KR20140018319A - Negative photosensitive resin composition, cured film, partition wall, black matrix, method for producing partition wall, method for producing black matrix, color filter, and organic el element - Google Patents

Abstract

The negative photosensitive resin composition which has favorable ink repellency and the reproduction of the line width of a mask is favorable, and the homogeneous partition obtained using this composition is provided.
-CFXR ^f [X is a hydrogen atom, a fluorine atom or a trifluoromethyl group, R ^f is a fluoroalkyl group in which at least one of hydrogen atoms having 20 or less carbon atoms which may have an ether oxygen atom is substituted with a fluorine atom, or Fluorine atom] or-(SiR ¹ R ² -O) _n -SiR ³ R ⁴ R ⁵ [R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, alkyl groups, cycloalkyl groups or aryl groups, R ⁵ is hydrogen A photoinitiator (B) which is an ink repellent agent (A) which has a side chain containing the atom or the organic group of 1-10 carbon atoms, n is an integer of 1-200, and an oxime ester compound which has a nitro group in 1 molecule. And alkali-soluble resin (C). The negative photosensitive resin composition characterized by the above-mentioned.

Description

NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION, CURED FILM, PARTITION WALL, BLACK MATRIX, METHOD FOR PRODUCING PARTITION WALL, METHOD FOR PRODUCING BLACK MATRIX , COLOR FILTER, AND ORGANIC EL ELEMENT}

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

The resist composition partitions the partition between the pixels of the color filter, the partition between the pixels of the organic EL (Electro-Luminescence) display element, the partition between the elements of the organic EL illumination, and each TFT of the organic TFT (Thin Film Transistor) array. It attracts attention as a material which forms a permanent film, such as a partition, a partition of an ITO electrode of a liquid crystal display element, and a partition of a circuit wiring board.

In manufacture of a circuit wiring board, the inkjet method which spray-coats a metal dispersion liquid at the time of forming a circuit wiring is proposed. Formation of a circuit wiring pattern is performed by photolithography from a resist composition, and the coating film hardened | cured material of a resist composition is used as a partition.

In the inkjet method, it is necessary to prevent the occurrence of ink mixing between neighboring pixels, and the material ejected by the inkjet to adhere to a portion other than a predetermined region, and to stick to the resist composition comprising a ink repellent agent. It is proposed (patent documents 1-3).

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

Exposure of a resist composition is performed using an exposure machine. Although the wavelength irradiated from an exposure machine changes with the specification of an apparatus, generally, in the proximity exposure system used for a color filter, light of 330 nm or less is irradiated. In contrast, in the mirror projection (MPA) system, light of 330 nm or less is shielded and irradiated. Therefore, the resist composition may require the composition which can respond to an MPA system. Moreover, the projection type MPA system also has an advantage over the proximity exposure system, such as being able to form a sharp partition wall shape. In the MPA system, fine patterning may be required.

An object of the present invention is to provide a negative photosensitive resin composition having a good ink repellency and good reproduction of a line width even when shielding an exposure ray of 330 nm or less, and a homogeneous cured film, partition wall and black matrix obtained using the composition, and Provision of the manufacturing method. Another object of the present invention is to provide a color filter and an organic EL device having a partition or black matrix having good performance.

This invention is the following [1]-[15].

[1] Ink repellent agent (A) which has a side chain containing group represented by following formula (1) or group represented by following formula (2), and

Photoinitiator (B) which is an oxime ester compound which has a nitro group in 1 molecule,

It contains alkali-soluble resin (C), The negative photosensitive resin composition characterized by the above-mentioned.

-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 fluorine having 20 or less carbon atoms in which at least one of the hydrogen atoms which may have an ether oxygen atom is substituted with a fluorine atom. Or a fluoro atom.

In formula (2), R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group independently, R <^5> represents a hydrogen atom or an organic group of 1-10 carbon atoms, n represents the integer of 1-200.

[2] The negative photosensitive resin composition of [1], wherein the photopolymerization initiator (B) is a compound composed of the following Formula (3).

[Formula 1]

In formula (3), R <^31> represents a C1-C20 alkyl group, a C6-C30 aryl group, a C7-C30 arylalkyl group, or a cyano group. R <^32> represents R <^41> or OR <^42> , R <^41> and R <^42> represents a C1-C20 alkyl group, a C6-C30 aryl group, or a C7-C30 arylalkyl group, respectively. R ³³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R ³⁴ and R ³⁵ each independently represent R ⁴¹ , OR ⁴² , cyano group, or halogen atom. a and b are the integers of 0-3 each independently, and c is an integer of 1-3.

[3] The negative photosensitive resin composition of [1] or [2], further comprising a black colorant (D).

[4] The negative photosensitive resin composition according to any one of [1] to [3], further comprising a crosslinking agent (G).

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

[6] The negative photosensitive resin composition of [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) is a compound having a group (1) in the side chain and the main chain is an organopolysiloxane chain.

[8] The negative photosensitive resin composition according to any one of [5] to [7], wherein the ink repellent agent (A) has an ethylenic double bond.

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

[10] A partition wall formed for providing a partition on a substrate, the partition wall including the cured film of [9].

[11] A black matrix formed to form a partition on a substrate, the black matrix comprising a cured film of [9] formed of the negative photosensitive resin composition of [3].

[12] A process of forming a coating film by applying the negative photosensitive resin composition according to any one of [1] to [8] above, heating the coating film to a film, and then exposing only a predetermined portion of the film. A method of manufacturing a partition wall, which comprises a step of photocuring, a step of removing films other than the photocured portion, and a step of heating the photocured portion to obtain a partition, the photocuring before and after removing the film. The film thickness change of one part is 60 nm or less, The manufacturing method of a partition.

[13] The method for producing a black matrix according to the production method of [12], wherein the partition is obtained as a black matrix using the negative photosensitive resin composition of [3].

[14] a substrate, a plurality of pixels on the substrate, and partitions positioned between adjacent pixels, the partitions comprising a cured film of the negative photosensitive resin composition according to any one of [1] to [8]. Color filter.

[15] a substrate, a plurality of pixels on the substrate, and partitions positioned between adjacent pixels, the partitions comprising a cured film of the negative photosensitive resin composition according to any one of [1] to [8]. Organic EL device.

According to the present invention, even when the exposure amount is reduced, or when the exposure light is shielded by 330 nm or less, the exposure is good, and the negative wall capable of producing a partition wall having good ink reproducibility and good reproduction of the line width of the mask can be produced. Provision of a type photosensitive resin composition is possible. According to this invention, the homogeneous cured film using the said negative photosensitive resin composition of this invention, a partition with good performance, a black matrix, and its manufacturing method can be provided. Moreover, according to this invention, the color filter and organic electroluminescent element with the favorable performance provided with the partition and black matrix of the said invention are obtained.

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

The acid value in this specification means the number of milligrams of potassium hydroxide required in order to neutralize the resin acid etc. in 1 g of samples, and is a value which can be measured according to the measuring method of JISK0070. The unit is mgKOH / g.

The total solid content in this specification means the partition formation component among the components which a negative photosensitive resin composition contains, and shows all components other than the volatile components volatilized by the heating etc. in the partition formation process, such as a solvent (H). .

The term &quot; (meth) acryloyl &quot; The term "methacryloyl ... "And" Acrylonitrile ... ". (Meth) acrylate, (meth) acrylamide, (meth) allyl... , And (meth) acrylic resin are the same.

Hydrocarbon group in this specification shows the organic group comprised only with carbon and hydrogen.

In this specification, the film | membrane which apply | coated the film | membrane which applied the negative photosensitive resin composition to the "coating film" and the state which dried it is called "film", and the film | membrane obtained by hardening it is called "curing film."

In this specification, the &quot; surface &quot; of the partition wall is used as a term indicating only the upper surface of the partition wall. Therefore, the &quot; surface &quot; of the partition does not include the side surface of the partition.

The ink in this specification refers to the liquid which has an optical and electrical function, for example after drying and hardening, and is not limited to the coloring material conventionally used. In addition, the "pixel" formed by injecting the above ink is similarly used as showing a division having optical and electrical functions in each partitioned by a partition.

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

Hereinafter, embodiments of the present invention will be described. In addition, in this specification, when there is no description in particular,% represents the mass%.

Ink repellent (A)

Ink repellent agent (A) of this invention contains group represented by following formula (1) (henceforth also called group (1)), or group represented by following formula (2) (hereinafter also called group (2)). It is a compound which has a side chain.

-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 fluorine having 20 or less carbon atoms in which at least one of the hydrogen atoms which may have an ether oxygen atom is substituted with a fluorine atom. Or a fluoro atom.

In formula (2), R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group independently, R <^5> represents a hydrogen atom or an organic group of 1-10 carbon atoms, n represents the integer of 1-200.

Ink repellent agent (A) has a side chain containing group (1) or group (2), and therefore has surface transferability, and is applied when heating and drying a coating film formed of a negative photosensitive resin composition to form a film. Transition to the membrane surface. As a result, the surface of the partition wall formed of the cured film that cured the film exhibits ink repellency, and the ink injected by the inkjet method does not overflow from the openings between the partition walls (points that become pixels) called dots, and thus, color mixture between adjacent pixels. This does not happen well.

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

When at least one of the hydrogen atoms which may have an etheric oxygen atom is a fluoroalkyl group having 20 or less carbon atoms substituted with a fluorine atom, R ^f in the formula (1) is a hydrogen atom in the fluoroalkyl group other than the fluorine atom. May be substituted with another halogen atom. As another halogen atom, a chlorine atom is preferable. Moreover, an ether oxygen atom may exist between the carbon-carbon bonds of the fluoroalkyl group, and may exist in the terminal of the fluoroalkyl group. Moreover, the structure of this fluoroalkyl group is a linear structure, a branched structure, a ring structure, or the structure which has a ring partially, A linear structure is preferable.

As group (1), it is preferable that it is a perfluoroalkyl group or the polyfluoroalkyl group containing one hydrogen atom, and a perfluoroalkyl group is especially preferable (those containing an ether oxygen atom). Thereby, ink repellency of the partition formed from the negative photosensitive resin composition becomes favorable.

The carbon atom number of the group (1) is 20 or less, and 4-6 are preferable. In this case, sufficient ink repellency is provided to a partition, and compatibility with the ink repellent agent (A) and the other component which comprises a negative photosensitive resin composition is favorable, and a negative photosensitive resin composition is apply | coated and a coating film is formed. When the ink repellent agent (A) does not aggregate when it does, the favorable partition of an external appearance can be formed.

As the group (1), a perfluoroalkyl group having 4 to 6 carbon atoms or a perfluoroalkyl group having 4 to 9 carbon atoms having an etheric oxygen atom is preferable.

As a specific example of group (1), the following is mentioned.

-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 1-5.

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

In Formula (2), R <^1> and R <^2> may be same or different for every siloxane unit. From the point that the partition formed from the negative photosensitive resin composition exhibits excellent ink repellency, R ¹ and R ² are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and a hydrogen atom, It is more preferable that it is a methyl group or a phenyl group, and it is especially preferable that R <^1> , R <^2> of all siloxane units is a methyl group.

In Formula (2), R <^3> , R <^4> and R <^5> are group couple | bonded with the silicon atom of the terminal of a siloxane bond, As R <^3> and R <^4> , it can be made the same as R <^1> , R <^2>, and a preferable aspect The same is true. Moreover, when R <^5> is an organic group, a nitrogen atom, an oxygen atom, etc. may be contained and it is preferable that R <^5> is a hydrogen atom or a C1-C5 alkyl group. n is preferably an integer of 1 to 200, more preferably an integer of 2 to 100.

As 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 ink repellent agent (A) also has an acidic group. When ink repellent agent (A) has an acidic group, it is preferable at the point which can improve the solubility to the developing solution of a negative photosensitive resin composition.

As an acidic group, 1 or more types of acidic groups chosen from the group which consists of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group are preferable.

It is preferable that an acidic group exists in a side chain from the point which is easy to synthesize | combine. The side chain which has an acidic group may be formed by the polymerization reaction of the monomer which has an acidic group, and may be formed by the chemical conversion after a polymerization reaction.

It is preferable that ink repellent agent (A) has a polyoxyalkylene group. When ink repellent agent (A) has a polyoxyalkylene group, ink repellency can be continued even if the pressure is raised in a image development process. Moreover, it is preferable at the point which can prevent generation | occurrence | production of the residual film which remain | survives in a dot part without fully removing by development. In addition, examples of the polyoxyalkylene group used in the present invention include groups represented by the following formula (11) (hereinafter sometimes referred to as group (11)) and the like.

-(R ²¹ O) _m (R ²² O) _j R ²³ . (11)

In formula (11), R ²¹ and R ²² each independently represent an alkylene group having 2 to 4 carbon atoms, and R ²³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. and m are 0-100, j represents the integer of 0-100, respectively, 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. R ²¹ and R ²² may be the same or different. Among these R ²¹ and R ^{22, both of} them are each independently —CH ₂ CH ₂ — or —C ₃ H ₆ —, or a combination of —CH ₂ CH ₂ — and —C ₄ H ₈ —, and 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 group 11, m represents 0-100 and j shows the integer of 0-100, respectively, It is preferable that m and j are 0-50, respectively, It is especially preferable that it is 0-30.

Moreover, although m + j is an integer of 4-100, the integer of 6-50 is preferable and the integer of 8-30 is especially preferable. When m + j is more than the lower limit of the said range, when the jet rinse process using high pressure water is performed after the image development process, ink repellency will not fall easily. In addition, the residual film is hardly generated. When m + j is below the upper limit of the above range, the ink repellent agent (A) does not migrate to the opening portion at the time of post-baking, and the ink repellency of the opening between the partitions is sufficient, and when the ink is applied using the inkjet method, the opening portion The ink gets wet enough to spread.

The group (11) represents having m (R ²¹ O) units and j (R ²² O) units, and is particularly limited with respect to the order of bonding of (R ²¹ O) units and (R ²² O) units. It is not. That is, in the group 11, m (R ²¹ O) units and j (R ²² O) units may be combined, for example, alternately or randomly or in blocks.

In group (11), when R <^23> is a C1-C10 alkyl group which may have a substituent, the structure may be a linear structure, a branched structure, a ring structure, the structure which has a ring partially, etc. may be sufficient as it. Specific examples of the substituent include a carboxyl group, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms. In this invention, as R <^23> in group (11), a C1-C5 linear and unsubstituted alkyl group is preferable, and a methyl group and an ethyl group are especially preferable.

In the specific examples of (R ²¹ O) and (R ²² O) in the group (11), -CH ₂ C ₆ H ₁₀ CH ₂ O- (wherein C ₆ H ₁₀ is a cyclohexylene group) , -CH ₂ O-, -CH ₂ CH ₂ O-, -CH ₂ CH (CH ₃ ) O-, -CH (CH ₃ ) O-, -CH ₂ CH ₂ CH ₂ O-, -C (CH ₃ ) ₂ O-, -CH (CH ₂ CH ₃ ) O-, -CH ₂ CH ₂ CH ₂ CH ₂ O-, -CH (CH ₂ CH ₂ CH ₃ ) O-, -CH ₂ (CH ₂ ) ₃ CH _{2 O-, -CH (CH 2 CH} (CH 3) 2) may be mentioned, such as O-. Specific examples of the group (11) include a group in which (R ²¹ O) and (R ²² O) are together selected from the oxyalkylene group exemplified above, m + j is 4 to 100 and R ²³ is CH ₃ . Can be.

