, one of the two R ^H1 may be R ^H1 . The reactive group is preferably a (meth)acryloyloxy group, an amino group, a hydrocarbon-substituted amino group, an epoxy group, or the like. Reactive groups having an ethylenic double bond, such as a (meth)acryloyloxy group, are especially preferable.

Preferred silane compounds (a9) are hydrolyzable silane compounds having reactive groups having ethylenic double bonds, particularly preferably trialkoxysilanes, dialkoxysilanes having (meth)acryloyloxy-substituted alkyl groups, base silane. The ink repellent agent (A2) which has an ethylenic ^double bond can be obtained by using the silane compound (a9) which has an ethylenic double bond.

Specific examples of the particularly preferable 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, particularly preferably 4 mol, based on 1 mol of the total amount of the silane compound (a7) and the silane compound (a8). the following.

In the hydrolyzable silane compound mixture, a monofunctional silane compound can be blended as the hydrolyzable silane compound. The monofunctional silane compound functions as a molecular weight regulator when the hydrolyzable silane compound mixture is hydrolyzed and condensed to form a partially hydrolyzed condensate. That is, it is used for the purpose of producing a partially hydrolyzed condensate having a low molecular weight, preventing the partially hydrolyzed condensate from becoming insoluble in a solvent due to an excessively high molecular weight, and the like. It is preferable to appropriately adjust the amount thereof to be used based on the molecular weight of the target partial hydrolysis condensate.

As the monofunctional silane compound, a compound having a structure in which p in the aforementioned formula (15) is 3, and hexaalkyldisiloxane are preferable. The alkyl group in these compounds preferably has 4 or less carbon atoms, and is particularly preferably methyl or ethyl.

The ink repellent agent (A ² ) used in the negative photosensitive resin composition of the present invention is preferably a hydrolyzable silane compound mixture or a partial hydrolyzed condensate of the above-mentioned raw materials, and is composed of various condensates with different degrees of polymerization, etc. A mixture of partially hydrolyzed condensates. That is, it is preferable that the ink repellent agent (A ² ) is a partially hydrolyzed condensate produced using a silane compound (a7) and a silane compound (a8) as an essential component, and optionally using a silane compound (a9). The partial hydrolysis condensate is preferably a condensate produced by mixing a silane compound (a7), a silane compound (a8), and an optional silane compound (a9), and then subjecting the mixture to partial hydrolysis and condensation. In addition, instead of silane compound (a7), silane compound (a8), and silane compound (a9), you may use each partial hydrolysis-condensation product.

The partially hydrolyzed condensate produced using the silane compound (a7) and the silane compound (a8) has a structure of the average composition formula represented by the following formula (16). However, it is actually a product (partially hydrolyzed condensate) in which a hydrolyzable group or a silanol group remains, so it is difficult to represent this product in a chemical formula. The average composition formula represented by formula (16) is a chemical formula when all hydrolyzable groups or silanol groups in the partially hydrolyzed condensate produced as described above are completely hydrolyzed and condensed to form siloxane bonds.

[R ^f -CFX-Q ¹ -SiO _3/2 ] _s ·[R ^H1 _p -SiO _(4-p)/2 ] _t (16)

In formula (16), preferable ranges of R ^f , R ^H1 , Q ¹ and p are the same as above. s and t are the average number of moles of each unit present in a plurality of partially hydrolyzed condensates having different degrees of polymerization.

It is estimated that units derived from the silane compound (a7) and the silane compound (a8) are randomly arranged in the partially hydrolyzed condensate having the structure of the average composition formula represented by formula (16). In addition, regarding s/t (molar ratio) in the average composition formula (16) when using a silane compound (a7) and a silane compound (a8), as an average value of the whole ink repellent agent (A2 ⁾ , The content of the silane compound (a7) relative to the silane compound (a8) in the hydrolyzable silane compound mixture is preferably within the above range, that is, 10/1 to 90 (molar ratio), particularly preferably 10/5 to 90 (molar ratio). Compare).

When the ink repellent (A ² ) is produced using a silane compound (a7), a silane compound (a8), and a silane compound (a9), the units derived from the silane compound (a9) in the formula (16) are further co-condensed The resulting average compositional structure.

As the ink repellent agent (A ² ), a partial hydrolysis condensate 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 compounds: 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-acryloxypropyltrimethoxysilane or 3-methacryloxypropyltrimethoxysilane.

(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-acryloxypropyltrimethoxysilane or 3-methacryloxypropyltrimethoxysilane,

Monofunctional silane compounds: hexamethyldisiloxane or trimethylmethoxysilane.

(combo 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-Glycidoxypropyltrimethoxysilane,

Monofunctional silane compounds: hexamethyldisiloxane or trimethylmethoxysilane.

It is considered that the ink repellent agent (A ² ) in the negative photosensitive resin composition of the present invention further condenses the silanol groups contained in the process of exposure, curing, etc. Ink-repellent partition wall.

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, particularly preferably less than 10,000. When a number average molecular weight (Mn) is more than the lower limit of the said range, when forming a partition using a negative photosensitive resin composition, it can prevent that an ink repellent agent (A2 ⁾ falls off from a board|substrate surface. When the number average molecular weight (Mn) is less than the upper limit of the above-mentioned range, the solubility in a solvent is favorable and the handleability 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 (A ² ))

When the ink repellent agent (A ² ) in the negative photosensitive resin composition of the present invention is a partially hydrolyzed condensate, it can be produced by hydrolyzing and partially condensing the above-mentioned hydrolyzable silane compound mixture (hereinafter also referred to as a reaction step.) . The hydrolysis and partial condensation are reactions in which a silanol group is formed by a hydrolysis reaction of a hydrolyzable group and a siloxane bond is formed by a dehydration condensation reaction of silanol groups as described above. In the reaction step, the reaction conditions generally used for the reaction of hydrolytic condensation of a hydrolyzable silane compound can be applied without particular limitation, for example, water, a catalyst, an organic solvent, etc. can be used.

When water is used in the reaction step, the amount is preferably 25 to 9900 parts by mass, particularly preferably 100 to 1900 parts by mass, relative to 100 parts by mass of the hydrolyzable silane compound mixture. Control of hydrolysis and condensation reaction becomes easy by making the quantity of water into the said range.

As a catalyst used in the reaction step, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as acetic acid, oxalic acid, and maleic acid are preferably used. 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, relative to 100 parts by mass of the hydrolyzable silane compound mixture.

An organic solvent can also be used in the above reaction step. As this organic solvent, the organic solvent normally used when hydrolyzing a hydrolyzable silane compound and performing condensation reaction, Specifically, the organic solvent mentioned in (manufacture of ^an ink repellent agent (A1)) can be used. An organic solvent may be used individually by 1 type, and may use it in combination of 2 or more types.

In the reaction step, the amount of the organic solvent is preferably 25 to 9900 parts by mass, particularly preferably 100 to 1900 parts by mass, relative to 100 parts by mass of the hydrolyzable silane compound mixture.

The obtained partial hydrolysis-condensation product is blended together with the solvent used in the reaction process to the negative photosensitive resin composition. Therefore, it is preferable to use the solvent which stabilized the silanol group in an ink repellent agent (A2 ⁾ as a solvent used in a reaction process. As a solvent which stabilizes a silanol group, the compound which has a hydroxyl group and the relative dielectric constant (ε) in 25 degreeC is 5-20 is mentioned.

Specifically, glycol-based monoalkyl ether acetate solvents, glycol-based monoalkyl ether solvents, ethylene glycol dimethyl ether (glyme)-based solvents, carbon atom 2 to 4 hydrocarbon-based alcohols and the like. More specifically, examples of glycol-based monoalkyl ether acetate solvents include propylene glycol monomethyl ether acetate (ε: 8.3); examples of glycol-based monoalkyl ether solvents include propylene glycol monomethyl ether ( ε: 12.3); Examples of hydrocarbon-based alcohols include 2-propanol (ε: 19.92) and the like. Propylene glycol monomethyl ether is particularly preferable from the viewpoint of high stabilization effect of silanol groups.

The reaction step is preferably carried out at a temperature from room temperature to the boiling point of the solvent under appropriate stirring conditions. The reaction time varies depending on the amount of raw material components used, the reaction temperature, stirring conditions, etc., but is generally 0.5 to 24 hours, preferably 1 to 10 hours. After completion of the reaction, the obtained ink repellent agent (A ² ) may be included in the negative photosensitive resin composition of the present invention without removing the organic solvent. After removing an organic solvent by a normal method, you may isolate|separate an ink repellent agent (A2 ⁾ , and you may make it contain in a negative photosensitive resin composition after that.

It is preferable that the content rate of the ink repellent agent (A) in the negative photosensitive resin composition of this invention is 0.01-10 mass % in the total solid content of a negative photosensitive resin composition.

When using an ink repellent agent (A1) as an ink repellent agent ( ^A ), its content is more preferably 0.05-5 mass %, Especially preferably, it is 0.2-1 mass %. When the content rate of an ink repellent agent (A) is more than the lower limit of the said range, the effect which reduces the surface tension of the partition formed is excellent and the partition excellent in ink repellency can be obtained. The adhesiveness of a partition and a base material becomes favorable that it is below the upper limit of the said range.

