TW201248326A - 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

Provided are: a negative photosensitive resin composition which has good ink repellency and good reproducibility of a line width of a mask; and a partition wall which is obtained using the composition and has uniform quality. This negative photosensitive resin is characterized by containing: (A) an ink-repellent agent that has a side chain containing -CFXRf (wherein X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and Rf represents a fluorine atom or a fluoroalkyl group which may have an ether oxygen atom and has 20 or less carbon atoms, while having at least one hydrogen atom substituted by a fluorine atom) or -(SiR1R2-O)n-SiR3R4R5 (wherein, each of R1, R2, R3 and R4 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R5 represents a hydrogen atom or an organic group having 1-10 carbon atoms, and n represents an integer of 1-200); (B) a photopolymerization initiator that is an oxime ester compound having a nitro group in each molecule; and (C) an alkali-soluble resin.

Description

201248326 VI. Description of the invention: C ^"Ming's chair chair mussels 3 FIELD OF THE INVENTION The present invention relates to a negative photosensitive resin composition, a cured film, a partition wall and a black matrix, a method for producing the same, a color filter, and an organic EL element. L jIu-Invention Background The photoresist composition is formed as a partition between pixels such as a color filter, a partition between pixels of an organic EL (Electro-Luminescence) display element, a partition between elements of an organic EL illumination, and an organic TFT. In the (Thin Film Transistor) array, the partition walls of the TFTs, the partition walls of the liquid crystal display elements, the partition walls of the ITO electrodes, and the partition walls of the circuit wiring board are attracting attention. In the manufacture of circuit wiring boards, an ink jet method in which a metal dispersion is spray-coated while forming a circuit wiring has been proposed. The circuit wiring pattern is formed by a photoresist composition in accordance with a photolithography method, and the cured film of the photoresist composition is used as a partition wall. In the inkjet method, it is necessary to prevent the occurrence of ink mixed color between adjacent pixels, and to prevent agglomeration of a material which is ejected by inkjet ejection in a portion other than a predetermined region, and thus a photoresist composition containing an ink-repellent agent has been proposed. (Patent Documents 1 to 3). PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT 1: International Publication No. 2/8/6855 No. 3, No. 2010/001976 Patent Document 2: International Publication No. 2010/013816 [Explanation] Summary of Invention Invention The problem to be solved is that the exposure of the photoresist composition is performed using an exposure machine. The wavelength of the exposure from the exposure machine varies depending on the device. Generally, the light exposure at 33 〇 nnm is used for the proximity exposure method used in the color filter. In contrast, in the mirror projection type (MPA) method, light of 33 〇 11111 or less is shielded from light. Therefore, it is also necessary to have a composition corresponding to the MpA mode for the photoresist composition. Further, in the mirror projection type MPA method, there is an advantage that the shape of the partition wall which can be sharpened can be formed with respect to the proximity exposure method. In the βκΜΡΑ method, fine patterning may be sought. An object of the present invention is to provide a negative photosensitive resin composition which is excellent in ink repellent even when light is exposed to light of 3 〇 nm or less, and which has good line width reproducibility of a mask, and a homogeneous cured film obtained by using the composition Further, another object of the present invention is to provide a color filter having a good barrier or a black matrix and an organic EL element. Means for Solving the Problems The present invention is the following [1] to [15].负] A negative photosensitive resin composition comprising: an ink-repellent agent (A) having a side chain, and the side chain contains a group represented by the following formula (1) or a group represented by the following formula (2) a photopolymerization initiator (B) which is esterified with a nitro group in a molecule of 201248326; and an alkali-soluble resin (c); -CFXRf (1) -(SiR'R2-〇)n_siR3R4R5 ( 2) In the formula (1), 'X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and Rf represents a fluoroalkyl group having 20 or less carbon atoms which may have an etheric oxygen atom and at least one hydrogen atom is substituted with a fluorine atom. Or a fluorine atom; in the formula (2), R1, R2, R3 and R4 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R5 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and η represents 1 An integer of ~200. [2] The negative photosensitive resin composition according to [1], wherein the photopolymerization initiator (Β) is a compound composed of the following formula (3);

In the formula (3), R31 represents a decyl group having 1 to 2 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a cyano group; and R32 represents R41 or OR42. R41 and R42 each represent a condensed group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms; and R33 represents an alkyl group having 1 to 20 carbon atoms and a carbon atom. An aryl group of 6 to 30 or an aralkyl group having a carbon number of 7 to 30, 201248326; R34 and R35 are each independently represented by R41, OR42, a cyano group or a halogen atom; and a and b are each independently an integer of 〇~3' c An integer from ι~3. [3] The negative photosensitive resin composition of [1] or [2], which further contains a black coloring agent (〇). [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 side of the ink-repellent (A) has a group (1) or a group (2) and the main chain is a smoke. Chain compound. [6] The negative photosensitive resin composition according to [5], wherein the ink repellent (a) has an acidic group. [7] The negative photosensitive resin composition according to any one of [1] to [4] wherein the ink-repellent agent (A) has a group (1) in a side chain and the main chain is an organic poly-crushed oxygen. The compound of the bond. [8] The negative photosensitive resin composition according to any one of [5] to [7] wherein the ink repellent (A) has an ethylenic double bond. [9] A cured film is obtained by curing a coating film of a negative photosensitive resin composition of any one of [1] to [8] formed on a substrate. [10] A partition wall formed by forming a divisional region on a substrate, which is composed of a cured film such as [9]. [11] A black matrix formed by providing a divisional region on a substrate, which is composed of a cured film of [9], and the cured film is composed of a negative photosensitive resin composition such as [3] Former. [12] A method for producing a partition wall, comprising the steps of: forming a coating film by coating the negative photosensitive resin composition of any one of [1] to [1] to the substrate in the following step: 201248326; a step of heating a coating film to form a film, exposing only a predetermined portion of the film to photohardening; a step of removing the film other than the photohardened portion; and heating the photohardened portion a step of partitioning; wherein 'the film thickness of the photohardened portion before and after the removal of the film is 6 〇 nm or less. [13] A method for manufacturing a black matrix is as follows. In the production method of 2], the partition wall is made to be a black matrix using the negative photosensitive resin composition of [3]. [14] The color ray has a substrate, a plurality of pixels on the substrate, and a partition wall between the adjacent pixels, wherein the partition wall is composed of a negative photosensitive resin such as [丨] to [#. The hardened film of the object is composed. [15] An organic EL device having a substrate, a plurality of pixels on the substrate, and a partition wall between the adjacent pixels, wherein the partition wall is negatively photosensitive according to any one of [1] to [8] A cured film of a resin composition. Advantageous Effects of Invention According to the present invention, it is possible to provide a negative-type photosensitive resin composition which can be manufactured by exposing exposure light of 330 nm or less to light exposure even when the exposure amount is reduced, and the ink repellency is good, and the mask is The line width reproduces well next door. According to the present invention, it is possible to provide a homogeneous cured film of the negative photosensitive resin composition of the present invention, a partition wall having good properties, and a black moment 201248326

Array and its manufacturing method. Further, according to the present invention, a color filter and an organic ELS device having excellent performance of the partition wall and the black matrix of the present invention described above can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a manufacturing example of a partition for an optical element using a negative photosensitive resin composition of the present invention. I: Embodiment 3 In the present specification, the acid value refers to the number of milligrams of potassium hydroxide required to neutralize the resin acid or the like in the lg sample, and the method can be measured according to JIS K 0070. The value measured. The unit is mgKOH/g. In the present specification, the total solid portion refers to a component forming a partition wall in the component contained in the negative photosensitive resin composition, and indicates a volatile component which is volatilized by heating or the like during the formation of the partition wall such as the solvent (H). All ingredients except. In the present specification, "(sulfenyl acrylonitrile)" is a general term for "mercapto propylene sulfhydryl..." and "acrylic fluorenyl...". The (meth) acrylate, (mercapto) acrylamide, and (fluorenyl) acryl resin are also the same. In the present specification, the hydrocarbon group means an organic group composed only of carbon and hydrogen. In the present specification, a film obtained by coating a negative photosensitive resin composition is referred to as a "coating film", and a state in which it is dried is referred to as a "film", and a film obtained by curing the film is referred to as " Hardened film." In this specification, the "surface" of the partition wall is used only as the upper surface of the partition wall for use in 201248326. Therefore, the accompanying #", complex surface" does not include the side of the partition. The ρ ink in the present specification is a general term for a liquid having, for example, optical properties and electrical functions after drying and hardening, and is not limited to a conventionally used coloring material, and a "pixel" formed by the ink being introduced into the ink. The same is true; 乍 is the interval between the optical and electrical functions of the table τ. In the present specification, the π 拨 ink repellency refers to a characteristic of a moderately oily property for plucking the ink, and the side can be evaluated by a method described later. Hereinafter, embodiments of the present invention will be described. Further, in the case where it is not particularly described in the present specification, % indicates mass%. [Ink-repellent agent (Α)] The ink-repellent agent (Α) of the present invention is a compound having a side chain, and the side chain contains a group represented by the following formula (1) (hereinafter also referred to as a group (1)) or a formula (2) ) The basis of the expression (hereinafter also referred to as the base (2)). -CFXRf (1) -(SiR'R2-〇)n-SiR3R4R5 (2) In the formula (1), X represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group, to indicate that it may have a squamous oxygen atom and at least 1 Each of the hydrogen atoms is substituted with a fluorine atom having a number of carbon atoms of 20 or less, or a deficient atom. In the formula (7), R1, R2, R3 and R4 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R5 represents a hydrogen atom or an organic group having 1 to 1 carbon atom, and η represents an integer of 1 to 200. . Since the ink-repellent (Α) has a side chain containing a base (1) or a base (2), it has a surface migration property of 9 201248326, and the coating film formed of the negative photosensitive resin M is added and dried to form a film. Will migrate to the surface of the coating (4). Thereby, the surface of the partition wall formed by the cured film which hardens the film exhibits ink repellency, and (4) the ink which is injected by the ink does not overflow from the opening portion (which becomes a pixel) between the partition walls called the dot matrix. Color mixing between adjacent pixels is not easy to occur. The side chain containing the group (1) or the group (2) may be directly formed by a polymerization reaction or may be formed by chemical conversion after the polymerization reaction. When Rf in the formula (1) is a sulfhydryl group having at least (10) nitrogen atoms substituted by a fluorine atom, the hydrogen atom in the sulphur group may also be a gas atom. Other than the 素 atom substitution. Other elements of the atom are preferably a gas atom. X '啰 oxygen atom can hide from the carbon-carbon _ of the deficient base, can also exist at the end of the 6 base. The structure may be "chain structure, branched structure, ring structure, or local structure having a ring structure, and a linear structure is preferred. The base (1) aspect is preferably a perfluoroalkyl group or a multi-nuclear group containing one hydrogen atom. It is especially preferable to use a perfluoroalkyl group (except for those having a hard-atomic atom). Thereby, the ink-repellent property of the partition formed of the negative-type photosensitive resin composition can be improved. The number is 20 or less, preferably 4 to 6. In this case, it is possible to impart sufficient compatibility between the partition walls and the other components constituting the quinoid photosensitive resin composition. (4) The photosensitive resin composition is coated and formed into a coating, and the ink-repellent agent (Α) does not aggregate with each other, and can form a good appearance next door. 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 201248326 oxygen atom is preferred. Specific examples of the group (1) may be used. As follows: -CF3 ^ -CF2CF3 ' -CF2CHF2 . >(CF2)2CF3 ' -(CF2)3CF3 λ -(CF2)4cf3, -(cf2)5CF3, -(CF2)6cf3, _(CF2)7cf3,- (cf2) 8cf3, -(CF2)9CF3, (CF2)"CF3, -(CF2)I5cf3, CF(CF3)0(CF2)5CF3, -CF2〇(CF2CF2〇)pCF3 (p is an integer from 1 to 8 ), -CF(CF3)〇(CF2CF(CF3)0)qC6Fi3 (q is an integer of 4), _CF(CF3)〇(CF2CF(CF3)0)rC3F7 (r is an integer of i~5). (1) In particular, _(CF2)3CF3 or _(CF2)5CF3 is preferred. In the formula (2), 'R1 and R2' may be the same or different in each of the money-burning units. It is separated by Wei (4) ink-repellent point = say 'R1, R2 is preferably a hydrogen atom, a carbon atom (4), a cyclosyl group, or an aryl group, preferably a hydrogen atom or a fluorenyl group. R1 and R2 of the money-burning unit are preferably sulfhydryl groups. In the formula (2), R3 and R1R5 are bonded to the base of the Shixi oxygen (10) terminal, and the R3 and R4 can be combined with R1 and R2. 'The appropriate pattern is also the same. Also, when R5 is an organic group', it may also contain #(四)子, oxygen, etc., and the heart is preferably a gas atom or an alkyl group having 1 to 5 carbon atoms. n is an integer Preferably, the integer of 2 to 100 is particularly preferable. As the base (7), it is preferable that all of RW and RW are methyl groups. It is preferred that the ink repellent (A) further has an acidic group. It is preferable that the ink-repellent (A) has an acidic group, and the solubility of the negative-type photosensitive residual composition to the developer is improved. The acidic group is preferably one or more kinds of acidic groups selected from the group consisting of silk, sulphate, and sulphate 11 201248326. In terms of ease of synthesis, the acidic group is preferably present in the side chain. The side chain having an acidic group can be formed by polymerization of an acidic group monomer or by chemical conversion after polymerization. The ink repellent (A) is preferably a polyoxyalkylene group. If the ink-repellent (a) has a polyoxyalkylene group, the ink repellent property can be maintained even if the pressure is increased in the developing step. Further, it is preferable to prevent the residual film from remaining in the lattice portion which cannot be completely removed by development. In addition, the polyoxyalkylene group used in the present invention may specifically be represented by the following formula (hereinafter referred to as the group (11)). -(R2,0)m(R220)jR23 (H) In the formula (11), R and R 2 each independently represent an alkylene group having 2 to 4 carbon atoms, R23 represents a hydrogen atom, or may have The alkyl group of the substituent carbon number (7), individually, m represents an integer of 〇~1〇〇, j represents an integer of 〇~1〇〇, and m+j is an integer of 4 to 100. In the group (11), R21 and R22 each independently represent an alkylene group having 2 to 4 carbon atoms. The structure of the alkyl group may be either a linear structure or a branched structure. R2i and R22 may be the same or different. Among these R21 and R22, each of them is independently -CH2CH2- or -C3H6-, or a combination of -CH2CH2- and -C4H8- is preferred as either -CH2CH2_' or -CH2CH2- and - A combination of CH2CH(CH3)- is preferred. In the group (11), m represents an integer of 〇~100, j represents an integer 〇~100, and m and j are preferably 0 to 50, respectively, and 〇~3〇 is particularly preferable. Further, m+j is an integer of 4 to 100, preferably an integer of 6 to 50, and 8 to 30 of 12 201248326 • Recorded by Yu Jia. When m + j is at least the lower limit of the above range, the ink repellency is not easily lowered when the jet rinsing step using high pressure water is carried out after the development step. Further, the residual film is less likely to occur. When m+j is in the above range: the limit is not more than the limit, the ink-repellent (A) does not move to the opening during the post-baking, and the ink resistance of the opening between the partition walls becomes sufficient, and the ink is applied by the inkjet method. In the case of ink, the ink can be sufficiently wetted and diffused at the opening. The base (11) indicates that there are m (R21〇) units and "Han 22" units, and there is no (four) restriction on the bonding order of the (R21Q) unit and the (R22〇) unit. In summary, the 'm(R2i0) unit and the j (heart) unit in the base (11) may be, for example, interactive or random, or a rice field bond. In the group (11), when R23 is an alkyl group having a carbon atom number i~1〇 which may have a substituent, the structure of the structure is a direct bond structure, a bond structure, a ring structure, and a local structure. It’s all right. Further, specific examples of the substituent include a carboxyl group, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms. In the present invention, R23 in the group (11) is preferably a linear or unsubstituted alkyl group having 1 to 5 carbon atoms, particularly preferably an anthracenyl group or an ethyl group.

Specific examples of '(R210) and (R220) in the group (11) include Η2(:6Η10(:Η2 〇-(wherein c6h10 is a cyclohexyl group), -CH20-, -CH2CH20-, -CH2CH

(ch3)o-, -ch(ch3)o-, -ch2ch2ch2o-, -c(ch3)2o-, -CH(ch2ch3)o-, -ch2ch2ch2ch2o-, -CH(CH2CH2CH3)0-, -CH2(CH2 ) 3CH20-, -CH(CH2CH(CH3)2)0-, and the like. Specific examples of the group (11) include (R210) and (R22), which are selected from the above-exemplified oxygen alkyl groups, m+j is 4 to 100, and R23 is CH3. The base (11) may be used alone or in combination of two or more. Further, the side chain having the 13 201248326 group (11) is introduced into the ink-repellent (A), and as will be described later, when the ink-repellent (A) is produced by polymerization of the original 祠 monomer, the base (11) is provided. The blending amount of the monomer with respect to the entire raw material monomer is appropriately adjusted so as to impart the above-described developability improving effect to the ink-repellent (A) without impairing the blending amount of the effect of the present invention. The ink-repellent agent (A) preferably has an ethylenic double bond. If the ink-repellent (A) has an ethylenic double bond, the ink-repellent (A) which migrates to the surface of the film upon drying is obtained by the ink-repellent (A) or the ink-repellent (A) at the time of exposure. The alkali-soluble resin (c) reacts easily and is easily immobilized on the surface of the partition wall, which is quite suitable in this point. Examples of the ethylenic double bond include a (fluorenyl) acrylonitrile group, an allyl group, a vinyl group, and a vinyl ether group addition polymerizable unsaturated group. Some or all of the nitrogen atoms of the groups may be substituted by a hydrocarbon group. The methyl group is preferably a methyl group. The introduction of the side chain having the ethylenic double bond to the ink-repellent (A) is as described later, and the monomer having the reactive group is added to the raw material monomer at the time of producing the ink-repellent (A). The copolymerization is carried out, followed by reacting a compound having a functional group bondable with the above reactive group and an ethylenic double bond with the obtained copolymer. As the ink-repellent agent (A), a compound having a group (1) or a group (2) in the side chain and a main chain of a hydrocarbon chain is preferred. Hereinafter, the ink-repellent agent whose main chain is a hydrocarbon chain is referred to as "inking agent (A1)". The ink-repellent (A) can be produced, for example, by co-nucleating a raw material monomer having a component: a monomer having a radical (al) or a monomer having a radical (2) ( A2), and a monomer (a3) having an acidic group if necessary, and a monomer (a4) having a polyoxyalkylene group as needed. 201248326 Further, when the ink-repellent (A1) has an ethylenic double bond, it can be produced by copolymerizing a raw material monomer which has been added with a monomer (4) having a reactive group in the above-mentioned raw materials. Then, the obtained copolymer is reacted with a compound (zl) having a functional group bonded to a reactive group such as -, and a double bond. (Monomer (al)) In terms of the monomer (al) having a group (1), the following monomer (aU) is preferred. CH2 = CR6CO〇. Y-CFXRf (all) wherein R6 represents a hydrogen atom, a fluorine atom, a gas atom, a bromine atom, an iodine atom thiol group, or a difluoromethyl group β represents a single bond or a carbon number of 1 to 6 It is preferable to use a divalent organic group having 2 to 4 carbon atoms. X and 1^ have the same meaning as the base (1), and the appropriate aspect is also the same. Examples of the monomer (all) include the following. CH2 = CR6COOR7CFXRf CH2 = CR6C00R8NR9S02CFXRf CH2 = CR6COOR10NRnCOCFXRf CH2 = CR6COOCH2CH(OH)R12CFXRf Here, R6 represents the same meaning as above, and R7, R8 and R10 represent a condensed group having 1 to 6 carbon atoms. R9 and R11 represent a hydrogen atom or Indenyl, r12 represents a single bond or an alkylene group having 1 to 4 carbon atoms. Specific examples of R7, R8 and R1Q include -CH2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -C(CH3)2-, -CH(CH2CH3)-, -CH2CH2CH2CH2-, respectively. -CH(CH2CH2CH3)-, -CH2(CH2)3CH2-, 15 201248326 -CH(CH2CH(CH3)2)- and the like. Specific examples of R include -CH2_, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-'-C(CH3)2. '-CH(CH2CH3)- '-CH2CH2CH2CH2-'-CH(CH2CH2CH3)4 Specific examples of the fluorene monomer (al l) include (meth)acrylic acid 2_(perfluorohexyl)ethyl ester and (meth)acrylic acid 2-(perfluorobutyl)ethyl ester. One type of the monomers (all) may be used alone or two or more types may be used in combination. (Monomer (a2)) The monomer (a2) having the group (2) is preferably the following monomer (a2i). CH2 = CR13COO-Z-(SiR'R2-〇)n-SiR3R4R5 (a21) wherein R13 represents a hydrogen atom or a fluorenyl group, and Z represents a single bond or a divalent organic group having 1 to 6 carbon atoms. R1, R2, R3, Han 4 and 1^, and n are the same meanings as the base (2). Z is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include _ch 2-, -CH2CH2-, -ch(ch3)-, -CH2CH2CH2-, -C(CH3)2-, -ch(ch2ch3)-, -CH2CH2CH2CH2-, -CH(CH2CH2CH3)- , -CH2 (ch2)3ch2-, -ch(ch2ch(ch3)2)-, and the like.