The group 11 may be used individually by 1 type, and 2 or more types may be used together. In addition, introduction of the side chain which has group 11 into ink repellent agent (A) is a monomer which has group 11 when manufacturing ink repellent agent (A) by superposition | polymerization of a raw material monomer as mentioned later. It adjusts suitably so that the compounding quantity with respect to the whole raw material monomer of may be a compounding quantity which can give the ink repellent agent (A) the effect of the said developability improvement, without impairing the effect of this invention.

It is preferable that ink repellent agent (A) has an ethylenic double bond. If the ink repellent agent (A) has an ethylenic double bond, the ink repellent agent (A) which has shifted to the film surface at the time of drying is the ink repellent agent (A) or the ink repellent agent (A) It is preferable at the point which is easy to fix on the partition surface by reacting with alkali-soluble resin (C).

As ethylenic double bond, addition-polymerizable unsaturated groups, such as a (meth) acryloyl group, an allyl group, a vinyl group, and a vinyl ether group, etc. are mentioned. Some or all of the hydrogen atoms of these groups may be substituted with a hydrocarbon group. As a hydrocarbon group, a methyl group is preferable.

Introduction of the side chain which has an ethylenic double bond to ink repellent agent (A) adds the monomer which has a reactive group to the raw material monomer at the time of manufacturing ink repellent agent (A), adjusting a compounding quantity suitably as mentioned later. Copolymerization is carried out, and then, the obtained copolymer is reacted with a compound having an ethylenic double bond with a functional group capable of bonding with the reactive group.

As ink repellent agent (A), the compound which has group (1) or group (2) in a side chain, and a principal chain is a hydrocarbon chain is preferable. It is hereinafter also referred to as the main chain of the ink repellent (A) a hydrocarbon chain "to the ink (A ^1)."

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

In addition, to print the (A ¹⁾ is ethylene when sex having a double bond, copolymerizing a monomer (a5) a raw material monomer added with a reactive group in addition to the raw material monomer, and then the copolymer and the reactive group coupled obtained It can manufacture by making compound (z1) which has a functional group and ethylenic double bond which can be made to react.

(Monomer (a1))

As a monomer (a1) which has 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 divalent organic group which does not contain a single bond or a fluorine atom having 1 to 6 carbon atoms, and is preferably an alkylene group having 2 to 4 carbon atoms for ease of acquisition. X and ^Rf represent the same meaning as group (1), and its preferable aspect is 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 described above, R ⁷ , R ⁸ and R ¹⁰ represent an alkylene group having 1 to 6 carbon atoms, R ⁹ and R ¹¹ represent a hydrogen atom or a methyl group, and R ¹² is Single-bond or C1-C4 alkylene group is shown.

Specific examples of R ⁷ , R ⁸ and R ¹⁰ are -CH _2- , -CH ₂ CH _2- , -CH (CH ₃ )-, -CH ₂ CH ₂ CH _2- , -C (CH ₃ ) _2- , -CH (CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH _2- , -CH (CH ₂ CH ₂ CH ₃ )-, -CH ₂ (CH ₂ ) ₃ CH _2- , -CH (CH ₂ CH (CH ₃ ) ₂ )-and the like.

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 )-and the like.

As a specific example of a monomer (a11), 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, etc. are mentioned.

1 type may be used for a monomer (a11), and may use 2 or more types together.

(Monomer (a2))

As a monomer (a2) which has group (2), the following monomer (a21) is preferable.

CH ₂ = CR ¹³ COO-Z- (SiR ¹ R ² -O) _n -SiR ³ R ⁴ R ⁵ (a21)

In the formula, R ¹³ represents a hydrogen atom or a methyl group, and Z represents a single bond or a divalent organic group having 1 to 6 carbon atoms. R <^1> , R <^2> , R <^3> , R <^4> , and R <^5> and n show the same meaning as group (2), and its preferable aspect is also the same.

Z is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms. Specifically, -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. can be mentioned.

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 the like. In addition, n is about 4, 60, 160.

As a monomer (a21), a commercial item can be used. As a commercial item, the following are mentioned by all, a brand name. X-22-174DX (made by Shin-Etsu Chemical Co., Ltd.), X-22-2426 (made by Shin-Etsu Chemical Co., Ltd.), X-22-2475 (made by Shin-Etsu Chemical Co., Ltd.).

1 type may be used for a monomer (a21), and may use 2 or more types together.

(Monomer (a3))

If the ink repellent first (A ¹⁾ having an acidic group, it is preferable that the copolymerized monomer (a3) having an acidic group with a monomer (a1) ~ (a2).

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.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and salts thereof.

As a monomer which has a phenolic hydroxyl group, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, etc. are mentioned. At least one hydrogen atom of these benzene rings is an alkyl group such as methyl group, ethyl group, n-butyl group, alkoxy group such as methoxy group, ethoxy group, n-butoxy group, halogen atom, at least one hydrogen atom of alkyl group is halogen A compound substituted with the haloalkyl group, the nitro group, the cyano group, the amide group substituted by the atom, etc. are mentioned.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid, (meth) acrylic acid-2-sulfoethyl, and (meth) acrylic acid-2. -Sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, and 2- (meth) acrylamide-2-methylpropanesulfonic acid.

As a monomer (a3), acrylic acid or methacrylic acid is preferable at the point which is easy to obtain.

1 type may be used for a monomer (a3), and may use 2 or more types together.

(Monomer (a4))

The monomer having a group (11) for use in the manufacture of ink repellent first (A ¹⁾ is a compound represented by the formula (12) (hereinafter referred to as compound (12) also known as is) or (13) as shown compounds (hereinafter referred to as It is also referred to as compound (13)). These may be used singly or in combination of two or more.

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

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

In formulas (12) and (13), R ²⁴ and R ²⁵ each represent a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 7 to 20 carbon atoms It is a substituted alkyl group, a C6-C20 aryl group, or a C3-C20 cycloalkyl group. W is a divalent organic group that does not have a single bond or a fluorine atom having 1 to 10 carbon atoms. -(R ²¹ O) _m (R ²² O) _j R ²³ is a group (11), R ²¹ , R ²² , R ²³ , m and j represent the same meaning as the group (11), and the preferred range is also the same. .

In the compound (12) and the compound (13), when W is a divalent organic group having no fluorine atom having 1 to 10 carbon atoms, a linear structure, a branched structure, or a ring structure other than R ²¹ O and R ²² O And an oxyalkylene group having 1 to 10 carbon atoms, a single bond, or the like having a ring structure partially. As the oxyalkylene groups _{Specifically, CH 2 C 6 H 10 CH} 2 O (C 6 H 10 wherein R is cyclohexyl the xylene _{group), CH 2 O, CH 2} CH 2 O, CH 2 CH (CH 3) O , CH (CH ₃ ) O, CH ₂ CH ₂ CH ₂ O, C (CH ₃ ) ₂ O, CH (CH ₂ CH ₃ ) O, CH ₂ CH ₂ CH ₂ CH ₂ O, CH (CH ₂ CH ₂ CH ₃ ) O, CH ₂ (CH ₂ ) ₃ CH ₂ O, CH (CH ₂ CH (CH ₃ ) ₂ ) O, and the like. Especially, as W in the compound (12) and (13), the oxyalkylene group of 2-4 carbon atoms is preferable from the ease of acquisition.

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

Examples of the compound represented by 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 formula, m and j show the same meaning as group (11), and its preferable range is also the same. C ₆ H ₁₀ is a cyclohexylene group. C ₂ H ₄ , C ₃ H ₆ and C ₄ H ₈ are either linear or branched. R <^23> represents the same meaning as group (11), The preferable range is a C1-C10 linear and unsubstituted alkyl group, and its methyl group is especially preferable.

As the compounds (12) and (13), it is possible to use a commercial item. The following are mentioned as a commercial item.

Blenmer PME-400 (trade name, manufactured by Nippon Oil Industries, Ltd., CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH _3. K represents a mean value between molecules, and the value of k is about 9. hereinafter, represents a k, m, the average all j is the molecular of the molecular formulas of the respective commercial products.), Blenmer PME-1000 (trade name, Nippon maintained _{manufactured, CH 2 = C (CH 3} ) COO (CH 2 CH ₂ O) _k CH _3. expression of k represents an average value of inter-molecular, the value of k is 23.), NK ester M-230G :( trade name, manufactured by Shin-Nakamura Chemical Co. _{manufacture, CH 2 = C (CH 3} ) COO (CH ₂ CH ₂ O) _k CH ₃ , wherein k is about 9.), New Frontier NF Bisoma PEM6E (trade name, Daiichi Kogyo Pharmaceutical Co., Ltd., CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _k H: wherein, k is from about 6), Light ester 130A (trade name, manufactured Ischia Chemical Co. in _{Tokyo, CH 2 = CHCOO (CH 2} CH 2 O) k CH 3 wherein, k is from about 9. Blender AE-400 (trade name, manufactured by Nippon Oil Industries, Ltd., CH ₂ = CHCOO (CH ₂ CH ₂ O) _k H: In the formulas, k Is about 10), blender PP-800 (trade name, manufactured by Nippon Oil Industries, Ltd., CH ₂ = C (CH ₃ ) COO (C ₃ H ₆ O) _k H. wherein k is about 13), Lenmer AP-800 (trade name, manufactured by Nippon Yuji Co., Ltd., CH ₂ = CHCOO (C ₃ H ₆ O) _k H. wherein k is about 13.), Blenmer 70PEP-350B (brand name, Nippon Yuji Co., Ltd., 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, j is about 2.), Blender 55PET-800 , Nippon Oil Industries, Ltd., 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, 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 ethylenic double bond, the monomer which has a carboxyl group, the monomer which has an epoxy group, etc. are mentioned. In addition, it is preferable that monomer (a5) does not contain group (1) and group (2) substantially.

When the monomer which has a carboxyl group is used as a monomer (a3) which has an acidic group, and when the monomer which has a carboxyl group is used also as the monomer (a5) which has the said reactive group, an ethylenic double bond is not finally introduced and what remains as a carboxyl group is a monomer ( a3).

Ink repellent agent which has a side chain which has an ethylenic double bond by reacting the reactive group which the monomer (a5) after copolymerization has with the functional group which can couple | bond with the said reactive group (z1) which has an ethylenic double bond (A1) ¹ ) is formed.

As a specific example of the monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth ) Acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3- Chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl Ether, N-hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide, etc. are mentioned.

Moreover, 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 (where h is an integer from 1 to 100, the same below), CH ₂ = CHOC ₄ H ₈ O (C ₂ H ₄ O) _h H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _h H, CH ₂ = C (CH ₃ ) COOC ₂ H ₄ O (C ₂ H ₄ O) _h H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _i (C ₃ H ₆ O) _g H (where i is an integer from 0 to 100, g is an integer from 1 to 100, i + g is from 1 to 100 The same applies to the following), and CH ₂ = C (CH ₃ ) COOC ₂ H ₄ O (C ₂ H ₄ O) _i (C ₃ H ₆ O) _g H.

Specific examples of the acid anhydride monomer having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid, and 3,4 anhydride. , 5,6-tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic acid, 2-buten-1-ylsuccinic anhydride and the like.

Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.

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

(Monomer (a6))

As a monomer used for the superposition | polymerization in this invention, the monomer (a2) which has a monomer (a1) or group (2) which has group (1), the monomer (a3) which has an acidic group as needed, and poly as needed When the monomer (a4) having an oxyalkylene group and the ink repellent agent (A ¹ ) have an ethylenic double bond, the monomer (a5) having a reactive group are included, but other monomers (a6) other than these monomers are included. You may be.

As the monomer (a6), hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic acid esters, (meth) acrylamides and aromatic vinyls The compound, chloroolefin, and conjugated diene are mentioned. A functional group may be contained in these compounds, and a functional group includes a carbonyl group, an alkoxy group, etc., for example. In particular, (meth) acrylic acid esters or (meth) acrylamides are preferable at the point which is excellent in the heat resistance of a partition.

Moreover, the monomer which has an epoxy group as the monomer (a5) which has the said reactive group, for example, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl methyl acrylate, etc. can be used also as a monomer (a6). Do. That is, when the monomer which has these epoxy groups is used for superposition | polymerization in this invention, and when an ethylenic double bond is not introduce | transduced after copolymerization, the monomer which has these epoxy groups is classified into other monomers (a6). Moreover, also when an ethylenic double bond is introduce | transduced, what is left as an epoxy group without finally introducing an ethylenic double bond shall be regarded as another monomer (a6).

(Production of Ink Repellent Agent (A ¹ ))

The ink repellent agent (A ¹ ) can be synthesized by, for example, the following method. First, the monomer is dissolved in a solvent and heated, and a polymerization initiator is added to copolymerize. In a copolymerization reaction, it is preferable to exist a chain transfer agent as needed. A monomer, a polymerization initiator, a solvent, and a chain transfer agent may be added continuously.

Examples of the solvent include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and ethylene glycol; ketones such as acetone, 2-butanone, methyl isobutyl ketone and cyclohexanone; 2-methoxyethanol , Cellosolves such as 2-ethoxyethanol and 2-butoxyethanol; 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxye) Carbitols such as methoxy) ethanol; methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol Diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, butyl lactate, γ-butyrolactone, 3-methyl-3-methoxybutyl acetate, ethyl lactate, n-butyl lactate, γ-butyro Esters such as lactone, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and glycerin triacetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene Glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutyl ether, diethylene glycol ethyl methyl ether and the like.

Examples of the polymerization initiator include known organic peroxides, inorganic peroxides, and azo compounds. An organic peroxide and an inorganic peroxide can also be used as a redox catalyst in combination with a reducing agent.

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

Examples of the chain transfer agent include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-thiohexyl 2-ethylhexyl and 2-mercaptoethanol; chloroform, And halogenated alkyl such as carbon tetrachloride and carbon tetrabromide.

Also, if the ink repellent first (A ¹⁾ having an ethylenic double bond include, to react the copolymer and a reactive group coupled compound (z1) having a functional group with an ethylene double bond that can be obtained in the manner described above Ink agent (A ¹ ) is obtained.

As a combination of the compound (z1) which has a functional group and ethylenic double bond which can couple | bond with the said reactive group with respect to a reactive group, the following combination is mentioned, for example.

(1) an acid anhydride having an ethylenic double bond with respect to a hydroxyl group,

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

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

(4) to an acid anhydride, a compound having a hydroxyl group and an ethylenic double bond,

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

(6) The compound which has a carboxyl group and ethylenic double bond with respect to an epoxy group.

After reacting a compound having a carboxyl group and an ethylenic double bond with respect to the epoxy group, an acid anhydride of a compound having two or more carboxyl groups in one molecule is allowed to react with the resulting hydroxyl group, and an acidic group is reacted with the ink repellent agent (A ¹ ). You can also introduce.

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

When making a copolymer react with the compound (z1) which has an ethylenic double bond, and the functional group which can couple | bond with a reactive group, the solvent illustrated in the synthesis | combination of the said copolymer can be used as a solvent used for reaction.

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

A catalyst or a neutralizing agent may be added. For example, when making the copolymer which has a hydroxyl group, and the compound which has an isocyanate group and ethylenic double bond react, tin compounds, such as dibutyltin dilaurate, etc. can be used. When a copolymer having a hydroxyl group and a compound having an acyl chloride group and an ethylenic double bond are reacted, a basic catalyst may be used.