When using the ink repellent agent (A ² ) as the ink repellent agent (A), the content thereof is more preferably 0.1 to 6 mass %, particularly preferably 0.2 to 3 mass %. When the content of the ink repellent agent (A ² ) is in the above range, the storage stability of the negative photosensitive resin composition is excellent, and the ink repellency of the partition wall of the optical element obtained from the negative photosensitive resin composition is excellent, Has a smooth surface.

The ink repellent agent (A) of this invention may have both the side chain which has a group (1) and the side chain which has a group (2) in 1 molecule. In addition, the negative photosensitive resin composition of the present invention may also contain an ink repellent agent (A) having a side chain having a group (1) and an ink repelling agent (A) having a side chain having a group (2). ) of both. In these cases, the negative photosensitive resin composition can express high ink repellency and ink releasability.

[Photopolymerization initiator (B)]

The photopolymerization initiator (B) which is an oxime ester compound which has a nitro group in 1 molecule is contained in the negative photosensitive resin composition of this invention.

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 aralkyl group having 7 to 30 carbon atoms, or a cyano group. R ³² represents R ⁴¹ or OR ⁴² , and R ⁴¹ and R ⁴² represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, respectively. R ³³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl 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 above. a and b are each independently an integer of 0-3, and c is an integer of 1-3.

As R ³¹ , the hydrogen atom of the alkyl group, aryl group and aralkyl group can be further replaced by OR ⁴³ , COR ⁴⁴ , SR ⁴⁵ , NR ⁴⁶ R ⁴⁷ , -NCOR ⁴⁸ -OCOR ⁴⁹ , cyano group, halogen atom, -CR ⁵⁰ = CR ⁵¹ R ⁵² or -CO-CR ⁵³ = CR ⁵⁴ R ⁵⁵ 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 each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or an alkyl group with 2 to 20 carbon atoms. heterocyclyl.

As R ³² , the hydrogen atom of the alkyl group, aryl group and aralkyl group may be further substituted with a halogen atom.

The methylene group of the alkylene part of the substituent represented by R ³¹ , R ³³ , R ⁴³ to R ⁵⁵ above may be replaced by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or an amino group The formate bond is interrupted 1 to 5 times, the alkyl portion of the substituent may have a branched side chain, or may be a cyclic alkyl group, and the alkyl terminal of the substituent may be an unsaturated bond. R ³³ can also jointly form a ring with an adjacent benzene ring.

The oxime ester compound of the present invention has geometric isomers due to the double bond of the oxime, but there is no difference between them, and the formula (3) and the exemplified compounds described later represent a mixture of both or either, and are not limited to isomers Structure.

Examples of the alkyl group represented by R ⁴¹ to R ⁵⁵ above include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl , tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl , tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, vinyl, allyl, butenyl, ethynyl, propynyl , Methoxyethyl, Ethoxyethyl, Propoxyethyl, Pentyloxyethyl, Octyloxyethyl, Methoxyethoxyethyl, Ethoxyethoxyethyl, C Oxyethoxyethyl, methoxypropyl, 2-methoxy-1-methylethyl and the like.

Examples of the aryl group represented by R ⁴¹ to R ⁵⁵ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthracenyl, phenanthrenyl, and one place substituted with the above-mentioned alkyl groups. The above phenyl, biphenyl, naphthyl, anthracenyl, etc.

Examples of the aralkyl group represented by R ⁴¹ to R ⁵⁵ include benzyl, chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, styryl and the like.

As the heterocyclic group represented by R ⁴³ to R ⁵⁵ , preferably pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydro Pyranyl, pyrrolyl, imidazolidinyl, pyrazolyl, thiazolidinyl, isothiazolidinyl, oxazolidinyl, isoxazolidinyl, piperidinyl, piperazinyl, morpholinyl, etc. 5-7 Member heterocycle.

The ring that ^R33 can form together with an adjacent benzene ring includes cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, lactam ring, etc. 5-7 membered rings such as rings.

Examples of the halogen atoms that may substitute for R ⁴¹ to R ⁵⁵ and the halogen atoms represented by R ³⁴ and R ³⁵ include fluorine, chlorine, bromine, and iodine.

The methylene group of the alkylene part of the above-mentioned substituent can 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 carbamate bond. The bond group to be interrupted may be one type or two or more types of groups, and in the case of a group capable of continuous interruption, two or more groups may be continuously interrupted. In addition, the alkyl portion of the substituent may have a branched side chain or may be a cyclic alkyl group, and the alkyl terminal of the substituent may be an unsaturated bond.

Among the oxime ester compounds of the present invention, the following compounds are easy to synthesize and have high sensitivity, and when used as a photopolymerization initiator, they are preferably dissolved in a solvent at 1% by mass or more and satisfy the requirements as a photopolymerization initiator. The compound is: in formula (3), R ³¹ is an alkyl group with 11 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or an aralkyl group with 7 to 30 carbon atoms; R ³³ It is a compound of an alkyl group with 1 to 12 carbon atoms or an alkyl group with 13 to 20 carbon atoms interrupted 1 to 5 times by an ether bond or an ester bond; especially R31 is an alkane with ¹¹ to 20 carbon atoms or a compound of an aryl group with 6 to 30 carbon atoms; or a branched group with 8 or more carbon atoms in which the methylene group of the alkylene part where ^R33 is an alkyl group can be interrupted 1 to 5 times by an ether bond or an ester bond Alkyl compounds; R ³³ is an alkyl compound with 13 or more carbon atoms in which the methylene group of the alkylene part of the alkyl group can be interrupted 1 to 5 times by ether bonds or ester bonds; R ³³ is A compound with an alkyl group whose bond is interrupted 1 to 5 times; a compound where ^R33 is an alkyl group interrupted 1 to 5 times by an ester bond. The measurement of its solubility is preferably carried out 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 also be dimerized by R ³¹ or R ³² as shown in the following formula (4) and the following formula (5).

Specific examples of the oxime ester compound represented by formula (3) include compounds represented by the following compound Nos. 1 to 71.

The oxime ester compound represented by formula (3) can be produced by the following method according to the reaction formula of following formula (6), for example. First, the acyl compound 3 is obtained by reacting the nitrocarbazole compound 1 and the acid chloride 2 in the presence of zinc chloride. Next, the acyl compound 3 was reacted with hydroxylamine hydrochloride in the presence of DMF to obtain the oxime compound 4 . Next, the oxime compound 4 is reacted with the acid anhydride 5 or the acid chloride 5' to obtain the 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 mass %, more preferably 2 to 10 mass %, in the total solid content of the negative photosensitive resin composition %, particularly preferably 3 to 6% by mass. When it is the said range, curability is favorable, and the pattern and line width similar to a mask pattern can be formed in an exposure process and an image development process. In particular, even when the surface of the cured film is shielded from exposure light of 330 nm or less by a cut filter or the like, ink repellency is favorable even at a low exposure amount.

In the negative photosensitive resin composition of the present invention, photoinitiators other than the photoinitiator (B) may be used in combination.

Examples of photopolymerization initiators that can be used in combination include α-diketones such as benzil, diacetyl, methylphenylglyoxylate, and 9,10-phenanthrenequinone; and azoins such as benzoin. ; Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and other azoin ethers; Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethyl Thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, thioxanthone-4- Sulfonic acid and other thioxanthones; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone and other benzophenones Ketones; acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenyl Acetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)-butane-1-one and other acetophenones; anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone and other quinones; 2- Ethyl Dimethylaminobenzoate, Ethyl 4-Dimethylaminobenzoate, (n-Butoxy)ethyl 4-Dimethylaminobenzoate, Isoamyl 4-Dimethylaminobenzoate, 4 -Aminobenzoic acids such as 2-ethylhexyl dimethylaminobenzoate; halogen compounds such as phenacyl chloride and trihalomethylphenyl sulfone; acylphosphine oxides; di-tert-butyl peroxide Peroxides such as hydrogen oxide; 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), acetaldehyde 1-[9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime) and other oxime esters; triethanolamine, methyldiethanolamine, triisopropanolamine, Aliphatic amines such as n-butylamine, N-methyldiethanolamine, and diethylaminoethyl methacrylate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, Thiol compounds such as 1,4-butanol bis(3-mercaptobutyrate), tris(2-mercaptopropionyloxyethyl)isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), etc.

Among these, benzophenones, aminobenzoic acids, aliphatic amines, and thiol compounds are preferable because they may exhibit a sensitizing effect when used together with other photopolymerization initiators.

When a photopolymerization initiator other than the photopolymerization initiator (B) is contained in the negative photosensitive resin composition, the content ratio thereof is preferably 20 mass % or less in the total solid content of the negative photosensitive resin composition, more preferably It is 1-15 mass %, Especially preferably, it is 2-10 mass %.

[Alkali-soluble resin (C)]

The alkali-soluble resin (C) is not particularly limited, and examples thereof include a resin (C1-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy resin in which an acidic group has been introduced. A resin (C1-2) having a group and an ethylenic double bond, a monomer (C1-3) having a side chain having an acidic group and a side chain having an ethylenic double bond, etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

The resin (C1-1) can be synthesized by combining a copolymer having a side chain having a reactive group and a side chain having an acidic group with a functional group capable of bonding to the reactive group and an ethylenic bismuth The compound of the bond is dissolved in a solvent and reacted, and the copolymer having a side chain with a reactive group and a side chain with an acidic group is obtained by making the reactive group having a hydroxyl group, a carboxyl group, an epoxy group, etc. It is obtained by copolymerizing monomers with monomers having acidic groups.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (methyl) 4-hydroxybutyl acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, neopentyl glycol mono (Meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl Glycol monovinyl ether, 2-hydroxyethyl allyl ether, N-methylol(meth)acrylamide, N,N-bis(hydroxymethyl)(meth)acrylamide, etc.

Acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, these salts, etc. are mentioned as a monomer which has a carboxyl group. In addition, these monomers can also be used as a monomer which has an acidic group.

Examples of the monomer having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl acrylate, and the like.

Although it does not specifically limit as a monomer which has an acidic group, In addition to the said monomer which has a carboxyl group, as a monomer which has a phosphoric acid group, 2-(meth)acryloyloxyethane phosphoric acid etc. are mentioned.

Copolymerization of the above-mentioned monomer having a reactive group and a monomer having an acidic group can be performed according to a conventionally known method.

Examples of the monomer having a hydroxyl group as a reactive group include acid anhydrides having an ethylenic double bond, compounds having an isocyanate group and an ethylenic double bond, compounds having an acid chloride group and an ethylenic double bond, and the like.

Examples of acid anhydrides having ethylenic double bonds include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydro Phthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, etc.

Examples of compounds having an isocyanate group and an ethylenic double bond include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc. .

(meth)acryloyl chloride etc. are mentioned as a compound which has an acid chloride group and an ethylenic double bond.

As a monomer which has a carboxyl group as a reactive group, the compound which has an epoxy group and an ethylenic double bond is mentioned. Examples of such compounds include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl acrylate, and the like. Here, the carboxyl group may be introduced into the resin (C1-1) by reacting the generated hydroxyl group with an acid anhydride in which the dehydration condensation portion of the carboxylic acid becomes a part of the ring structure.

As a monomer which has an epoxy group as a reactive group, the compound which has a carboxyl group and an ethylenic double bond is mentioned. 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. Here, the carboxyl group may be introduced into the resin (C1-1) by reacting the generated hydroxyl group with the acid anhydride in which the dehydration condensation portion of the carboxylic acid becomes a part of the ring structure.

The 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 polyvalent carboxylic acid or an acid anhydride thereof.

Specifically, an ethylenic double bond is introduced into an 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 introduced by reacting the epoxy resin into which the ethylenic double bond was introduced with a polycarboxylic acid or an acid anhydride thereof.

The epoxy resin is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, and bisphenol novolak type epoxy resin. Oxygen resin, epoxy resin with naphthalene skeleton, epoxy resin with biphenyl skeleton represented by the following formula (C1-2a), epoxy resin represented by the following formula (C1-2b), epoxy resin with the following formula (C1- 2c) Epoxy resin with a biphenyl skeleton, etc.

(In the formula (C1-2a), v is 1 to 50, preferably 2 to 10. In addition, the hydrogen atoms of the benzene ring may be independently replaced by an alkyl group with 1 to 12 carbon atoms, a halogen atom, or may have a substituent phenyl substitution.)

(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 with 1 to 5 carbon atoms, and w is 0 to 10.)

(In the formula (C1-2c), the hydrogen atoms of the benzene ring may be independently substituted by an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent. u is 0 to 10.)

It should be noted that when the epoxy resin represented by the formulas (C1-2a) to (C1-2c) is reacted with a compound having a carboxyl group and an ethylenic double bond, and then reacted with a polycarboxylic acid anhydride, as a polycarboxylic acid anhydride, Preference is given to using mixtures of dicarboxylic anhydrides and tetracarboxylic dianhydrides. Molecular weight can be controlled by changing the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride.

Resin (C1-2) can use a commercial item. Commercially available products include KAYARADPCR-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 (above, manufactured by Nippon Kayaku Co., Ltd.), EX1010 (manufactured by Nagase ChemteX Corporation), etc.

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

As an alkali-soluble resin (C), it is possible to obtain a high-resolution pattern from the viewpoint of suppressing peeling of the coating film during development, from the viewpoint of good linearity of the line, to maintain the appearance after the post-baking process, and to easily obtain smoothness From the viewpoint of the surface of the coating film, the resin (C1-2) is preferably used.

As the resin (C1-2), particularly preferred are: resins in which an acidic group and an ethylenic double bond have been introduced into a bisphenol A epoxy resin, and resins in which an acidic group and an ethylenic double bond have been introduced into a bisphenol F epoxy resin. Resin with ethylenic double bond, resin with acidic group and ethylenic double bond introduced into phenol novolak type epoxy resin, resin with acidic group and ethylenic double bond introduced into cresol novolak type epoxy resin Resin, a resin in which an acidic group and an ethylenic double bond have been introduced into a trisphenolmethane type epoxy resin, an acidic group and a Resins with ethylenic double bonds.

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 . In addition, the number average molecular weight (Mn) is preferably 500 to 20×10 ³ , particularly preferably 1.0×10 ³ to 10×10 ³ . When mass average molecular weight (Mw) and number average molecular weight (Mn) are more than the lower limit of the said range, hardening at the time of exposure is sufficient, and when it is below the upper limit of the said range, developability is favorable.

The number of ethylenic double bonds that the alkali-soluble resin (C) has in 1 molecule is preferably 3 or more on average, particularly preferably 6 or more. When the number of ethylenic double bonds is more than the lower limit of the said range, the alkali solubility of an exposed part and a non-exposed part tends to differ, and a fine pattern can be formed with less 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, particularly preferably 50 to 100 mgKOH/g. The storage stability and developability of a negative photosensitive resin composition become favorable that an acid value exists in the said range.

The alkali-soluble resin (C) contained in a negative photosensitive resin composition may be 1 type, and may be a mixture of 2 or more types.

The content ratio of the alkali-soluble resin (C) in the negative photosensitive resin composition of the present invention is preferably 10 to 50% by mass, more preferably 12 to 40% by mass, in the total solid content of the negative photosensitive resin composition , particularly preferably 15 to 30% by mass. When the content ratio is within the above range, developability is favorable.

[Negative Photosensitive Resin Composition]

The negative photosensitive resin composition of the present invention contains an ink repellent (A), a photopolymerization initiator (B), an alkali-soluble resin (C), if necessary, a black colorant (D), and a polymer dispersant (E) , dispersing aid (F), crosslinking agent (G) and solvent (H). Further, the following thermal crosslinking agent (I), silane coupling agent (J), microparticles (K), phosphoric acid compound (L) and other additives may be contained.

By using the negative photosensitive resin composition of the present invention, even if the exposure light of 330 nm or less is blocked, a negative photosensitive resin composition with good ink repellency and good reproduction of the line width of the mask and the use of the combination can be produced. A homogeneous partition wall obtained from the material. Therefore, it is also possible to cope with the case where fine pattern formation is required. The reason for this is considered as follows.

As the photopolymerization initiator, a highly sensitive compound that effectively absorbs and is activated by exposure light exceeding 330 nm is required, and the photopolymerization initiator (B) can be selected.

According to the knowledge of the present inventors, when the exposure light of 330 nm or less is blocked, the hardening property of the surface of a partition will fall extremely, and the ink repellent part of a surface will fall off easily, and there exists a tendency for ink repellency to fall. If it is a negative photosensitive resin composition containing a photoinitiator (B), the curability of the surface of a partition can be improved. For the negative photosensitive resin composition containing a compound with poor migration to the surface of the partition as the ink repellent, when the surface of the partition is cured, the ink repellent has not completely moved to the surface of the partition, but by using the The ink repellent agent with favorable migration property on the partition wall surface becomes favorable in ink repellency.

The combination of an ink repellent agent and a photoinitiator (B) needs the viscosity and stable combination which can apply|coat a negative photosensitive resin composition other than said curability and surface migration property. According to the studies of the present inventors, the combination of the ink repellent agent (A) and the photoinitiator (B) was discovered.

[Black Colorant (D)]

The negative photosensitive resin composition of this invention contains a black coloring agent (D) further.

When a negative-type photosensitive resin composition is used to form a black matrix, which is a grid-like black portion surrounding pixels of three colors of R, G, and B in a color filter of a liquid crystal display element, it is preferable to contain a black colorant (D) .

Examples of the black colorant (D) include carbon black, aniline black, anthraquinone-based black pigments, and perylene-based black pigments, and specifically, C.I. Pigment Black 1, 6, 7, 12, 20, 31, and the like. Organic pigments such as red pigments, blue pigments, green pigments, and yellow pigments, or mixtures of azomethine-based black pigments and inorganic pigments can also be used. The black colorant (D) is preferably carbon black in terms of price and light-shielding properties, and the carbon black may be surface-treated with a resin or the like. In addition, in order to adjust the color tone, a blue pigment and a purple pigment may be used in combination. For black matrix on array type color filters and organic EL elements, coating films and partition walls with low dielectric constant and high resistance are required. In order to obtain the aforementioned coating film and partition wall, it is preferable to use a mixture of the above-mentioned organic pigments and an azomethine-based black pigment.

As carbon black, carbon black whose specific surface area is 50-200 m< ² >/g by the BET method is preferable from a viewpoint of the shape of a black matrix. When the specific surface area is 50 m ² /g or more, the shape of the black matrix is less likely to deteriorate. When it is 200 m ² /g or less, the carbon black does not excessively adsorb the dispersing aid, and it is not necessary to compound a large amount of the dispersing aid in order to express various physical properties.

In addition, as carbon black, from the viewpoint of sensitivity, carbon black having an oil absorption of dibutyl phthalate of 120 cc/100 g or less is preferable, and the smaller the oil absorption, the more preferable.