Specific examples of the monomer (a21) include CH2 = CHCOO-CH2CH2-(S i(CH3)2-〇)n-Si(CH3)3, CH2 = CCH3COO-CH2CH2-(Si(CH3)2-〇) n-Si(CH3)3 'CH2 = CHC00-CH2CH2CH2-(Si(CH3)2-0)n-Si(CH3)3, CH2 = CCH3C00-CH2CH2CH2-(Si(CH3)2-0)n-Si( CH 3) 3 and so on. Further, n is about 4, 60, and 160. A commercially available product can be used for the monomer (a21). Commercial products include the following, all of which are trade names. X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.), 16 201248326. X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd.), Χ-22-2475 (manufactured by Shin-Etsu Chemical Co., Ltd.). One type of the monomer (a21) may be used, or two or more types may be used in combination. (Monomer (a3)) When the ink repellent (A1) has an acidic group, it is preferred to copolymerize the monomer (a3) having an acidic group together with the monomers (al) to (a2). The monomer having an acidic group (a3) may, for example, be a monomer having a carboxyl group, a monomer having a condensed hydroxyl group, or a monomer having a sulfonic acid group. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, ethylene glycol acetate, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and the like. Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxybenzene, ethylene, and p-hydroxystyrene. Further, one or more hydrogen atoms of the benzene ring may be substituted with an alkyl group such as a mercapto group, an ethyl group or a n-butyl group, or an alkyl group such as a methoxy group, an ethoxy group or a n-butoxy group. A compound of an oxy group, a halogen atom or an alkyl group in which one or more hydrogen atoms are substituted by a ii atom, a nitro group, a cyano group or a guanamine group. Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth) propyl sulfonic acid, 2-hydroxy-3-(methyl)allyloxypropane sulfonic acid, ( Mercapto)-2-sulfoethyl acrylate, 2-propane propyl (meth)acrylate, 2-hydroxy-3-(methyl) propylene oxypropyl sulfonate ' 2 —(fluorenyl) propylene oxime The amine 2 - methylpropane sulfonic acid 0 monomer (a3) aspect is preferably acrylic or methacrylic acid in terms of ease. One type of the monomer (a3) may be used, or two or more types may be used in combination. 17 201248326 (monomer (a4)) The monomer having a group (11) for the production of the ink-repellent (A1), preferably a compound represented by the following formula (12) (hereinafter also referred to as a compound (12)) or (13) A compound (hereinafter also referred to as a compound (13)). These may be used alone or in combination of two or more. CH2 = CR24-COO-W-(R210)m(R220)jR23 (12) CH2 = CR25-0-W-(R210)m(R220)jR23 (13) In equations (12) and (13), R24 and R25 is a hydrogen atom, a gas atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an aryl group having 7 to 20 carbon atoms, and a carbon number of 6 to 20; An aryl group or a cycloalkyl group having 3 to 20 carbon atoms. W is a single bond or a carbon atom number of 10 which does not have a divalent organic group of a fluorine atom. -(R21〇)m(R22〇)jR23 is a group (11), and R21, R22, R23, m and j are the same meanings as the group (11), and the appropriate ranges are also the same. In the case of the compound (12) and the compound (13), when W is a divalent organic group having no fluorine atom and having 1 to 10 carbon atoms, a linear structure, a branched structure or a ring other than R2l〇 and R22〇 may be mentioned. An oxygen-expanding group having a structure of a ring having a ring structure of 1 to 10, a single bond, or the like. Specific examples of the oxygen stretching base include CH2C6H10CH2O (wherein C6H10 is a cyclohexyl group), CH20, ch2ch2o, ch2ch(ch3)o, ch(ch3)o, CH2CH2CH20, C(CH3)20, and ch(ch2ch3). o, ch2ch2ch2ch2o, ch(ch2ch2ch3)o 'ch2(ch2)3ch2o, ch(ch2ch(ch3)2)o, and the like. Among them, W in the compounds (12) and (13) is easily obtained, and an oxygen alkyl group having 2 to 4 carbon atoms is preferred. In the compounds (12) and (13), R24 and R25 are each preferably a hydrogen atom, a gas 18 201248326 atom, a fluorenyl group, a phenyl group or a benzyl group, and particularly preferably a hydrogen atom, a gas atom or a methyl group. The compound represented by the compound (12) is as follows. CH2=CHOCH2C6Hi〇CH20(CH2CH20)mR23 > CH2 = CHO(CH2)40(CH2CH20)mR23. The compound represented by the compound (13) is as follows. CH2 = CHC00(CH2CH20)mR23, CH2 = C(CH3)C00(CH2CH20)mR23, CH2 = CHC00(CH2CH20)m(C3H60)jR23, CH2 = C(CH3)C00(CH2CH20)m(C3H60)jR23, CH2 = CHC00(C2H40)m(C4H80)jR23. In the formula, m and j have the same meaning as the base (11), and the appropriate range is also #目HHw is a cyclohexyl group. QH4, (:3 private, C#8 is a linear structure or a support structure. R23 represents the same meaning as the base (11), and the appropriate range is a linear, unsubstituted alkyl group having a subnumber of 1 to 10. For the compound (12) and (13), a commercially available product can be used. The following products are commercially available. The product can be used as a BLEMMER PME-400 (trade name, manufactured by Nippon Oil & Fats Co., Ltd., C(CH3). COO(CH2CH2〇)kCH3. wherein k represents an intermolecular average value, and 匕値 is about 9. Hereinafter, k, m, and j in the molecular formula of each of the commercially available products represent an intermolecular average value), BLEMMER PME-1000 ( Product name, manufactured by Nippon Oil & Fats Co., Ltd., CH2=C(CH3)C00(CH2CH20)kCH3. In the formula, k represents the intermolecular average value, k値 is 23), and NKESTERM-230G: (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., CH2 = C(CH3)C00(CH2CH20)kCH3. In the formula, 19 201248326 k is about 9), NEW FRONTIER NF Bisomer PEM6E (trade name, manufactured by Daiichi Kogyo Co., Ltd., CH2 = C(CH3)C00(CH2CH20)kH In the formula, k is about 6), Light Ester 130A (trade name, manufactured by Kyoeisha Chemical Co., Ltd., CH2 = CHCOO(CH2CH20) kCH3. where k is about 9), BLEMMER ΑΕ-4〇0 (trade name, Japan) grease System, CH2 = CHC00(CH2CH20)kH: where k is about 10), BLEMMER PP-800 (trade name, manufactured by Nippon Oil Co., Ltd., CH2 = C(CH3)C00(C3H60)kH. where k is about 13), BLEMMER Gossip-800 (trade name, manufactured by Nippon Oil & Fats Co., Ltd., (:112 = (:11(:00((:3^160)1{1^. where k is about 13), BLEMMER 70PEP- 350B (trade name, 曰本油杜制, CH2 = C(CH3)COO(C2H40)m(C3H60)jH. where m is about 5, j is about 2), BLEMMER 55PET-800 (trade name, transcript) 'CH2 = C(CH3)C00(C2H40)m(C4H80)|H. In the formula, m is about 10 and j is about 5) (monomer (a5)) monomer having a reactive group (a5) In terms of a monomer having a hydroxyl group, an acid anhydride monomer having an ethylenic double bond, a monomer having a carboxyl group, a monomer having an epoxy group, etc. Further, the monomer (a5) is substantially free of a group. And a base is preferred. When a monomer having a carboxyl group is used as the monomer having an acidic group (a3), and a monomer having a carboxyl group is also used as the monomer having the reactive group (a5), it is not finally introduced. The ethylenic double bond and the carboxyl group remain as a monomer (a3). The reactive group of the monomer (a5) after the copolymerization is reacted by a compound (z 1) having a functional group bonded to the reactive group at 20 201248326 and an ethylenic double bond, thereby forming An ink-repellent (A1) having a side chain and having an ethylenic double bond. Specific examples of the monomer having a transradical group may be exemplified by 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ) 4-hydroxybutyl acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl diol mono Propionate, 3-methyl-2-propyl (meth)acrylate, glycerol mono(decyl) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, ring Hexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxydecyl (decyl) acrylamide, N, N-bis(hydroxymethyl) (fluorenyl) acrylamide, and the like. Further, in the case of a monomer having a hydroxyl group, a monomer having a polyoxyalkylene group having a terminal hydroxyl group may also be used. For example, ch2 = choch2c6h1q CH20(C2H4〇)hH (here, h is an integer from !100, the same applies hereinafter), CH2 = CHOC4H80(C2H40)hH, CH2 = CHC00C2H40(C2H40)hH, CH2 = C(CH3) C00C2H40(C2H40)hH, CH2 = CHCOOC2H40 (C2H40)i(C3H60)gH (here, i is an integer of 0 to 100, g is an integer of l~l〇〇, i+g is 1 to 100. The same applies hereinafter) , CH2 = C(CH3)COOC2H40(C2 H40)i(C3H60)gH, etc. Specific examples of the acid anhydride monomer having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, decyl-5-norbornene-2,3-dicarboxylic anhydride, 3, 4, 5, 6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl succinic anhydride, and the like. Specific examples of the monomer having a carboxyl group include acrylic acid and mercaptopropene 21 201248326 acid, ethyl acetate acetonate, crotonic acid, itaconic acid, and maleic acid, fumaric acid, cinnamic acid, or the like. Specific examples of the monomer having an epoxy group include (meth)acrylic acid oxypropyl ester and 3,4-epoxycyclohexyl methyl acrylate. (Monomer (a6)) The monomer used for the polymerization in the present invention has a monomer (al) having a group (1) or a monomer (10) having a group (2) and a monomer (4) having an acidic group as necessary) If the monomer having a polyoxyalkylene group (such as an ink repellent) has an ethylene double bond, it may contain a monomer having the reactive group (a5), but may contain the same Other monomer (a6) other than the body. Examples of the monomer (a6) include hydrocarbon olefins, vinyl ethers, isopropyl ethers, allyl ethers, vinyl esters, allyl esters, and (mercapto) acrylic acid. _, (methyl) propylene riding, aromatic ethyl compounds, gas olefins, conjugated dienes. These compounds may also contain a functional group, and examples of the functional group include a few groups, a oxy group, and the like. It is preferable that the heat resistance of the partition wall is excellent, and it is preferable to use (meth) acrylate or (fluorenyl) acrylamide. Further, as the monomer having an epoxy group as the monomer (a5) having the above reactive group, for example, (meth)acrylic acid propyl acrylate, acrylic acid 3,4-epoxycyclohexyl decyl ester, etc. It can be used as a monomer (a6). In the present invention, in the case where a monomer having an epoxy group such as a quinone is used for the polymerization, if the ethylenic double bond is not introduced after the copolymerization, the monomers having an epoxy group are classified into other monomers. (a6) ° and 'even if the four (4) double bond is introduced, if the epoxy double bond is not introduced but the epoxy group remains, it is regarded as another monomer 22 201248326 (a6) 〇 Production of Agent (A1) The ink-repellent (A1) 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 it. In the copolymerization reaction, a chain transfer agent may be present as needed. The monomer, polymerization initiator, solvent and chain transfer agent can be continuously added. Examples of the solvent include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; and ketones such as acetone, 2-butanone, decyl isobutyl ketone, and cyclohexanone; 2-cetoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.; sulphone; 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxy ethoxy) Carbenol such as ethanol, 2-(2-butoxyethoxy)ethanol; methyl acetate, acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monoterpenes Ethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monodecyl ether acetate, diethylene glycol monoethyl ether acetate Ester, diethylene glycol monobutyl ether acetate, propylene glycol monodecyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxy propionate, ring Hexanol acetate, butyl lactate, butyrolactone, 3-mercapto-3-methoxybutyl acetate, ethyl lactate, n-butyl lactate, T-butyrolactone, 3-methoxy Esters such as butyl acetate, 3-mercapto-3-indolyl butyl acetate, glycerol triacetate; Dimercaptoether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol didecyl ether, tetraethylene glycol didecyl ether, propylene glycol dimethyl hydrazine, dipropylene glycol Mercapto ether, dibutyl ether, diethylene glycol ethyl decyl ether and the like. The polymerization initiator may, for example, be an organic peroxide, an inorganic peroxide 23 201248326 or an azo compound. The organic peroxide and the inorganic peroxide can be used in combination with a reductant as a redox catalyst. The organic peroxide may, for example, be a benzyl peroxide, a lauryl peroxide, an isobutylene peroxide, a tertiary butyl hydroxy peroxide or a tertiary butyl cumene peroxide. Examples of the inorganic peracid include ammonium sulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, percarbonate and the like. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexanone-1-carbonitrile), and 2,2'-azobis (2,4-). Dimethylvaleronitrile), 2,2'-azobis(4-decyloxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyric acid dimethyl ester, 2, 2'-Azobis(2-methylamidinopropane) dicarbonate. Examples of the chain transfer agent include n-butyl mercaptan, n-dodecyl mercaptan, tributyl thiol, ethyl thiolate, 2-ethylhexyl thiolate, 2-thiol ethanol, and the like. Mercaptans; halogenated alkyl groups such as gas, tetra-carbonized carbon, and carbon tetrabromide. Further, when the ink repellent (Α1) has an ethylenic double bond, the copolymer obtained as described above and the compound having a functional group bonded to a reactive group and an ethylenic double bond (zl) can be used. The reaction was carried out to obtain an ink repellency agent (Α1). The combination of the compound (zl) having a functional group bondable to the reactive group and the ethylenic double bond with respect to the reactive group may, for example, be the following combination. (1) An acid anhydride having an ethylenic double bond to a hydroxyl group, (2) a compound having an isocyanate group and an ethylenic double bond to a hydroxyl group, (3) a compound having a vaporized thiol group and an ethylenic double bond to a hydroxyl group, (4) a compound having a hydroxyl group and an ethylenic double bond for an acid anhydride, (5) a compound having an epoxy group and an ethylenic double bond to a carboxyl group, and a compound having a hydroxyl group and an ethylenic double bond in the group 201224326 (6). = The compound having a green and ethylenic double bond reacts with an epoxy group to give a compound having a 2-domain-like group in one molecule, and reacts with the generated hydroxyl group to introduce an acidic group into the ink-repellent (A1). . Specific examples of the acid anhydride having a vinyl double bond include the above examples. Specific examples of the compound having an isocyanic acid and an ethyl double bond can be exemplified by 2 (methyl) propyloxyethyl isocyanate s, m ((methyl) propyl sulfonyl methyl) ethyl Isocyanate vinegar. As an example of the compound having a ruthenium chloride group and an ethylenic double bond, (meth)(tetra)indenyl chloride can be mentioned. The more the face of the compound having a radical and an ethylenic compound, the above-mentioned monomer having a radical. Specific examples of the compound having an epoxy group and a double bond of the ethyl group are exemplified by the above monomer having an epoxy group. Specific examples of the compound having a reduced double bond and a double bond include the above-mentioned examples of the monomer. Further, specific examples of the acid anhydride of the compound having two or more carboxyl groups in one molecule include an acid anhydride having an ethylene double bond represented by the above monomer (IV). When the copolymer is reacted with a compound (zl) having a functional group capable of bonding with a reactive group and an ethylenic double bond, a solvent exemplified in the synthesis of the above copolymer can be used as a solvent for the reaction. . Further, it is preferred to incorporate the polymerization inhibiting agent. As the polymerization inhibiting agent, for example, 2,6-di-tertiary butyl-p-cresol or tertiary butyl-p-benzoquinone can be mentioned. Further, a catalyst or a neutralizing agent may also be added. For example, when a copolymer having a hydroxyl group and a compound having an isocyanate group and an ethylenic double bond are reacted, a tin compound such as dibutyltin dilaurate or the like can be used. In the case where a copolymer having a hydroxy 25 201248326 group is reacted with a compound having a vaporized thiol group and an ethylenic double bond, an inert catalyst can be used. The appropriate ratio of each monomer to the total mass of the monomers copolymerized is as follows. The ratio of the monomer (al) or the monomer (a2) is preferably from 20 to 80% by mass, particularly preferably from 30 to 60% by mass. When the ratio is at least the lower limit of the above range, the ink repellent (A1) lowers the surface tension of the partition wall formed of the formed cured film, and imparts high ink repellency to the partition wall. When the upper limit is less than or equal to the upper limit of the above range, the adhesion between the partition wall and the base material is good. When the monomer (a3) is contained, the ratio is preferably 2 to 20% by mass, more preferably 4 to 12% by mass. When it is in the above range, the developability of the negative photosensitive resin composition becomes good. In the case where the monomer (a4) is contained, the ratio is preferably 5 to 70% by mass, preferably 10 to 60% by mass, more preferably 15 to 50% by mass. If it is in the above range, the liquid repellency can be maintained even if the pressure is increased in the developing step. Further, the residual film can be prevented from occurring. In the case where the monomer (a5) is contained, the ratio is preferably 20 to 70% by mass, more preferably 30 to 50% by mass. By the polymerization unit derived from the monomer (a5) contained in the above range, an ethylenic double bond is introduced, and the ink-repellent (A1) is fixed to the surface of the partition wall and developability is improved. When the other monomer (a6) is contained, the ratio is preferably 70% by mass or less, more preferably 50% by mass or less. When it is in the above range, alkali solubility and developability are good. A suitable combination of the monomers in the manufacture of the ink-repellent (A1) is as follows. (Combination 1) 26 201248326 Monomer (al): selected from the group consisting of 2-(perfluorobutyl)ethyl (meth)acrylate and 2-(perfluorohexyl)ethyl (meth)acrylate At least one of the monomers (a3): at least one selected from the group consisting of acrylic acid and methacrylic acid, and the monomer (a4) selected from the group consisting of BLEMMER PME-400 and BLEMMER PME-1000 At least one of the groups, monomer (a5): (mercapto)acrylic acid 2- to ethyl ke. After copolymerizing the above monomers to obtain a copolymer, a group selected from the group consisting of 2-(indenyl)acryloxyethyl isocyanate and anthracene, fluorenyl bis-indenyl) propylene fluorenyl) ethyl isocyanate At least one reaction of the group, a compound in which an ethylenic double bond is introduced. (combination 2) monomer (al): at least one of a group consisting of (meth)acrylic acid 2_(perfluorobutyl)ethyl ester and (meth)acrylic acid 2-(allylhexyl)acetic acid (a3): at least one of a group consisting of acrylic acid and methacrylic acid, and a monomer (a4): at least one of a group consisting of BLEMMER PME-400 and BLEMMER PME-1000, and a monomer required (a6) : selected from (meth)acrylic acid propyl acrylate, 3,4-epoxycyclohexyl acrylate, methyl (meth) acrylate, isodecyl acrylate and (fluorenyl) acrylate ring At least one of the groups consisting of hexyl esters. (Combination 3) Monomer (al): at least selected from the group consisting of 2-(perfluorobutyl)ethyl (meth)acrylate and 2-(perfluorohexyl)ethyl (meth)acrylate Species, 27 201248326