The preferable ratio of each monomer with respect to the monomer total mass to copolymerize is as follows. 20-80 mass% is preferable, and, as for the ratio of a monomer (a1) or a monomer (a2), 30-60 mass% is especially preferable. If the ratio is more than the lower limit of the above range, the ink repellent (A ¹⁾ is to lower the surface tension of the partition walls made of a cured film to be formed, it is possible to give a high ink repellency to the partition wall. If it is below the upper limit of the said range, the adhesiveness of a partition and a base material will become favorable.

When it contains a monomer (a3), 2-20 mass% is preferable, and, as for the ratio, 4-12 mass% is especially preferable. The developability of a negative photosensitive resin composition becomes it favorable that it is the said range.

When it contains a monomer (a4), 5-70 mass% is preferable, as for the ratio, 10-60 mass% is more preferable, 15-50 mass% is especially preferable. If it is the said range, even if the pressure is raised in a image development process, liquid repellency can be continued. In addition, it is possible to prevent the generation of residual film.

When it contains a monomer (a5), 20-70 mass% is preferable, and, as for the ratio, 30-50 mass% is especially preferable. When the ethylenic double bond introduced through a polymerization unit of a monomer (a5) origin included in the above range, the developability and fixing of a partition wall surface of the ink repellent (A ¹⁾ becomes fine.

When it contains another monomer (a6), 70 mass% or less is preferable and, as for the ratio, 50 mass% or less is especially preferable. Alkali solubility and developability are favorable in it being the said range.

A preferred combination of monomers for the manufacture of ink to the (A ¹⁾ are as follows.

(Combination 1)

Monomer (a1): at least 1 sort (s) chosen from the group which consists of 2- (perfluorobutyl) ethyl (meth) acrylate and 2- (perfluorohexyl) ethyl (meth) acrylate,

Monomer (a3): at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid,

Monomer (a4): at least 1 sort (s) chosen from the group which consists of blender PME-400 and blender PME-1000,

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

After copolymerizing the monomer to obtain a copolymer, at least one member selected from the group consisting of 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate The compound which reacted and introduce | transduced ethylenic double bond.

(Combination 2)

Monomer (a1): at least 1 sort (s) chosen from the group which consists of 2- (perfluorobutyl) ethyl (meth) acrylate and 2- (perfluorohexyl) ethyl (meth) acrylate,

Monomer (a3): at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid,

Monomer (a4): at least 1 sort (s) chosen from the group which consists of blender PME-400 and blender PME-1000,

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

(Combination 3)

Monomer (a1): at least 1 sort (s) chosen from the group which consists of 2- (perfluorobutyl) ethyl (meth) acrylate and 2- (perfluorohexyl) ethyl (meth) acrylate,

Monomer (a4): at least 1 sort (s) chosen from the group which consists of blender PME-400 and blender PME-1000,

Monomer (a5): glycidyl (meth) acrylate

Monomer (a6): At least 1 sort (s) chosen from the group which consists of 3, 4- epoxycyclohexyl methyl acrylate, methyl (meth) acrylate, isobornyl (meth) acrylate, and cyclohexyl (meth) acrylate.

After copolymerizing the monomer to obtain a copolymer, at least one selected from the group consisting of acrylic acid and methacrylic acid is reacted, followed by 3,4,5,6-tetrahydrophthalic anhydride and cis-1 anhydride, A compound in which at least one selected from the group consisting of 2,3,6-tetrahydrophthalic acid is reacted to introduce an acidic group and an ethylenic double bond.

(Combination 4)

Monomer (a1): at least 1 sort (s) chosen from the group which consists of 2- (perfluorobutyl) ethyl (meth) acrylate and 2- (perfluorohexyl) ethyl (meth) acrylate,

Monomer (a2): at least 1 sort (s) chosen from the group which consists of X-22-174DX, X-22-2426, and X-22-247,

Monomer (a3): at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid,

Monomer (a4): at least 1 sort (s) chosen from the group which consists of blender PME-400 and blender PME-1000,

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

After copolymerizing the monomer to obtain a copolymer, at least one member selected from the group consisting of 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate The compound which reacted and introduce | transduced ethylenic double bond.

(Combination 5)

Monomer (a2): at least 1 sort (s) chosen from the group which consists of X-22-174DX, X-22-2426, and X-22-247,

Monomer (a3): at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid,

Monomer (a4): at least 1 sort (s) chosen from the group which consists of blender PME-400 and blender PME-1000,

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

After copolymerizing the monomer to obtain a copolymer, at least one member selected from the group consisting of 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate The compound which reacted and introduce | transduced ethylenic double bond.

When the ink repellent agent (A ¹ ) has an ethylenic double bond, the copolymer and the compound (z1) have a value of the equivalent ratio of [functional group of compound (z1)] / [reactive group of copolymer] of 0.5 to 2.0 It is preferable to add as much as possible, and 0.8-1.5 are especially preferable. Is above the lower limit of the range, the partition walls to the immobilization of the ink of the first (A ¹⁾ becomes fine. If it is below the upper limit of the said range, the impurity which is an unreacted compound (z1) increases, and a coating film external appearance deteriorates. In addition, the amount of the monomer (a3) and the monomer (a4) in the case of using a monomer having a carboxyl group as both the foot print first (A ¹⁾ acid value to a predetermined value, the copolymer and the compound (z1) of You can adjust it.

When to print the (A ¹⁾ having a group (1), and the content of fluorine atom in the ink repellent first (A ¹⁾ is 5 to 50% by mass is preferable, and more preferably 10 to 40% by weight, 20 to 35 mass% is especially preferable. Is above the lower limit of the above range, the ink repellent (A ¹⁾ is excellent in the effect of lowering the surface tension of the partition wall, and can be obtained is excellent in ink-repellent partition walls. If it is below the upper limit of the said range, the adhesiveness of a partition and a base material will become favorable.

If the ink repellent (A ¹⁾ having a group (2), the content of the silicon atoms of the ink repellent (A ¹⁾ is preferably 0.1 to 25 mass%, and 0.5 to 10 mass% is particularly preferred. Is above the lower limit of the above range, the ink repellent (A ¹⁾ is given a raising effect, and the ink descends sex (轉落性) lowering the surface tension of the partition walls to be formed effect. If it is below the upper limit of the said range, the adhesiveness of a partition and a base material will become favorable.

The acid of the ink to the (A ¹⁾ going 150 ㎎KOH / g or less, and preferably, 10 ~ 100 ㎎KOH / g is particularly preferred. If it is the said range, both the solubility with respect to the developing solution of a negative photosensitive resin composition and ink repellency expression are compatible.

When the ink repellent agent (A ¹ ) contains an ethylenic double bond, the amount thereof is preferably 0.5 × 10 ⁻³ to 5 × 10 ⁻³ mol / g, and 1 × 10 ⁻³ to 4.5 × 10 ⁻³ mol / g This is particularly preferred. If the above-mentioned range, the developability and fixing of the partition wall of the ink repellent (A ¹⁾ becomes fine.

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 , more preferably 1 × 10 ⁴ to 7 × 10 ⁴ is particularly preferred. Alkali solubility and developability are favorable in it being the said range.

The mass average molecular weight (Mw) of the ink repellent agent (A ¹ ) is preferably 1.2 × 10 ⁴ to 20 × 10 ⁴ , more preferably 2 × 10 ⁴ to 15 × 10 ⁴ , and 3 × 10 ⁴ to 12 × 10 ⁴ is particularly preferred. Alkali solubility and developability are favorable in it being the said range.

As ink repellent agent (A), the compound which has group (1) in a side chain, and whose main chain is an organopolysiloxane chain is also preferable. Hereinafter, the ink to claim yi main chain of the organopolysiloxane chain (A) is known as the "ink to the (A ^2)."

As the ink repellent agent (A ² ), a hydrolyzable silane compound represented by the following formula (14) (hereinafter also referred to as a silane compound (a7)) or its partially hydrolyzed condensate, and hydrolyzable represented by the following formula (15) It is preferable that it consists of a hydrolyzable silane compound mixture containing a silane compound (henceforth a silane compound (a8)) or its partial hydrolysis-condensate, or the partial hydrolysis-condensation product of this mixture.

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 described above,

Q ¹ : A divalent organic group containing no fluorine atoms having 1 to 10 carbon atoms,

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

X ¹ , X ² : Hydrolyzable group,

p ： 0, 1 or 2,

However, three X <^1> in Formula (14) and (4-p) X <^2> and p R <^H1> in Formula (15) may respectively mutually differ or may be the same.)

The content of fluorine atom in the ink repellent first (A ²⁾ is preferably from 10 to 55 mass%, far preferably from 12 to 40% by mass is more preferable, and 15 - and 30% by weight is particularly preferred, if the content of fluorine atoms the range It is possible to impart excellent ink repellency and ink-resistant ultraviolet ray / ozone resistance to the partition obtained from the negative photosensitive resin composition.

It is preferable that ink repellent agent (A2) has a silanol group (that is, the hydroxyl group ^{couple |} bonded with the silicon atom). As a number of silanol groups, 0.2-3.5 pieces are preferable per silicon atom, 0.2-2 pieces are more preferable, 0.5-1.5 pieces are especially preferable. Is above the lower limit of the above range, the formation of the partition wall by using the negative-type photosensitive resin composition, it is possible to prevent the elimination of the ink to the (A ²⁾ from the substrate surface. It is less than the upper limit of the range, from the ink to the (A ²⁾ of negative-type photosensitive resin composition is excellent in compatibility with a solvent or other components.

In addition, the number of silanol groups to the ink (A ²⁾ is calculated by the peak area ratio of the Si group not having an Si group, a silanol having silanol groups, as measured by ²⁹ Si-NMR.

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 partial hydrolysis-condensation product of a hydrolyzable silane compound means the high molecular weight body which is a grade which is melt | dissolved in a solvent among the oligomers (multimers) produced by hydrolyzing and dehydrating condensation of a polyfunctional hydrolyzable silane compound. Moreover, comparatively low molecular weight multimers, such as 2-4 tetramer of a hydrolyzable silane compound, are also the partial hydrolysis-condensation products in this invention. The partially hydrolyzed condensate may have a silanol group formed by hydrolysis of the hydrolyzable group, and may have an unreacted hydrolyzable group. The relatively high molecular weight partial hydrolysis condensate mainly has silanol groups, and the relatively low molecular weight partial hydrolysis condensate may further have a hydrolyzable group.

The partially hydrolyzed condensate has the property of becoming a high molecular weight cured product that is not finally dissolved in a solvent as a result of further condensation or hydrolysis. The partial hydrolysis condensate may be a mixture of oligomers having different degrees of multimerization.

The partially hydrolyzed condensate can be produced, for example, by stirring the hydrolyzable silane compound in the presence of an acid catalyst and water for a predetermined time under a predetermined reaction temperature condition. The degree of multimerization of the partial hydrolysis-condensation product obtained can be suitably adjusted according to an acid concentration, reaction temperature, reaction time, etc.

In addition, the molar ratio which shows the ratio of the following hydrolyzable silane compound is a ratio of the number of the silicon atoms derived from each hydrolyzable silane compound, when at least any one of the following hydrolyzable silane compounds is a partial hydrolysis-condensation product.

(Hydrolysable silane compound represented by formula (14))

As shown by the said Formula (14), a silane compound (a7) is a hydrolysable silane compound which has group (1). In the formula (14), Q ¹ is a divalent organic group connecting the group (1) and the hydrolyzable silyl group (-SiX ¹ ₃ ), and is a divalent non-containing fluorine atom having 1 to 10 carbon atoms. It is an organic group. In the case where Q ¹ is represented as Si bonded to the right bond water and R ^f -CFX- is respectively bonded to the left bond water, specifically,-(CH ₂ ) _i 1-(i 1 is an integer of 1 to 5), _{-CH 2 O (CH 2) i2} - (i2 is an integer of _{1 ~ 4), -SO 2 NR} 1 - (CH 2) i3 - (R 1 represents a hydrogen atom, a methyl group, or ethyl group, i3 is at least 1, and R 4 totals an integer of not less to the number of atoms of carbon and ^{1), - (C = O} ) -NR 1 - (CH 2) i4 - and (R ¹ are the same as above, i4 is greater than or equal to 1, ^one of R Group represented by an integer of 4 or less in total with the number of carbon atoms) is preferable. As Q ¹ , - (CH ₂ ) _{i 1} -, in which i ¹ is 2 or 3, is more preferable, and - (CH ₂ ) ₂ - is particularly preferable.

When the group (1) is a perfluoroalkyl group having 1 to 6 carbon atoms, Q ¹ is preferably a group represented by - (CH ₂ ) _{i 1} - (i 1 is as defined above). i1 is preferably an integer of 2 to 4, and particularly preferably - (CH ₂ ) ₂ - in which i1 is 2.

Group 1 is the case of a perfluoroalkyl group of carbon atoms containing an etheric oxygen atom 4-9, the roneun _{^{Q 1, - (CH 2)}} i1 -, -CH 2 O (CH 2) i2 -, Groups represented by -SO ₂ NR ^1- (CH ₂ ) _i3 -and-(C = O) -NR ^1- (CH ₂ ) _i4- (i1 to i4 and R ¹ are the same as above) are preferable. Also 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 a group in which hydrogen of an alkoxy group, a halogen atom, an acyl group, an isocyanato group, an amino group and an amino group is substituted with an alkyl group. The alkoxy group or halogen atom of 1 to 4 carbon atoms is preferable, and a methoxy group, an ethoxy group, and a chlorine atom are especially preferable. The group becomes a hydroxyl group (silanol group) by a hydrolysis reaction, and the reaction which forms a Si-O-Si bond by condensation reaction between molecules easily advances easily.

As specific examples of the silane compound (a7), the following compounds may be mentioned.

F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , F (CF ₂ ) ₄ CH ₂ CH ₂ SiCl ₃ , F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , F (CF ₂ ) ₆ CH ₂ CH ₂ SiCl ₃ .

CF ₃ OCF ₃ CF ₂ CF ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , CF ₃ OCF (CF ₃ ) CF ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .

F (CF ₂ ) ₂ OCF ₂ CF ₂ OCF ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₂ O (CF ₂ ) ₂ O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .

F (CF ₂ ) ₃ OCF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , F (CF ₂ ) ₃ OCF (CF ₃ ) CF ₂ O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .

As the silane compound (a7), among 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 ) Particular preference is given to ₆ CH ₂ CH ₂ SiCl ₃ , F (CF ₂ ) ₃ OCF (CF ₃ ) CF ₂ O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) _3, and the like.

As a hydrolyzable silane compound contained in a hydrolyzable silane compound mixture, a silane compound (a7) may be used individually by 1 type, or may use 2 or more types together.

Moreover, the said hydrolyzable silane compound mixture may contain the partial hydrolysis-condensation product of a silane compound (a7). However, it is preferable that it is a silane compound (a7) single body rather than a partial hydrolysis-condensation product.

(Hydrolysable silane compound represented by formula (15))

The silane compound (a8) represented by said formula (15) is used as a hydrolyzable silane compound contained in a hydrolyzable silane compound mixture with the said silane compound (a7).

In Formula (15), R <^H1> has a C1-C4 alkyl group, A methyl group or an ethyl group is more preferable, A methyl group is especially preferable. As R ^H1 other than an alkyl group, the hydrocarbon group which has rings, such as alkenyl groups, such as a vinyl group and an allyl group, a phenyl group, and a cycloalkyl group, is mentioned.

X <^2> is a hydrolysable group and is the same including X <^1> in said Formula (15), and a preferable aspect. p is 0, 1 or 2; However, two R <^H1> and (4-p) X <^2> in case p is ² may mutually differ or may be same.