Furthermore, it is preferable that the average primary particle diameter of carbon black by transmission electron microscope observation is 20-50 nm. When the average primary particle diameter is 20 nm or more, it is easy to obtain a negative photosensitive resin composition capable of dispersing at a high concentration in the negative photosensitive resin composition and having good temporal stability. When it is 50 nm or less, the shape of a black matrix is hard to deteriorate. Moreover, as an average secondary particle diameter by transmission electron microscope observation, it is preferable that it is 80-200 nm.

When the negative photosensitive resin composition of the present invention contains a black colorant (D) and is used for forming a black matrix, etc., the content ratio of the black colorant (D) in the negative photosensitive resin composition is preferably between It is 15-80 mass % in the total solid content of a negative photosensitive resin composition, More preferably, it is 20-70 mass %, Especially preferably, it is 25-65 mass %. When it is the said range, the sensitivity of the negative photosensitive resin composition obtained is favorable, and the light-shielding property of the partition formed is excellent.

[Polymer dispersant (E)]

When the negative photosensitive resin composition contains a dispersible material such as the above-mentioned black colorant (D), it is preferable to contain a polymer dispersant (E) in order to improve its dispersibility. The polymer dispersant (E) is not particularly limited, and examples thereof include urethane-based, polyimide-based, alkyd-based, epoxy-based, polyester-based, melamine-based, phenol-based, acrylic-based, poly Ether-based, vinyl chloride-based, vinyl chloride-vinyl acetate-based copolymer-based, polyamide-based, polycarbonate-based, etc., preferably urethane-based or polyester-based. In addition, the polymer dispersant (E) may have a structural unit derived from ethylene oxide and/or propylene oxide.

When using a polymer dispersant (E) for dispersing a black colorant (D), it is preferable to use a polymer dispersant (E) having a basic group in consideration of affinity for the black colorant (D). Although it does not specifically limit as a basic group, A primary amino group, a secondary amino group, or a tertiary amino group is mentioned.

A commercial item can also be used as a polymer dispersant (E). Examples of commercially available products include DISPARLONDA-7301 (trade name, manufactured by Kusumoto Kasei Co., Ltd.); BYK161, BYK162, BYK163, BYK182 (all of the above are brand names, manufactured by BYK-Chemie K.K.), SOLSPERSE5000, SOLSPERSE17000 (above All are trade names, manufactured by Zeneca Inc.), etc.

The content ratio of the polymer dispersant (E) is preferably 5 to 30% by mass, particularly preferably 10 to 25% by mass, based on the black colorant (D). When it is more than the lower limit of the said range, the dispersibility of a black coloring agent (D) will improve, and when it is below the upper limit of the said range, the developability of a negative photosensitive resin composition will become favorable.

[Dispersion aid (F)]

The negative photosensitive resin composition may further contain a phthalocyanine pigment derivative and a metal phthalocyanine sulfonamide compound as a dispersion aid (F). It is considered that the dispersing aid (F) is adsorbed to dispersing materials such as the black colorant (D) and the polymer dispersant (E), and has a function of improving dispersion stability.

[Crosslinking agent (G)]

The negative photosensitive resin composition of the present invention may further contain a crosslinking agent (G) as an optional component that promotes radical curing. As a crosslinking agent (G), it is preferable that it is a compound which has 2 or more ethylenic double bonds in 1 molecule, and does not have an acidic group. By making the negative photosensitive resin composition contain a crosslinking agent (G), the hardening property of the said alkali-soluble resin (C) at the time of exposure improves, and the exposure dose 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 not having an acidic group is not particularly limited as long as it is a compound that meets this condition, and examples include diethylene glycol bis(methyl) Acrylates, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate ester, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta (Meth)acrylates, dipentaerythritol hexa(meth)acrylate, ethoxylated isocyanurate triacrylate, ε-caprolactone modified tris-(2-acryloyloxyethyl)isocyanate Urate, 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, etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

A commercial item can be used as a crosslinking agent (G). Examples of commercially available products include KAYARADDPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NKESTERA-9530 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)), V#802 (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd., mixture of dipentaerythritol acrylate, tripentaerythritol acrylate, tetrapentaerythritol acrylate), NKESTERA -9300 (trade name, Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanurate triacrylate), NKESTERA-9300-1CL (trade name, Shin-Nakamura Chemical Co., Ltd., ε-caprolactone modified Xingtris-(2-acryloyloxyethyl)isocyanurate), BANI-M (trade name, manufactured by Maruzen Petrochemical Co., Ltd., bis{4-(allylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboximide)phenyl}methane), BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd., N,N'-m-xylylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)), etc. Urethane acrylates include KAYARADUX SERIES manufactured by Nippon Kayaku Co., Ltd., and specific brand names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, and UX -5002D-P20 etc.

Among these, KAYARADDPHA and NKESTERA-9530 are preferable for the reason of improving the sensitivity of the cured film obtained from a negative photosensitive resin composition. NKESTERA-9300, BANI-M, and BANI-X are preferable from the viewpoint of imparting hardness to a cured film and suppressing thermal sagging. NKESTERA-9300-1CL is preferable from the viewpoint of providing flexibility to a cured film. Urethane acrylate is preferable since moderate developing time can be realized and developability becomes favorable.

The content ratio 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 of the negative photosensitive resin composition , particularly preferably 7 to 15% by mass. The alkali developability of a negative photosensitive resin composition becomes favorable as it is the said range.

[Solvent (H)]

The negative photosensitive resin composition of this invention contains a solvent (H) as needed. When a solvent (H) is contained, since the viscosity of a negative photosensitive resin composition falls, it becomes easy to coat the board|substrate of a negative photosensitive resin composition. A uniform coating film of a negative photosensitive resin composition 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 is the same as the film of a negative photosensitive resin composition.

The solvent (H) contained in the negative photosensitive resin composition of the present invention has the above-mentioned ink repellent agent (A), photopolymerization initiator (B), alkali-soluble resin ( C), if necessary, black colorant (D), polymer dispersant (E), dispersion aid (F) and crosslinking agent (G), and any components described later are uniformly dissolved or dispersed, so that the negative The photosensitive resin composition has the function of uniform and simple coating on the substrate forming the partition wall, and it has no reactivity with these components, so there is no particular limitation. For example, it can be used in the synthesis of The same solvent as the solvent used.

The content ratio of the solvent (H) contained in the negative photosensitive resin composition varies depending on the composition, application, etc. of the negative photosensitive resin composition, and it is preferable to mix 50 to 99% by mass of the negative photosensitive resin composition. %, more preferably 60 to 95% by mass, particularly preferably 65 to 90% by mass.

The negative photosensitive resin composition of the present invention contains an ink repellent (A), a photopolymerization initiator (B), an alkali-soluble resin (C), if necessary, a black colorant (D), and a polymer dispersant (E) , dispersing aid (F), crosslinking agent (G) and solvent (H). Further, the following thermal crosslinking agent (I), silane coupling agent (J), microparticles (K), phosphoric acid compound (L) and other additives may be contained.

[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), increases the crosslinking density of the cured film, and improves heat resistance.

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

The content ratio of the thermal crosslinking agent (I) in the negative photosensitive resin composition of the present invention is preferably 1 to 50 mass %, particularly preferably 5 to 30 mass %, in the total solid content of the negative photosensitive resin composition %. The developability of the negative photosensitive resin composition obtained as it is the said range becomes favorable.

[Silane coupling agent (J)]

When a silane coupling agent (J) is used, the base material adhesiveness of the cured film formed from the obtained negative photosensitive resin composition will improve.

Specific examples of the silane coupling agent (J) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3 -Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and the like. These may be used individually or in combination of 2 or more types.

A commercial item can be used as a silane coupling agent (J). As a commercial item, KBM5013 (trade name, Shin-Etsu Chemical Co., Ltd. make, 3-acryloyloxypropyltrimethoxysilane) etc. are mentioned.

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, particularly preferably 1 to 10% by mass, based on the total solid content of the negative photosensitive resin composition. . The base material adhesiveness of the cured film formed from a negative photosensitive resin composition improves that it is more than the lower limit of the said range, and ink repellency becomes favorable when it is below the upper limit of the said range.

[Particles (K)]

The negative photosensitive resin composition may contain fine particles (K) as needed. By blending fine particles (K), it is possible to prevent thermal sagging of the partition wall obtained from the negative photosensitive resin composition.

The particles (K) are not particularly limited, and include inorganic particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO); polyethylene, polymethyl Organic microparticles such as methyl acrylate (PMMA) are preferably inorganic microparticles in consideration of heat resistance, and particularly preferably silica or zirconia in consideration of availability and dispersion stability. In addition, when the negative photosensitive resin composition contains the black colorant (G) and the polymer dispersant (E), it is preferable that the fine particles (K) be negatively charged in consideration of the adsorption capacity of the polymer dispersant (E). Furthermore, if the exposure sensitivity of the negative photosensitive resin composition is considered, it is preferable that the microparticles do not absorb the irradiated light during exposure, and particularly preferably do not absorb i-rays (365nm) and h-rays ( 405nm), g-rays (436nm).

The fine particles (K) are preferably silica. As silica, colloidal silica is preferred. Generally, colloidal silica includes a silica hydrosol dispersed in water and an organosilica sol in which water is replaced by an organic solvent, and an organosilica sol in which an organic solvent is used as a dispersion medium is preferable.