Monomer (a4): at least one selected from the group consisting of BLEMmeR PME-400 and BLEMMER PME-_, monomer (a5): glycidyl (meth)acrylate monomer (a6): 3 At least one selected from the group consisting of 4_epoxycyclohexyl acrylate, (mercapto)acrylic acid, (meth)isodecyl decanoate, and (fluorenyl)cyclohexyl acrylate. After copolymerizing the above monomers to obtain a copolymer, at least one selected from the group consisting of acrylic acid and methacrylic acid is selected, followed by being selected from 3,4,5,6-tetrahydrobenzal A compound in which at least one of a group consisting of an acid anhydride and cis-1,2,3,6-tetrahydrophthalic anhydride is introduced into an acid group and an ethylenic double bond. (Combination 4) Monomer (al): at least anthracene, monomer of a group consisting of 2-(perfluorobutyl)ethyl (meth)acrylate and 2-(hexa-hexyl)ethyl (meth)acrylate (a2) : at least one of a group consisting of X-22-174DX, X-22-2426, and X-22-247, and at least one of a group consisting of a monomer (a3): acrylic acid and methacrylic acid, Monomer (a4): At least one of the groups consisting of BLEMMER PME-400 and BLEMMER PME-1000, monomer (a5): 2-hydroxyethyl (meth) acrylate. After copolymerizing the above monomers to obtain a copolymer, 2-(meth)acrylomethoxyethyl isodecanoate and U-bis((fluorenyl)acryloxymethyl)ethyl isocyanate are added. A compound in which at least one of the groups is reacted to introduce an ethylenic double bond. 28 201248326 (combination 5) monomer (a2): at least one of the groups consisting of X-22-174DX, X-22-2426 and X-22-247, monomer (a3): acrylic acid and methacrylic acid At least one of the group, monomer (a4): at least one of the group consisting of BLEMMER PME-400 and BLEMMER PME-1000, monomer (a5): (mercapto) acrylate 2-ethyl ester . After copolymerizing the above monomers to obtain a copolymer, at least 1 of the group consisting of 2_(indenyl) propylene oxiranyl ethyl isocyanate and fluorenyl methoxymethyl) ethyl isocyanate The compound is introduced into a compound having an ethylenic double bond. When the ink-repellent (A1) has an ethylenic double bond, the copolymer and the compound (zl) have an equivalent ratio of [the functional group of the compound (zl)] / [reactive group of the copolymer] to 0.5. ~2.0 to insert is better, 〇·8~1·5 is especially good. If it is at or above the lower limit of the above range, the fixing of the ink-repellent (Α1) to the partition wall becomes good. When the upper limit of the above range is 値 or less, the amount of impurities which are unreacted compounds (ζ1) increases, and the appearance of the coating film deteriorates. Further, in the case where both the monomer (a3) and the monomer (a4) use a monomer having a carboxyl group, the adjustment of the amount of the copolymer and the compound (zl) is adjusted so that the ink repellent (A) is The acid price becomes a predetermined price. In the case where the ink-repellent (A1) has the base (1), the fluorine atom content of the ink-repellent (Α1) is preferably 5 to 50% by mass, preferably 1 〇 to 4 〇% by mass, and 2 〇 to 35 mass%. /〇 Especially good. When the ink is at or above the lower limit of the above range, the ink-repellent (Αι) is excellent in the effect of lowering the surface tension of the partition wall, and a partition wall excellent in ink-repellent property can be obtained. When the upper limit is less than or equal to the above range, the adhesion to the partition wall and the substrate becomes good. 29 201248326 In the case where the ink repellent (A1) has the base (2), the sand atomic probability of the ink repellent (a1) is preferably 0.1 to 25% by mass, and 0.5 to 10% by mass. /〇尤佳. If it is at least the lower limit of the above range, the ink-repellent (A1) imparts an effect of lowering the surface tension of the formed partition walls and improving the ink drop. If it is less than or equal to the above range, the adhesion to the partition wall and the substrate becomes good. The acid value of the ink-repellent (A1) is preferably 150 mgKOH/g or less, and more preferably 10 to 100 mgKOH/g. When it is in the above range, the negative photosensitive resin composition can have both solubility to the developer and ink repellency. The amount of the ink-repellent (A1) containing the ethylenic double bond is preferably 〇5χΐ〇3~5χ l〇-Wl/g, lxl(^~4.5xl (r3_/g is especially good. If in the above range: The fixing of the ink-repellent (A1) to the partition wall and the developability are good. The number average molecular weight (Mn) of the ink-repellent (V) is preferably 5χ1〇3~Curry4, 8XH)3~9xl〇4 It is preferable that it is excellent in alkali solubility and developability in the above range. The amount (Mw) is preferably ΐ.2χΐ〇4~2〇χ1〇4 to 12xl〇4. The mass average molecular weight of the above-mentioned ink-repellent agent (A1) is preferably '2x10~15xl〇4, and the alkali solubility and developability of 3χ1〇4 are good. Further, the side chain has a group (1) and the main substance is oxygenated. The compound of the chain is preferred. Hereinafter, the Φ 1 ^ ink-repellent (4) is the "inking agent (a2)". * The main chain is the organic polylithic eclipse: the ink is given (four) contains the hydrolysis and (4) the following formula (15) It is composed of a hydrolyzed granule or a hydrolyzed condensate of the mixture of 30 201248326 S sin.

Rf-CFX-Q'.Six.3 · . . (Η) R P'SlXVP) · · · (15) (The symbols in equations (14) and (15) are as follows. Also 1^/ is the same as above , Q _ carbon atom number 1 to 1 〇 of a fluorine-free atom of a divalent organic group, rHI: a hydrocarbon group having 1 to 6 carbon atoms, X1, X2: a hydrolyzable group, P: 0, 1 or 2, only ' Among the three formulas in the formula (14), the formula (15) (4__χ2 ρ furnaces may be different from each other.) The (4) sub-content of the ink-repellent (A2) is preferably from 1 〇 to 55 mass%. u is preferably a mass%, and is preferably 15 to 30% by mass. When the fluorine atom content is in the above range, it is possible to impart excellent ink repellency and ink repellent resistance to the partition wall obtained from the negative photosensitive resin composition. Ozone. The ink-repellent (A2) is preferably a decyl group (ie, a hydroxyl group bonded to a ruthenium atom). The number of the base group is 〇. 2~3 5 is preferred. 〇2~2 is preferable, and 〇5~丨.5 is particularly preferable. When the partition wall is formed by using the negative-change photosensitive resin composition at the lower limit of the above range, the ink repellent (A2) can be prevented. Detach from the surface of the substrate. If it is below the upper limit of the above range, The ink-repellent (A2) is preferably compatible with the solvent or other components in the negative-type photosensitive resin composition. Further, the number of the base alcohol groups in the ink-repellent agent (A2) is determined by 29_· The ratio of the Si group of the (4) group to the peak of the & base group without a phenolic group 31 201248326. The content thereof contains (4) the compound (a7) or the substance, the decane compound (a8) or a partial hydrolysis thereof. The condensable jinming hydrolyzable Shixi compound compound can be hydrolyzed by a water-hydrolyzed compound, which is a hydrolyzable 2 solution obtained by polycondensation and subsequent dehydration condensation. a high molecular weight body at a solvent level. Further, a 2~4 quantity body of the present month is a partial hydrolysis condensate of a lower molecular weight multimer. The partial hydrolysis condensate has hydrolysis to a relative f. M 'Ceco unreacted hydrolyzable group. The partial condensate of the genus / L sub-mass mainly has a mercaptan group, and the partially hydrolyzed condensate of low molecular weight will even have hydrolyzability::: the decondensate has a - the result of condensation or hydrolysis =!?: the nature of the high molecular weight hardened material. Part of the water Decondensing a mixture of oligomers having different degrees of polymerization. In the presence of the precondensate, the hydrolyzed (tetra) complex is allowed to be paid by the amount of time in the presence of (4) such as money touch water. The degree of multimerization of the partially hydrolyzed condensate can be appropriately adjusted, such as concentration, reaction temperature, reaction time, etc. ^, the following shows the molar ratio of the hydrolyzable money compound in the 3 hydrolysis (four) compound compound at least The above molar ratio is derived from the ratio of each hydrolyzable sulphur compound. 32 201248326 (hydrolyzable decane compound represented by formula (14)) It is shown that the compound (4) of the Shixia compound has a hydrolyzable stone compound of the group (1). In the above formula (4), Q1 is a divalent organic group of a linking group (1) and a hydrolyzable stone base (-SiXS), and the number of carbon atoms is 1 valent. When Q1 is represented by bonding Si on the key on the right side and R-CFX- on the key on the left side, specifically, the integer is ^^(1) is the integer of 5), _CH2〇(CH2) I2 (i2 is an integer of 4), _s〇2NRl-(CH2)i3_ (R1 is a hydrogen atom, a methyl group, or an ethyl group, and i3 is 1 or more and the total number of carbon atoms of R is an integer of 4 or less) - (C == 0) - NR - (CHJiHR1 is the same as above, and i4 is 1 or more and the total number of hindered atoms of Ri is an integer of 4 or less). In terms of Qi, -HCH2*3 - (CH2) ii - preferably ‘ -(CH2)2- is preferably. When the group (1) is a perfluoroalkyl group having 1 to 6 carbon atoms, the above Q1 is preferably a group represented by -(CHJi^il and the above). The u is preferably an integer of 2 to 4, and the il is 2 - (CH2) 2 - preferably. When the group (1) is a perfluoroalkyl group having 4 to 9 carbon atoms and having an etheric oxygen atom, the above Q1 is -(CH2)ir, -CH2〇(CH2)i2-, -SC^NR^-CCH %-, -(c sOVNR^CHJi4· indicates that the base (1) ~ the bucket and the !^ are the same as above). In this case, '-(CH2)2- is especially good. In the formula (14), X1 represents a hydrolyzable group bonded to a ruthenium atom, and a hydrogen group of the alkoxy group, the sulfonate group, the isocyanate group, the amine group and the amine group may be substituted with an alkyl group. The alkoxy group or the atom of the atom having a carbon number of i to 4 is preferred, and the decyloxy group, the ethoxy group or the gas atom is particularly preferred. The reaction is carried out by a hydrolysis reaction to a hydroxyl group (sterol group), and an intermolecular condensation reaction is carried out to form a Si-0-Si bond. The reaction of 201248326 can be smoothly carried out. Specific examples of the decane compound (a7) include the following compounds. F(CF2)4CH2CH2Si(OCH3)3, F(CF2)4CH2CH2Si(OCH2CH3)3, F(CF2)4CH2CH2SiCl3, F(CF2)6CH2CH2Si(OCH3)3, F(CF 2)6CH2CH2Si(OCH2CH3)3, F(( CF2) 6CH2CH2SiCl3. CF3OCF3CF2CF2CH2CH2Si(OCH3)3'F(CF2)20CF2CF20CF2CF2OCF2CF2OCF2CH2CH2Si(OCH2CH3)3, CF3OCF(CF3) CF2CH2CH2CH2Si(OCH3)3. F(CF2)2OCF2CF2OCF2CH2CH2CH2Si(OCH3)3, F(CF2)20(CF2)20(CF2)2CH2CH2Si(0CH3)3. F(CF2)3OCF2CF2CH2CH2SiCl3, F(CF2)30CF(CF3)CF20(CF2)2CH2CH2Si(OCH3)3. As the decane compound (a7), among them, F(CF2)6CH2CH2Si(0 CH3)3, F(CF2)6CH2CH2Si(〇CH2CH3)3, F(CF2)6CH2CH2SiCl3, F(CF2)3〇CF(CF3)CF2 It is particularly preferable that 〇(CF2)2CH2CH2Si(OCH3)3 or the like. In the hydrolyzable compound compound, the decane compound (a7) may be used singly or in combination of two or more kinds. Further, the hydrolyzable decane compound mixture may further contain a partial water hybrid of the decane compound (6). However, the monomer (a7) monomer is preferred over the partially hydrolyzed condensate. (hydrolyzable decane compound represented by the formula (15)) The compound (a8) represented by the above formula (15) is a hydrolyzable decane compound contained in the hydrolyzable (tetra) compound mixture. 34 201248326 In the formula (15), RHI is preferably an alkyl group having a carbon number of 丨~4, preferably a fluorenyl group or an ethyl group, preferably a methyl group, and a rHI other than the alkyl group. a hydrocarbyl group having a ring such as an alkenyl group such as a allylic group, a phenyl group or a cycloalkyl group, etc. X2 is a hydrolyzable group, and is the same as X1 in the above formula (15), including a suitable state. ρ is 0, 1 or 2. Two RH1 and (4-ρ) X2 each having ρ is 2 may be mutually different or the same. The decane compound (a8) is a tetrafunctional compound having ρ as a ruthenium or a 4^3 function. The compound is preferred. The ink-repellent (A2)' exhibits water repellency by the 11-derived from the decane compound (a7) and from the decane compound 08), mainly by the base (1). Show oily. Further, when the cured product of the ink-repellent (A2) is to exhibit sufficient oil repellency, the ratio of the base (1) is preferably higher than the total of the base (1) and RHi in the ink-repellent (A2). When p = 〇, the ratio of the base (1) in the ink-repellent (A2) becomes high, and the oil repellency is improved, or the film forming property is good. When p = 1 or 2, the ink repellent (A2) becomes readily soluble in the hydrocarbon solvent by the presence of RH1 to a certain extent, and a relatively inexpensive solvent can be selected when a negative photosensitive resin composition coating film is formed on the surface of the substrate. . The decane compound (a8) is preferably the following compound. Further, a partial hydrolysis condensate of the decane compound (a8) may be used instead of the decane compound (ag). Partially hydrolyzed condensates are preferably relatively low molecular weight compounds. The partially hydrolyzed condensate may, for example, be as follows.

Si(OCH3)4, Si(OCH2CH3)4, CH3Si(OCH3)3, CH3Si(OCH2CH3)3, CH3CH2Si(OCH3)3, CH3CH2Si(OCH2CH3)3, (CH3)2Si(OCH3)2, (CH3)2Si( OCH2CH3)2, (C6H5)Si(OCH2CH3)3, 35 201248326

a partially hydrolyzed condensate of Si(OCH3)4 (for example, methylthioate 51 (trade name) manufactured by cqlcOAT),