As for a silane compound (a8), the tetrafunctional compound whose p is 0, or the trifunctional compound whose p is 1 is preferable.

In the ink repellent agent (A ² ), water repellency is expressed by the group (1) derived from the silane compound (a7) and R ^H1 derived from the silane compound (a8), and oil repellency is mainly expressed by the group (1). . In addition, to the cured product of the ink repellent first (A ²⁾ exhibit sufficient oil repellency, to the sum of the groups (1) and R ^H1 of the ink repellent first (A ^2), preferably a high proportion of the group (1) Do. In the case of p = 0, the ratio of the group (1) in the ink repellent agent (A ² ) is increased, so that the oil repellency is improved and the film formation is excellent. In the case of p = 1 or 2, R ^H1 is either by what extent, to print the (A ²⁾ is becomes easy to be dissolved in a solvent of the hydrocarbon type, is relatively cheap in forming the coating of a negative-type photosensitive resin composition film on the substrate surface The solvent can be selected.

As a silane compound (a8), the following compounds are preferable. Moreover, the partial hydrolysis-condensation product of a silane compound (a8) can be used instead of a silane compound (a8). It is preferable that it is a comparatively low molecular weight compound as a partial hydrolysis-condensation product. As a partial hydrolysis-condensation product, the following are 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 ,

Si (OCH _{3) 4} partially hydrolyzed condensate (e.g., Cole coat the product of methyl silicate 51 (trade name)) of,

Partial hydrolyzed condensates of Si (OCH ₂ CH ₃ ) ₄ (for example, ethyl silicate 40 and ethyl silicate 48 (all trade names) manufactured by Colcoat Co.).

As a hydrolyzable silane compound contained in the hydrolyzable silane compound mixture of this invention, a silane compound (a8) may be used individually by 1 type, or may use 2 or more types together. When two or more compounds are used in combination, a bifunctional compound may be used together with a tetrafunctional compound and / or a trifunctional compound.

As for content of a silane compound (a8) in a hydrolyzable silane compound mixture, 0.1-9 mol of a silane compound (a8) is preferable with respect to 1 mol of a silane compound (a7), and 0.5-9 mol is especially preferable. Moreover, hydrolyzable silane compounds (henceforth a silane compound (a9)) other than a silane compound (a7) and a silane compound (a8), and the partial hydrolysis-condensation product of a silane compound (a9) may be included.

(Silane compound (a9))

As a silane compound (a9), if it is a bifunctional or trifunctional silane compound which has a hydrolysable group, and a compound co-condensed with a silane compound (a7) and a silane compound (a8), a well-known silane compound can be used.

The silane compound (a9) roneun, it is preferred that the formula of (15) a silane compound of a structure having a hydrocarbon group substituted with a reactive group or more than 7 carbon atoms in the hydrocarbon rather than in R ^H1. However, when p is 2 in the formula (15), one of the two R ^H1 is or may be R ^H1. As a reactive group, a (meth) acryloyloxy group, an amino group, a hydrocarbon group substituted amino group, an epoxy group, etc. are preferable. In particular, the reactive group which has ethylenic double bonds, such as a (meth) acryloyloxy group, is preferable.

Preferred silane compound (a9) is a hydrolyzable silane compound having a reactive group having an ethylenic double bond, and a trialkoxysilane or dialkoxysilane having a (meth) acryloyloxy group substituted alkyl group is particularly preferable. The silane compound to the ink (A ²⁾ containing an ethylenic double bond by using an (a9) having an ethylenic double bond are obtained.

As a specific example of especially preferable compound silane compound (a9), the following is mentioned.

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 a hydrolyzable silane compound contained in the hydrolyzable silane compound mixture of this invention, a silane compound (a9) may be used individually by 1 type, or may use 2 or more types together.

5 mol or less is preferable with respect to 1 mol of the total amount of a silane compound (a7) and a silane compound (a8), and, as for the compounding quantity of the silane compound (a9) in the hydrolyzable silane compound mixture of this invention, 4 mol or less is especially preferable. .

A monofunctional silane compound can be mix | blended with a hydrolyzable silane compound mixture as a hydrolyzable silane compound. The monofunctional silane compound functions as a molecular weight modifier when hydrolytically condensing the hydrolyzable silane compound mixture to form a partially hydrolyzed condensate. That is, it is used for the purpose of manufacturing the comparatively low molecular weight partial hydrolysis-condensation product, the purpose of preventing the partial hydrolysis-condensation product from becoming too high molecular weight, and becoming solvent insoluble. It is preferable to adjust the usage-amount appropriately according to the molecular weight of the target partial hydrolysis-condensation product.

As monofunctional silane compound, the compound of the structure whose p is 3, and hexaalkyl disiloxane in said Formula (15) are preferable. The alkyl group in these compounds is preferably 4 or less carbon atoms, and particularly preferably a methyl group or an ethyl group.

The ink repellent agent (A ² ) used for the negative photosensitive resin composition of this invention is a hydrolyzable silane compound mixture of the said raw material, or its partial hydrolysis-condensation product, and partial hydrolysis comprised from several condensation products from which a polymerization degree etc. differ. It is preferred that it is a mixture of condensates. That is, the ink repellent (A ^2), it is preferable that the silane compound is water (a7) and the silane compound (a8) the use, as an essential component, and optionally a partial hydrolysis condensate prepared using a silane compound (a9). It is preferable that this partial hydrolysis-condensation product is manufactured by mixing a silane compound (a7), a silane compound (a8), and optionally a silane compound (a9), and then partially hydrolyzing-condensing the mixture. In addition, you may use the partial hydrolysis-condensation product instead of a silane compound (a7), a silane compound (a8), and a silane compound (a9), respectively.

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

(2)

In Formula (16), the preferable ranges of R ^f , R ^H1 , Q ¹ and p are the same as described above. s and t are the average number of moles of each unit in some partial hydrolysis-condensation products from which a polymerization degree differs.

In the partial hydrolysis-condensation product which has a structure of the average composition formula represented by Formula (16), it is estimated that the units derived from a silane compound (a7) and a silane compound (a8), respectively, are arranged at random. Further, the silane compound (a7) and the silane compound the average formula s / t (molar ratio) of the (16), as the total average to print the (A ^2), the hydrolyzable silane compound mixture in the case of using the (a8) As content of the silane compound (a7) with respect to the silane compound (a8) in the above-mentioned range, ie, 10/1-90 (molar ratio) is preferable, and 10/5-90 (molar ratio) are especially preferable.

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

Roneun to the ink (A ^2), it is preferable to the partially hydrolyzed condensate of the mixture of the silane compound.

(Combination 6)

Silane compound (a7): at least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane,

Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane.

(Combination 7)

Silane compound (a7): at least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane,

Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane,

Monofunctional silane compound: Hexamethyldisiloxane or trimethylmethoxysilane.

(Combination 8)

Silane compound (a7): at least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane,

Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane,

Silane compound (a9): 3-acryloyloxypropyl trimethoxysilane or 3-methacryloyloxypropyl trimethoxysilane.

(Combination 9)

Silane compound (a7): at least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane,

Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane,

Silane compound (a9): 3-acryloyloxypropyltrimethoxysilane or 3-methacryloyloxypropyltrimethoxysilane,

Monofunctional silane compound: Hexamethyldisiloxane or trimethylmethoxysilane.

(Combination 10)

Silane compound (a7): at least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane,

Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane,

Silane compound (a9): 3-glycidyloxypropyltrimethoxysilane,

Monofunctional silane compound: Hexamethyldisiloxane or trimethylmethoxysilane.

The ink repellent agent (A ² ) in the negative photosensitive resin composition of this invention further condenses the silanol groups contained in processes, such as exposure and hardening, and is excellent in ink repellency even if it irradiates ultraviolet-ray / ozone. It is thought to form the partition shown.

The number average molecular weight (Mn) of the ink to the (A ²⁾ in the negative photosensitive resin composition of the present invention is preferably 500 or more and less than 1,000,000 is preferable, and is particularly preferably less than 10,000. When number average molecular weight (Mn) is more than the lower limit of the said range, when forming a partition using negative photosensitive resin composition, desorption from a board | substrate surface can be prevented. When number average molecular weight (Mn) is less than the upper limit of the said range, solubility to a solvent is favorable and it is excellent in workability. The number average molecular weight (Mn) of the ink repellent (A ²⁾ can be adjusted by selecting the reaction conditions such as.

(Production of Ink Repellent Agent (A ² ))

When the ink repellent agent (A ² ) in the negative photosensitive resin composition of this invention is a partial hydrolysis-condensation product, it hydrolyzes and partially condenses the above-mentioned hydrolyzable silane compound mixture (henceforth a reaction process. ) Can be produced. Hydrolysis and partial condensation are reaction which produces | generates the silanol group by the hydrolysis reaction of a hydrolysable group, and produces | generates the siloxane bond by dehydration condensation reaction of silanol groups as mentioned above. In the reaction step, the reaction conditions usually used for the reaction for hydrolytically condensing the hydrolyzable silane compound can be applied without particular limitation, and for example, water, a catalyst, an organic solvent, or the like can be used.

When water is used in the reaction step, the amount is preferably 25 to 9,900 parts by mass, and particularly preferably 100 to 1,900 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compound mixture. By carrying out the quantity of water in the said range, it becomes easy to control hydrolysis and condensation reaction.

As the catalyst to be used in the reaction step, it is preferable to use inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid, oxalic acid and maleic acid. As for the quantity of the catalyst to be used, 0.01-10 mass parts is preferable with respect to 100 mass of a hydrolyzable silane compound mixture, and 0.1-1 mass part is especially preferable.

You may use an organic solvent for the said reaction process. In that the organic solvent is a hydrolyzable silane compound upon hydrolysis, a condensation reaction, an organic solvent commonly used, and specifically there may be used any organic solvent (to manufacture of the ink of claim (A ^1)). An organic solvent may be used individually by 1 type, or may use 2 or more types together.

In the reaction step, the amount of the organic solvent is preferably 25 to 9,900 parts by mass, and particularly preferably 100 to 1,900 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compound mixture.

The partial hydrolysis-condensation product obtained is mix | blended with a negative photosensitive resin composition with the solvent used at the reaction process. Therefore, a solvent used in the reaction step, it is preferred to use a solvent for stabilizing a silanol group in the ink repellent (A ^2). As a solvent which stabilizes a silanol group, the compound which has a hydroxyl group and the dielectric constant ((epsilon)) in 25 degreeC is the range of 5-20 is mentioned.

Specifically, the C2-C8 glycol type | system | group monoalkyl ether acetate solvent, the glycol-type monoalkyl ether solvent, the glimmer type | system | group solvent, a C2-C4 hydrocarbon alcohol, etc. are mentioned. More specifically, it is a propylene glycol monomethyl ether acetate ((epsilon: 8.3)) as a glycol type | system | group monoalkyl ether acetate solvent, a propylene glycol monomethyl ether ((epsilon): 12.3) as a glycol type | system | group monoalkyl ether solvent, and a hydrocarbon alcohol. 2-propanol ((epsilon): 19.92) etc. are mentioned. Propylene glycol monomethyl ether is particularly preferable in view of high stabilizing effect of the silanol group.

It is preferable to perform a reaction process at the temperature from room temperature to the boiling point of a solvent on moderate stirring conditions. Although reaction time changes also with quantity of the raw material component to be used, reaction temperature, stirring conditions, etc., it is 0.5 to 24 hours generally, Preferably 1 to 10 hours is mentioned. After completion of the reaction, the resultant ink to the (A ^2), without removing the organic solvent, may be contained in the negative photosensitive resin composition of the present invention. By a conventional method and then removing the organic solvent and then isolated and the ink repellent (A ^2), it may be contained in the negative photosensitive resin composition.

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

When using the ink to the (A ¹⁾ as the ink repellent (A), the content thereof is more preferably 0.05 to 5% by weight and particularly preferably 0.2 to 1% by weight. If the content rate of ink repellent agent (A) is more than the lower limit of the said range, the effect of reducing the surface tension of the formed partition is excellent, and the partition excellent in ink repellency is obtained. If it is below the upper limit of the said range, the adhesiveness of a partition and a base material will become favorable.

When using the ink to the (A ²⁾ as to the ink (A), the content thereof is more preferably 0.1 to 6% by weight and is particularly preferably 0.2 to 3% by weight. If this to the content of the ink of claim (A ²⁾ the above-mentioned range, the partition wall of the optical element obtained has excellent storage stability of the negative-type photosensitive resin composition, and further from the negative-type photosensitive resin composition to the ink is excellent, and the smooth surface Have

The ink repellent agent (A) in this invention may have both the side chain which has group 1, and the side chain which has group 2 in one molecule. Moreover, the negative photosensitive resin composition of this invention contains both ink repellent agent (A) which has a side chain which has group (1), and ink repellent agent (A) which has a side chain which has group (2), and You may be. In these cases, the negative photosensitive resin composition can express high ink repellency and ink degradability.

[Photoinitiator (B)]

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

It is preferable that a photoinitiator (B) is a compound represented by following formula (3).

(3)

In formula (3), R <^31> represents a C1-C20 alkyl group, a C6-C30 aryl group, a C7-C30 arylalkyl group, or a cyano group. R <^32> represents R <^41> or OR <^42> , R <^41> and R <^42> represents a C1-C20 alkyl group, a C6-C30 aryl group, or a C7-C30 arylalkyl group, respectively. R ³³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R ³⁴ and R ³⁵ each independently represent R ⁴¹ , OR ⁴² , cyano group, or halogen atom. R ⁴¹ and R ⁴² are the same as above. a and b are the integers of 0-3 each independently, and c is an integer of 1-3.

As R ³¹ , the hydrogen atom of an alkyl group, an aryl group and an arylalkyl group is also represented 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 may be substituted with R ⁵⁵ , 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 having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a 2 to 20 carbon atom Heterocyclic group is shown.

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

The methylene group of the alkylene part of the substituent represented by said R <^31> , R <^33> , R <^43> -R <^55> is 1-5 by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond. It may be interrupted once, the branched side chain may be sufficient as the alkyl part of the said substituent, cyclic alkyl may be sufficient, and the alkyl terminal of the said substituent may be an unsaturated bond. R ³ may be combined with an adjacent benzene ring to form a ring.

Although the geometric isomer by the double bond of an oxime exists in the oxime ester compound in this invention, these are not distinguished, Formula (3) and the exemplary compound mentioned later show both a mixture or either one, It is not limited to the structure shown.

Examples of the alkyl group represented by R ⁴¹ to R ⁵⁵ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl and iso Octyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isocil, cyclopentyl, cyclohexyl, cyclohexylmethyl, vinyl , Allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, pentyloxyethyl, octyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyoxyethyl, 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, anthryl, phenanthrenyl, and phenyl, biphenylyl and naphthyl substituted with at least one alkyl group. , Anthryl and the like.

^Examples of the arylalkyl group represented by R ⁴¹ to R ⁵⁵ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and phenylethenyl.

Examples of the heterocyclic group represented by R ⁴³ to R ⁵⁵ include pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxoranyl, benzoxazol-2-yl, tetrahydropyranyl, pyrididyl and imidazoli 5-7 membered heterocycles, such as dill, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazil, and morpholinyl, are mentioned preferably.

Examples of the ring in which R ³³ may be formed as an adjacent benzene ring include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring. 5-7 membered rings are mentioned.