As such an organosilica sol, a commercially available product can be used, and one of the following products manufactured by Nissan Chemical Industry Co., Ltd. under the trade name PMA-ST (silica particle size: 10 to 20 nm, Silica solid content: 30% by mass, propylene glycol monomethyl acetate: 70% by mass.), NPC-ST (silica particle size: 10-20nm, silica solid content: 30% by mass, n-propyl Cellosolve: 70 mass %.), IPA-ST (silica particle diameter: 10-20 nm, silica solid content: 30 mass %, IPA: 70 mass %.), etc.

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

[Phosphoric acid compound (L)]

The negative photosensitive resin composition may also contain a phosphoric acid compound (L) as needed. By making the negative photosensitive resin composition contain a phosphoric acid compound (L), the adhesiveness of a negative photosensitive resin composition and a board|substrate can be improved. Examples of the phosphoric acid compound (L) include mono(meth)acryloyloxyethyl phosphate, di(meth)acryloyloxyethyl phosphate, and tri(meth)acryloyloxyethyl phosphate. Esters etc.

[Other additives]

The negative photosensitive resin composition of the present invention may further contain a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, an anti-repellent agent, an ultraviolet absorber, and the like as necessary.

[Preferred Combination of Negative Photosensitive Resin Composition]

It is preferable to select a composition and a compounding ratio of the negative photosensitive resin composition of this invention according to a use and required characteristics.

The preferable composition of various compounding components in the negative photosensitive resin composition of this invention is shown below.

Ink repellent (A): Preferred combinations 1 to 5 of the aforementioned ink repellent (A ¹ ) or preferred combinations 6 to 10 of the aforementioned ink repellent (A ² ), in the total solid content of the negative photosensitive resin composition 0.01 to 10% by mass;

Photopolymerization initiator (B): Compound Nos. 1 to 58 described in International Publication No. 2008/078678, 0.01 to 10% by mass in the total solid content of the negative photosensitive resin composition;

Alkali-soluble resin (C): Composed of resins selected from (C1-2a), (C1-2b), (C1-2c) and cresol novolac type epoxy resins with acid groups and ethylenic double bonds introduced At least one of the group of 12 to 40% by mass in the total solid content of the negative photosensitive resin composition;

Solvent (H): selected from 2-propanol, γ-butyrolactone, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, propylene glycol At least one kind selected from the group consisting of monomethyl ether acetate, cyclohexanone, and butyl lactate is 50 to 99% by mass in the negative photosensitive resin composition.

[Manufacturing method of negative photosensitive resin composition]

As a method of producing a negative photosensitive resin composition, an ink repellent (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a black colorant (D), and a polymer dispersant ( E), dispersing aid (F), crosslinking agent (G) and solvent (H), and then, preferably, with the following thermal crosslinking agent (I), silane coupling agent (J), microparticles (K ), a method of mixing phosphoric acid compound (L) and other additives.

The negative photosensitive resin composition of the present invention is used as a material for photolithography and the like in the same way as a general negative photosensitive resin composition, and the cured film obtained by curing the coating film of the composition can be used as a A component of an optical element of a cured film of a negative photosensitive resin composition.

[Manufacturing method of partition wall for optical element]

Applied to the manufacture of partitions for optical elements that have a plurality of pixels on a substrate and partitions between adjacent pixels.

The negative photosensitive resin composition of the present invention is coated on the above-mentioned substrate to form a coating film (coating film forming process), then, the above-mentioned coating film is heated (pre-baking process), and then only the Part of the partition wall is exposed to light to cure (exposure process), and then, the coating film other than the above-mentioned photo-cured part is removed to form a partition wall formed by the photo-cured part of the above-mentioned coating film (development process), and then , by heating the partition wall formed above (post-baking process), the partition wall for optical elements 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 in the form of a black matrix.

The material of the substrate is not particularly limited, and for example, various glass plates can be used; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethacrylic acid Thermoplastic sheets such as methyl ester, polysulfone, polyimide, and poly(meth)acrylic resins; cured sheets of thermosetting resins such as epoxy resins and unsaturated polyesters, etc. In particular, from the viewpoint of heat resistance, heat-resistant plastics such as glass plates and polyimide are preferable.

FIG. 1 is a schematic cross-sectional view showing a production example of a partition for an optical element using the negative photosensitive resin composition of the present invention. (I) of FIG. 1 is a figure which shows the cross section of the state which formed the coating film 2 which consists of the negative photosensitive resin composition of this invention on the board|substrate 1. (II) is a schematic diagram showing the exposure process. (III) is a cross-sectional view showing the substrate 1 and the partition walls 6 formed on the substrate after the development step.

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 forming process)

As shown in the cross section of FIG. 1(I), the above-mentioned negative photosensitive resin composition of the present invention is coated on a substrate 1 to form a coating film 2 made of the negative photosensitive resin composition. It should be noted that, before forming the coating film 2 of the negative photosensitive resin composition on the substrate 1, it is preferable to clean the coated surface of the negative photosensitive resin composition of the substrate 1 with alcohol cleaning, ultraviolet/ozone cleaning, etc. .

The coating method of the negative photosensitive resin composition is not particularly limited as long as it can form a coating film with a uniform film thickness, and examples thereof include spin coating method, spray coating method, slit coating method, A roll coating method, a spin coating method, a bar coating method, and the like are used for general coating film formation.

The film thickness of the coating film 2 is determined according to the height of the finally obtained partition. The film thickness of the coating film 2 is preferably 100 to 3000% of the height of the finally obtained partition, particularly preferably 100 to 2000%. The film thickness of the coating film 2 is preferably 0.3 to 325 μm, particularly preferably 1.3 to 65 μm.

(pre-baking process)

The coating film 2 formed on the substrate 1 in the above coating film forming step is heated to obtain the film 2 . By heating, the volatile components contained in the negative photosensitive resin composition constituting the coating film, including the solvent, are volatilized and removed to obtain a non-adhesive film. In addition, the ink repellent agent (A) migrates to the vicinity of the coating film surface. As a method of heating, a method of heat-treating the substrate 1 and the coating film together at 250 to 120° C. for about 10 to 2000 seconds using a heating device such as a hot plate or an oven is exemplified.

It should be noted that volatile components such as solvents can also be removed by heating in the prebaking process as described above, but a vacuum other than heating (drying) can also be provided before the prebaking process in order to remove volatile components such as solvents. Drying and other drying processes. In addition, in order to dry efficiently without causing unevenness in the appearance of the coating film, it is more preferable to use heating and vacuum drying in combination with drying by the above-mentioned prebaking step. The conditions of vacuum drying also vary depending on the type of each component, the compounding ratio, etc., but it is preferable to carry out in a wide range of about 10 to 300 seconds at 500 to 10 Pa.

(Exposure process)

As shown in (II) of FIG. 1 , the film 2 is irradiated with light 5 through a mask 4 having a predetermined pattern. The light 5 reaches the film on the substrate 1 only through the predetermined pattern portion divided by the mask 4 , and only this portion undergoes photocuring. Therefore, when forming the partition wall, the above-mentioned predetermined pattern is provided in a shape suitable for the shape of the partition wall.

For example, the average width of the partition walls after the post-baking step is preferably 100 μm or less, particularly preferably 20 μm or less. In addition, the average distance between adjacent partition walls is preferably 500 μm or less, particularly preferably 300 μm or less. It is preferable to use a mask patterned in such a manner as to achieve the above-mentioned range.

In (II) of FIG. 1 , the exposed portion 3 of the film irradiated with light is formed by a cured film of the negative photosensitive resin composition, and on the other hand, the unexposed portion is an uncured film of the negative photosensitive resin composition. 2 The remaining state of itself.

Examples of the light 5 to be irradiated include visible light; ultraviolet light; far ultraviolet light; KrF excimer laser, ArF excimer laser, F2 excimer laser, _Kr2 excimer laser, _KrAr excimer laser, _Ar2 excimer laser, etc. Excimer laser; X-ray; electron beam, etc. In addition, as the irradiation light 5, it is preferably an electromagnetic wave with a wavelength of 100 to 600 nm, more preferably a light with a distribution in the range of 300 to 500 nm, particularly preferably i-ray (365 nm), h-ray (405 nm) and g-ray (436 nm). ). In addition, for example, when using the exposure method in the mirror projection (MPA) method, the electromagnetic wave of 330 nm or less is shielded, and exposure light is irradiated. Thus, in the manufacturing method of this invention, you may perform exposure which shields the electromagnetic wave of 330 nm or less as needed.

As the irradiation device, a known ultra-high pressure mercury lamp or the like can be used. The exposure amount is based on i-rays when electromagnetic waves of 330 nm or less are blocked by a cut filter or the like, and is preferably 5 to 1000 mJ/cm ² , more preferably 5 to 200 mJ/cm ² , and even more preferably 10 to 100 mJ/cm ² , Particularly preferably, it is 15 to 50 mJ/cm ² . When an exposure amount is more than the lower limit of the said range, hardening of the negative photosensitive resin composition used as a partition is sufficient, and it is hard to melt and peel from the board|substrate 1 in the subsequent image development. High resolution can be obtained as it is below the upper limit of the said range. Even when the surface of the cured film obtained from the negative photosensitive resin composition of the present invention blocks electromagnetic waves of 330 nm or less by a cut filter or the like, ink repellency is particularly favorable.

The exposure time also varies depending 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, particularly preferably 5 to 20 seconds.