A partially hydrolyzed condensate of Si (〇CH2CH3) 4 (e.g., ethyl Silicate 40 manufactured by CoLCOAT Co., Ltd., ethyl Silicate 48 (all trade name)). The hydrolyzable decane compound (a8) which is contained in the hydrolyzable decane compound mixture of the present invention may be used alone or in combination of two or more. When two or more kinds are used in combination, a bifunctional compound may be used in combination with a tetrafunctional compound and/or a trifunctional compound. The content of the decane compound (a8) in the hydrolyzable decane compound mixture is preferably 1 to 9 moles per mole of the decane compound (a7), and preferably 0.5 to 9 moles. Further, a partially hydrolyzed condensate of a hydrolyzable decane compound (hereinafter referred to as decane compound (a9)) or a decane compound (a9) other than the decane compound (a7) and the Shixiyuan compound (a8) may be contained. (Shi Xiyuan Compound (a9)) The decane compound (a 9) is a bifunctional or trifunctional decane compound having a hydrolyzable group, and may be a compound which is co-condensed with a decane compound (a7) and a decane compound (a8). A well-known > The decane compound (a9) is preferably a compound of the above formula (丨5), and it is preferred to substitute RH1 as a compound having a structure of a hydrocarbon group having a hydrocarbon group of 7 or more or a hydrocarbon group substituted with a reactive group. However, when p is 2 in the formula (15), 1 of the two RHIs may be RHI. The reactive group is preferably a (mercapto) acryloxy group, an amine group, a hydrocarbon group-substituted amine group, an epoxy group or the like. In particular, a reactive group having an ethylenic double bond such as a (fluorenyl) acryloxy group is preferred. Suitable decane compound (a9) is a hydrolyzable decane compound having an ethylenic double bond having a reactive group 36 201248326, and a trialkoxy decane or dialkoxy group having a (meth) propylene oxime group substituted alkyl group. Decane is especially good. An ink-repellent (A2) having an ethylenic double bond can be obtained by using a decane compound (a9) having an ethylenic double bond. Specific examples of the compound decane compound (a9) which are particularly suitable are exemplified below. CH2 = C(CH3)COO(CH2)3Si(OCH3)3, CH2= C(CH3)COO(CH2)3Si(OCH2CH3)3, CH2 = CHCOO(CH2)3Si(OCH3)3 ' CH2 = CHCOO(CH2) 3Si(OCH2CH3)3, [CH2 = C(CH3)COO(CH2)3]CH3Si(OCH3)2, [CH2 = C(CH3)COO(CH2)3]CH3Si(OCH2CH3)2, (C6H5)NH(CH2 ) 3Si(OCH3)3. In the hydrolyzable decane compound contained in the hydrolyzable decane compound mixture of the present invention, the decane compound (a9) may be used singly or in combination of two or more. In the blend of the Shixiyuan compound (W) in the hydrolyzable Shixia compound mixture of the present invention, the total amount of the decane compound (a7) and the decane compound (W) is 1 mole, preferably 5 moles or less. 4 or less is especially good. The hydrolyzable Wei compound mixture t can be blended with a ruthenium functional compound as a water-frequency compound. The Neuwei compound is a function of a molecular weight modifier when the hydrolyzable compound mixture is hydrolyzed to a partial hydrolysis condensate. That is, it is intended to produce a lower molecular weight condensate of a lower molecular weight or to prevent excessive conversion of a partial conversion condensate to the purpose of solvent insolubility. Partial hydrolysis according to purpose 37 201248326 The molecular weight of the condensate can be appropriately adjusted. In the case of the monofunctional external compound, the structure of p in the above formula (10) is 3. The substance or, the base of the Wei Wei is better. The pit base in the compounds is preferably a carbon number of 4 or less, and a mercapto group or an ethyl group is particularly preferred. The ink-repellent (8-2) used in the composition of the U-negative photosensitive resin is a hydrolyzable money compound mixture of the above-mentioned raw materials or a partially hydrolyzed condensate thereof. A mixture of partially hydrolyzed condensates composed of a plurality of different condensates is preferred. That is, the ink-repellent (A2) is preferably an essential component of the compound (a) and the compound (4), and is preferably a hydrolyzed condensate of the compound (a9). The water-synthesis component is preferably a compound prepared by mixing the compound (4) of the compound (a7), arbitrarily mixing the compound (4), and then partially hydrolyzing and condensing the hydrate. Further, as a substitute for the compound of the ceramsite (a7), the residual compound (10), and the compound (4), the respective partial hydrolysis condensates may be used. In the case where the hydrolyzable group or the sterol group is completely hydrolyzed, the chemical formula using the cerium compound (a7) and the cerium compound (4) is used to form a hydrazine hydrolysis condensate, and the hydrazine has the following formula (16) to have an average composition. Type: However, it is actually a product (part = decondensed product) remaining in the hydrolyzable sterol group, and it is difficult to express the product by a chemical formula. The average composition of the formula (1: 7) is obtained by condensing part of the water produced as described above ^= 院 ̄ ̄ ̄; δ 夕 38 (16) (16) 201248326 [Chemical 2] Rf~CFX~Q1'Si 〇3/2 • S . _ In formula (16), the appropriate ranges of Rf, rhi, 卩丨 and 卩 are the same as above. The average presence of each unit in the partial hydrolysis condensate of different t and t polymerization degrees is Mohr. The partial hydrazine of the partially hydrolyzed condensate having the average compositional structure represented by the formula (16) is a random arrangement of the compound (4) and the compound (4), and the compound (a7) And the average composition of the compound (a8) and the s/t (mole ratio) in the formula (16), and the ink-repellent agent (A2) as a whole is two. It is used as the compound of the smelting compound (a7) relative to the hydrolyzability. The content of the decane compound (a8) in the mixture of the smelting compound is in the above range, that is, preferably 10/1 to 90 (mole ratio), and more preferably 10/5 to 90 (mole ratio). In the case where the ink-repellent agent (A2) is produced by the compound of the ceremonial compound (a7), the compound of the kiln (4), and the compound of the shixi compound (4), the compound (10) is derived from the compound (a9). The average composition of the step-co-co-condensation. It is preferred that the ink-repellent agent (A2) is a partially hydrolyzed condensate of a mixture of the following compounds: (combination 6) Shi Xiyuan compound (6): selected from 2-全 己 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) Burned with methyltriethoxydecane. 39 201248326 (combination 7) decane compound (a7): selected from 2-(perfluorohexyl)ethyltrimethoxydecane and 2-(perfluorobutyl)ethyltriazine At least one of oxoxane, decane compound (a8): tetraethoxy decane or tetraethoxy decane with methyl triethoxy decane, monofunctional decane compound: hexamethyldioxane or trimethyl a combination of a decane compound (a7): selected from the group consisting of 2-(perfluorohexyl)ethyltrimethoxy decane and 2-(perfluorobutyl)ethyltrimethoxy decane At least one, decane compound (a8): tetraethoxy decane or tetraethoxy decane and decyl triethoxy pulverization, decane compound (a9): 3-propene oxime a propyl decyloxy decane or a 3-mercapto propylene methoxy propyl trimethoxy decane. (Combination 9) a decane compound (a7): selected from the group consisting of 2-(perfluorohexyl)ethyltrimethoxynonane and At least one of 2-(perfluorobutyl)ethyltrimethoxy decane, decane compound (a8): tetraethoxy decane or tetraethoxy decane with methyl triethoxy decane, decane compound (a9 : 3-propenyloxypropyltrimethoxy decane or 3-mercaptopropenyloxypropyltrimethoxy oxan, 1-functional decane compound: hexamethyldioxane or trimethyl The methoxy stone is burned. (Combination 10) 40 201248326 Shi Xia Shao Compound (a7): at least one selected from the group consisting of 2-(perfluorohexyl)ethyltrimethoxydecane and 2-(perfluorobutyl)ethyltrimethoxylate , decane compound (a8): tetraethoxy decane or tetraethoxy decane with methyl triethoxy decane, shixi burning compound (a9): 3-glycidoxypropyl trimethoxy decane, A 1-functional decane compound: hexamethylene dioxane or trimethyl methoxy fluorene. In the negative photosensitive resin composition of the present invention, the ink repellent (A2) is further condensed in the process of exposure, hardening, etc., and it is presumed that it can form an excellent ink repellency even if it is irradiated with ultraviolet light/ozone. . In the negative photosensitive resin composition of the present invention, the number of the ink-repellent agent (A2) is preferably 500 or more, more preferably less than ιοοο, οοο, and less than iO'OOO. When the number average molecular weight (?n) is at or below the lower limit of the above range, when the partition wall is formed by the negative photosensitive resin composition, detachment from the surface of the substrate can be prevented. When the number average molecular weight (?n) is less than the upper limit 値' of the above range, the solubility in a solvent is good and workability is good. The number average molecular weight (?n) of the ink-repellent (?2) can be adjusted by selecting reaction conditions and the like. (Production of ink-repellent agent (Α2)) The ink-repellent agent (A2) in the negative-type photosensitive resin composition of the present invention can be hydrolyzed by hydrolyzing the above-mentioned hydrolyzed stone compound mixture if it is a partially hydrolyzed condensate. It is produced by partial condensation (hereinafter also referred to as a reaction step). The hydrolysis and partial condensation are as described above, and the reaction of the sterol group formation by the hydrolysis reaction of the hydrolyzable group with the formation of the oxime bond by the dehydration condensation reaction of the sterol groups with each other. In the reaction step, a reverse component which is usually hydrolyzed by a hydrolyzable decane compound can be used, such as water, a catalyst, an organic solvent, and the like. Restriction 'may be used in the case where water is used in the reaction step, the amount is a mixture of the compound (10) parts by mass, 25~9, 9 (10) = hydrolyzable money 100~1 900%% gossip / / + beacon, preferably 1 900 parts by mass is especially good. By making the amount of water on the controlled side of the upper reaction. ' 'The catalyst used for hydrolysis and reduction in the reaction step can be used as a mineral acid such as salt strontium, λ, acid, acid, oxalic acid, maleic acid, etc., nitric acid, disc medium, relative to hydrolyzable calcined compound Mix and use the touch 〇 〇 1 1. The mass portion is preferred, and the 0.W mass portion is particularly preferred. 〇 〇 〇 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以Specifically, an organic solvent which has been exemplified (manufactured by the ink-repellent (A)) is used. The organic solvent can be used in one type or in two or more types. In the reaction step, the amount of the organic solvent is relatively good, and the hydrolyzable decane compound full compound (10 parts by mass) is preferably 25 to 9,900 parts by mass. The partially hydrolyzed condensate obtained is blended with the solvent/reaction used in the reaction step to a negative photosensitive resin composition. In the county ruler, as a solution for the lack of wealth in the township (four) system can make money (a2) cut alcohol-based stable roller is better. The solvent which can stabilize the sterol group is exemplified by hydroxymei and in oxime. The ratio of the dielectric ratio (ε) of the underarm is in the range of 5 to 20. Specifically, a diol-based single-chamber fine acetic acid having a carbon number of 2 to 8 may be used. 201200326: a diol-based monoalkyl ether solvent, a kiss (10) (ethylene glycol ruthenium-based) bath, A hydrocarbon-based alcohol having 2 to 4 carbon atoms. More specifically, the dialkyl squamous acid _ solvent can be exemplified by two diol monomethyl ketone acetate vinegar u : 8 · 3), monool monomolecular ether lyophilized surface can be propylene glycol monomethyl ^ (ε 12:3) The hydrocarbon-based alcohol may, for example, be 2-propanol (ε: 19 92). The propylene glycol monomethyl scale is particularly suitable because of its high stabilizing effect. The reaction step is carried out at a temperature from room temperature to the boiling point of the solvent, under appropriate agitation conditions; The reaction time depends on the amount of the raw material component to be used, the reaction/dish degree, the mixing conditions, and the like, and is approximately 〜5 to 24 hours, as appropriate. After the completion of the reaction, the obtained ink-repellent (?2) may not be shown. The agent is contained in the negative photosensitive resin composition of the present invention. Alternatively, the organic solvent may be removed by a usual method and the ink-repellent (?2) may be left alone to be contained in the negative-type photosensitive resin composition. The content of the ink repellent (Α) in the negative photosensitive resin composition of the present invention is preferably 0 to 10% by mass in the total solid portion of the negative photosensitive resin composition. In the case where an ink-repellent (Α1) is used as the ink-repellent (Α), the content thereof is preferably in the amount of shell/°, and particularly preferably in G·2 to 1% by mass. When the content of the ink repellent (Α) is at least the lower limit of the above range, the partition wall formed is excellent in the effect, and the partition wall having excellent ink repellency can be obtained. If it is below the upper limit of the above range, then the partition wall and the substrate have good properties. In the case where the ink repellent (A) is used as the ink repellent (4), the content thereof is preferably 2% by mass or more preferably 2% by mass to 3% by mass. The content of the ink-repellent agent (Eight 2) is as follows: the storage stability of the negative-type photosensitive resin composition is excellent, and the optical component obtained from the negative-type photosensitive resin composition is excellent in ink-repellent property. With a smooth surface. The ink-repellent (A) in the present invention can have both a side chain having a group (1) and a side chain having a group (2) in one molecule. Further, the negative photosensitive resin composition of the present invention may further contain both an ink-repellent (A) having a side chain of the group (1) and an ink-repellent (A) having a side chain of the base (2). In these cases, the negative photosensitive resin composition exhibits high ink repellency and ink drop property. [Photopolymerization Initiator (B)] The negative photosensitive resin composition of the present invention contains a photopolymerization initiator (B) 'The δ ray photopolymerization initiator (b) is esterified with a nitro group in one molecule. character. The photopolymerization initiator (Β) is preferably a compound represented by the following formula (3). [Chemical 3]

In the formula (3), R31 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a cyano group. R32 represents R41 or OR42, and R41 and R42 each represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. R33 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. R34 and R35 are each independently and represent R41, 〇R42, cyano or a halogen atom. R41 and R42 are the same as described above. a and b are each independent, and are integers of 〇3, and c is an integer of 1 to 3. In the case of R31, the atoms of the alkyl group, the aryl group and the aralkyl group may further be subjected to OR43, COR44, SR45, NR46R47, -NCOR48-〇COR49, cyano, a functional atom '~CR50=CR51R52 or -CO-CR53 = CR54R55 Substituting, R43, R44, R45, R46, R47, R48, R49, R50, R51, R52, R53, R54 and R55 are each independently represented by a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 6 to 30. An aryl group, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms. As the R32, a hydrogen atom of an alkyl group, an aryl group and an aralkyl group may be further substituted by a halogen atom. The fluorenyl group of the extended-burning moiety of the substituent represented by the above R31, R33, R43 to R55 is bonded by an unsaturated bond, an ether bond, a thioether bond, a vinegar bond, a sulfur bond, a guanamine bond or an amine oxime. The acid ethyl ester bond may be interrupted 1 to 5 times. The alkyl moiety of the above substituent may be a branched side chain or a cyclic alkyl group, and the alkyl terminal of the above substituent may be an unsaturated bond. R3 may also form a ring together with an adjacent benzene ring. The oxime ester compound of the present invention has geometric isomers due to the double bond of ruthenium, but does not distinguish between them. The formula (3) and the exemplified compounds described below represent a mixture or a combination of the two, and are not limited thereto. Indicates the structure of the isomer. The alkyl group represented by the above R41 to R55 may, for example, be an alkyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group or an isopentyl group. Tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethyl 45 201248326 hexyl, tertiary octyl, decyl, isodecyl, fluorenyl, isodecyl, fluorene-hospital, ten Dialkyl, fourteen base, sixteen base, eighteen yard base, twenty burn base, cyclopentyl, cyclohexyl, cyclohexyldecyl, vinyl, allyl, butenyl, vinyl, Propylene, methoxyethyl, ethoxyethyl, propoxyethyl, pentyloxyethyl, octyloxyethyl, decyloxyethoxyethyl, ethoxyethoxyethyl , propoxyethoxyethyl, methoxypropyl, 2-decyloxy-1-methylethyl and the like. Examples of the aryl group represented by R41 to R55 include a phenyl group, a decyl group, a diphenylene group, an ethylphenyl group, a gas phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and one or more of the above alkyl groups. Phenyl, biphenyl, naphthyl, anthryl and the like. Examples of the aralkyl group represented by R41 to R55 include a benzyl group, a gastriphenyl group, an α-methylbenzyl group, a dimethylphenyl fluorenyl group, a phenylethyl group, and a phenylvinyl group. Examples of the heterocyclic group represented by R43 to R55 include a pyridyl group, a pyrimidinyl group, a fluorenyl group, a thienyl group, a tetrahydrofuranyl group, a dioxypentacycloalkyl group, and a benzo σ group. Sitting 2-yl, tetra-argon beta-mercapto,. More than 11 ° pyrylidyl, ° meters. Sitting on the basis of α. It is more specific than 嗤α, thiophene α, and iso-plug. sit. Fixed base, alpha number. Sit D base, different sigma number. Set the base, send. Fixed base, brigade, taste Linji and other 5 to 7 members of the heterocyclic ring. The ring formed by R33 together with the adjacent benzene ring may be a 5 to 7 member such as a cyclopentane ring, a cyclohexane ring, a cycloheptyl group, a benzene ring, a piperidine ring, a porphyrin ring, a lactone ring or an indoleamine ring. ring. The halogen atom of R41 to R55 and the halogen atom represented by R34 and R35 may be substituted for gas, gas, moisture and hydrazine. The fluorenylene group of the above-mentioned substituent is interrupted by an unsaturated bond, 46 201248326 screaming bond, sulfur crypto bond, ester bond, thioester bond, urethane bond or amine acetoacetate bond. In this case, the key group to be interrupted may be one or two or more types. If the base can be continuously interrupted, the line is interrupted continuously by two or more. Further, the alkyl moiety of the above substituent may be a branched side chain or a cyclic alkyl group, and the terminal of the substituent may be an unsaturated bond. In the oxime ester compound of the present invention, in the formula (3), R31 is an alkyl group having 11 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms; R33 is an alkyl group having 1 to 12 carbon atoms and an alkyl group having 13 to 20 carbon atoms interrupted by an ether bond or an ester bond, and particularly, R31 is a carbon atom or carbon having 11 to 20 carbon atoms. The aryl group having an atomic number of 6 to 30; or, the methylene group of the radical group of the group of the alkyl group may be interrupted by an ether bond or an ester bond for 1 to 5 times, and a branched alkyl group having 8 or more carbon atoms; The fluorenyl group of the alkyl group is an alkyl group having 13 or more carbon atoms interrupted by a singly or vinegar bond; R33 is an alkyl group interrupted by an ether bond for 1 to 5 times; When the ester bond is interrupted for 1 to 5 times, the synthesis is easy and the sensitivity is high, or when it is used as a polymerization initiator, it is dissolved in the solvent at a mass ratio of 1% by mass or more, and is required to be a photopolymerization initiator. suitable. The solubility is measured at 20 to 30. (The following is preferred. The above-mentioned cargo agent is a propylene glycol compound in which propylene glycol-1-monomethyl ether-2-acetate or cyclohexyl is preferred. The following formula (4) and the following formula are used. The factory, so that it is quantified by R31 or R32. ', can 47 (4) 201248326 [4]

[Chemical 5]

(5) Specific examples of the oxime ester compound represented by the formula (3) include the compounds represented by the following compounds No. 1 to 71. 48 201248326 [化6] 合合袂N〇. i : 佥化化化化禅叫.3

Debate for special suppression >.4 characterization "0, 'S: ft; Μ物Μ α 6

Compounding and changing 7 Chemicals (No/8 ft inclusion No, 9

49 201248326 [Chem. 7]

Also drug substance α 1 β compound to, 17 compound Np: t S

Compound J. 2? Compound H〇.?3: conjugate Να 24

Compounds such as .28

Compound N〇.:29 Compound No. 30

50 201248326 [Chem. 8] Compound No. 31

Compound Edition 34

Q- v.O :J〇:

Chemical composition "α 37 Ο

ο化含物No. 38

0丫r° u化·k妫 Also 杳物No. 40

Compound you.41 Chemicals Νρ·42

Ft台Να 43

51 201248326 [化9] 合合!^)...44 化台物私..舡化全触

Compound 珣14? iU0m〇.48 Food N. ,49

Article No. 吣 钕 仏 I 仏 Other Taiwan — 0. 52

Compound Cylinder 53 彳匕物物 No. 54:

52 201248326 [化 ίο] 含物洳.57 化物物 No:玷

Compound No,: 5S containing 铯1<〇.00

53 201248326 [化 li]

The oxime ester compound represented by the formula (3) can be produced by the following method, for example, according to the reaction formula of the following formula (6). First of all, make a master. The compound 1 and the sulfhydryl group 2 are reacted in the presence of zinc hydride to obtain a ruthenium matrix 3. Next, the hydrazine base 3 is reacted with hydroxylamine hydrochloride in the presence of DMF to obtain hydrazine compound 4. Next, the hydrazine compound 4 is reacted with the acid anhydride 5 or the hydrazine-based vaporized product 5' to obtain an ester compound represented by the formula (3). 54 201248326 [化12] (N〇j)e