R ⁴¹ ~ R ⁵⁵ halogen atoms which may be substituted, and R ^34, a halogen atom represented by R ^35, there may be mentioned fluorine, chlorine, bromine and iodine.

The methylene group of the alkylene moiety of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond. It may be a species or two or more kinds of groups, and in the case of a group which can be stopped continuously, two or more kinds may be stopped continuously. Moreover, a branched side chain may be sufficient as the alkyl part of the said substituent, cyclic alkyl may be sufficient, and an unsaturated bond may be sufficient as the alkyl terminal of the said substituent.

Among the oxime ester compounds of the present invention, in formula (3), R ³¹ is an alkyl group having 11 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, or R ³³ is an alkyl group having 1 to 12 carbon atoms and an alkyl group having 13 to 20 carbon atoms interrupted 1 to 5 times by an ether bond or ester bond, in particular R ³¹ is an alkyl group having 11 to 20 carbon atoms or carbon An aryl group having 6 to 30 atoms, or R ³³ is a branched alkyl group having 8 or more carbon atoms which may be interrupted 1 to 5 times by an ether bond or ester bond; alkylene of an alkyl group the number of carbon atoms of methylene groups of parts which may be interrupted 1 to 5 times with an ether bond or ester bond that is at least 13 alkyl group; R ³³ is an alkyl group which is interrupted 1 to 5 times with a ether bond One; R ³³ is that the alkyl group is interrupted 1 to 5 times by an ester bond, the synthesis is easy and when used as a road, and a photopolymerization initiator, a high sensitivity, is dissolved at least 1% by weight in a solvent, satisfying the demand as a photopolymerization initiator Therefore, it is preferable. It is preferable to perform this measurement of solubility at 20-30 degreeC. As the solvent, propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone is preferable.

The oxime ester compound of this invention can also be dimerized via R <^31> or R <^32> as shown to following formula (4) and following formula (5).

[Chemical Formula 4]

[Chemical Formula 5]

As a specific example of the oxime ester compound represented by Formula (3), following compound No. The compound represented by 1-71 is mentioned.

[Chemical Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

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

[Chemical Formula 12]

As for the content rate of the photoinitiator (B) in the negative photosensitive resin composition of this invention, 1-15 mass% is preferable in the total solid in a negative photosensitive resin composition, 2-10 mass% is more preferable, 3 -6 mass% is especially preferable. If it is the said range, sclerosis | hardenability is favorable and a pattern and a line | wire width close | similar to a mask pattern can be formed in an exposure process and a developing process. Especially when the surface of a cured film shields the exposure light of 330 nm or less with a cut filter etc., even if it is a low exposure amount, ink repellency is favorable.

In the negative photosensitive resin composition of this invention, you may use photoinitiators other than a photoinitiator (B) together.

As a photoinitiator which can be used together, (alpha)-diketones, such as benzyl, diacetyl, methylphenylglyoxylate, 9,10-phenanthrenequinone; acyl phosphorus, such as benzoin; benzoin methyl ether, benzoin ethyl ether Acyloin ethers such as benzoin isopropyl ether; thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4 -Thioxanthones such as diethyl thioxanthone, 2,4-dichloro thioxanthone, 2,4-diisopropyl thioxanthone and thioxanthone-4-sulfonic acid; benzophenone, 4,4'-bis Benzophenones such as (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylamino Acetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2 Benzyl-2-dimethyla Acetophenones such as no-1- (4-morpholinophenyl) -butan-1-one; quinones such as anthraquinone, 2-ethylanthraquinone, camphorquinone and 1,4-naphthoquinone; Aminobenzoic acids such as ethyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoic acid isoamyl and 4-dimethylaminobenzoic acid 2-ethylhexyl; Halogen compounds such as silchloride and trihalomethylphenyl sulfone; acyl phosphine oxides; peroxides such as di-t-butylperoxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- Oxime esters such as (O-benzoyl oxime) and ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl oxime); Aliphatic amines such as triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate; 2-mercaptobenzimidazole, 2 Mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,4-butanolbis (3-mercaptobutylate), tris (2-mercaptopropaneyloxyethyl) isocyanurate, pentaerythritol tetra Thiol compounds, such as a kiss (3-mercapto butyrate), etc. are mentioned.

Among them, benzophenones, aminobenzoic acids, aliphatic amines, and thiol compounds are preferably used when used in combination with other photopolymerization initiators.

When it contains photoinitiators other than the photoinitiator (B) in a negative photosensitive resin composition, 20 mass% or less is preferable in the total solid in a negative photosensitive resin composition, and, as for the content rate, 1-15 mass% is more preferable. It is preferable and 2-10 mass% is especially preferable.

[Alkali Soluble Resin (C)]

Although it does not specifically limit as alkali-soluble resin (C), Resin (C1-1) which has a side chain which has an acidic group, and a side chain which has an ethylenic double bond, Resin which introduce | transduced the acidic group and ethylenic double bond into the epoxy resin ( C1-2), the monomer (C1-3) which has a side chain which has an acidic group, and the side chain which has ethylenic double bond, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

Resin (C1-1) has a side chain which has a reactive group obtained by copolymerizing the monomer which has a reactive group, such as a hydroxyl group, a carboxyl group, an epoxy group, and a monomer which has an acidic group, the copolymer which has a side chain which has an acidic group, and a reactive group It can synthesize | combine by dissolving and reacting the compound which has a functional group which can couple | bond, and an ethylenic double bond in a solvent.

As a monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2 -Hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N -Hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide, and the like.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and salts thereof. In addition, these monomers are used also 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, 2- (meth) acryloyloxyethane phosphoric acid etc. are mentioned as a monomer which has a phosphoric acid group other than the monomer which has the said carboxyl group.

Copolymerization of the monomer which has the said reactive group, and the monomer which has an acidic group can be performed by a conventionally well-known method.

As a monomer which has a hydroxyl group as a reactive group, the acid anhydride which has an ethylenic double bond, the compound which has an isocyanate group, and the ethylenic double bond, the compound which has an acyl chloride group and ethylenic double bond, etc. are mentioned.

Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, Tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride and the like.

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

Examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride and the like.

As a monomer which has a carboxyl group as a reactive group, the compound which has an epoxy group and ethylenic double bond is mentioned. Examples of the compound include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate. The dehydration condensation part of the hydroxyl group and carboxylic acid which generate | occur | produce here may react the acid anhydride which forms a part of cyclic structure, and may introduce a carboxyl group in resin (C1-1).

As a monomer which has an epoxy group as a reactive group, the compound which has a carboxyl group and ethylenic double bond is mentioned. Specific examples of the compound include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. The dehydration condensation part of the hydroxyl group and carboxylic acid which generate | occur | produce here may react the acid anhydride which forms a part of cyclic structure, and may introduce a carboxyl group in resin (C1-1).

Resin (C1-2) can be synthesize | combined by making a polybasic carboxylic acid or its anhydride react, after making an epoxy resin and the compound which has a carboxyl group and ethylenic double bond react.

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

Examples of the epoxy resin include, but are not particularly limited to, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, trisphenol methane type epoxy resins, epoxy resins having a naphthalene skeleton, Epoxy resin which has a biphenyl skeleton represented by following formula (C1-2a), the epoxy resin represented by following formula (C1-2b), the epoxy resin which has biphenyl skeleton represented by following formula (C1-2c), etc. are mentioned. .

[Chemical Formula 13]

(V is 1-50 in a formula (C1-2a), and 2-10 are preferable. Moreover, the hydrogen atom of a benzene ring each independently has a C1-C12 alkyl group, a halogen atom, or a substituent. The phenyl group may be substituted.)

[Formula 14]

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

[Chemical Formula 15]

(In formula (C1-2c), the hydrogen atom of a benzene ring may respectively independently be substituted by the C1-C12 alkyl group, a halogen atom, or the phenyl group which may have a substituent. U is 0-10. .)

Moreover, when making polybasic carboxylic anhydride react after making the epoxy resin represented by Formula (C1-2a)-(C1-2c) and the compound which has a carboxyl group and ethylenic double bond react, polybasic carboxylic acid Preference is given to using mixtures of dicarboxylic acid anhydrides and tetracarboxylic dianhydrides as anhydrides. By changing the ratio of the dicarboxylic acid anhydride and the tetracarboxylic acid dianhydride, the molecular weight can be controlled.

A commercial item can be used for resin (C1-2). As a commercial item, all are brand names, KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR-1535H, ZAR -2002H, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H, ZCR-1761H, ZAR-2001H (or above, Nippon Kayaku Co., Ltd.), EX1010 (made by Nagase Chemtex Co., Ltd.), etc. are mentioned.

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

As alkali-soluble resin (C), peeling of the coating film at the time of image development is suppressed, the point which can obtain a high resolution pattern, the point of linearity of a line, the external appearance after a postbaking process are maintained, and the smooth coating film surface is obtained. It is preferable to use resin (C1-2) from the point which is easy to hold.

Examples of the resin (C1-2) include a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin, and a phenol novolac type epoxy resin. Resin which introduce | transduced group and ethylenic double bond, Resin which introduce | transduced acidic group and ethylenic double bond to cresol novolak-type epoxy resin, Resin which introduce | transduced acidic group and ethylenic double bond to trisphenolmethane type epoxy resin, Formula (C1- Resin which introduce | transduced the acidic group and ethylenic double bond into the epoxy resin represented by 2a)-(C1-2c) is especially preferable.

It is preferable that the mass mean molecular weight (Mw) of alkali-soluble resin (C) is 1.5 * 10 <^3> -30 * 10 <^3> , and 2 * 10 <^3> -15 * 10 <^3> is especially preferable. Moreover, it is preferable that number average molecular weights (Mn) are 500-20x10 <^3> , and 1.0 * 10 <^3> -10 * 10 <^3> is especially preferable. If mass mean molecular weight (Mw) and mass mean molecular weight (Mn) are more than the lower limit of the said range, hardening at the time of exposure will be enough, and developability is favorable if it is below the upper limit of the said range.

It is preferable that the number of ethylenic double bonds which alkali-soluble resin (C) has in 1 molecule is three or more on average, and 6 or more are especially preferable. If the number of ethylenic double bonds is more than the lower limit of the said range, the alkali solubility of an exposed part and an unexposed part tends to differ, and fine pattern formation by a less exposure amount is attained.

It is preferable that the acid value of alkali-soluble resin (C) is 10-200 mgKOH / g, 30-150 mgKOH / g is more preferable, 50-100 mgKOH / g is especially preferable. If an acid value is the said range, the storage stability and developability of a negative photosensitive resin composition will become favorable.

Alkali-soluble resin (C) contained in a negative photosensitive resin composition may be 1 type, or 2 or more types of mixtures may be sufficient as it.

As for the content rate of alkali-soluble resin (C) in the negative photosensitive resin composition of this invention, 10-50 mass% is preferable in the total solid in a negative photosensitive resin composition, 12-40 mass% is more preferable, 15-30 mass% is especially preferable. If the content ratio is the said range, developability is favorable.

[Negative photosensitive resin composition]

The negative photosensitive resin composition of this invention is a ink repellent agent (A), a photoinitiator (B), alkali-soluble resin (C), a black coloring agent (D), a polymeric dispersing agent (E), and a dispersal auxiliary agent (F) as needed. , Crosslinking agent (G) and solvent (H). Furthermore, you may contain the following thermal crosslinking agents (I), a silane coupling agent (J), microparticles | fine-particles (K), a phosphoric acid compound (L), and other additives.

By using the negative photosensitive resin composition of this invention, even if it shields the exposure light of 330 nm or less, ink repellency is favorable and the uniform partition obtained by using the negative photosensitive resin composition and the composition which are good in reproducing the line width of a mask is obtained. It can manufacture. Therefore, even when fine patterning is required, it can respond. The reason is considered as follows.

As a photoinitiator, the high sensitive compound which absorbs and activates the exposure light exceeding 330 nm efficiently is needed, and a photoinitiator (B) can be selected.

According to the knowledge of the present inventors, when the exposure light of 330 nm or less is shielded, the hardenability of the partition surface is extremely lowered, the ink repellent portion on the surface tends to be scraped, and the ink repellency tends to be lowered. If it is a negative photosensitive resin composition containing a photoinitiator (B), the curability of a partition surface can be made high. In the negative photosensitive resin composition containing a compound having poor migration to the partition surface as the ink repellent agent, when the barrier surface is cured, the ink repellent agent cannot move to the partition wall surface yet, but the transition to the partition surface is good. Ink repellency becomes favorable by using an ink repellent agent.

The combination of an ink repellent agent and a photoinitiator (B) is a viscosity which can apply the negative photosensitive resin composition besides the said curability and surface transfer property, and a stable combination is needed. By examination of this inventor, the combination of ink repellent agent (A) and a photoinitiator (B) was found out.

[Black Coloring Agent (D)]

The negative photosensitive resin composition of this invention may contain the black coloring agent (D).

When using a negative photosensitive resin composition for black-matrix formation which is a grid | lattice black part surrounding the pixel of R, G, B 3 color of the color filter of a liquid crystal display element, it is preferable to contain a black coloring agent (D). .

As a black coloring agent (D), carbon black, aniline black, anthraquinone type black pigment, a perylene type black pigment, C. I. pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned specifically ,. You may use the mixture of organic pigments, such as a red pigment, a blue pigment, a green pigment, and a yellow pigment, an azomethine type black pigment, and an inorganic pigment. As a black coloring agent (D), carbon black is preferable from a price and light-shielding magnitude | size, and carbon black may be surface-treated with resin etc. Moreover, in order to adjust color tone, a blue pigment and a purple pigment can be used together. As for the black matrix-on-array color filter and the organic EL element, a coating film and a partition wall having low dielectric constant and high resistance are required. In order to obtain the above-mentioned coating film and a partition, it is preferable to use the mixture of the said organic pigment and an azomethine type black pigment.

As carbon black, it is preferable that the specific surface area by BET method is 50-200 m <2> / g from a viewpoint of the shape of a black matrix. If the specific surface area is 50 m &lt; 2 &gt; / g or more, the black matrix shape is not deteriorated well. If it is 200 m <2> / g or less, a dispersion adjuvant will not be adsorbed excessively to carbon black, and it will become unnecessary to mix | blend a large amount of dispersion adjuvant in order to express various physical properties.

Moreover, as carbon black, it is preferable that the oil absorption amount of dibutyl phthalate is 120 kPa / 100g or less from a viewpoint of a sensitivity, and it is more preferable that it is small.

Moreover, it is preferable that the average primary particle diameter by the transmission electron microscope observation of carbon black is 20-50 nm. If the average primary particle diameter is 20 nm or more, it can disperse | distribute to high concentration in a negative photosensitive resin composition, and the negative photosensitive resin composition with favorable time-lapse stability is easy to be obtained. If it is 50 nm or less, the black matrix shape does not deteriorate well. Moreover, as average secondary particle diameter by transmission electron microscope observation, 80-200 nm is preferable.

When the negative photosensitive resin composition of the present invention contains a black colorant (D) and is used for forming a black matrix, the content ratio of the black colorant (D) in the negative photosensitive resin composition is in the negative photosensitive resin composition. 15-80 mass% is preferable in a total solid, 20-70 mass% is more preferable, 25-65 mass% is especially preferable. Within the above range, the resulting negative-working photosensitive resin composition has good sensitivity and the formed barrier rib is excellent in light shielding property.