(developing process)

Development is performed using a developer to remove the unexposed portion 2 on the substrate 1 shown in (II) of FIG. 1 . Thereby, the structure of the board|substrate 1 and the partition wall 6 formed with the cured film of the negative photosensitive resin composition on the board|substrate 1 like the cross-sectional view shown in FIG. 1 (III) is obtained. In addition, 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 inkjet optical element through a post-baking step described later.

As a developing solution, an aqueous alkali solution containing alkalis such as inorganic alkalis, amines, alcoholamines, and quaternary ammonium salts can be used. In addition, organic solvents such as surfactants and alcohols may be added to the developing solution in order to improve solubility and remove residues.

The development time (time of contact with the developer) is preferably 5 to 180 seconds. In addition, examples of the image development method include a stirring method, a dipping method, a shower method, and the like. Water on the substrate 1 and the partition wall 6 can be removed by performing high-pressure water washing, running water washing, and air-drying with compressed air or compressed nitrogen after the development.

In addition, the film thickness change of the cured film at the portion serving as the partition before and after the developing step is preferably 60 nm or less, more preferably 50 nm, particularly preferably 45 nm or less. When the film thickness change is 60 nm or less, the ink repellency layer for expressing the ink repellency of the surface layer of the cured film after exposure sufficiently remains on the surface, and the ink repellency of the cured film after post-baking becomes favorable.

(post-baking process)

The partition wall 6 on the substrate 1 is heated. As a heating method, the method of heat-processing the board|substrate 1 and the partition wall 6 together at 150-250 degreeC for 5 to 90 minutes is mentioned using a heating apparatus, such as a hot plate and an oven. By heat treatment, the partition wall 6 formed of the cured film of the negative photosensitive resin composition on the substrate 1 is further cured, and the shape of the dot 7 surrounded by the partition wall 6 and the substrate 1 is further fixed. In addition, it is especially preferable that the said heating temperature is 180 degreeC or more. When the heating temperature is too low, the curing of the partition wall 6 is insufficient, so sufficient chemical resistance cannot be obtained, and when the ink is injected into the dots 7 in the subsequent inkjet coating process, there may be a problem due to the solvent contained in the ink. However, there is a fear that the partition wall 6 may swell or the ink may bleed. On the other hand, when the heating temperature is too high, there is a possibility that the partition wall 6 may be thermally decomposed.

The average width of the partition walls of the negative photosensitive composition of the present invention is preferably 100 μm or less, particularly preferably 20 μm or less. In addition, the average distance between adjacent partition walls (dot width) is preferably 500 μm or less, particularly preferably 300 μm or less. Moreover, it is preferable that the average of the height of a partition is 0.05-50 micrometers, and it is especially preferable that it is 0.2-10 micrometers.

The ink repellency of the cured coating film formed from the negative photosensitive resin composition of the present invention can be estimated using 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. In addition, the contact angle of PGMEA is preferably 30 degrees or more, more preferably 35 degrees or more, and particularly preferably 40 degrees or more. In the ink repellency of the cured film of the coating film, it is particularly preferable that the contact angle of water is 90 degrees or more and the contact angle of PGMEA is 30 degrees or more.

[Manufacturing method of optical element]

After the partition wall is formed on the substrate by the above-mentioned manufacturing method, the surface of the substrate exposed in the area surrounded by the above-mentioned substrate and the above-mentioned partition wall is subjected to an ink-attracting treatment (ink-attracting treatment process), and then, the ink-jet method is applied to the above-mentioned Ink is injected into the region to form the above-mentioned pixels (ink injection step). In addition, in the manufacture of an optical element, the ink affinity treatment step is not an essential step, and the ink affinity treatment step may not be performed depending on the optical element to be manufactured.

(ink affinity treatment process)

As the method of the ink affinity treatment, methods such as washing treatment with an aqueous alkali solution, ultraviolet washing treatment, ultraviolet light/ozone washing treatment, excimer washing treatment, corona discharge treatment, and oxygen plasma treatment are mentioned.

The cleaning treatment with an alkaline aqueous solution is a wet process for cleaning the substrate surface with an alkaline aqueous solution (potassium hydroxide, tetramethylammonium hydroxide aqueous solution, etc.).

Ultraviolet cleaning treatment is a dry treatment that uses ultraviolet rays to clean the substrate surface.

Ultraviolet/ozone cleaning treatment is a dry treatment that uses low-pressure mercury lamps that emit light of 185nm and 254nm to clean the substrate surface.

The excimer cleaning process is a dry process for cleaning the substrate surface using a xenon excimer lamp emitting light of 172 nm.

Corona discharge treatment is a dry treatment that uses high frequency and high voltage to generate corona discharge in the air and clean the surface of the substrate.

Oxygen plasma treatment is a dry treatment that mainly uses a high-frequency power source in a vacuum to excite oxygen and put it in a highly reactive "plasma state" to clean the surface of the substrate.

As the method of the ink affinity treatment, dry treatment methods such as ultraviolet light/ozone cleaning treatment are preferable from the viewpoint of simplicity. UV/ozone can be generated using commercially available equipment. The ink-attracting treatment can be performed by placing the substrate with the partition wall inside the ultraviolet/ozone device, and performing treatment for about 1 to 10 minutes in the air at room temperature within a range that does not impair the oil repellency of the partition wall. In addition, what is necessary is just to adjust to the time of the range which does not impair the oil repellency of a partition according to each ultraviolet/ozone apparatus about processing time.

By this ink-attracting treatment, impurities and the like remaining in the dots after the formation of the above-mentioned partition walls are sufficiently removed, so that the dots can be sufficiently ink-attained, and white spots in color display devices using the obtained optical element can be prevented. Phenomenon.

(Ink injection process)

The ink injection step is a step of injecting ink into dots after the ink affinity treatment step by an inkjet method to form pixels. This step can be performed in the same manner as a normal method using an inkjet device generally used in the inkjet method. The inkjet device used in the formation of such pixels is not particularly limited, and an inkjet device that utilizes the following methods: a method of continuously ejecting charged ink and controlling it with a magnetic field; intermittently ejecting ink using a piezoelectric element Various methods such as a method of ink; a method of intermittently ejecting ink by heating and foaming it.

As an optical element manufactured using the negative photosensitive resin composition of this invention, a color filter, an organic electroluminescent display element, an organic TFT array, etc. are mentioned.

[production of color filter]

The formation of the partition, the ink affinity treatment of the dots, and the ink injection by the inkjet method are as described above. In the color filter, the shape of the pixels formed may be any known arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type.

The ink used to form pixels mainly contains a coloring component, a binder resin component, and a solvent. As the coloring component, pigments and dyes excellent in heat resistance, light resistance, etc. are preferably used. The binder resin component is preferably transparent and excellent in heat resistance, and examples thereof include acrylic resins, melamine resins, and urethane resins. The water-based ink contains water and, if necessary, a water-soluble organic solvent as a solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary. In addition, the oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.

In addition, it is preferable to perform drying, heat curing, and ultraviolet curing as necessary after injecting the ink by the inkjet method.

After forming the pixels, a protective film layer is formed as necessary. It is preferable to form a protective film layer for the purpose of improving the flatness of the surface and for the purpose of blocking eluted substances in the ink from the partition wall and the pixel portion from reaching the liquid crystal layer. When forming a protective film layer, it is preferable to remove the ink repellency of a partition beforehand. When ink repellency is not removed, since the coating liquid for overcoat layers will be repelled and a uniform film thickness cannot be obtained, it is unpreferable. As a method of removing the ink repellency of a partition, a plasma ashing process, a photo-ashing process, etc. are mentioned.

Furthermore, it is preferable to form a photo-spacer on the black matrix which consists of partition walls in order to improve the quality of the liquid crystal panel manufactured using a color filter as needed.

[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 if necessary. Next, the negative-type photosensitive resin composition of the present invention is used to form a partition, and after the dots are subjected to ink affinity treatment, the dots are sequentially coated with a solution of a hole transport material and a luminescent material using an inkjet method and dried to form a void. Hole transport layer, light emitting layer. Thereafter, an electrode of aluminum or the like is formed by a vapor deposition method or the like to obtain a pixel of an organic EL display element.

[Manufacture of organic TFT array]

An organic TFT array can be manufactured through the following steps (i) to (iii).

(i) A partition is formed on transparent base materials, such as glass, using the negative photosensitive resin composition of this invention. After the ink affinity treatment of the dots, a solution of a gate electrode material 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. Use the negative photosensitive resin composition of the present invention to form a partition wall on the gate insulating film, perform ink affinity treatment on the dots, apply a solution of the source-drain electrode material to the dots using the inkjet method, and form the source-drain electrodes .

(iii) After forming the source-drain electrodes, the negative-type photosensitive resin composition of the present invention is used to form a partition so as to surround a region including a pair of source-drain electrodes, and after the ink affinity treatment of the dots, use The inkjet method applies a dotted solution of an organic semiconductor to form an organic semiconductor layer between source and drain electrodes.

In addition, (i)-(iii) may utilize the partition using the negative photosensitive resin composition of this invention only in each process, and may utilize and use it in two or more processes. The partition wall of the negative photosensitive resin composition of this invention.

[Manufacture of organic EL lighting elements]

It can manufacture in the same manner as the manufacture of an organic EL display element. In the luminescent layer, luminous bodies emitting various colors such as red, green, and blue may be laminated by inkjet, or the luminous bodies may be separately coated on a flat surface.