(N〇2) 〇 Into warm base telluride 2

Acid base 3

(N〇2)o ^OH

(6) C1 mercapto halide 51 (3) (BSI compound) 肟 compound 4 The photopolymerization initiator (Β) content ratio in the negative photosensitive resin composition of the present invention, in the negative photosensitive resin composition In the total solid portion, it is preferably 1 to 15% by mass, preferably 2 to 1% by mass, more preferably 3 to 6% by mass, and if it is in the above range, the curability is good 'in the exposure step and the development step, it is close to each other. The pattern or the line width of the mask pattern. In particular, even when the exposure light of 330 nm or less is shielded by a cut filter or the like on the surface of the cured film, the ink repellency is good even at a low exposure amount. In the resin composition, a photopolymerization initiator other than the photopolymerization initiator (B) may be used in combination. The photopolymerization initiator which may be used in combination may, for example, be a fluorenyl group, a diethyl fluorenyl group or a methylbenzene group. Α-diketones such as acetaldehyde, 9,1, and phenanthrene; acetoin such as benzoin; benzoin thiol ether, benzoin ethyl ether, benzoin isopropyl ether Etc 55 201248326 醯 姻 醚 ether; thioxanthone, 2- thioxanthone, 2-mercaptothioxanthone, 2,4-dimethyl ° 嘲 @ @ ^, Propyl cyproterone, 2,4-diethyl thiopentanone, 2,4-dioxathioxanthone, 2,4-diisopropylthioxanthone, thioxanthone-4-transacid a thioxanthone; a benzophenone such as benzophenone, 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)diphenyl ketone; acetophenone , 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-diguanylacetophenone, 2,2·-dimethoxy-2-phenylacetophenone, peptone Oxyacetophenone, 2-mercapto-[4-(indolyl)phenyl]-2-indolyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4) Acetophenones such as -porphyrinylphenyl)-butan-1-one; anthraquinones such as hydrazine, 2-ethylhydrazine, anthracene, and 1,4-naphthoquinone; 2-diaminophenylbenzene Ethyl formate, ethyl 4-diguanyl benzoate, 4-diammonium benzoic acid (n-butoxy)ethyl ester, isoamyl 4-diguanyl benzoate, 4-diamine Aminobenzoic acid such as 2-ethylhexyl benzoate; acetophenone, sulfonium trihalide benzoate, etc.; fluorenyl phosphine oxide; peroxide such as dibutyl butyl peroxide; 1,2-octanedione, phenylthio)_,2-(anthracene-benzoquinone), acetylene 1-[9-ethyl-6·(2-曱Anthracene esters such as benzamidine)-9H-methylindol-3-yl]-l-(〇-acetamidine); triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N - an aliphatic amine such as methyldiethanolamine or diethylaminoethyl methacrylate; 2-thiolbenzimidazole, 2-thiolbenzoxazole, 2-thiol-based , hydrazine, 4 · butanol bis (3-thiol butyrate), tris (2-thiol propyl methoxyethyl) iso-cyanate, neopentyl alcohol tetrakis (3-thiol) A thiol compound or the like. Among them, the 'diphenyl-based, the aminobenzoic acid, the aliphatic amine and the thiolated Q are preferred to be used together with other photopolymerization initiators to exhibit a sensitizing effect. 56 201248326 When the negative photosensitive resin composition material contains a photopolymerization initiator other than the photopolymerization initiator (8), the content ratio is (in the total solid portion of the negative photosensitive resin composition, (4) f%% or less Good, 丨 ~ 15 quality recorded good, 2 ~ 10 quality. /. Especially good. [Alkali-soluble resin (C)] The alkali-soluble resin (C) is not particularly limited, but may be exemplified by a side chain having an acidic group and a __^Μ having an acetyl group, and an acidic group introduced into the epoxy resin. Although it is continued with i b), the side key with a bribe base and the single (C1_3) of the ship with a double double bond. The materials may be used alone or in combination of two or more. The resin (CM) can be synthesized by copolymerizing a monomer having a reaction group of a radical, a silk, an epoxy group, and the like, to obtain a reactivity. a side chain of a base and a copolymer having a side bond of an acidic group, and the copolymer, a compound having a functional group bonded to a reactive group and an ethylenic double bond, dissolved in a solvent to cause occurrence The reaction is thereby synthesized by the person. The monomer having a mercapto group can be exemplified by 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-(meth)acrylic acid 4- Hydroxybutyl ester, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, (fluorenyl) 3-chloro-2-hydroxypropyl acrylate, glycerol mono(meth) acrylate, 2- hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexane diol monoethylene Ethyl ether, 2-hydroxyethyl allyl ether, N-hydroxydecyl (meth) acrylamide, ν, ν-bis(hydroxymethyl)(fluorenyl) acrylamide, and the like. 57 201248326 The monomer having a carboxyl group may, for example, be acrylic acid, mercaptoacrylic acid, vinyl acetate, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid or the like. Further, these monomers can also be used as a monomer having an acidic group. Examples of the epoxy group-containing monomer include epoxypropyl (meth)acrylate and 3,4-epoxycyclohexyldecyl acrylate. The monomer having an acidic group is not particularly limited, and examples of the monomer having a phosphate group in addition to the above-mentioned monomer having a carboxyl group include, for example, 2-(indenyl)acryloxyethoxyacetic acid. The copolymerization of the above-mentioned monomer having a reactive group and a monomer having an acidic group can be carried out by a conventional method. The monomer having a hydroxyl group as a reactive group may, for example, be an acid anhydride having an ethylenic double bond, a compound having an isocyanate group and an ethylenic double bond, or a compound having a vaporized thiol group and an ethylenic double bond. Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, and 3,4,5,6-tetrahydrogen. Anthracene anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl succinic anhydride, and the like. The compound having an isocyanate group and an ethylenic double bond may, for example, be 2-(meth)acryloyloxyethyl isocyanate or 1,1-bis((meth)acrylomethoxymethyl)ethyl isocyanate. The compound having a vaporized thiol group and an ethylenic double bond may, for example, be (meth) acrylonitrile or the like. The monomer having a carboxyl group as a reactive group may, for example, be a compound having an epoxy group and an ethylenic double bond. The compound can be exemplified by epoxypropyl (indenyl) propylene 58 201248326 acid ester, 3,4-epoxycyclohexyl methacrylate or the like. It is also possible to introduce a carboxyl group into the resin (C1-1) by causing the acid-hepatic reaction which is a part of the cyclic structure to be formed by the dehydration condensation portion of the base and the acid-reducing portion. The monomer having an epoxy group as a reactive group may be a compound having a slow group and an ethylenic double bond. Specific examples of the compound include acrylic acid, methacrylic acid, ethyl acetate vinegar, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and the like. Further, the resulting group may be reacted with an acid needle which is a cyclic structure-partially dehydrated condensed portion, and a carboxyl group is introduced into the resin (CM). The resin (C1-2) can be synthesized by reacting an epoxy resin with a compound having a repellent and an ethylenic double bond, and reacting with a polybasic slow acid or an anhydrate thereof. Specifically, by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, an ethylene double bond is introduced into the epoxy resin. Then, the multi-inspective S is changed or the dehydrated product thereof is reacted with an epoxy resin into which an ethylene double bond has been introduced, whereby the carboxyl group can be introduced. The % oxygen resin is not particularly limited, but may be exemplified by a double-presence A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, a nonphenolic novolac type epoxy resin, and a trisphenol methane type epoxy resin. A resin, an epoxy resin having a naphthalene skeleton, an epoxy resin having a biphenyl skeleton represented by the following formula (Cl-2a), an epoxy resin represented by the following formula (Cl_2b), and a combination represented by the following formula (Cl-2c) An epoxy resin such as a benzene skeleton. 59 201248326 [Chem. 13]

(In the formula (Cl_2a), 'v is 1 to 5 Å, preferably 2 to 1 Å. The hydrogen atoms of the benzene ring are each independently, and may be substituted with an alkyl group having a carbon number of 1212 or 12, or may have a halogen atom or may have Substituent phenyl.) [Chem. 14]

(In the formula (C1-2b), ',, ..., the heart and r64 are each independently a gas atom, a gas atom or a carbon number of 1 to 5; w is 〇~1〇.) [Chem. 15]