[Polymer Dispersant (E)]

When a negative photosensitive resin composition contains dispersible materials, such as said black coloring agent (D), in order to improve the dispersibility, it is preferable to contain a polymeric dispersing agent (E). The polymer dispersant (E) is not particularly limited and may be urethane, polyimide, alkyd, epoxy, polyester, melamine, phenolic, acrylic, polyether, vinyl chloride or vinyl chloride vinyl acetate copolymer. Although a system, a polyamide type, a polycarbonate type etc. are mentioned, a urethane type or polyester type is preferable. In addition, the polymer dispersant (E) may have a structural unit derived from ethylene oxide and / or propylene oxide.

When the polymer dispersant (E) is used for dispersing the black colorant (D), it is preferable to use a polymer dispersant (E) having a basic group in consideration of the affinity for the black colorant (D). Basic groups include, but are not limited to, primary, secondary or tertiary amino groups.

As a polymeric dispersant (E), you may use a commercial item. As a commercial item, Disparon DA-7301 (brand name, product made by Kusumoto Kasei Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (all brand name, BYK-Chemie company make), Solsper 5000, Solsper 17000 (all the above) And Geneca Co., Ltd.) may be mentioned.

It is preferable that it is 5-30 mass% with respect to a black coloring agent (D), and, as for the content rate of a polymer dispersing agent (E), 10-25 mass% is especially preferable. The dispersibility of a black coloring agent (D) improves that it is more than the lower limit of the said range, and developability of a negative photosensitive resin composition becomes it favorable that it is below the upper limit of the said range.

[Dispersion Aids (F)]

The negative photosensitive resin composition may contain a phthalocyanine pigment derivative and a metal phthalocyanine sulfonamide compound as a dispersion adjuvant (F). Dispersion adjuvant (F) is considered to have a function to adsorb | suck to dispersible materials, such as a black coloring agent (D), and a polymeric dispersing agent (E), and to improve dispersion stability.

[Cross-linking system (G)]

The negative photosensitive resin composition of this invention may also contain a crosslinking agent (G) as an arbitrary component which accelerates radical hardening. As a crosslinking agent (G), the compound which has two or more ethylenic double bonds in one molecule, and does not have an acidic group is preferable. When a negative photosensitive resin composition contains a crosslinking agent (G), the hardenability of the said alkali-soluble resin (C) at the time of exposure improves, and the exposure amount at the time of forming a partition can be reduced.

Although it will not specifically limit, if it is a compound which has this condition as a crosslinking agent (G) which has two or more ethylenic double bonds in one molecule, and does not have an acidic group, Diethylene glycol di (meth) acrylate and tetraethylene glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tree (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, e Isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, bis {4- (allylbicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide) phenyl} methane, N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), urethane acryl The rate etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

A commercial item can be used as a crosslinking agent (G). As a commercial item, KAYARAD DPHA (brand name, Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9530 (brand name, Shin-Nakamura Chemical Co., Ltd. make, dipentaeryt A mixture of lititol pentaacrylate and dipentaerythritol hexaacrylate)), V # 802 (trade name, product of Osaka Organic Chemical Industry Co., Ltd., dipentaerythritol acrylate, tripentaerythritol acrylate, tetrapentaerythritol acrylate Mixture), NK ester A-9300 (brand name, the product made by Shin-Nakamura Chemical Co., Ltd., ethoxy isocyanuric acid triacrylate), NK ester A-9300-1CL (brand name, the product made by Shin-Nakamura Chemical Co., Ltd., ε-caprolactone modified tris -(2-acryloxyethyl) isocyanurate), BANI-M (brand name, the product made by Maruzen petrochemical company, bis {4- (allylbicyclo [2.2.1] hepto-5) -En-2,3-dicarboxyimide) phenyl} methane), BANI-X (trade name, manufactured by Maruzen Petrochemical, N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-) 5-ene-2,3-dicarboxyimide)) etc. are mentioned. As urethane acrylate, KAYARAD UX series by Nippon Kayaku Co., Ltd. is mentioned, As a specific brand name, UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D-P20, etc. Can be mentioned.

Among them, KAYARAD DPHA and NK Ester A-9530 are preferable because they enhance the sensitivity of the cured film obtained from the negative-type photosensitive resin composition. NK Ester A-9300, BANI-M and BANI-X are preferred in that they give hardness to the cured film to suppress heat sagging. NK Ester A-9300-1CL is preferred in that flexibility is imparted to the cured film. Since urethane acrylate can implement | achieve an appropriate image development time, and developability becomes favorable, it is preferable.

As for the content rate of the crosslinking agent (G) in the negative photosensitive resin composition of this invention, 3-30 mass% is preferable in the total solid in a negative photosensitive resin composition, 5-20 mass% is more preferable, 7-20 15 mass% is especially preferable. Within this range, the alkali developability of the negative-working photosensitive resin composition is improved.

[Solvent (H)]

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

The solvent (H) which the negative photosensitive resin composition of this invention contains is the said ink repellent agent (A), photoinitiator (B), alkali-soluble resin (C) which a negative photosensitive resin composition contains, and black as needed. Colorant (D), polymeric dispersant (E), dispersing aid (F) and crosslinking agent (G), and further, dissolving or dispersing any component mentioned later uniformly and apply | coating negative photosensitive resin composition to the base material in which a partition is formed Although it does not restrict | limit especially if it has a function which makes uniform and simple, and does not have reactivity with these components, For example, the same solvent as the solvent used at the time of synthesis | combination of ink repellent agent (A) can be used.

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

The negative photosensitive resin composition of this invention is a ink repellent agent (A), a photoinitiator (B), alkali-soluble resin (C), a black coloring agent (D), a polymeric dispersing agent (E), and a dispersal auxiliary agent (F) as needed. , Crosslinking agent (G) and solvent (H). Furthermore, you may contain the following thermal crosslinking agents (I), a silane coupling agent (J), microparticles | fine-particles (K), a phosphoric acid compound (L), and other additives.

[Heat crosslinking system (I)]

Thermal crosslinking agent (I) is a compound which has 2 or more groups which can react with a carboxyl group and / or a hydroxyl group. The thermal crosslinking agent (I) has the effect of reacting with the alkali-soluble resin (B) when the alkali-soluble resin (B) has a carboxyl group and / or a hydroxyl group, thereby increasing the crosslinking density of the cured film and improving heat resistance.

As thermal crosslinking agent (I), at least 1 sort (s) chosen from the group which consists of an amino resin, an epoxy compound, an oxazoline compound, a polyisocyanate compound, and a polycarbodiimide compound is mentioned preferably. These compounds may be used alone or in combination of two or more.

As for the content rate of the thermal crosslinking agent (I) in the negative photosensitive resin composition of this invention, 1-50 mass% is preferable in a total solid in a negative photosensitive resin composition, and 5-30 mass% is especially preferable. Within this range, the developability of the resulting negative-working photosensitive resin composition is improved.

[Silane coupling agent (J)]

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

Specific examples of the silane coupling agent (J) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, and 3-acryloyloxypropyltrimethoxy Silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltri Methoxysilane, polyoxyalkylene chain-containing triethoxysilane, etc. are mentioned. These may be used alone or in combination of two or more.

A commercial item can be used as a silane coupling agent (J). As a commercial item, KBM5013 (brand name, the Shin-Etsu Chemical company make, 3-acryloyloxypropyl trimethoxysilane) etc. are mentioned.

As for the content rate of the silane coupling agent (J) in the negative photosensitive resin composition of this invention, 0.1-20 mass% is preferable in the total solid in a negative photosensitive resin composition, and 1-10 mass% is especially preferable. The base material adhesiveness of the cured film formed of a negative photosensitive resin composition improves that it is more than the lower limit of the said range, and ink repellency is favorable for it being below the upper limit of the said range.

[Particulate matter (K)]

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

The fine particles (K) are not particularly limited, and inorganic fine particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO); organic type such as polyethylene and polymethyl methacrylate (PMMA) Although microparticles | fine-particles are mentioned, Inorganic microparticles | fine-particles are preferable in consideration of heat resistance, and silica or zirconia is especially preferable in consideration of availability and dispersion stability. Moreover, when a negative photosensitive resin composition contains a black coloring agent (G) and a polymeric dispersing agent (E), when the adsorption capacity of the polymeric dispersing agent (E) is considered, microparticles | fine-particles (K) are negatively charged, and It is desirable to have. In consideration of the exposure sensitivity of the negative photosensitive resin composition, it is preferable that the fine particles do not absorb light irradiated at the time of exposure, i-line (365 nm) and h-line (405 nm), which are the main emission wavelengths of an ultrahigh pressure mercury lamp. It is particularly preferable not to absorb the g line (436 nm).

As microparticles | fine-particles (K), a silica is preferable. As silica, colloidal silica is preferable. In general, colloidal silica includes silica hydrosol dispersed in water and organo silica sol in which water is substituted with an organic solvent. However, organo silica sol using an organic solvent as a dispersion medium is preferable.

As such an organo silica sol, a commercial item can be used, and as a commercial item, all are the brand name of Nissan Chemical Industries, Ltd. made, and PMA-ST (silica particle diameter: 10-20 nm, silica solid content: 30 mass%, propylene glycol) Monomethyl acetate: 70 mass%.), NPC-ST (silica particle diameter: 10-20 nm, silica solid content: 30 mass%, n-propyl cellosolve: 70 mass%.), IPA-ST (silica particle diameter : 10-20 nm, silica solid content: 30 mass%, IPA: 70 mass%.) Etc. are mentioned.

As for the content rate of the microparticles | fine-particles (K) in the negative photosensitive resin composition of this invention, 3-40 mass% is preferable in the total solid in a negative photosensitive resin composition, and 5-30 mass% is especially preferable. Most preferably, they are 7 mass% or more and less than 25 mass%. When the content ratio is within the above range, ink repellency is good, and storage stability of the negative photosensitive resin composition is good.

[Phosphoric acid compound (L)]

The negative photosensitive resin composition may contain the phosphoric acid compound (L) as needed. By including the phosphoric acid compound (L) in the negative-working photosensitive resin composition, adhesion with the substrate can be improved. Examples of the phosphoric acid compound (L) include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, and tris (meth) acryloyloxyethyl phosphate.

[Other additives]

The negative-working photosensitive resin composition of the present invention may further contain a curing accelerator, a thickener, a plasticizer, a defoaming agent, a leveling agent, an anti-cratering agent, and an ultraviolet absorber.

[Preferred Combinations of Negative Photosensitive Resin Composition]

The negative photosensitive resin composition of the present invention is preferably selected in composition and mixing ratio in accordance with the application and required characteristics.

Preferable compositions of various compounding components in the negative-working photosensitive resin composition of the present invention are shown below.

To print the (A): a preferred combination of 6-10 the preferred combination of 1 to 5 or the ink repellent first (A ²⁾ of the ink repellent first (A ^1), 0.01 in the total solid content of the negative photosensitive resin composition -10 mass%,

Photoinitiator (B): The compound No. of the international publication 2008/078678. It is 1-58, 0.01-10 mass% in the total solid in the negative photosensitive resin composition,

Alkali-soluble resin (C): (C1-2a), (C1-2b), (C1-2c) and at least 1 selected from the group which consists of resin which introduce | transduced the acidic group and ethylenic double bond to cresol novolak-type epoxy resin. It is a species, 12-40 mass% in the total solid in a negative photosensitive resin composition,

Solvent (H): 2-propanol, γ-butyrolactone, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, cyclohexa It is at least 1 sort (s) chosen from the group which consists of a rice paddy and butyl lactate, 50-99 mass% in a negative photosensitive resin composition.

[Method of producing negative-type photosensitive resin composition]

As a method of manufacturing a negative photosensitive resin composition, ink repellent agent (A), a photoinitiator (B), alkali-soluble resin (C), a black coloring agent (D), a polymeric dispersing agent (E), a dispersal auxiliary agent (F) as needed. ), A crosslinking agent (G) and a solvent (H). Moreover, the method of mixing with the following heat crosslinking agents (I), a silane coupling agent (J), microparticles | fine-particles (K), a phosphoric acid compound (L), and other additives is preferable.

The negative photosensitive resin composition of this invention is used as materials, such as photolithography, similarly to the conventional negative photosensitive resin composition, and the cured film obtained by hardening the coating film of this composition is an optical element in which the cured film of a normal negative photosensitive resin composition is used. It is possible to use as a member of.

[Method for Manufacturing Bulkhead for Optical Element]

It is applied to manufacture of a partition for an optical element having a partition located between a plurality of pixels and adjacent pixels on a substrate.

The negative photosensitive resin composition of this invention is apply | coated on the said board | substrate, and a coating film is formed (coating film formation process), then the said coating film is heated (prebaking process), and then only the part used as a partition of the said coating film is exposed. Photocure (exposure step), and then, the coating film other than the photocured portion is removed to form a partition wall formed of the photocured portion of the coating film (developing step), and then the formed partition wall is heated (post-baking). Process), the partition for an optical element can be manufactured.

In addition, when the negative photosensitive resin composition of this invention contains a black coloring agent (D), the partition for optical elements is formed as a black matrix.

Although the material of a board | substrate is not specifically limited, For example, various glass plates; polyester (polyethylene terephthalate etc.), polyolefin (polyethylene, polypropylene etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, Thermoplastic plastic sheets such as poly (meth) acrylic resins; cured sheets of thermosetting resins such as epoxy resins and unsaturated polyesters; Particularly, a heat-resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance.

1: is sectional drawing which shows typically the manufacture example of the partition for optical elements using the negative photosensitive resin composition of this invention. FIG. 1 (I) is a figure which shows the cross section of the state in which the coating film 2 which consists of the negative photosensitive resin composition of this invention was formed on the board | substrate 1. FIG. (II) is a diagram schematically showing an exposure process. (III) is sectional drawing which shows the board | substrate 1 after the image development process, and the partition 6 formed on the board | substrate.

Hereinafter, a method for producing an optical element barrier rib using the negative photosensitive resin composition of the present invention will be described in detail with reference to Fig.

(Coating film forming step)

As shown in FIG. 1 (I), the negative photosensitive resin composition of this invention is apply | coated on the board | substrate 1, and the coating film 2 which consists of a negative photosensitive resin composition is formed. In addition, before forming the coating film 2 of the negative photosensitive resin composition on the board | substrate 1, it is preferable to wash the coating surface of the negative photosensitive resin composition of the board | substrate 1 by alcohol washing | cleaning, ultraviolet / ozone washing, etc. Do.

The coating method of the negative photosensitive resin composition is not particularly limited as long as it is a method of forming a coating film having a uniform film thickness, and the spin coating method, the spray method, the slit coating method, the roll coating method, the rotation coating method, the bar coating method, and the like. The method used for normal coating film formation is mentioned.

The film thickness of the coating film 2 is determined in consideration of the finally obtained height of the partition wall. As for the film thickness of the coating film 2, 100-3,000% of the height of the partition wall finally obtained is preferable, and 100-2,000% is especially preferable. The film thickness of the coating film 2 is preferably 0.3 to 325 mu m, particularly preferably 1.3 to 65 mu m.

(Pre-bake process)

In the coating film forming step, the coating film 2 formed on the substrate 1 is heated to obtain a film 2. By heating, the volatile component containing the solvent contained in the negative photosensitive resin composition which comprises a coating film is volatilized and removed, and the film with no adhesiveness is obtained. Moreover, ink repellent agent (A) moves to the coating film surface vicinity. As a heating method, the method of heat-processing the coating film 2 with a board | substrate 1 with a heating apparatus, such as a hotplate and oven, at 50-120 degreeC for about 10 to 2,000 second is mentioned.