Example

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In addition, Examples 1-21 are an Example, and Examples 31-33 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 content rate of the fluorine atom in an ink repellent agent (A) made 1, 4- bis (trifluoromethyl) benzene a standard substance, and calculated by measuring by ¹⁹ FNMR. The quantity of the ethylenic double bond in an ink repellent agent (A) made 1, 4- bis (trifluoromethyl) benzene a standard substance, and calculated by ¹ HNMR measurement.

The acid value (mgKOH/g) and the number of ethylenic double bonds in one molecule are theoretical values calculated from the compounding ratio of the raw material monomers.

Abbreviations of compounds used in Synthesis Examples and Examples are as follows.

(Compound used for synthesis of ink repellent (A ¹ ))

MEK: 2-butanone.

C6FMA: _CH2 =C( _CH3 ) _COOCH2CH2 ( _{CF2 ) 6F} .

MAA: methacrylic acid.

MMA: methyl methacrylate.

PME400: BLEMMERPME-400 (manufactured by NOF Corporation. α-methyl-ω-methacryloyloxypoly(ethylene oxide). CH ₂ =C(CH ₃ )COO(CH ₂ CH ₂ O) _k CH ₃ : The k in the formula represents the average value between molecules, and the value of k is about 9.).

PME1000: BLEMMERPME-1000 (manufactured by NOF Corporation. α-methyl-ω-methacryloyloxypoly(ethylene oxide). CH ₂ =C(CH ₃ )COO(CH ₂ CH ₂ O) _k CH ₃ : The k in the formula represents the average value between molecules, and the value of k is 23.).

V-65: brand 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 Co., Ltd., brand name: Karenz AOI.).

DBTDL: dibutyltin dilaurate.

TBQ: tert-butyl-p-benzoquinone.

(Compound used in the synthesis of ink repellent (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 CO., Ltd.).

Compound (a9-1): CH ₂ =CHCOO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ (manufactured by Tokyo Chemical Industry 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))

Compounds represented by the above-mentioned 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. 53-58 .

(Photopolymerization initiators other than photopolymerization initiator (B))

OXE02: Acetaldehyde 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime) (manufactured by Ciba Specialty Chemicals Corp., brand name : OXE02.).

IR907: brand name; IRGACURE907, manufactured by BASF Corporation, 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: A resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin represented by the upward formula (C1-2b) (manufactured by Nagase ChemteX Corporation, trade name: EX-1010. Solid content: 60% by mass, PGMEA: 40% by mass .).

ZCR1761: A resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the upward formula (C1-2a) (manufactured by Nippon Kayaku Co., Ltd., trade name: ZCR-1761H. Solid content : 60% by mass, PGMEA: 40% by mass.).

ZCR1642: A resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the upward formula (C1-2a) (manufactured by Nippon Kayaku Co., Ltd., trade name: ZCR-1642H. Solid content : 60% by mass, PGMEA: 40% by mass.).

C-1: Reaction of cresol novolac type epoxy resin with acrylic acid, followed by reaction with 1,2,3,6-tetrahydrophthalic anhydride to introduce acryloyl group and carboxyl group, and the obtained resin is purified with hexane to obtain The resulting resin had a solid content of 70%, an acid value of 60 mgKOH/g, and PGMEA: 30% by mass.

ZAR2002: brand name; KAYARADZAR-2002, manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin with carboxyl group and ethylenic double bond introduced, solid content 70%, acid value 60 mgKOH/g, PGMEA: 30 mass %.

(Black Colorant (D))

CB: Carbon black dispersion (average secondary particle diameter: 120 nm, carbon black: 20% by mass, polyurethane-based polymer dispersant with an amine value of 18 mgKOH/g: 5% by mass, PGMEA: 75% by mass.).

Mixed organic pigment: 10:5:5:5 mixture of C.I. Pigment Blue 156, C.I. Pigment Red 254, C.I. Pigment Yellow 139, and polymer dispersant (solid content: 25% by mass, PGMEA: 75% by mass.).

(Crosslinking agent (G))

UX5002: Polyfunctional urethane acrylate oligomer (manufactured by Nippon Kayaku Co., Ltd., brand name: KAYARADUX-5002D-P20. Solid content: 80% by mass, PGMEA: 20% by mass.).

A9300CL: ε-caprolactone-modified tris-(2-acryloyloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name: NKESTERA-9300-1CL.).

A9530: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name: NKESTERA-9530.).

(Solvent (H))

PGMEA: Propylene glycol-1-monomethyl ether-2-acetate.

IPA: 2-propanol.

(Silane coupling agent (J))

KBM5013: brand name (Shin-Etsu Chemical Co., Ltd. make. 3-acryloyloxypropyltrimethoxysilane.).

(Particles (K))

IPA-ST: brand 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 (A ¹ -1)]

Put MEK (420g), C6FMA (90g), MAA (9g), PME1000 (81g) and polymerization initiator V-65 (0.2g) into a 1L autoclave equipped with a stirrer, and stir in nitrogen , while polymerizing at 50° C. for 24 hours, a crude polymer was synthesized. After adding hexane to the solution of the obtained crude polymer, and reprecipitating and purifying, it vacuum-dried and obtained the ink repellent agent (A-1) (158.6g). The number average molecular weight (Mn) of the ink repellent agent (A ¹ -1) was 64690, and the mass average molecular weight (Mw) was 92270.

[Synthesis Example 2: Synthesis of Ink Repellent (A ¹ -2)]

MEK (420g), C6FMA (85g), 2-HEMA (50g), PME400 (36g), MAA (9g) and polymerization initiator V-65 (0.7g ), while stirring in nitrogen, polymerized at 50° C. for 24 hours to obtain a solution of polymer (1).

(Introduction of ethylenic double bond)

A solution (500 g), AOI (45.6 g), DBTDL (0.13 g), TBQ (1.6 g) and MEK (17.1 g) of the above-mentioned polymer (1) were put into an autoclave having a stirrer and an inner volume of 1 L, The reaction was carried out at 40° C. for 24 hours with stirring to introduce ethylenic double bonds into the polymer (1). Hexane was added to the obtained solution, and it reprecipitated and purified, and vacuum-dried, and the ink repellent agent (A1-2) ( ^165.0g ) was obtained. The number average molecular weight (Mn) of the ink repellent agent (A ¹ -2) was 41200, the mass average molecular weight (Mw) was 110800, the content rate of fluorine atoms was 20.6% by mass, and the amount of ethylenic double bonds (C=C amount, ×10 ^-3 mol/g) was 1.66×10 ^-3 mol/g, and the acid value was 25.0 mgKOH/g.

[Synthesis Examples 3-4: Synthesis of Ink Repellent Agents (A ¹ -3) and (A ¹ -4)]

Ink repellents (A ¹ -3) and (A ¹ -4) were obtained by the same copolymerization reaction except having changed the recipe of a raw material in the synthesis|combination of ink repellent (A ^1-1 ) as shown in Table 1. The number average molecular weight (Mn), mass average molecular weight (Mw), fluorine atom content (mass %), and acid value (mgKOH/g) of the obtained ink repellent agents (A ¹ -3) and (A ¹ -4) are shown in Table 1.

[Synthesis Example 5: Synthesis of Ink Repellent (A ¹ -5)]

Polymer (2) was obtained by the same copolymerization reaction except that the formulation of the raw material was changed to that in Table 1 during the synthesis of polymer (1). In the synthesis of the ink repellent (A ¹ -2), except that the compounding of the raw materials was changed as shown in Table 1, the ethylenic double bond was introduced into the polymer (2) by the same reaction to obtain the ink repellent (A ¹ -5). The weight-average molecular weight (Mn), number ^- average molecular weight (Mw), fluorine atom content (mass %), acid value (mgKOH/g), and the amount of olefinic double bonds ( C=Amount of C, ×10 ^-3 mol/g) is shown in Table 1.

[Table 1]

[Synthesis Example 6: Production of ink repellent agent (A ² -1)]

11.8 g of compound (a7-1), 29.4 g of compound (a8-1), 29.4 g of compound (a9-1), and 29.4 g of TMMS were charged into a 1000 cm ³ three-necked flask equipped with a stirrer to obtain a hydrolyzable silane compound mixture. Next, 564.7 g of PGMEA was added to this mixture to prepare a solution (raw material solution).

To the obtained raw material solution, 52.0 g of a 1.0% aqueous hydrochloric acid solution was added dropwise while stirring at 40°C. After completion of the dropwise addition, it was stirred at 40°C for 5 hours to obtain ink repellency as a PGMEA solution (ink repellent agent (A ² -1) concentration: 10% by mass. Hereinafter referred to as "(A ² -1) liquid") agent (A ² -1). In addition, the reaction liquid was measured using a gas chromatograph, and it was confirmed that each compound used as a raw material was below the detection limit.

The number-average molecular weight (Mn), mass-average molecular weight (Mw), fluorine atom content of the obtained ink repellent (A ² -1) and the composition (mol %) of the ink repellent (A ² -1) are shown together. in Table 2.