(In the formula (Cl-2c), the hydrogen atoms of the 'benzene ring are each independently, and may be substituted with an alkyl group having 1 to 12 carbon atoms, a ii atom, or a benzene having a substituent of 0 to 10. , in the case of reacting an epoxy resin represented by the formula (Cl-2aHCl-2c) with a compound having a carboxyl group and an ethylenic double bond of 60 201248326, and reacting with a polybasic acid acid needle, a polybasic acid retardation It is preferred that the liver system use a mixture of two tacrotic needles and four retinoic acid dianhydrides. The molecular weight can be controlled by changing the ratio of the dicarboxylic anhydride and the tetra-baric acid dianhydride. A commercially available product can be used for the resin (C1-2). Commercially available products (for example, trade 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 (all of which are manufactured by Nippon Kayaku Co., Ltd.) and EX1010 (manufactured by Nagase Chemex Co., Ltd.). In the case of the monomer (C1-3), for example, 2,2,2-tripropenyloxymethylethyl phthalate (NKESTERCBX-1, manufactured by Shin-Nakamura Chemical Co., Ltd.) or the like can be mentioned. In the case of the soluble resin (C), it is possible to suppress the peeling of the coating film during development, to obtain a high-resolution pattern, to obtain a line with good linearity, and to maintain the appearance after the post-baking step, and to easily obtain a smooth coating film surface. In general, it is preferred to use a resin (C1-2). In the case of the resin (C1-2), it is particularly preferable to introduce a resin having an acidic group and an ethylenic double bond into a bisphenol A type epoxy resin, and to introduce an acidic group and an ethylenic double bond to the bisphenol F type epoxy resin. Resin, a resin in which an acidic group and an ethylenic double bond are introduced to a novolac type epoxy resin, a resin in which an acidic group and an ethylenic double bond are introduced to a p-cresol novolac type epoxy resin, or a trisphenol methane type epoxy resin is introduced. A resin having an acidic group and an ethylenic double bond, and a resin having an acidic group and an ethylene double bond introduced into the epoxy resin represented by the formula (Cl-2a) to (Cl-2c) 61 201248326. The mass average molecular weight (Mw) of the alkali-soluble resin (C) is preferably from 1. 5 χ 103 to 3 〇χ 103, and particularly preferably from 2 χ 103 to 15 χ 103. Further, the number average molecular weight (??) is preferably 500 to 2? 103, and more preferably 1 to 〇χ103 to ΙΟχΙΟ3. When the mass average molecular weight (Mw) and the mass average molecular weight (?n) are at least the lower limit of the above range, the curing at the time of exposure is sufficient. When the upper limit of the above range is 値 or less, the developability is good. The number of the ethylenic double bonds which the alkali-soluble resin (C) has in one molecule is preferably 3 or more, and more preferably 6 or more. When the number of the ethylenic double bonds is more than the lower limit 値 of the above range, the alkali solubility of the exposed portion and the unexposed portion is likely to be different, and a fine pattern can be formed with a lower exposure amount. The acid value of the alkali-soluble resin (C) is preferably from 10 to 200 mgKOH/g, more preferably from 30 to 150 mgKOH/g, even more preferably from 50 to 100 mgKOH/g. When the acid value is in the above range, the storage stability and developability of the negative photosensitive resin composition are good. The test soluble resin (C) contained in the negative photosensitive resin composition may be one type or a mixture of two or more types. The content ratio of the alkali-soluble resin (C) in the negative photosensitive resin composition of the present invention is preferably 10 to 50% by mass in the total solid portion of the negative photosensitive resin composition, and preferably 12 to 40% by mass, preferably 15 ~30% by mass is especially good. When the content is in the above range, the developability is good. [Negative photosensitive resin composition] The negative photosensitive resin composition of the present invention contains an ink-repellent (A), photopolymerization 62 201248326 initiator (B), an alkali-soluble resin (C), and optionally a black colorant. (D), a polymer dispersant (E), a dispersing aid (F), a crosslinking agent (G), and a solvent (Η). Further, it may contain the following thermal crosslinking agent (I), decane coupling agent (J), fine particles (Κ), acid-filling compound (L), and other additives. By using the negative photosensitive resin composition of the present invention, even if the exposure light of 330 nm or less is shielded from light, the ink repellency is good, and a negative photosensitive resin composition having good line width reproducibility of the mask can be produced, and the negative photosensitive resin composition can be produced. The homogeneous partition obtained from the composition. Therefore, even a case where a fine pattern is required is sufficient. The reason is presumed as follows. As the photopolymerization initiator, it is necessary to be a high-sensitivity compound which can efficiently absorb an exposure light exceeding 330 nm, and a photopolymerization initiator (B) can be selected. According to the inventors' knowledge, when the exposure light of 330 nm or less is shielded, the hardenability of the surface of the partition wall is extremely lowered, and the ink-repellent portion of the surface is easily reduced, and the ink-repellent property tends to be inferior. The negative photosensitive resin composition containing the photopolymerization initiator (B) can improve the surface hardenability of the partition walls. In the negative photosensitive resin composition containing a compound having poor mobility toward the surface of the partition wall as an ink-repellent agent, when the surface of the partition wall is hardened, or the ink-repellent agent is not completely moved to the surface of the partition wall, by using the surface toward the partition wall The ink-repellent agent with good mobility has a good ink repellency. The combination of the ink-repellent agent and the photopolymerization initiator (B) must be a combination of a workable viscosity and a stable composition of the negative-type photosensitive resin composition in addition to the above-mentioned hardenability and surface migration property. According to the review by the inventors, a combination of the ink-repellent (a) and the photopolymerization initiator (B) was found. 63 201248326 [Black coloring agent (D)] The negative photosensitive resin composition of the present invention may further contain a black coloring agent (9). When the negative photosensitive resin composition is used for the lattice black portion of the R, G, and B color pixels of the color filter which forms the black matrix, that is, the liquid crystal display element, it is preferable to contain the black colorant (D). . Examples of the black colorant (D) include carbon black, aniline black, an anthraquinone black pigment, and an anthraquinone black pigment, specifically as C. I. Color black 1, 6, 7, 12 '20, 31, etc. For example, a mixture of an organic pigment such as a red pigment, a blue pigment, a green pigment, or a methine azo pigment, or an inorganic pigment may be used. The black coloring agent (D) is preferably carbon black in terms of price and shading size, and the carbon black may be subjected to surface treatment using, for example, a resin. Further, in order to adjust the color tone, a blue pigment or a purple pigment may be used in combination. Regarding the black matrix, ON · ARRAY type color filter, or organic EL element, a coating film or a partition wall having a low dielectric constant or high resistance is sought. In order to obtain a coating film or a partition wall as described above, it is preferred to use a mixture of the above organic pigments and a fluorene-based azo black pigment. From the viewpoint of the shape of the black matrix, it is preferred that the carbon black is a specific surface area of 50 to 20 〇 m 2 /g as measured by the BET method. When the specific surface area is 50 m 2 /g or more, the shape of the black matrix is not easily deteriorated. On the other hand, when it is 2 〇〇 m 2 /g or less, the carbon black does not excessively adsorb the dispersing aid. Therefore, it is not necessary to mix a large amount of dispersing aid in order to exhibit physical properties. Further, from the viewpoint of sensitivity, as the carbon black, the oil absorption amount of dibutyl phthalate is preferably 120 cm 3 / 100 g or less, and the smaller the better. 64 201248326 Further, the average primary particle diameter of the carbon black measured by a transmission electron microscope is preferably 20 to 50 nm. When the average primary particle diameter is 20 nm or more, the dispersion can be carried out at a high concentration, and a negative photosensitive resin composition having good stability with time can be easily obtained. When it is 50 nm or less, the shape of the black matrix is not easily deteriorated. Further, the average secondary particle diameter observed by a transmission electron microscope is preferably 80 to 200 nm. When the negative color photosensitive resin composition of the present invention contains a black coloring agent (D) and is used for black matrix formation or the like, the content ratio of the black coloring agent (D) in the negative photosensitive resin composition In the total solid portion of the negative photosensitive resin composition, the black colorant (G) is 15 to 80 mass. /. Preferably, 20 to 70% by mass is preferred, and 25 to 65% by mass is particularly preferred. When it is in the above range, the sensitivity of the negative photosensitive resin composition obtained is good, and the barrier rib formed by the barrier is excellent. [Polymer dispersing agent (E)] When the dispersible material such as the black coloring agent (D) is contained, the polymer dispersing agent (E) is preferably a polymer dispersing agent (E). The polymer dispersant (E) is not particularly limited, and examples thereof include urethane type, polyimide type, alkyd type, epoxy type, polyester type, melamine type, phenol type, and acrylonitrile type. A polyether system, a vaporized ethylene system, a vaporized ethylene vinyl acetate copolymerization system, a polyamidamide system, a polycarbonate system, etc., preferably an amine phthalate type or a polyester type. Further, the polymer dispersant (E) may have a constituent unit derived from ethylene oxide and/or propylene oxide. In the case where the polymer dispersant (E) is used to disperse the black colorant (G), the affinity for the black colorant (D) is considered, and it is preferable to use the base group 65 201248326 polymer dispersant (E) By. The basic group is not particularly limited, and may be exemplified by a grade 1, a grade 2 or a grade 3 amine group. Commercially available products can also be used as the polymer dispersant (E). Commercial products can be exemplified by DISPARLON DA-7301 (trade name, manufactured by Nanben Chemical Co., Ltd.), b YK161, BYK162, BYK163, BYK182 (all of which are trade names, B YK-CHEMIE company), SOLSPERSE 5000, SOLSPERSEi 7〇00 ( All of the above are trade names, manufactured by Zeneca Corporation, etc. The amount of the polymer dispersant (E) to be used is preferably 5 to 30% by mass, more preferably 10 to 25% by mass based on the black colorant (D). When the amount of use is at least the lower limit of the above range, the dispersibility of the black colorant (G) is improved. When the amount is less than or equal to the upper limit of the above range, the developability of the negative photosensitive resin composition is good. [Dispersing aid (F)] The negative photosensitive resin composition may contain a phthalocyanine pigment derivative or a metal phthalocyanine sulfonamide compound in terms of the dispersing aid (F). The dispersing aid (F) has a function of adsorbing a dispersible material such as a black coloring agent and a high molecular dispersing agent (E) to enhance dispersion stability. [Crosslinking Agent (G)] The negative photosensitive resin composition of the present invention may contain a crosslinking agent (G) as an optional component for promoting radical hardening. The crosslinking agent (G) is preferably a compound having two or more ethylenic double bonds in the oxime and having no acidic group. By including the crosslinking agent (G) in the negative photosensitive resin composition, the curability of the alkali-soluble resin (C) at the time of exposure can be improved, and the amount of exposure at the time of forming the partition walls can be reduced. 1 66 201248326 A crosslinking agent (G) having two or more ethylenic double bonds in one molecule and having no acidic group is not particularly limited as long as it is a compound having such a condition, and examples thereof include diethylene glycol. Di(meth)acrylic acid vinegar, tetraethylene glycol di(meth) acrylate, tripropylene glycol bis(indenyl) acrylate, neopentyl glycol bis(indenyl) acrylate, 1,9- Decanediol bis(indenyl) acrylate, trimethylolpropane tris(decyl) acrylate, pentaerythritol tris(decyl) acrylate, pentaerythritol tetrakis(meth) acrylate, two or three Hydroxymethylpropane tetrakis(meth)acrylate, dipentaerythritol penta(meth)acrylate dipentaerythritol hexa(meth)acrylate, ethoxylated trimeric isocyanate triacrylate, ε-Caprolactone modified tris-(2-propenyl oxiranyl) trimeric isocyanate, bis{4-(allylbicyclo[2. 2. 1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}decane, fluorene, fluorene 1-inter-extension thiol-bis(allylbicyclo[2. 2. 1] hept-5-ene-2,3-dicarboxy quinimine), ethyl citrate acrylate, and the like. These may be used alone or in combination of two or more. A commercially available product can be used as the crosslinking agent (G). Commercially available products include, for example, KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate); NK ESTER A-9530 (trade name, new a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nakamura Chemical Industry Co., Ltd.); V#802 (trade name, Osaka Organic Chemical Industry Co., Ltd., dipentaerythritol acrylate vinegar, a mixture of dipentaerythritol acrylate and tetrapentaerythritol acrylate), NK ester A-9300 (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ethoxylated trimeric isocyanate triacrylate); NK ESTERA- 9300-1CL (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ε-caprolactone modified tris-(2-propenyl oxiranyl) trimeric isocyanate); ΒΑΝΙ-Μ (trade name, manufactured by Jiushan Petrochemical Co., Ltd.) , bis (4_(dihydropropyl 67 201248326 bisbicyclo[2·2·1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane); and BANI-X (trade name, Maruzen Oil Chemical system, ν, ν · - m-extension thiol-bis (allyl bicyclo [2. 2. 1] Hept-5-ene-2,3-dicarboxy quinone imine)) and the like. The urethane acrylate can be exemplified by the KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd. The specific trade names can be exemplified by: UX-3204, UX-61 (H, UX-0937, DPHA-40H 'UX-5000, UX -5002D-P20, etc. Among them, KAYARAD DPHA and NK ESTER A-9530 are preferred because they can improve the sensitivity of the cured film obtained from the negative photosensitive resin composition. NK ESTER A-9300, BANI-M and BANI-X is preferred from the viewpoint of imparting hardness to the cured film and suppressing thermal collapse. NK ESTER A-9300-1CL is preferred from the viewpoint of imparting flexibility to the cured film. The ester is preferable because it can realize an appropriate development time and has good developability. The content ratio of the crosslinking agent (G) in the negative photosensitive resin composition of the present invention is the total of the negative photosensitive resin composition. In the solid portion, it is preferably 3 to 3 Å by mass, preferably 5 to 20% by mass, and preferably 7 to 15% by mass. If it is in the above range, the alkali developability of the negative photosensitive resin composition may be [Solvent (H)] The negative photosensitive resin composition of the present invention contains a solvent (H) as needed. When the solvent (H) is contained, the viscosity of the negative photosensitive resin composition is lowered, and the coating of the negative photosensitive resin composition on the substrate is facilitated. A uniform negative photosensitive resin composition coating film can be formed. When the negative photosensitive resin composition contains no solvent (H), the coating film of the negative photosensitive resin composition, that is, the film of the negative photosensitive resin composition is the same as 68 201248326. The solvent (Η) contained in the negative photosensitive resin composition of the present invention can be used as the above-mentioned ink repellent (Α), photopolymerization initiator (Β), and alkali solubility in the negative photosensitive resin composition. Resin (〇, if necessary, black colorant (D), polymer dispersant (Ε), dispersing aid (F), and cross-linking agent (G), even if any of the components described later are uniformly dissolved or dispersed' and have a negative The solvent of the photosensitive resin composition is uniform and simple to the coating of the substrate to be formed, and the solvent is not particularly limited, and the solvent can be used, for example, in combination with a synthetic ink (Α). The solvent used in the same solvent. Negative photosensitive resin The content ratio of the solvent (Η) contained in the product varies depending on the composition or use of the negative photosensitive resin composition, and the negative photosensitive resin composition is preferably mixed with 50 to 99 mass%. It is preferably 6 to 95% by mass, more preferably 65 to 90% by mass. The negative photosensitive resin composition of the present invention contains an ink-repellent agent, a photopolymerization initiator (yttrium), and an alkali-soluble resin. (C), and if necessary, contain a black colorant 〇D), a polymer dispersant (Ε), a dispersing aid (f), a crosslinking agent (g), and a solvent (H), and may also contain the following heat A coupling agent (1), a decane coupling agent (j), a fine particle (K), an acid-filling compound (L), and other additives. [Thermal Crosslinking Agent (I)] The thermal crosslinking agent (1) is a compound having two or more groups capable of reacting with a carboxyl group and/or a hydroxyl group. When the soluble resin (B) has a carboxyl group and/or a hydroxyl group, the hot-parent (I) reacts with the alkali-soluble resin (B) to increase the crosslinking density of the cured film and improve heat resistance. effect. The thermal crosslinking agent (1) is preferably selected from the group consisting of an amine resin, a ring 69 201248326 oxygen compound, an oxazoline compound, a polyisocyanate compound, and a polycarbodiimide compound. One kind. These compounds may be used singly or in combination of two or more. The content ratio of the thermal crosslinking agent (F) in the negative photosensitive resin composition of the present invention is preferably 50 mass%/〇 in the total solid portion of the negative photosensitive resin composition, and 5 to 30 mass. % is better. When it is in the above range, the developability of the resulting negative photosensitive resin composition is good. [Centane Coupling Agent (J)] When the decane coupling agent (J) is used, the substrate adhesion of the cured film formed of the obtained negative photosensitive resin composition is improved. Specific examples of the decane coupling agent (J) include, for example, tetraethoxy decane, 3-glycidoxypropyltrimethoxy oxalate, decyltrimethoxy sulphur, and vinyltrimethoxy. Decane, 3-methacryloxypropyltrimethoxy decane, 3-apropylpropyltrimethoxy decane, 3-thiolpropyltrimethoxydecane, 3-aminopropyltriethoxylate Base decane, heptafluorooctylethyltrimethoxy decane, triethoxy decane containing a polyoxyalkylene chain, and the like. These may be used alone or in combination of two or more. Commercially available products can be used as the cockroach coupling agent (J). Commercially available products include KBM5013 (trade name, Shin-Etsu Chemical Co., Ltd., 3_acryloxypropyltrimethoxydecane). The content ratio of the decane coupling agent (j) in the negative photosensitive composition of the present invention is preferably 〇 1 to 2 〇 in the total solid portion of the negative photosensitive resin composition. /. Very good for 1 to 10% by mass. When it is more than the lower limit of the above range, the hardening_substrate adhesion formed by the negative photosensitive resin composition is increased by 70 201248326, and if it is _ or less of the above range, the ink repellency is good. [Microparticle (κ)] + Negative photosensitive resin composition may contain fine particles (κ) as needed. It is possible to prevent thermal collapse of the partition wall obtained by the negative photosensitive resin composition by 4 plantings. The fine particles (Κ) are not particularly limited, and examples thereof include: oxidized oxidized stone, oxidized cone, magnesia, and indium doped tin oxide, inorganic fine particles such as tin oxide (ΑΤ0), polyethylene, polymethyl propylene In the case of organic fine particles such as dilute acid vinegar (ΡΜ祖), it is preferable to use inorganic fine particles when heat resistance is used. If oxygen transfer or dispersion stability is taken into consideration, oxygen cut or oxidation error is preferable. In the case where the negative photosensitive resin composition contains a black coloring agent (6) and a polymer dispersing agent (Η), the amount of fine particles (Κ) of the polymer dispersing agent (Η) is considered. New Zealand. Further, in consideration of the exposure sensitivity of the 贞-type photosensitive resin composition, the fine particles are preferably such that they do not absorb the illuminating light during exposure, and do not absorb the main illuminating wavelength of the ultrahigh pressure mercury lamp... 'ray (365 nm), Η Radiation (persuasion (4), G-ray (436 nm) is preferred. Microparticles (K) are preferred for silica dioxide. Separate silica dioxide is preferred for colloidal cerium oxide. In general, as colloidal cerium oxide. There are two organic bismuth sols which are dispersed in water and dissolved in water, and organic sols which are organically dissolved in water, but it is preferably used as an organic solvent as a dispersing medium. As an organic cerium oxide sol, commercially available products can be used as follows, and any of them is a product name of PMA-ST manufactured by Nissan Chemical Industries Co., Ltd. (dioxy-cut size·1Q~2Gnm, dioxane) Cut solid portion ^ 71 201248326 Quality: %, propylene glycol monodecyl acetate: 70% by mass), Npc ST (cerium dioxide particle size: 10 to 20 nm, cerium oxide solid portion: 3 〇 mass%, positive C Kisei Lusu: 70% by mass.), IPA-ST (cerium dioxide particle size: 1〇~2 Nm, cerium oxide solid portion: 30% by mass '1 卩 8: 7 〇 mass, etc. The content ratio of fine particles (κ) in the negative photosensitive resin composition of the present invention, the total solid state of the negative photosensitive resin composition In the part, it is preferably 3 to 4% by mass, more preferably 5 to 30% by mass, and most preferably 7% by mass or more and less than 25% by mass. If the content ratio is in the above range, the ink repellent property is good, and negative. The storage stability of the photosensitive resin composition is good. [Phosphate Compound (L)] The negative photosensitive resin composition of the present invention may contain a phthalic acid compound (L) as needed. By forming a negative photosensitive resin The compound containing the phosphoric acid compound (L)' can improve the adhesion to the substrate. As the phosphoric acid compound (L), mono (meth) acryloxyethyl phosphate, bis(indenyl) propylene oxy group B can be mentioned. Phosphate, tris(methyl) propylene methoxyethyl phosphate, etc. [Other Additives] The negative photosensitive resin composition of the present invention may further contain a hardening accelerator, a tackifier, a plasticizer, or Defoamer, leveling agent, anti-cratering agent, UV absorption [Appropriate Combination of Negative Photosensitive Resin Composition] The negative photosensitive resin composition of the present invention preferably has a composition and a blend ratio in accordance with the use or desired characteristics. The negative photosensitive resin composition of the present invention is various. The preferred composition of the blending component is as follows: 72 201248326 Ink-repellent (A): a suitable combination of the above-mentioned ink-repellent (A1) 丨 5 or a suitable combination of the above-mentioned ink-repellent (A2) 6 to 10, The total solid portion of the negative photosensitive resin composition is 〇. 〇1 to 10% by mass, the photopolymerization initiator (B): Compound No. 1-58 to 58 in the International Publication No. 2008/078678, which is 0 in the total solid portion of the negative photosensitive resin composition. 01 ~ 10 quality. /〇, alkali-soluble resin (C): a group of resins in which an acidic group and an ethylenic double bond are introduced in (Cl-2a), (Cl-2b), (Cl-2c) and an anthraquinone novolac type epoxy resin. At least one of the groups is 12 to 40% by mass in the total solid portion of the negative photosensitive resin composition, and the solvent (H): 2-propanol, butyrolactone, 3-methoxybutyl acetate At least 1 group consisting of diethylene glycol didecyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol didecyl ether, propylene glycol monomethyl ether hexanoate, cyclohexanone, and butyl lactate The amount is 50 to 99% by mass in the negative photosensitive resin composition. [Manufacturing Method of Negative Photosensitive Resin Composition] A method of producing a negative photosensitive resin composition is an ink repellent (A), a photopolymerization initiator (B), an alkali soluble resin (C), and optionally Black coloring agent (D), polymer dispersing agent (E), dispersing aid (F), crosslinking agent (G), and solvent (E), and further, mixing the following thermal crosslinking agent (I), decane coupling agent The method of (J), fine particles (K), phosphoric acid compound (L) and other additive phases is preferred. The negative photosensitive resin composition of the present invention is a general negative photosensitive composition, and can be used as a material such as photolithography, and the cured film obtained by curing the composition coating film can be used as a general negative. Type photosensitive tree 73 201248326 Optical element member used for the cured film of the fat composition. [Manufacturing Method of Partition for Optical Element] It is applied to a partition wall for an optical element having a plurality of pixels on a substrate and a partition wall between adjacent pixels. The negative photosensitive resin composition of the present invention is applied onto the substrate to form a coating film (coating sand); then, the heating is performed (pre-compensation step); then, the coating film is simply formed as a partition wall. a part of which is subjected to exposure to be photohardened (exposure step); then, the coating film other than the photohardenable portion is removed, and (4) a partition wall composed of the photocured portion of the coating film (development step); The partition wall which has been formed is subjected to heating (post-baking step), whereby the partition wall for the optical element can be produced. Further, when the negative photosensitive resin composition of the present invention contains a black coloring agent (D), the partition walls for optical elements are formed of a black matrix. The material of the substrate is not particularly limited, and for example, various glass plates can be used; polyacetic acid (polypyrene diacetate, etc.), poly (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate Thermoplastic plastic sheets such as acid methyl vinegar, poly-milling, poly-imine, poly(methyl) acryl resin; hardened sheets of thermosetting wax such as epoxy resin and unsaturated polyester. In particular, based on heat resistance, a heat-resistant plastic such as a glass plate or a polyacrylonitrile is preferred. Fig. 1 is a cross-sectional view showing a manufacturing example of a partition for an optical element using the negative photosensitive resin composition of the present invention. Fig. 1(1) is a front view showing a state in which the coating film 2 composed of the negative photosensitive resin composition of the present invention is formed on the substrate 1. The first (11) diagram schematically shows a diagram of the exposure step. The first ι(πι) diagram shows a cross-sectional view of the substrate 后 after the development step and the partition wall 6 74 201248326 formed on the substrate. Hereinafter, a method for producing a partition for an optical element using the negative photosensitive resin composition of the present invention will be specifically described with reference to Fig. 1 . (Coating film forming step) As shown in the cross section of Fig. 1 (1), the negative photosensitive composition of the present invention is applied onto the substrate ' to form a negative photosensitive resin composition. Coating film 2° X 'Before forming the coating film 2 of the negative (tetra) photoresin composition on the substrate 1 'It is preferable to first wash the coated surface of the substrate with the negative photosensitive material composition by alcohol or ultraviolet/ozone In the method of applying the method of washing, etc., the coating method of the photosensitive resin composition is not particularly limited as long as it is a uniform coating method, and examples thereof include spin coating, spray coating, and narrow coating. A method for forming a general coating film such as a slit coating method, a roll coating method, a spin coating method, or a bar coating method. The film thickness of the coating film 2 is determined in consideration of the height of the partition wall finally obtained. The film # of the coating film 2 is preferably 100 to 3,000 Å/〇, preferably 100 to 2,000%, of the height of the finally obtained partition wall. 3~65μιη especially good. The film thickness of the coating film 2 is preferably 〇 3 to 325 μηι (pre-baking step): in the above-described forming step, M4 is formed on the substrate i, and the film J is obtained. By this heating, the negative photosensitive tree constituting the coating film 2 ==? The _ component will evaporate 'removal and get closer. Heated film. In addition, the 'inking agent (A) migrates to the surface of the coating film. The method is, for example, heating the substrate 1 and the _2- using a hot plate such as a 75 201248326, an oven, etc., and applying 50 to 120 ° C and A method of heat treatment for about 10 to 2,000 seconds. Further, as described above, the volatile component such as a solvent may be removed by heating in the prebaking step, but a drying step such as vacuum drying other than heating (drying) may be additionally provided before the prebaking step to remove volatile components such as a solvent. Further, in order not to cause unevenness in the appearance of the coating film and to perform drying efficiently, it is more preferable to use a combination of the drying function performed by the pre-baking step and vacuum drying. The conditions for vacuum drying vary depending on the type of each component, the blending ratio, and the like, and are preferably carried out in a wide range of about 500 to 10 Pa and about 10 to 300 seconds. (Exposure step) As shown in Fig. 1 (11), the light 5 is irradiated to the film 2 through the mask 4 of a predetermined pattern. The light 5 penetrates only the predetermined pattern portion of the gap of the above-mentioned mask 4 and reaches the film on the substrate 1, and only this portion is photohardened. Therefore, when the partition wall is formed, the shape of the predetermined pattern is appropriately designed into the shape of the partition wall. For example, after the post-baking step, the width of the partition walls is preferably ΙΟΟμηι or less, and preferably 20 μΓη or less. Further, the distance between the adjacent partition walls is preferably 500 μm or less on average, and preferably 300 μηη or less. The mask to be used is preferably constructed so that the pattern can be formed in the above range. In the first (11) diagram, the exposed portion 3 of the light-irradiated film is composed of a cured film of a negative photosensitive resin composition; on the other hand, the unexposed portion is composed of an uncured negative photosensitive resin. The state in which the film 2 itself remains. The irradiated light 5 may be, for example, visible light; ultraviolet light; far ultraviolet light; KrF excimer laser, ArF excimer laser, F2 excimer laser, Kr2 quasi-segment 76 201248326 sub-laser, KrAr excimer laser, Excimer lasers such as μ excimer lasers; X-rays, electron beams, etc. X, the illumination light 5 is preferably an electromagnetic wave having a wavelength of 1 〇〇 to 6 〇〇 nm, preferably having a light distribution in the range of 3 〇〇 to 5 〇〇 nm, i-ray (365 nm), h-ray (405 nm). ), g-ray (436nm) is especially good. Further, in the case of, for example, a mirror projection type (MPA) exposure method, electromagnetic waves of 330 nm or less are turned off to illuminate the exposure light. As described above, in the production method of the present invention, exposure to an electromagnetic wave of 330 nm or less can be performed as needed. As the irradiation device, a known ultrahigh pressure mercury lamp or a deep ultraviolet lamp or the like can be used. The amount of exposure is preferably 5 to 1 based on the twist line in the case where the electromagnetic wave of 33 〇 nm or less is cut off by a cut-off waver or the like, preferably 5 to 2 (K) mj/cm 2 and preferably 10 100 mJ/cm. More preferably, 15~5〇mJ/cm2 is especially good. When the amount of exposure is at least the lower limit of the above range, the 感光-type photosensitive resin composition which is a partition wall is sufficiently hardened to be dissolved or peeled off from the substrate i during subsequent development. When the right is below the upper limit of the above range, high resolution can be obtained. The surface of the cured film obtained by the f-type negative photosensitive resin composition is particularly excellent in the ink repellency even when the electromagnetic wave of 33 Å or less is cut off by a cut-off ferrite or the like. ★The light time is preferably based on the exposure amount, the composition of the photosensitive composition for the negative type, the thickness of the coating film, etc., preferably 5 to 20 seconds. (Developing Step) Development was carried out using a developing solution to remove the unexposed 2 on the substrate 1 shown in Fig. 1 (11). Thus, the structure of the first plate 1 and the M6 as shown in the cross-sectional view of Fig. 1 (111) is obtained, which is formed of a cured film of a negative photosensitive material 77 201248326 resin composition on the substrate. Further, the partition wall 6 and the substrate [the portion surrounded by the ink are injected by ink or the like to form a portion of the pixel which is called the dot matrix 7. The obtained substrate 10 is subjected to a post-baking step which will be described later, and is used as a substrate for producing an optical element by an ink jet method. As the developer, an aqueous solution containing an alkali such as an inorganic base, an amine, an alcohol amine or a quaternary salt can be used. Further, in order to improve the solubility and remove the residue in the developer, an organic solvent such as a surfactant or an alcohol may be added. The development time (the time for bringing the developer into contact) is preferably 5 to 180 seconds. Further, the developing method may, for example, be a flooding method, a dip coating method, a shower method or the like. After development, the substrate crucible and the moisture on the partition wall 6 can be removed by performing high-pressure water washing or running water washing and air-drying with compressed air or compressed nitrogen. Further, the film thickness of the cured film which is a part of the partition wall before and after the development step is preferably 60 nm or less, more preferably 5 Å, and particularly preferably 45 nm or less. When the film thickness is changed to 60 nm or less, the ink-repellent layer for exhibiting the ink-repellent property of the surface of the cured film after the exposure sufficiently remains on the surface, and the ink-repellent property of the cured film after the post-baking becomes good. (Post-baking step) The partition wall 6 on the substrate 1 is heated. The method of heating is, for example, a method in which the substrate 1' and the barrier 6 are heated by a heating means such as a hot plate or an oven to perform a heat treatment of 15 〇 to 250 C 5 90 knives. By this heat treatment, the partition wall 6 composed of the cured film of the negative photosensitive resin composition on the substrate is further hardened, and the shape of the dot matrix 7 surrounded by the partition wall 6 and the substrate is also fixed. In addition, it is preferable to treat the heating temperature at 180 ° C or higher. If the heating degree is too low, the hardening of the partition wall 6 is insufficient, and sufficient resistance cannot be obtained, and in the subsequent ink-jet coating step, when the ink is injected into the dot matrix 7, there is a fear that the ink is printed in the dot matrix 7. The solvent contained in the solvent causes the partition wall 6 to swell or the ink to ooze out. On the other hand, if the heating temperature is over the surface, there is a possibility that the partition wall 6 may thermally decompose. In the negative photosensitive resin composition of the present invention, the average width of the partition walls is preferably 1 μm or less, more preferably 20 μπ 1 Η, and the average distance between the adjacent partition walls (dot array width) is 500 μm or less. Good, 3〇〇μιη is very good. Also, the average height of the partition wall is 0. 05~50μιη is better, 〇. 2~1〇μιη especially good. The ink of the cured film of the coating film formed by the negative photosensitive resin composition of the present invention can be estimated from the contact angle of water and propanol 1 _ monomethyl _ 2 - acetate (hereinafter also referred to as PGMEA). The contact angle of water is preferably 90 degrees or more, and more preferably 95 degrees or more. Further, the contact angle of PGMEA is preferably 30 degrees or more, more preferably 35 degrees or more, and still more preferably 40 degrees or more. The ink repellency of the film-hardened film is preferably 90 degrees or more with respect to water and a contact angle of PGOEA of 30 degrees or more. [Manufacturing Method of Optical Element] After the partition wall is formed on the substrate by the above-described manufacturing method, the ink-repellent treatment is performed on the surface of the substrate and the substrate of the spacer package (the ink-printing process step); Next, the ink is injected into the above region by an inkjet method to form the aforementioned pixel (ink injection step). Further, in the manufacture of the optical element, the step of the ink-printing process is not an essential step, and the optical element to be manufactured may not be performed. (Phi-inking treatment step) The method of the ink-removing treatment may be, for example, a washing treatment by an aqueous solution, a treatment of impurities, a UV treatment, a treatment of excimer 79 201248326, and a treatment. Halo discharge treatment, oxygen I * milk plasma treatment and other methods. The washing place by the aqueous alkali solution is washed with an alkali aqueous solution (potassium hydroxide, tetramethyl hydroxide, etc.) to clean the substrate. The ultraviolet cleaning treatment is a dry treatment in which the surface of the substrate is washed with ultraviolet rays. UV/Ozone cleaning treatment, you use the dry treatment of the surface of the substrate with a low-pressure mercury lamp emitting 185nm and 254nm light. Excimer washing treatment is based on the use of Erli net substrate for mosquito dryness. The illusion of 72nm light Μ molecular lamp wash corona discharge treatment, the use of, the 颂 voltage, so that the corona discharge in the atmosphere, the surface of the substrate is washed by the dry treatment oxygen polymerization, mainly used in the trigger The oxygen is excited, and the anti-coupling power source is formed as the conformation_"electric t state", and it is used to check the surface of the substrate. In terms of simplicity, in terms of simplicity, the hinged UV/money wash material dry core method = better commercially available device to produce. In the case of potential ice and odor, the substrate placed inside the Μ external line/ozone device can be used in the air at room temperature, K1. In about minutes, the oil is drained (4) in the next door, so that it can be handled. In addition, it is only necessary to adjust the temperature of the 睥Μ Ρ Ρ 不会 不会 不会 不会 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 By performing the ink-printing process, it is possible to prevent the formation of impurities remaining in the lattice, and thus it is possible to prevent the color display device 80 of the optical element for the printed ink which can sufficiently achieve the dot matrix. White speckle phenomenon. (Ink Injecting Step) This is a step of forming a pixel by using ink in the dot matrix after the step of the ink-printing process. This step can be carried out by using an ink jet for blasting, and is carried out in a conventional manner. Such a pixel shape==the ink jet device to be used is not particularly limited, and a method in which the ink is continuously ejected and controlled by a magnetic field, a method of intermittently printing the ink, and heating the ink can be used. _ The shirt is foamed and intermittently sprayed out of the various methods of the ink device. The optical element produced by using the negative photosensitive resin composition of the present invention may, for example, be a color filter, an organic rainbow display element, or an organic tft: column. [Manufacturing of Color Filter] The formation of the partition walls, the dot-inking ink treatment of the dot matrix, and the ink jetting by the ink jet method are as described above. In the color filter, the pixel shape to be formed may be any known arrangement such as a stripe type, a mosaic type, or a triangular type '4-pixel arrangement type. The ink used for pixel formation mainly contains a coloring component, a binder resin component, and a solvent. The coloring component is preferably a pigment or a dye which is excellent in heat resistance and light resistance. The resin component of the binder is preferably a resin which is transparent and excellent in heat resistance, and examples thereof include an acrylic resin, a melamine resin, and an amine formic acid S resin. The water-based ink contains water as a solvent and, if necessary, water, a gluten-based organic solvent, and contains a water-soluble resin or a water-dispersible resin as a binder resin component, and optionally contains various auxiliary agents. Further, 'Oilability 81 201248326 Ink contains an organic solvent as a solvent, and contains a resin which is soluble in an organic solvent as a binder resin component, and optionally contains various auxiliary agents. Further, after the ink is injected by the ink jet method, it is preferred to perform drying, heat curing, and ultraviolet curing as needed. After the formation of the pixel, a protective film layer is formed as needed. The protective film layer is preferably formed for the purpose of improving the flatness of the surface and preventing the ink eluate from the partition wall or the pixel portion from reaching the liquid crystal layer. In the case where a protective film layer is formed, it is preferable to remove the ink repellency of the partition wall in advance. If the ink-repellent property is not removed, the protective coating liquid is repelled, and the uniform film thickness cannot be obtained, so it is preferable to avoid it. The method of removing the ink repellency of the partition wall may be a laser ashing process or a light ashing process. Further, as needed, in order to optimize the quality of the liquid crystal panel obtained by using the color filter, a photo spacer should be formed on the black matrix composed of the partition walls. [Production of Organic EL Display Element] Before forming the partition walls, a transparent electrode such as silver-doped indium oxide (IT〇) is formed on a transparent substrate such as glass by a money ore method, and a transparent electrode is formed as needed. Etching is a pattern of hope. Next, the negative photosensitive resin composition of the present invention is used to form a partition wall, and after the ink-printing process of the dot matrix is performed, the solution of the hole transport material and the light-emitting material is sequentially applied to the dot matrix by an inkjet method. Drying forms a hole transport layer and a light-emitting layer. Thereafter, an electrode such as aluminum is formed by an evaporation method or the like to obtain a pixel of the organic EL display element. [Manufacture of Organic TFT Array] 82 201248326 An organic tft array can be manufactured through the following steps (i) to (in). (1) On the _ etc. flip the substrate on the hair" _ light resin electricity ° °. After the ink-repellent treatment of _, use the inkjet method, right. The gate electrode is formed by coating the solution of the electrode material between the electrodes. (8) After the idle electrode is formed, the gate insulating film is formed thereon. After using the Shuming negative photosensitive resin composition to form a partitioning treatment on the gate ', 'Using the inkjet method for the ~ 极 electrode (4) solution (4), (4) «极•秘电极" (4) in the source of the secret After the electrode is formed, the negative photosensitive resin composition of the present invention is used to form a partition wall to surround the region covering the source and the electrodeless electrode, and after performing the inking treatment of the dot matrix, the dot matrix is subjected to the organic semiconductor solution. The coating is performed such that an organic semiconductor layer is formed between the source and drain electrodes. Further, in the '(i) to (iii)', the partition wall to which the negative photosensitive resin composition of the present invention has been used may be used only in the step i, or the negative type of the present invention may be used in two or more steps. The partition wall of the photosensitive resin composition. [Manufacture of Organic EL Lighting Element] This can be produced in the same manner as the production of an organic EL display element. The luminescent layer can be formed by laminating an illuminant of various colors such as red, green, and blue by inkjet, or the illuminant can be applied to a flat surface. EXAMPLES Hereinafter, the present invention will be described in further detail by way of the examples, but the invention should not be construed as limited. Further, the examples ～21 are examples, and the examples 31 to 33 are comparative examples. 83 201248326 Each measurement was performed by the following method. The number average molecular weight (??) is determined by gel permeation chromatography using polystyrene as a standard substance. The content ratio of fluorine atoms in the ink-repellent (Α) was determined by 19F NMR measurement using 1,4-ditrifluoromethylbenzene as a standard material. The amount of the ethylenic double bond in the ink-repellent (Α) was determined by 1H NMR measurement using 1,4-ditrifluoromethylbenzene as a standard material. The acid value (mgKOH/g) and the number of ethylenic double bonds in one molecule are theoretically determined from the blending ratio of the raw materials. The compounds used in the synthesis examples and the examples are abbreviated as follows. (Compound for the synthesis of ink-repellent (A1)) MEK: 2-butanone. C6FMA : CH2 = C(CH3)COOCH2CH2(CF2)6F. MAA: methacrylic acid. MMA: methyl methacrylate. PME400 : BLEMMER PME-400 (manufactured by 曰本油月株式会社. α-Mercapto-ω-methacryloxyloxypoly(oxyethylene). CH2 = C(CH3)C00(CH2CH20)kCH3: k in the formula Indicates the intermolecular mean enthalpy, k 値 is about 9). PME1000 : BLEMMER PME-1000 (manufactured by Nippon Oil & Fats Co., Ltd. α-methyl-ω-methacryloxyloxypoly(oxyethylene). CH2 = C(CH3)C00(CH2CH20)kCH3: where k represents intermolecular The average 値, k値 is 23).乂-65: Trade name (made by Wako Pure Chemical Industries, Ltd. 2,2'-azobis (2,4-dimercapto 84 201248326 valeronitrile.)). 2-HEMA: 2-hydroxyethyl methacrylate. GMA: glycidyl methacrylate. AOI: 2-propenyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., trade name: Karenz AOI.). DBTDL · Dibutyltin dilaurin vinegar. TBQ: tertiary butyl-p-benzoquinone. (Compound for the synthesis of the ink-repellent (A2)) Compound (a7-l): CF3(CF2)5CH2CH2Si(OCH3)3 (manufactured by Asahi Glass Co., Ltd.). Compound (a8-1): Si(0C2H5)4 (C0LC0AT). Compound (a9-l): CH2 = CHCOO(CH2)3Si(OCH3)3 (manufactured by Tokyo Chemical Industry Co., Ltd.). TMMS: trif-methoxy methoxy sulphate [(Yang Cheng (1) Yangchong Tokyo Chemical Industry Co., Ltd.). PGME: propylene glycol monothiol bond. PGMEA: propylene glycol monomethyl hydrazine acetate. (Photopolymerization initiator (B)) The above compounds Νο·1~3, compound No. 7. Compound Ν〇 ι〇, compound NCU2, compound No. 20. Compound Ν〇·33, compound n〇 each compound Νο·53~58. (Photopolymerization initiator other than photopolymerization initiator (Β)) ΟΧΕ02 : B _ (ethanone) i_r〇-, „ 1 A hexyl _6·(2_methylbenzoinyl)-9Η-carbazole oxime _3-基]-1-(0-乙制社G 醯基)(Ciba Specialty 85 201248326