In addition, although it is also possible to remove volatile components, such as a solvent, by the heating in a prebaking process as mentioned above, in order to remove volatile components, such as a solvent, drying processes, such as vacuum drying other than heating (drying), are prebaking process You may provide separately before. Moreover, in order to dry efficiently, without making the nonuniformity of a coating film external appearance generate | occur | produce, it is more preferable to use together heating and vacuum drying which combined with the drying by the said prebaking process. Although vacuum drying conditions differ also according to the kind, compounding ratio, etc. of each component, Preferably, it can carry out in the wide range of about 10 to 300 second at 500-10 Pa.

(Exposure step)

As shown in Fig. 1 (II), the film 2 is irradiated with light 5 through a mask 4 having a predetermined pattern. Only the predetermined pattern portion cut in the mask 4 is transmitted through the light 5 to reach the film on the substrate 1 and only the portion is photocured. Therefore, when the barrier rib is formed, the predetermined pattern is formed in a shape suitable for the shape of the barrier rib.

For example, it is preferable that the mean of a partition width after a postbaking process is 100 micrometers or less, and 20 micrometers or less are especially preferable. Moreover, it is preferable that the average of the distance between adjacent partitions is 500 micrometers or less, and 300 micrometers or less are especially preferable. It is preferable to use the mask in which the pattern was formed so that it might become the said range.

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

As the light 5 to be irradiated, an excimer laser such as visible light, ultraviolet light, far ultraviolet light, KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, KrAr excimer laser or Ar ₂ excimer laser; Electron beam and the like. Moreover, as irradiation light 5, the electromagnetic wave of wavelength 100-600 nm is preferable, the light ray which has a distribution in the range of 300-500 nm is more preferable, i line (365 nm) and h line (405 nm) And g line (436 nm) are particularly preferred. For example, when using the exposure method by a mirror projection (MPA) system, exposure light is irradiated by cutting the electromagnetic wave of 330 nm or less. Thus, in the manufacturing method of this invention, exposure which cut the electromagnetic wave of 330 nm or less may be performed as needed.

A well-known ultrahigh pressure mercury lamp etc. can be used as an irradiation apparatus. The exposure amount is preferably 5 to 1,000 mJ / cm 2, more preferably 5 to 200 mJ / cm 2, more preferably 10 to 100 mJ / cm 2 on the i line basis when the electromagnetic wave of 330 nm or less is cut by a cut filter or the like. More preferably, 15-50 mJ / cm <2> is especially preferable. When exposure amount is more than the lower limit of the said range, hardening of the negative photosensitive resin composition used as a partition is enough, and melt | dissolution and peeling from the board | substrate 1 do not produce easily in subsequent development. When the upper limit of the above range is not exceeded, high resolution is obtained. Even when the surface of the cured film obtained from the negative photosensitive resin composition of this invention cuts the electromagnetic wave of 330 nm or less with a cut filter etc., ink repellency is especially favorable.

Although exposure time changes with exposure amount, the composition of a negative photosensitive composition, the thickness of a coating film, etc., 1 to 60 second is preferable and 5 to 20 second is especially preferable.

(Developing step)

Development is carried out using a developer, and the unexposed portions 2 on the substrate 1 shown in Fig. 1 (II) are removed. Thus, the structure of the partition 1 formed by the cured film of the negative photosensitive resin composition on the substrate 1 and the substrate as shown in the sectional view in Fig. 1 (III) is obtained. In addition, the part enclosed by the partition 6 and the board | substrate 1 is a part called the dot 7 in which a pixel is formed by ink injection etc. In FIG. The obtained board | substrate 10 becomes a board | substrate which can be used for manufacture of the optical element by an inkjet system through the post-baking process mentioned later.

As the developing solution, an aqueous alkali solution containing alkalis such as inorganic alkalis, amines, alcohol amines and quaternary ammonium salts can be used. In order to improve solubility and to remove residues, an organic solvent such as a surfactant or alcohol may be added to the developing solution.

The development time (the time for which the developer comes into contact with the developer) is preferably 5 to 180 seconds. Moreover, the image development method can be mentioned the mounting method, the dipping method, the shower method, etc. After the development, the water on the substrate 1 and the partition walls 6 can be removed by carrying out high pressure water washing or water washing and air drying with compressed air or compressed nitrogen.

Moreover, it is preferable that the film thickness change of the cured film of the part used as a partition before and behind a developing process is 60 nm or less, It is more preferable that it is 50 nm, It is especially preferable that it is 45 nm or less. When the film thickness change is 60 nm or less, the ink repellent layer for expressing ink repellency of the cured film surface layer after exposure remains sufficiently on the surface, and ink repellency of the cured film after postbaking becomes favorable.

(Post-bake process)

The partition wall 6 on the substrate 1 is heated. As a heating method, the partition 6 is heat-processed for 5 to 90 minutes at 150-250 degreeC with heating apparatuses, such as a hotplate and oven, with the board | substrate 1, for example. By heat processing, the partition 6 which consists of a cured film of the negative photosensitive resin composition on the board | substrate 1 hardens further, and the shape of the dot 7 enclosed by the partition 6 and the board | substrate 1 is also seen more. It is immobilized. It is particularly preferable that the heating temperature is 180 DEG C or higher. If the heating temperature is too low, hardening of the partition wall 6 is insufficient, so that sufficient chemical resistance is not obtained, and the solvent contained in the ink when ink is injected into the dot 7 in a subsequent inkjet coating step. Thereby, the partition wall 6 may swell or ink may spread. On the other hand, if the heating temperature is too high, thermal decomposition of the partition walls 6 may occur.

As for the negative photosensitive composition of this invention, the mean of a partition width is 100 micrometers or less, and 20 micrometers or less are especially preferable. Moreover, 500 micrometers or less are preferable and, as for the average of the distance between adjacent partitions (dot width), 300 micrometers or less are especially preferable. The average height of the barrier ribs is preferably 0.05 to 50 占 퐉, more preferably 0.2 to 10 占 퐉.

The ink repellency of the coating film cured film formed from the negative photosensitive resin composition of this invention can be estimated by the contact angle of water and propylene glycol 1-monomethyl ether 2-acetate (henceforth PGMEA), and the contact angle of water is 90 degree | times. The above is preferable, and 95 degree or more is more preferable. Moreover, 30 degree or more is preferable, as for the contact angle of PGMEA, 35 degree or more is more preferable, 40 degree or more is especially preferable. It is especially preferable that the ink repellency of a coating film cured film is 90 degree or more and the contact angle of PGMEA is 30 degree or more.

[Manufacturing method of optical element]

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

(An ink-lacquering step)

Examples of the method for treating the ink with an alkaline aqueous solution include a cleaning treatment with an alkaline aqueous solution, an ultraviolet cleaning treatment, an ultraviolet / ozone cleaning treatment, an excimer cleaning treatment, a corona discharge treatment, and an oxygen plasma treatment.

The cleaning treatment with the alkaline aqueous solution is a wet treatment in which the surface of the substrate is cleaned using an aqueous alkali solution (potassium hydroxide, tetramethylammonium hydroxide aqueous solution, or the like).

The ultraviolet ray cleaning process is a dry process for cleaning the surface of a substrate using ultraviolet rays.

The ultraviolet / ozone cleaning treatment is a dry treatment for cleaning the substrate surface using a low pressure mercury lamp emitting 185 nm and 254 nm.

An excimer washing process is a dry process which wash | cleans a board | substrate surface using the xenon excimer lamp which emits 172 nm.

The corona discharge treatment is a dry treatment in which corona discharge is generated in the air using a high frequency high voltage to clean the surface of the substrate.

The oxygen plasma treatment is a dry treatment which cleans the surface of a substrate by using a high-frequency "plasma" state in which oxygen is excited by a high-frequency power source or the like as a trigger in a vacuum.

As a method for treating the ink, a dry treatment method such as an ultraviolet / ozone cleaning treatment is preferable from the viewpoint of convenience. UV / ozone can be generated using commercially available equipment. It is possible to perform the chlorination treatment by performing the treatment in a range of 1 to 10 minutes in the air and at room temperature without deteriorating the oil repellency of the partition, with a substrate having a partition wall formed in the ultraviolet / ozone device. The treatment time may be adjusted in accordance with the individual ultraviolet / ozone device to a time that does not hinder the oil repellency of the partition wall.

By this inking process, sufficient ink removal of dots remaining after the formation of the partition wall can be sufficiently carried out to prevent the inking of the dots, and it is possible to prevent whitening phenomenon such as a color display device using the obtained optical element. It becomes possible.

(Ink injection process)

And ink is injected into the dots after the ink-affinity treatment step by the ink-jet method to form pixels. This process can be performed similarly to a conventional method using the inkjet apparatus generally used for the inkjet method. The inkjet device used for forming such a pixel is not particularly limited, but a method of continuously spraying charged ink and controlling the magnetic field, a method of intermittently spraying ink using a piezoelectric element, and heating the ink An inkjet device using various methods such as a method of intermittently jetting using the foaming can be used.

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 barrier ribs, the ink-philic treatment of dots, and the ink injection by the ink-jet method are as described above. In the color filter, the shape of the pixel to be formed may be any known arrangement among stripe, mosaic, triangle, four-pixel arrangement, and the like.

The ink used for pixel formation mainly contains a coloring component, a binder resin component, and a solvent. As the coloring component, it is preferable to use pigments and dyes excellent in heat resistance, light resistance, and the like. As the binder resin component, a transparent and heat-resistant resin is preferable, and acrylic resin, melamine resin, urethane resin and the like can be given. The aqueous ink contains water as a solvent and, if necessary, a water-soluble organic solvent, and contains a water-soluble resin or a water-dispersible resin as a binder resin component, and includes various auxiliaries as necessary. The oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and includes various auxiliaries as necessary.

Moreover, after injecting ink by the inkjet method, it is preferable to perform drying, heat-hardening, and ultraviolet curing as needed.

After forming the pixel, a protective film layer is formed as necessary. It is preferable to form a protective film layer for the purpose of raising surface flatness, and for the purpose of blocking the eluate from the ink of a partition and a pixel part from reaching a liquid crystal layer. In the case of forming the protective film layer, it is preferable to remove the ink repellency of the partition wall in advance. When ink repellency is not removed, it is not preferable because the coating liquid for overcoat is splashed and a uniform film thickness is not obtained. Examples of the method for removing the ink repellency of the barrier rib include a plasma ashing treatment and a light ashing treatment.

Moreover, it is preferable to form a photo spacer on the black matrix which consists of a partition for the high quality of the liquid crystal panel manufactured using a color filter as needed.

 [Production of organic EL display device]

Prior to forming the barrier ribs, a transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by a sputtering method or the like, and the transparent electrode is etched in a desired pattern as required. Next, a barrier rib is formed using the negative-working photosensitive resin composition of the present invention, and the hole transporting material and the solution of the light emitting material are sequentially applied to the dots and dried by the ink jet method after the dyeing of the dots by the ink- Transport layer, and light-emitting layer. Thereafter, an electrode such as aluminum is formed by a vapor deposition method or the like to obtain a pixel of the organic EL display element.

[Production of Organic TFT Array]

Organic TFT array can be manufactured through the process of the following (i)-(iii).

(i) A partition is formed in transparent base materials, such as glass, using the negative photosensitive resin composition of this invention. After the dyeing process of the dot, the solution of the gate electrode material is applied to the dots using the inkjet method to form the gate electrode.

(ii) After the gate electrode is formed, a gate insulating film is formed thereon. After the partition walls are formed on the gate insulating film using the negative photosensitive resin composition of the present invention, the solution of the source / drain electrode material is applied to the dots by using the ink jet method after the dyeing of the dots, .

(iii) after the source and drain electrodes are formed, a partition wall is formed using the negative photosensitive resin composition of the present invention so as to surround a region including a pair of source and drain electrodes, and after the inking treatment of the dots, The inkjet method is used to apply a solution of an organic semiconductor to dots, and an organic semiconductor layer is formed between the source and drain electrodes.

In addition, (i)-(iii) may use the partition which used the negative photosensitive resin composition of this invention each in only one process, and the partition which used the negative photosensitive resin composition of this invention in two or more processes is used. You may use it.

[Production of Organic EL Lighting Device]

It can manufacture similarly to manufacture of organic electroluminescent display element. A light emitting layer may laminate | stack the light emitting body which colors each color, such as red, green, blue, etc. by inkjet, and may apply | coat and apply | coat the said light emitting body on a plane.

Example

Although an Example demonstrates this invention further in detail below, this invention is not limited to these Examples. In addition, Examples 1-21 are Examples and Examples 31-33 are comparative examples.

Each measurement was carried out in the following manner.

The number average molecular weight (Mn) was measured by gel permeation chromatography using polystyrene as a standard.

The content rate of the fluorine atom in ink repellent agent (A) was computed by ¹⁹ F NMR measurement using 1, 4- ditrifluoromethylbenzene as a standard substance. The amount of ethylenic double bonds in the ink repellent agent (A) was calculated by ¹ H NMR measurement using 1,4-ditrifluoromethylbenzene as a standard substance.

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

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

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

MEK: 2-butanone.

C6FMA: CH ₂ = C (CH ₃ ) COOOCH ₂ CH ₂ (CF ₂ ) ₆ F.

MAA: Methacrylic acid.

MMA: Methyl methacrylate.

PME400: Blender PME-400 (manufactured by Nippon Oil Industries, Inc., α-methyl-ω-methacryloyloxypoly (oxyethylene) .CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ : K in the formula represents the mean value between molecules, and the value of k is about 9.).

PME1000: Blender PME-1000 (manufactured by Nippon Oil Industries, Inc., α-methyl-ω-methacryloyloxypoly (oxyethylene) .CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ : K in the formula represents the mean value between molecules, and the value of k is 23).

V-65: Brand name (made by Wako Pure Chemical Industries. 2,2'- azobis (2, 4- dimethylvaleronitrile.)).

2-HEMA: 2-hydroxyethyl methacrylate.

GMA: glycidyl methacrylate.

AOI: 2-acryloyloxyethyl isocyanate (Showa Denko make, brand name:

Karenz AOI).

DBTDL: dibutyltin dilaurate.

TBQ: t-butyl-p-benzoquinone.

(Compound used for the synthesis of ink repellent agent (A ² ))

Compound (a7-1): CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (manufactured by Asahi Glass Co., Ltd.).

Compound (a8-1): Si (OC ₂ H ₅ ) ₄ (manufactured by Cole Coat, Inc.).

Compound (a9-1): CH ₂ = CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (manufactured by Tokyo Kasei Co., Ltd.).

TMMS: trimethylmethoxysilane [(CH ₃ ) ₃ Si (OCH ₃ )] (manufactured by Tokyo Kasei Co., Ltd.).

PGME: Propylene glycol monomethyl ether.

PGMEA: Propylene glycol monomethyl ether acetate.

(Photoinitiator (B))

Compound No. 1-3, compound No. 7, compound No. 10, compound No. 12, Compound No. 20, compound No. 33, compound No. 45 to 51 and compound no. The compound represented by 53-58.

(Photoinitiators other than a photoinitiator (B))

OXE02: Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl oxime) (made by Chiba Specialty Chemicals, brand name: OXE02) .

IR907: Brand name; IRGACURE907, BASF Corporation make, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

EAB: 4,4'-bis (diethylamino) benzophenone (made by Tokyo Kasei Co., Ltd.).

(Alkali-soluble resin (C))

EX1010: Resin which introduce | transduced ethylenic double bond and acidic group into the epoxy resin represented by said Formula (C1-2b) (made by Nagase ChemteX, brand name: EX-1010. Solid content: 60 mass%, PGMEA: 40 mass%.) .