[Synthesis Example 7: Production of ink repellent agent (A ² -2)]

16.7 g of compound (a7-1), 41.7 g of compound (a8-1), and 41.7 g of compound (a9-1) were charged into a 1000 cm ³ three-necked flask equipped with a stirrer to obtain a hydrolyzable silane compound mixture. Next, 564.7 g of PGME was added to this 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 dripped, stirring at 40 degreeC. After completion of the dropwise addition, it was stirred at 40°C for 5 hours to obtain ink repellency as a PGME solution (ink repellent agent (A ² -2) concentration: 10% by mass. Hereinafter referred to as "(A ² -2) liquid") agent (A ² -2). In addition, the reaction liquid was measured using a gas chromatograph, and it was confirmed that each compound used as a raw material was below the detection limit.

The number average molecular weight (Mn), mass average molecular weight (Mw), and fluorine atom content of the obtained ink repellent (A ² -2) are shown together with the composition (mol %) of the ink repellent (A ² -2) in Table 2.

[Table 2]

[Examples 1 to 24 and Examples 31 to 33: Preparation of Negative Photosensitive Resin Composition, Formation and Evaluation of Partition Wall]

Ink repellent (A), photopolymerization initiator (B), alkali-soluble resin (C), black colorant (D), crosslinking agent ( G), solvent (H), silane coupling agent (J) and microparticles (K), to obtain a negative photosensitive resin composition.

After coating the negative photosensitive resin composition on a glass substrate using a spin coater, it was dried on a hot plate at 100° C. for 2 minutes to form a coating film with a film thickness of 2.0 μm. Next, through a mask (lattice pattern of 100 μm × 200 μm in the light-shielding part and 20 μm in the light-transmitting part), an ultra-high pressure mercury lamp (using a cut-off filter to block wavelengths below 330 nm. Mainly composed of i-rays, h-rays, and g-rays Mixed line.) The coating film was irradiated with the prescribed exposure shown in Table 3 and Table 4.

Next, the unexposed part was developed by immersing it in an inorganic alkali developer (manufactured by Yokohama Oil Industry Co., Ltd., a 10-fold diluted aqueous solution of SEMICLEANDL-A4, trade name), and the unexposed part was rinsed with water and dried.

Next, by heating at 220° C. for 1 hour on a hot plate, a patterned glass substrate ( 1 ) was obtained. Moreover, except having exposed without using the said mask, it carried out similarly to the above, and obtained the glass substrate (2) in which the cured film of the coating film was formed. Regarding the glass substrate (1) or (2), the line width, film weight loss after development, and ink repellency (PGMEA contact angle) were measured and evaluated by the methods shown below. The results are shown in Table 3 and Table 4.

(line width)

With respect to the glass substrate (1) above, the line width of the grid-like pattern with a light-transmitting portion of 20 μm was measured using an ultra-depth shape measuring microscope VK-8500 (manufactured by KEYENCE CORPORATION). The closer the line width is to 20 μm of the light-transmitting portion of the mask, the more the line width of the mask can be reproduced.

(film weight reduction after development)

For the glass substrate (1), the film thickness before development (THK1) and the film thickness after development (THK2) of the exposed part (cured film) were measured using a high-precision micro-shape measuring machine SURFCORDERET4000A (manufactured by Kosaka Laboratories). The value obtained by subtracting the film thickness after development from the film thickness before development was defined as the film weight loss after development. It shows that photocuring of a negative photosensitive resin composition is so favorable that this value is small.

(ink repellency)

Evaluation was performed based on the PGMEA contact angle (degrees) of the cured film surface of the glass substrate (2). The contact angle is an angle formed by a tangent to the surface of the liquid at the point where the solid and the liquid come into contact with the solid surface, and is defined as an angle of a side containing the liquid. The larger this angle is, the more excellent the ink repellency of the cured film is.

By the static drop method, based on JIS R3257 "Wettability Test Method of Substrate Glass Surface", PGMEA drops were placed at three places on the measurement surface on the base material, and each PGMEA drop was measured. The droplet size was 2 µL/drop, and the measurement was performed at 20°C. The contact angle is expressed as an average value (n=3) of three measured values.

[table 3]

[Table 4]

The photocuring of the negative photosensitive resin compositions of Examples 1 to 24 was all good. Moreover, the ink repellency of the cured film formed from this composition is favorable, and the line width of a mask can be reproduced.

On the other hand, 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, so the exposure amounts were 20 mJ/cm ² and 40 mJ/cm ² and developed The weight reduction of the back film exceeds 60nm, and the photocuring is not sufficient. In addition, the ink repellency of the formed cured film was insufficient and the line width of the mask could not be reproduced.

Industrial availability

Even when the negative photosensitive resin composition of this invention reduces an exposure amount or exposes by shielding the exposure light of 330 nm or less, ink repellency is favorable and the partition wall with favorable line width reproduction of a mask can be manufactured.

The negative photosensitive resin composition of the present invention can be suitably used for the formation of partitions for color filter production and organic EL display element production using inkjet recording technology.

In addition, all the contents of the Japanese Patent Application No. 2011-102039 filed on April 28, 2011, including the specification, claims, drawings, and abstract are cited here, and are incorporated as the disclosure of the specification of the present invention.

Explanation of reference signs

1...substrate, 2...coated film of negative photosensitive resin composition, 3...exposed portion of coated film, 4...mask, 5...light, 6...partition wall, 7...dot, 10...used in inkjet method Substrates for Optical Elements

Claims (15)

1. a negative light-sensitive resin combination, is characterized in that, it contains:

Refuse black agent (A), it is for to have shown in the group shown in following formula (1) or following formula (2) at side chainThe compound that group, main chain are hydrocarbon chain; Or, there is group, the master shown in following formula (1) at side chainChain is the compound of organopolysiloxane chain,

Photoepolymerizationinitiater initiater (B), it is the oxime ester compound in 1 molecule with nitro, and

Alkali soluble resin (C),

-CFXR^f(1)

-(SiR¹R²-O)_n-SiR³R⁴R⁵(2)

In formula (1), X represents hydrogen atom, fluorine atom or trifluoromethyl, R^fExpression can have ether oxygenFluoroalkyl or the fluorine of at least 1 carbon number being replaced by fluorine atom atom, hydrogen atom below 20Atom,

In formula (2), R¹、R²、R³And R⁴Represent independently hydrogen atom, alkyl, cycloalkyl or aryl,R⁵The organic group that represents hydrogen atom or carbon number 1～10, n represents 1～200 integer.

2. negative light-sensitive resin combination according to claim 1, wherein, described photopolymerization is drawnSending out agent (B) is the compound being made up of following formula (3),

In formula (3), R³¹The alkyl, the aryl of carbon number 6～30, the carbon that represent carbon number 1～20 are formerThe aralkyl of subnumber 7～30 or cyano group, R³²Represent R⁴¹Or OR⁴², this R⁴¹And R⁴²Represent respectively carbon atomThe aralkyl of several 1～20 alkyl, the aryl of carbon number 6～30 or carbon number 7～30, R³³Represent carbonThe aralkyl of the alkyl of atomicity 1～20, the aryl of carbon number 6～30 or carbon number 7～30, R³⁴With R³⁵Represent independently of one another R⁴¹、OR⁴², cyano group or halogen atom, a and b be independently of one another 0～3 wholeNumber, the integer that c is 1～3.

3. negative light-sensitive resin combination according to claim 1 and 2, it also comprises black colorantAgent (D).

4. negative light-sensitive resin combination according to claim 1 and 2, it also comprises crosslinking agent(G)。

5. negative light-sensitive resin combination according to claim 1 and 2, wherein, refuses black agent (A)For there is the compound that group (1) or group (2), main chain are hydrocarbon chain at side chain.

6. negative light-sensitive resin combination according to claim 5, wherein, refuses black agent (A)There is acidic-group.

7. negative light-sensitive resin combination according to claim 1 and 2, wherein, refuses black agent (A)For thering is group (1) at side chain, main chain is the compound of organopolysiloxane chain.

8. negative light-sensitive resin combination according to claim 5, wherein, refuses black agent (A)There is olefinic double bond.

9. a cured film, it is bearing described in any one in the claim 1～8 that makes to form on substrateThe curing of coating of type photosensitive polymer combination forms.

10. a partition wall, its partition wall for forming for subregion is set on substrate, it is by weighingProfit requires the cured film described in 9 to form.

11. 1 kinds of black matrix"s, its black matrix" for forming for subregion is set on substrate, itsFormed by cured film claimed in claim 9, described cured film is by negative-type photosensitive claimed in claim 3Resin combination forms.

The manufacture method of 12. 1 kinds of partition walls, is characterized in that, the method possesses following operation successively:Negative light-sensitive resin combination described in any one in claim 1～8 is coated on substrate and forms and be coated withThe operation of film; Described film heating is made after film, only the established part of this film is exposed and madeThe operation of its photocuring; Remove the operation except described film through the part of photocuring; And, by instituteState the operation that obtains partition wall through the part heating of photocuring,

The Thickness Variation of the described part through photocuring before removing described film and is afterwards below 60nm.

The manufacture method of 13. 1 kinds of black matrix"s, it,, in the manufacture method described in claim 12, makesObtain described partition wall as black matrix" with negative light-sensitive resin combination claimed in claim 3.

14. 1 kinds of colour filters, is characterized in that, it possesses: multiple pixels on substrate, substrate, withAnd being positioned at the partition wall between neighbor, this partition wall is by the minus described in any one in claim 1～8The cured film of photosensitive polymer combination forms.

15. 1 kinds of organic ELs, is characterized in that, it possesses: multiple pixels on substrate, substrate,And being positioned at the partition wall between neighbor, this partition wall is by bearing described in any one in claim 1～8The cured film of type photosensitive polymer combination forms.