Chemicals company, trade name: OXE02). IR907: trade name; IRGACURE 907, manufactured by BASF Corporation, 2-mercapto-1-[4-(methylthio)phenyl]-2-flavor. Lin Ke Bing Yi-1-嗣. EAB : 4,4'-bis(diethylamino)diphenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.). (Alkali-soluble resin (C)) EX1010: A resin obtained by introducing an ethylenic double bond and an acidic group into an epoxy resin represented by the above formula (Cl-2b) (manufactured by Nagase ChemteX, trade name: EX-1010. Solid portion: 60 Mass%, PGMEA: 40% by mass.). ZCR1761: A resin obtained by introducing an ethylenic double bond and an acidic group into an epoxy resin having a biphenyl skeleton represented by the above formula (Cl-2a) (manufactured by Nippon Kayaku Co., Ltd., trade name: ZCR-1761H. Solid portion: 60 mass) %, PGMEA: 40% by mass.). ZCR1642: a resin obtained by introducing an ethylenic double bond and an acidic group into an epoxy resin having a biphenyl skeleton represented by the above formula (ci-2a) (manufactured by Nippon Kayaku Co., Ltd., trade name: ZCR-1642H. Solid portion: 60 mass) %, PGMEA: 40% by mass). C-1: a resin obtained by reacting a phenolic phenol varnish type epoxy resin with an acrylic acid followed by a ruthenium 2,3,6-tetrahydrocaproic acid needle to introduce an acryl oxime group and a carboxyl group, and purifying the resin with hexane The resin, solid portion 70 〇 / 〇, acid value 6 〇 mg KOH / g, PGMEA: 30% by mass. ZAR2002: trade name; KAYARAD ZAR-2002, manufactured by Nippon Kayaku Co., Ltd., a resin in which a carboxyl group and an ethylenic double bond are introduced in a double-type A epoxy resin, a solid portion 70%, an acid value of 6〇mgK〇H/g, PGMEA : 3〇% by mass. 86 201248326 (black coloring agent (D)) CB: carbon black dispersion (average secondary particle diameter: 120 nm, carbon black: 20% by mass, amine valence: 18 mgKOH/g of polyamine phthalate polymer dispersant: 5 Mass %, PGMEA: 75 mass ° /.). Mixed organic pigment: C.I. Pigment Blue 156, C.I. Pigment red 254, C.I. Pigment yellow 139 and a polymer dispersant: a mixture of 5:5:5 (solid portion: 25% by mass, PGMEA: 75% by mass). (crosslinking agent (G)) UX5002: a polyfunctional amine phthalate acrylate oligomer (manufactured by Nippon Kasei Co., Ltd., trade name: KAYARAD UX-5002D-P20. Solid portion: 80% by mass, PGMEA: 20% by mass ). A9300CL: ε-caprolactone modified 叁·(2-propenyl methoxyethyl) isotrimeric polyisocyanate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade 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 (Η)) PGMEA: propylene glycol 1-monomethyl hydrazine 2-acetate. IPA: 2-propanol. (decane coupling agent (J)) KBM5013: trade name (manufactured by Shin-Etsu Chemical Co., Ltd.. 3_acryloxypropyl methoxymethoxy decane). (Microparticles (K)) 87 201248326 IPA-ST : Trade name (manufactured by Nissan Chemical Industries, Ltd. Organic cerium oxide gel, solid portion: 30% by mass, IPA: 70% by mass). [Synthesis Example 1: Synthesis of Ink Repellent (A^1)] MEK (420 g), C6FMA (90 g), MAA (9 g), and PME 1000 (8 lg) were placed in an autoclave having a volume of 1 L of a stirrer. Further, a polymerization initiator V-65 (0.2 g) was stirred while stirring under nitrogen for 24 hours at 50 ° C to synthesize a crude polymer. After the obtained crude polymer solution was added to hexane and further purified, vacuum drying was carried out to obtain an ink-repellent (A-1) (158.6 g). The ink-repellent (A^l) had a number average molecular weight (??) of 64,690 and a mass average molecular weight (Mw) of 92,270. [Synthesis Example 2: Synthesis of Ink Repellent (AL2)] MEK (420 g), C6FMA (85 g), 2-HEMA (50 g), PME400 (36 g), MAA were placed in an autoclave having a volume of 1 L of a stirrer. (9 g) and a polymerization initiator V-65 (0.7 g) were stirred while stirring under nitrogen for 24 hours at 50 ° C to obtain a polymer oxime solution. (Introduction of Ethylene Double Bond) The above polymer (1) solution (500 g), AOI (45.6 g) 'DBTDL (0.13 g), TBQ (1.6 g) and the autoclave having an internal volume of 1 L of a stirrer were placed. MEK (17.1 g), while stirring and one side at 4 Torr. The underarm was allowed to react for 24 hours, and the ethylenic double bond was introduced into the polymer (1). After the hexane was added to the obtained solution and then purified, vacuum drying was carried out to obtain an ink-repellent (0 2) (165.0 g). The ink-repellent (Bagua 2) has a number average molecular weight (Μη) of 41,200, a mass average molecular weight (Mw) of 11〇, a 800' fluorine atom content ratio of 2〇.6 mass%, and an amount of an ethylenic double bond. (C = C amount, 66xl0-3m〇1/g, acid value: 88 201248326 25.0 mgKOH/g. [Synthesis Example 3 to 4: ink-repellent (Ah) and (A1-" synthesis] In the synthesis of A1-:!), the blending of the raw materials was changed as shown in Table 1, and the ink-repellent (AL3) and (AU) were obtained by the same copolymerization reaction. The obtained ink-repellent (A1) The number average molecular weight (Μη), the mass average molecular weight (Mw), the fluorine atom content ratio (% by mass), and the acid value (mgKOH/g) of ^) and (AU) are shown in Table 1. [Synthesis Example 5: Dialing Synthesis of Ink (A1·^) In the synthesis of the polymer (1), the blending of the raw materials was changed as shown in Table 1, and the polymer (2) was obtained by the same copolymerization reaction. In the synthesis of the ink (A1-), except that the blending of the raw materials is changed as shown in Table 1, the same reaction is carried out, and an ethylenic double bond is introduced into the polymer (2) to obtain an ink-repellent agent (A1- 〗). The weight of the obtained ink (A]-5) The average molecular weight (Μη), the number average molecular weight (Mw), the fluorine atom content ratio (% by mass), the acid value (mgKOH/g), and the amount of the ethylenic double bond (C = C amount, xl (T3 mol/g) show In Table 1. 89 201248326 [Table i] Drawing 01 (A1-" (A1-2) (Α'-3) (A1 Η) (A'-5) C6FMA 80 85 99 108 85 MAA 9 9 9 18 9 m PME400 - 36 63 a 36 and PME1000 81 one-one-one 2-HEMA — 50 - _ 50 Gu Meng QMA - one 9 18 one material MMA — — - 36 one V-65 02 0.7 0.3 1.9 3 MEK 420 420 420 420 420 Polymer «Containment (1> 7 500 J - This SI solution » contains: (2 > / - / / 500 AOI / 45.6 / / 45.6 & DBTDL / 0.13 / / 0.13 into TBQ / 1.6 / / 1.6 MEK 17.1 / 17.1 锒 串 (β) 158.6 165 162.3 160.1 165 目) 目 Β 64 64 Μ 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 Single (霣fi%) 28>β 20.6 31.4 34.3 20.6 (mgKOH/g) 32.6 25 32.6 6&3 25 C=C Ft ( X lO^mol/g) 1.66 [Synthesis Example 6: Production of ink-repellent (A2-l)] In a 1,000 cm3 three-necked flask equipped with a stirrer, ll_8 g of the compound (a7-1) and a compound (a8) were placed. 29.4 g of -l), 29.4 g of compound (a9-1), and 29.4 g of TMMS' obtained a mixture of hydrolyzable decane compounds. Next, 564.7 g of PGMEA was placed in the mixture to prepare a solution (raw material solution). In the obtained raw material solution, at 40. (: 52.0 g of a 1.0% hydrochloric acid aqueous solution was added dropwise while stirring, and after the completion of the dropwise addition, the mixture was stirred at 40 ° C for 5 hours to obtain a PGMEA solution (liquid ink (a2)) concentration: 10% by mass. (A2_l) liquid") The ink-repellent (a2-1) was obtained. Further, the reaction liquid was measured by gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit. The obtained ink-repellent (A2- l) The number average molecular weight (Μη), the mass average molecular weight (Mw), the fluorine atom content ratio, and the ink-removing agent (α2-1) composition (mol%) are shown in Table 2. 90 201248326 [Synthesis Example 7: Production of Ink Repellent (A2-2)] 16.7 g of the compound (a7-1) and 41.7 g of the compound (a8-1) were placed in a 1,000 cm3 three-necked flask equipped with a mixer. 41.7 g of the compound (a9-1) was obtained as a mixture of hydrolyzable decane compounds. Next, 564.7 g of PGME was placed in the mixture to prepare a solution (raw material solution). The obtained raw material solution was at 40 ° C. While stirring, 65.7 g of an aqueous solution of nitric acid was added dropwise. After the completion of the dropwise addition, the mixture was stirred at 40 ° for 5 hours with a PGME solution ( The concentration of the ink (A2-2): 10% by mass. Hereinafter, the "(A2-2) liquid" is obtained). The ink-repellent (A2-2) is obtained, and the reaction liquid is measured by gas chromatography, and it is confirmed as a raw material. Each compound is below the detection limit. The number average molecular weight (Μη), mass average molecular weight (Mw), fluorine atom content ratio, and ink-repellent (Α2-2) of the obtained ink-repellent (A2-2) are placed. The composition of the amount (% by mole) - 倂 is shown in Table 2. [Table 2] Composition of the ink-repellent agent () 剤 剤 molecular weight oxygen atom content ratio (% > (a7-D (a8-1) Ca9-1) TMMS Teaching average molecular weight (Μη) Quality average molecular weight (Mw) Aa-1 12 29 29 29 PGMEA 780 850 21 A2-2 17 42 42 — PGME 805 860 26 [Examples 1 to 24 and Examples 31 to 33: Negative Preparation of photosensitive resin composition, formation and evaluation of partition walls] In the ratios (% by mass) shown in Tables 3 and 4, an ink-repellent (Α), a photopolymerization initiator (Β), an alkali-soluble resin was blended. (C), black colorant (D), crosslinking agent (G), solvent (Η), decane coupling agent (J), and fine particles (Κ) to obtain a negative photosensitive resin composition. 91 201248326 Using a spin coating method, On a glass substrate After coating the negative photosensitive resin composition, it was dried on a hot plate at 100 C for 2 minutes to form a coating film having a film thickness of 2 Å, and then passed through a mask (light shielding portion 1 〇〇 V mx2 〇〇 Am 'light transmission portion 20 μm grid pattern), by ultra-high pressure mercury lamp (shading wavelength below 330 nm by a wear stop filter). The coating film is mainly irradiated with a predetermined exposure amount shown in Tables 3 and 4 by a mixing line composed of a twist line, an h line, and a g line. Next, the unexposed portion was immersed in an inorganic alkali-type developing solution (manufactured by Yokohama Oil & Fats Co., Ltd., trade name: Semi-clean DL-A4, a 1-fold diluted aqueous solution), and the unexposed portion was washed with water to make the unexposed portion. Dry. Then, it was heated at 220 ° C for 1 hour on a hot plate, whereby a glass substrate (1) in which the pattern was formed was obtained. Further, the glass substrate (2) on which the cured film of the coating film was formed was carried out in the same manner as described above except that the above-mentioned mask was not used for exposure. With respect to the glass substrate (1) or (2), the line width, the film reduction after development, and the ink repellency (PGMEA contact angle) were measured and evaluated by the following methods. The results are shown in Tables 3 and 4. (Line width) The grid-like pattern line width of the light-transmitting portion 20 // m was measured by the ultra-depth shape measuring microscope VK-850 (manufactured by KEYENCE Co., Ltd.). The line width is closer to 20# m of the light transmitting portion of the mask, indicating that the line width of the mask can be reproduced. ψ (film reduction after development) The pre-development film thickness (THK1) of the exposed portion (cured film) and the developed image were measured by the high-precision micro-shape measuring machine SURFCORDER ET4000 A (manufactured by Otaru Laboratory) for the above-mentioned glass substrate (1) Film thickness (THK2). From 92 201248326 1 丨 main _, thickness minus the apparent film thickness as (four) (four) Xiao 1 丨 reduction. This 丄 丄 shows that the photohardening of the negative photosensitive resin composition is better. (Ink repellency) ~ was evaluated by the contact angle (degree) of the surface of the cured film of the above glass substrate (2). The contact angle is the angle formed by the solid surface to the liquid surface at the point where the solid is in contact with the liquid, and is defined by the angle containing the liquid. The greater the degree of diarrhea, the better the ink repellency of the sclerosing film. By placing the PGMEA drops on the surface of the substrate by the static drop method, JISR 3257 "wettable test method for the surface of the substrate glass", the needles were measured by dropping each PGMEA. The droplets were 2 core drops, and the measurement was carried out under grasping. The contact angle is expressed as the average enthalpy (n = 3) of 3 measurements. 93 201248326 Inch 1 A1—2 I in o' Combination “1 No.50 L^〇J 1 25.0 1 60.0 1 IO σί 1 60.0 1 ! 25.0 I 1 17.8 I ! 48.2 I 1 19.7 1 O CO LAS-B I CO r" A1-2 I ΙΩ d Compound i No.49 1 5Q 1 L^〇60.0 I ΙΟ αί I 60.0 | Ι25Ό I 17-9 ? 1 47.5 I '19.5 1 ¢0 CO 49.3 | w— i A1-5 I d Compound No. 48 1 -5-0 1 1 25 0 1 [βαρ 1 \Λ οΐ | 60.0 | L2A〇J 18-0 〇·« I 48.2 | 1 19-8 1 CJ C3 :50.1 | #· 1 A1 -4 IV) d compound tt No.47 [5.0" 25.0 | 1 60.0 1 Ift σ> I 60.0 I 1 25.〇J 1 17.9 I CM 丨48.0 1 1 19-9 I <M m 丨50-2 | 〇1 A1-3 I ΙΛ d Compound No.46 1 5.0 1 丨25』—I 1 60.0 1 ΙΑ αΐ 160.0 丨25 0 1 I 17.8 ! 1 48.2 1 I 18.8 1 CQ CQ 50.0 AI A1-2 I μ d | Compound! No.45 1 5Q 1 I 25^ I 1 35.0 1 1 7-〇1 1 2.5 1 L^pJ I 20.0 | 53.0 | 丨25.0 1 1 7.0 1 I 18-9 I 0Θ CO 1 480 ί 丨20.4 1 (〇CSJ | 50.9 | QC I a'-z I η d Compound No.33 i_5-〇1 ^5.0 I 1 35. 0 1 \ι^ 1 \Λ csi 1 5-Q 1 | 20.0 ] | 53.0 | 1 25.0 1 〇Μ.9-2| (A CO Li_8-〇J 20.5 m CM I 51.3 | I A1-2 I IA 0 1 compound| No.20 1 5-Q. 1 25-0J 1 35.0" Ι^-ο 1 1 2 5 1 丨5.0 1 1 20.0 | 53.0 1 1 25-Q 1 〇卜' 丨19.0 | CD n 1 48.0 1 I 20.3 1 U) CM | 50.5 | <DI ΑΊ-1 I - Compound No.12 1 5-0 -1 |25X) J 1 60.0 1 9^1 1 60.0 1 丨25.0 1 18.1" O 咿1 4Θ .5 丨19.7” 04 CO 1 52.3 | ΙΑ Ιαί-ι I m 〇 合 No.10 o tri |25.〇1 Ιθο.ο I αί | 60.0 1 L^so | Lie〇! o ·«· L4L7 1 1 19-8 | 44.4 1 La1-» 1 U) d : Compound No.7 1 5-Q 1 | 20 0 | 60.0 1^5 1 1 5.0 ; | 60.0 | [25.0 | 0) 1—still 1 l”0 -5 I to n 1 49.5 | « 1 AM i ΙΛ o' | Compound Xu! No.3 1 5.0 1 l25〇I 1 35.0 1 1 7.0 1 U) 1 5.0 | | 20.0 | | 53.0 1 125Q 1 1. 7 · 0 1 丨 18.2 1 m 1 2 1 I 20.6 | U) CJ 1 51.5 | Csl 1 ΑΊ-1 | I 0-5 I Compound No. 2 i 50 1 L25-Q I 35.0 1 丨7·0 1 \Ω Μ* 〇in' 1 2〇.〇! | 53 .0 | 1 25.0 | 丨7.0 1 卜 8.0 | CO CO 1 49.0 1 I 20.3 | 00 CM | 50.8 | - LamJ U) d Compound No.1 1 5.0 1 丨25.0 .1 60.0 1 ιτ> 0)' | 60.0 [25.0 1 LUAJ eg Ll9) o 03 1 49.9 | s I species 固 II solid part I 1 ! mm 1_ 1 solid part 1 1 diameter 1 1 1 solid part 1 | species 1 1 1 solid part 1 ΕΧ 1010 | I ZCR1761 | I ZCR1642 1 1_〇Σΐ_1 1 ZAR2002H 1 |gb+polymer split 1 mm cat 轾1 UX5002 1 1 A9300CL 1 1 Α9530 1 丨KB paper 013 | I IPAST | 1 PGMEA | I 顼己面 | 1_ΙΡΑ_I 1 PGME 1 think gram (/£〇0 | 颞 瞑 M M (nm> I 1 PGMEA contact angle Γ) 1 iISa ifL m> | Yan Zhang after film cut (run) | | PGMEA contact angle (e > Photopolymerization start (B) (Besides (B)> Detecting soluble m-fat (〇1_CB_1 Nirvana 楢 pigment*3 | 矽 IS 剤 剤 (J) I | ί3 〇〇 〇〇! ΐ 1 掇 性 ι i 祖 液 | 墨 墨 闭 闭 闭 闭 闭 闭 闭 闭 交 Q Q Q [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q The quality of the composition is 96 evaluation 94 201248326 (0 IamJ U) 6 [OXE02I I g-g_i | 20.0 | 60.0 ί 9-5" Ls, 〇_JI 60.0 | L25-〇J 1 16-2 1 Q0 MQQ J 丨17.8 I i 28.0 1 « ΓαΜ 1 ΙΑ d IOXE02 k 5-QI 1 1 1 35.0 | i^oJ in CsJ 〇tA m〇1 1 53.0 ] 25.0 1 q 卜' 1 _!§·〇” 〇| 23.0丨卫.5” \e> (〇32.0 1 η Γ^Ί v> d IOXE02I L 51” L25.0 J 1 60.0 1 U) 0) 1 60.0 j Lzs-o 1 □EE SI 20,0 | L 17.3 j 〇1 26.0 1 5 r· Compound tt No.33 ο in | 23.0 ] 34.5 L^〇” u> csi 0 to 1 20.0 1 1 53.0 ] 1 25.0 1 ο 1 1&-5J g lA^oJ 1 20.8 1 03 <0 1 44.4 1 C0 Csi 1 Aa-2 I 0.5 i compound fls| No.33 I 2.0 : IIR907 1 2.0 _ i § 〇147.5_| Ll2, 〇—” I 35.0 I 1 20.0 1 LAP J 1 60.0 1 120-1-1 U> Let La5>〇J 1-21-5J CO 147.2 1 Μ W r^=n T—Compound No.33 I g-〇I | IR907i L g-0 1 L_47.5 i 115 1 I 60.0 1 1 25.0 1 [20 5 1 A 145 5 1 1 22.0 1 CO CQ 1 48.1 I Ί·· Csi I A'il u> d 〇N〇>se O to 25,01 1 βο.ο | \n A ! 60.0 1 [25^_J 1 1 0> w 1 48.0 1 1 20.0I ψ· 〇I 50.1 I Ο CM d Compound No. 57 OU) L25.0J I 60.0 1 \Λ 〇i 1 60.0 1 ί.25·0" 1 17 s 1 L47.B_J Li^jJ CM t 49.5 | α> 1 A-2 JL〇^J Compound No.56 〇Ui 25,0 JI 60.0 1 U) 0> 25.0 I 1-17,9 J 1 48.1" 丨Ί9·8" ¢4 CO i 49.5 CO — I A1^ 1 tA 6 Compound No.55 o tn 25.0 1 60.0 1 \Λ Φ 1 βαο 1 125.0 II 17.8 1 N harsh 1 48.0 1 1 18.7 1 <0 0Ϊ 49.4 r· I A1-2| (A 6 compound No.54 o 1Λ 1 25.0 1 1 60.0 1 \Λ 〇ί I 60.0 I [ 25.0 I 1 13AJ 1 47.9_| 1 20.0 1 0 m 50.1 〇I A1-? I LA d Compound No. 53 o tn 25.0 1 βα.ο 1 ]Λ <n L§〇^ I 1? 5,0_| I17.9J M 417" CO 49.8 in T" La1-?" tA Compound No.51 〇25.—0—1 60.0 1 u> ai 1 βο.ο 1 [250 ! 1B.0 I 〇I 46,0 1 1 20.0 1 5 | 49.9 s L- species 頚..." | Solid part I species 頚I solid state Sub-IL—one light __________] 1 solid part j 1 type | 1___ solid part _I 1 EX1010 I 1 2CR17G1 I 1 2CR1642 I 1 . 0-1 1 1 ZAR2002H |〇曰+polymer dispersion drama | «ΓΝ- 如¢: I UX5002 1 I A9300CL 1 1 A9530 1 1 KBM5013 1 1 1PAST 1 1 PGMEA 1 i One "Β*_____________1 ! iPA 1 L_ PGME_I 芘Um) I 瓸髟 腥 腥 I I Lfgmea contact angle C > I iSS <Mm) 1 1 After the coloring, the gallbladder is destroyed <nm> 1 S m Si 2 0 a Ink 翊<A) Photopolymerization starts to (B) (Beyond (B)) 鹸Soluble Resin (C) 1 os.. 1 Mixed Organic Pigment 3 #-s 3 m As m % ΐ 1 Ancestral Liquidity! ! Liquid-emitting photopolymerization starting ring black coloring ring (D> Optical 垩 20mJ/cm2 硪 light s 40mJ/cm2 Solid part: Z 质灵% s% in the composition Φϋ韵I趟米女函 buried Cistanche 95 201248326 J 24 negative photosensitive resin composition Good for light hardening. Further, the cured film formed of the composition has good ink repellency and can reproduce the mask line width. On the other hand, the negative photosensitive resin compositions of Examples 31 to 33 were not used as a photopolymerization initiator in a knife, so that the exposure amount was 20 m; /em2 and 4〇m]/ Em2 is more than (9) (10) after development, and the photohardening is insufficient. In addition, the hardening of the singularity is insufficient, and the mask line width cannot be reproduced. INDUSTRIAL APPLICABILITY The negative photosensitive resin composition of the present invention can be manufactured by reducing the exposure amount by 30 or less. In the case of light-shielding exposure, the ink-repellent property is still good and the reproduction of the mask line width is good. The negative photosensitive resin composition of the present invention can be suitably used for the formation of a partition wall, and can be produced by a color filter manufactured by an ink jet recording technique or an organic EL. The disclosure of Japanese Patent Application No. 20-102039, filed on Apr. 28, 2011, the entire disclosure of which is incorporated herein in [Brief Description of the Drawings] Fig. 1 is a cross-sectional view showing a manufacturing example of a partition for an optical element using the negative photosensitive resin composition of the present invention. [Description of main component symbols] 1···substrate 3...coating film exposure part 2··•negative photosensitive resin composition 4...mask coating film 5...light 96 201248326 6··· partition 10...inkjet method Using optical elements with base 7...lattice plate 97