ZCR1761: Resin which introduce | transduced ethylenic double bond and acidic group into the epoxy resin which has a biphenyl skeleton represented by said formula (C1-2a) (made by Nippon Kayaku Co., brand name: ZCR-1761H. Solid content: 60 mass%, PGMEA: 40) mass%.).

ZCR1642: Resin which introduce | transduced ethylenic double bond and acidic group into the epoxy resin which has a biphenyl skeleton represented by said formula (C1-2a) (made by Nippon Kayaku Co., brand name: ZCR-1642H. Solid content: 60 mass%, PGMEA: 40 mass%.).

C-1: Resin which made cresol novolak-type epoxy resin, acrylic acid, and 1,2,3,6-tetrahydro phthalic anhydride react, and the resin which introduce | transduced the acryloyl group and the carboxyl group was refine | purified with hexane, solid content 70%, acid value 60 mgKOH / g, PGMEA: 30 mass%.

ZAR2002: Brand name; KAYARAD ZAR-2002, Resin which introduce | transduced the carboxyl group and ethylenic double bond into the bisphenol-A epoxy resin by Nippon Kayaku Co., Ltd., 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 mass%, Polyurethane type polymer dispersing agent of amine value 18 mgKOH / g: 5 mass%, PGMEA: 75 mass%).

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

(Cross-linking system (G))

UX5002: Polyfunctional urethane acrylate oligomer (The Nippon Kayaku Co., Ltd. make, brand name: KAYARAD UX-5002D-P20. Solid content: 80 mass%, PGMEA: 20 mass%.).

A9300CL: (epsilon) -caprolactone modified tris- (2-acryloxyethyl) isocyanurate (The Shin-Nakamura Chemical Co., Ltd. make, brand name: NK ester A-9300-1CL.).

A9530: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-9530.).

(Solvent (H))

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

IPA: 2-propanol.

(Silane coupling agent (J))

KBM5013: Brand name (manufactured by Shin-Etsu Chemical Co., Ltd. 3-acryloyloxypropyltrimethoxysilane.).

(Fine particles (K))

IPA-ST: Brand name (made by Nissan Chemical Co., Ltd. organo silica sol, solid content: 30 mass%, IPA: 70 mass%.).

Synthesis Example 1: Synthesis of Ink Repellent Agent (A ¹ -1)

MEK (420 g), C6FMA (90 g), MAA (9 g), PME1000 (81 g), and a polymerization initiator V-65 (0.2 g) were charged to a 1 liter autoclave equipped with a stirrer. It stirred for 24 hours at 50 degreeC, stirring in nitrogen gas, and synthesize | combined the crude polymer. After adding hexane to the solution of the obtained crude polymer and reprecipitation-refining and purifying, it dried under vacuum and obtained the ink repellent agent (A ^1-1 ) (158.6 g). The ink repellent agent (A ¹ -1) had a number average molecular weight (Mn) of 64,690 and a mass average molecular weight (Mw) of 92,270.

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

In a 1 liter autoclave with a stirrer, MEK (420 g), C6FMA (85 g), 2-HEMA (50 g), PME400 (36 g), MAA (9 g) and polymerization initiator V-65 (0.7g) was thrown in, and it superposed | polymerized at 50 degreeC for 24 hours, stirring in nitrogen gas, and obtained the solution of the polymer (1).

(Introduction of an ethylenic double bond)

Into a 1 liter autoclave with a stirrer was added a solution of the polymer (1) (500 g), AOI (45.6 g), DBTDL (0.13 g), TBQ (1.6 g) and MEK (17.1 g). It was made to react at 40 degreeC for 24 hours, stirring, and ethylenic double bond was introduce | transduced into the polymer (1). Hexane was added to the obtained solution for reprecipitation purification, and then vacuum dried to obtain an ink repellent agent (A ¹ -2) (165.0 g). The ink repellent (A ¹ -2) has a number average molecular weight (Mn) of 41 200, weight average molecular weight (Mw) of 110 800, the content of the fluorine atoms are 20.6% by weight, the amount of ethylenic double bonds (C = C amount, × 10 ^-3 mol / g) was 1.66x10 ^-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 )]

In the synthesis of the ink repellent agent (A ¹ -1), the ink repellent agents (A ¹ -3) and (A ^1-4 ) were obtained by the same copolymerization reaction except that the raw material formulation was changed as shown in Table 1. The number average molecular weight (Mn), the mass average molecular weight (Mw), the content rate (mass%) of the fluorine atom, and the acid value (mgKOH / g) of the obtained ink repellent agents (A ^1-3 ) and (A ^1-4 ) are shown in the table. 1 is shown.

Synthesis Example 5: Synthesis of the ink to the (A ¹ -5)]

In the synthesis of the polymer (1), the polymer (2) was obtained by the same copolymerization reaction except that the compounding of the raw materials was changed as shown in Table 1. In the synthesis of the ink repellent (A ¹ -2), except that the raw material blended was changed as shown in Table 1 by the same reaction, and introducing an ethylenic double bond in the polymer (2), to the ink (A ¹ - 5) was obtained. The weight-average of the obtained ink to the (A ¹ -5), molecular weight (Mn), the number average molecular weight (Mw), the content of fluorine atoms (mass%), acid value (㎎KOH / g), the amount of ethylenic double bonds (C = C amount, x 10 ^-3 mol / g) is shown in Table 1.

Synthesis Example 6: Preparation of Ink Repellent Agent (A ^2-1 )

Into a 1,000 cm 3 three-necked flask equipped with a stirrer, 11.8 g of compound (a7-1), 29.4 g of compound (a8-1), 29.4 g of compound (a9-1), and 29.4 g of TMMS were added thereto. A degradable silane compound mixture was obtained. Subsequently, 564.7 g of PGMEA was put into this mixture, and it was set as the solution (raw material solution).

52.0g of 1.0% hydrochloric acid aqueous solution was dripped at the obtained raw material solution, stirring at 40 degreeC. After completion of the addition, in 40 ℃ 5 sigan by stirring, to the ink (A ² -1) to PGMEA solution (to the ink (A ² -1) concentration: 10% by mass, "(A ² -1) solution It is said. " Moreover, the reaction liquid was measured using gas chromatography and it confirmed that each compound as a raw material became below a detection limit.

The number average molecular weight (Mn) of the obtained ink repellent agent (A ^2-1 ), the mass average molecular weight (Mw), and the content rate of a fluorine atom are shown in Table 2 with the addition amount composition (mol%) of an ink repellent agent (A ^2-1 ). Shown in

Synthesis Example 7: Preparation of ink to the (A ² -2)]

Into a 1,000 cm 3 three-necked flask equipped with a stirrer, 16.7 g of compound (a7-1), 41.7 g of compound (a8-1) and 41.7 g of compound (a9-1) were added thereto to prepare a hydrolyzable silane compound mixture. Got it. Subsequently, 564.7 g of PGME was put into this mixture, and it was set as the solution (raw material solution).

65.7g of 1.0% nitric acid aqueous solution was dripped at the obtained raw material solution, stirring at 40 degreeC. After completion of the addition, in 40 ℃ 5 sigan by stirring, to the ink (A ² -2) a PGME solution (to the ink (A ² -2) concentration: 10% by mass, "(A ² -2) solution It is said. " Moreover, the reaction liquid was measured using gas chromatography and it confirmed that each compound as a raw material became below a detection limit.

In Table 2 with a number of the resulting ink to the (A ² -2) The average molecular weight (Mn), weight average molecular weight (Mw), the fluorine atom content of the composition and the amount (mol%) of the ink repellent (A ² -2) Indicates.

[Examples 1-24 and Examples 31-33: Preparation of negative photosensitive resin composition, formation and evaluation of a partition]

In the ratio (mass%) shown in Table 3 and Table 4, an ink repellent agent (A), a photoinitiator (B), alkali-soluble resin (C), a black coloring agent (D), a crosslinking agent (G), a solvent (H), A silane coupling agent (J) and microparticles | fine-particles (K) were mix | blended and the negative photosensitive resin composition was obtained.

After apply | coating a negative photosensitive resin composition on the glass substrate using the spinner, it dried on a hotplate for 2 minutes at 100 degreeC, and formed the coating film of 2.0 micrometers in film thicknesses. Next, the ultra-high pressure mercury lamp (wavelength of 330 nm or less) was shielded by the cut filter to the coating film through the mask (grid pattern of light shielding part 100 micrometers x 200 micrometers, and light transmission part 20 micrometers). And a mixed line composed of g lines). The predetermined exposure amounts shown in Tables 3 and 4 were investigated.

Subsequently, the unexposed part was immersed and developed in an inorganic alkali type developing solution (10-fold diluted aqueous solution of the Yokohama fat-and-oil manufacturing company, brand name Semiclean DL-A4), and the unexposed part was wash | cleaned with water, and it dried.

Subsequently, the glass substrate 1 with a pattern was obtained by heating at 220 degreeC for 1 hour on a hotplate. Moreover, it carried out similarly to the above except having exposed without using the said mask, and obtained the glass substrate 2 with a coating film cured film. About the glass substrate 1 or (2), the line width, the film reduction after image development, ink repellency (PGMEA contact angle) were measured and evaluated by the method shown below. The results are shown in Tables 3 and 4.

(Line width)

About the said glass substrate 1, the line width of the grid pattern of 20 micrometers of light transmission parts was measured using the super-depth shape measurement microscope VK-8500 (made by Keyence Corporation). As the line width is closer to 20 μm of the light transmitting portion of the mask, it means that the line width of the mask can be reproduced.

(Membrane reduction after development)

About the said glass substrate 1, the film thickness THK1 before image development of the exposure part (cured film), and the film thickness THK2 after image development were measured using the high precision fine shape measuring device SURFCORDER ET4000A (made by Kosaka Research Institute). The film thickness after development is subtracted from the film thickness after development minus the film thickness after development. The smaller the value, the better the photocuring of the negative photosensitive resin composition.

(Ink-repellent)

The PGMEA contact angle (degree) of the cured film surface of the said glass substrate 2 was evaluated. The contact angle is defined as the angle formed by the tangent line to the liquid surface at the point where the solid contacts with the liquid and the solid surface, and the angle at which the liquid is contained. The larger the angle, the better the ink repellency of the cured film.

By the static method, PGMEA droplets were placed in three places of the measurement surface on a base material based on JISR3257 "wetting test method of the substrate glass surface", and it measured about each PGMEA droplet. The droplet was 2 [mu] l / drop, and measurement was carried out at 20 [deg.] C. The contact angle is expressed as an average value of three measured values (n = 3).

As for the negative photosensitive resin composition of Examples 1-24, photocuring was all favorable. In addition, the cured film formed from the composition had good ink repellency and could reproduce the line width of the mask.

On the other hand, since the negative photosensitive resin composition of Examples 31-33 did not use the oxime ester compound which has a nitro group in 1 molecule as a photoinitiator, the film | membrane decrease after image development with 60 mJ / cm <2> and 40 mJ / cm <2> is 60 nm. And photocuring was insufficient. In addition, the formed cured film had insufficient ink repellency and could not reproduce the line width of the mask.

Industrial availability

The negative photosensitive resin composition of this invention produces a partition with favorable ink repellency and favorable reproduction of the line width of a mask, even when it exposes by reducing an exposure amount or shielding the exposure light of 330 nm or less. can do.

The negative photosensitive resin composition of this invention is used suitably for formation of a partition for color filter manufacture and organic electroluminescent display element manufacture using the inkjet recording technique.

In addition, all the content of the JP Patent application 2011-102039, a claim, drawing, and the abstract for which it applied on April 28, 2011 is referred here, and it takes in as an indication of the specification of this invention.

1: substrate
2: coating film of negative photosensitive resin composition
3: coating film exposure part
4: Mask
5: Light
6:
7: Dot
10: substrate for optical element used in inkjet method

Claims (15)

Ink repellent agent (A) which has a side chain containing group represented by following formula (1) or group represented by following formula (2), and
Photoinitiator (B) which is an oxime ester compound which has a nitro group in 1 molecule,
It contains alkali-soluble resin (C), The negative photosensitive resin composition characterized by the above-mentioned.
-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 fluorine having 20 or less carbon atoms in which at least one of the hydrogen atoms which may have an ether oxygen atom is substituted with a fluorine atom. Or a fluoro atom.
In formula (2), R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group independently, R <^5> represents a hydrogen atom or an organic group of 1-10 carbon atoms, n represents the integer of 1-200. The method of claim 1,
The negative photosensitive resin composition whose said photoinitiator (B) is a compound which consists of following formula (3).
[Chemical Formula 1]

In formula (3), R <^31> represents a C1-C20 alkyl group, a C6-C30 aryl group, a C7-C30 arylalkyl group, or a cyano group. R <^32> represents R <^41> or OR <^42> , R <^41> and R <^42> represents a C1-C20 alkyl group, a C6-C30 aryl group, or a C7-C30 arylalkyl group, respectively. R ³³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R ³⁴ and R ³⁵ each independently represent R ⁴¹ , OR ⁴² , cyano group, or halogen atom. a and b are the integers of 0-3 each independently, and c is an integer of 1-3. 3. The method according to claim 1 or 2,
The negative photosensitive resin composition which further contains a black coloring agent (D). The method according to any one of claims 1 to 3,
The negative photosensitive resin composition which further contains a crosslinking agent (G). 5. The method according to any one of claims 1 to 4,
The negative photosensitive resin composition whose ink repellent agent (A) is group which has group (1) or group (2) in a side chain, and a principal chain is a hydrocarbon chain. The method of claim 5, wherein
The negative photosensitive resin composition in which a ink repellent agent (A) has an acidic group. 5. The method according to any one of claims 1 to 4,
The negative photosensitive resin composition whose ink repellent agent (A) has group (1) in a side chain, and a main chain is a compound which is an organopolysiloxane chain | strand. 8. The method according to any one of claims 5 to 7,
The negative photosensitive resin composition in which a ink repellent agent (A) has an ethylenic double bond. The cured film formed by hardening the coating film of the negative photosensitive resin composition in any one of Claims 1-8 formed on the board | substrate. The partition formed in order to provide a partition on a board | substrate, Comprising: The partition which consists of a cured film of Claim 9. The black matrix formed in order to provide a partition on a board | substrate, Comprising: The black matrix which consists of the cured film of Claim 9 formed from the negative photosensitive resin composition of Claim 3. The process of forming the coating film by apply | coating the negative photosensitive resin composition of any one of Claims 1-8 on a board | substrate, and heating the said coating film to a film, and exposing only the predetermined part of the film to photocuring A process for producing a partition wall, comprising the steps of: removing a film other than the photocured part; and heating the photocured part to obtain a partition wall, wherein the photocured part before and after removing the film. The film thickness change is 60 nm or less, The manufacturing method of a partition. The manufacturing method of the black matrix of the manufacturing method of Claim 12 which obtains the said partition as a black matrix using the negative photosensitive resin composition of Claim 3. It has a board | substrate, the some pixel on a board | substrate, and the partition wall located between adjacent pixels, Comprising: The partition wall consists of a cured film of the negative photosensitive resin composition of any one of Claims 1-8 characterized by the above-mentioned. , Color filters. It has a board | substrate, the some pixel on a board | substrate, and the partition wall located between adjacent pixels, Comprising: The partition wall consists of a cured film of the negative photosensitive resin composition of any one of Claims 1-8 characterized by the above-mentioned. , Organic EL device.

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