Claims (1)

201248326 VII. Patent application scope: 1. A negative photosensitive resin composition characterized by comprising: an ink-repellent agent (A) having a side chain, and the side chain contains a base represented by the following formula (1) or below a base represented by the formula (2); a photopolymerization initiator (B) which is an oxime ester compound having a nitro group in one molecule; and a soluble resin (C); -CFXRf (1) - (SiR'R2- 0) n-SiR3R4R5 (2) In the formula (1), X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and represents a carbon atom which may have an etheric oxygen atom and at least one hydrogen atom is substituted with a fluorine atom. a fluoroalkyl group or a fluorine atom of 20 or less; in the formula (2), R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R5 represents a hydrogen atom or a carbon atom number of 1 to 10; The organic group, η represents an integer of from 1 to 200. 2. The negative photosensitive resin composition of claim 1, wherein the photopolymerization initiator (Β) is a compound composed of the following formula (3); 98 201248326 In the formula (3), R31 represents an alkyl group having 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a cyano group; and R32 represents R41 or OR42. R41 and R42 each represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms; and R33 represents an alkyl group having 1 to 20 carbon atoms. An aryl group of 6 to 30 or an aralkyl group having 7 to 30 carbon atoms; R34 and R35 each independently represent R41, OR42, cyano or a halogen atom; and a and b are each independently an integer of 0 to 3' c is An integer from 1 to 3. 3. The negative plastic photosensitive resin composition according to claim 1 or 2, which further contains a black colorant (D). The negative photosensitive resin composition according to any one of claims 1 to 3, which further contains a crosslinking agent (G). 5. The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the side of the ink-repellent (A) has a group (1) or a group (2) and the main chain is a hydrocarbon chain. Compound. 6. The negative photosensitive resin composition of claim 5, wherein the ink-repellent (A) has an acidic group. 7. The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the ink-repellent agent (A) has a group (1) in a side chain and the main chain is an organic poly-stone. The compound of the bond. 8. The negative photosensitive resin composition of any one of claims 5 to 7, wherein the ink-repellent (A) has an ethylenic double bond. A cured film obtained by curing a coating film of a negative photosensitive resin composition according to any one of claims 1 to 8 which is formed on a substrate. A partition wall formed by forming a partition on a substrate, which is composed of a cured film as in claim 9 of the patent application. A black matrix formed by providing a divisional region on a substrate, which is composed of a cured film as in claim 9 of the patent application, and the cured film is negative as in the third item of the patent application. A type of photosensitive resin composition is formed. A method for producing a partition wall, which comprises the steps of: forming a coating film on a substrate by coating a negative photosensitive resin composition as in any of claims 1 to 8 on a substrate. a step of heating the film to a predetermined portion of the film to be photohardened; a step of removing the film other than the photohardened portion; and the photohardenable portion The step of heating to obtain a partition wall. The film thickness of the photohardened portion before and after the removal of the film is 60 nm or less. U. A method for producing a black matrix, which is obtained by using the negative photosensitive resin composition of claim 3 of the patent application, as the black matrix. 4. The color filter 'having a substrate, a plurality of pixels on the substrate, and a partition wall between the adjacent pixels, wherein the partition wall is a negative photosensitive resin according to any one of claims 1 to 8. The cured film of the composition is composed. An organic EL device having: a substrate, a plurality of pixels on the substrate, and a spacer 100 between the adjacent pixels, wherein the partition is made of any one of the first to eighth aspects of the patent application. A cured film of a negative photosensitive resin composition. 101