TW201835139A - Negative photosensitive resin composition - Google Patents

Abstract

Provided is a negative photosensitive resin composition which enables the achievement of a partition wall that has high development adhesion, while having good ink repellency in the upper surface, and which is sufficiently reduced in development residues in openings for dot formation. A negative photosensitive resin composition which contains (A) an alkali-soluble resin having a photocurable functional group, (B) a crosslinking agent containing (B1) a polyfunctional low-molecular-weight compound that has an acidic group and two or more photocurable functional groups in each molecule, (C) an ink repellent agent that has an acidic group and a fluorine atom, while having an acid value of 10-100 mgKOH/g, (D) a photopolymerization initiator, and (E) a solvent.

Description

Negative photosensitive resin composition

The present invention relates to a negative photosensitive resin composition.

BACKGROUND When manufacturing optical elements such as organic EL (Electro-Luminescence) elements, quantum dot displays, TFT (Thin Film Transistor) arrays, and thin-film solar cells, sometimes organic layers such as light-emitting layers are formed by the inkjet (IJ) method. A method for printing a pattern in the form of dots. In this method, a partition wall is provided along the outline of the point to be formed, and a printing ink containing an organic layer material is injected into a partition surrounded by the partition wall (hereinafter also referred to as an "opening portion"), and then dried by drying it. And / or heating to form a desired pattern.

When pattern printing is performed by the inkjet (IJ) method, in order to prevent mixing of ink between adjacent dots and to uniformly coat the ink when dots are formed, the upper surface of the partition wall must have ink repellency. On the other hand, the dot-forming openings including the side surfaces of the partition walls and surrounded by the partition walls need to have ink affinity. Therefore, in order to obtain a partition wall having ink repellency on the upper surface, a method is known in which a coating film is formed using a negative photosensitive resin composition containing an ink repellent, and photolithography having each step of exposure, development, and the like is used. Method to form the next wall corresponding to the dot pattern.

In the process of forming a partition wall using such a negative photosensitive resin composition, if residues of the composition (hereinafter also referred to as "development residues") are left in the opening portion after development, the printing ink supplied to the opening portion by the IJ method is Sometimes wetting and diffusion may be insufficient. In addition, as for a method for reducing the development residue in the opening portion, although there is a method of adjusting the negative photosensitive resin composition to a composition that can be easily removed by a developer, this method cannot sufficiently maintain the ink repellent on the upper surface of the partition wall. Sexual problems.

For example, Patent Document 1 describes a photosensitive composition for a partition of an active driving type organic electroluminescence element, which contains (A) a component, an ethylenically unsaturated compound, and (B) a component, a photopolymerization initiator. (C) component, an alkali-soluble adhesive having an ethylenically unsaturated group in the side chain; (D) component, a liquid repellent agent composed of a fluorine-based compound having an ethylenically unsaturated group in the side chain; and, (E ) Ingredients, fluorine-based surfactants and / or polysiloxane-based surfactants.

Patent Document 1 has described a purpose of improving the developability by introducing a carboxylic acid to a component other than the alkali-soluble binder, such as (A) component or (D) component, and an example is shown in the examples. According to the example, when the carboxylic acid is introduced into the component (A), both the developability and the ink repellency can be taken into account, but when the liquid repellent agent (the (D) component) introduced with the carboxylic acid is used, the developability is good but it cannot be obtained sufficiently. Repellency.

As mentioned above, although Patent Document 1 can use the composition to take into account the ink repellency of the upper surface of the partition wall and the ink wettability of the opening portion, it has not yet achieved the ink repellency and opening of the upper surface of the partition wall that can sufficiently respond to higher precision optical elements. The printing ink is wet.

In addition, Patent Document 2 describes a technique for improving the solubility of the ink repellent to an ink repellent by introducing an acidic group into the ink repellent to which a method for removing developing residues by UV / O ₃ irradiation is applied. However, when the ink repellent of Patent Document 2 is used for a negative-type photosensitive resin composition, as in the case of Patent Document 1, it is difficult to say that the ink repellency and development adhesion are sufficient. Prior technical literature Patent literature

[Patent Document 1] Japanese Patent Laid-Open No. 2011-165396 [Patent Document 2] International Publication No. 2014/046210

SUMMARY OF THE INVENTION Problems to be Solved by the Invention The present invention has been made based on the above-mentioned viewpoints, and an object thereof is to provide a negative-type photosensitive resin composition, which has high development adhesion and good ink repellency on the upper surface of the obtained partition wall. The development residue in the opening for formation is small enough.

The present invention has the following configuration. [1] A negative photosensitive resin composition comprising: an alkali-soluble resin (A) having a photocurable functional group; a cross-linking agent (B) containing a polyfunctional low molecular weight compound (B1), the polyfunctional The low molecular weight compound (B1) has an acidic group and two or more photocurable functional groups in one molecule; the ink repellent (C) has an acidic group and a fluorine atom, and the acid value is 10 to 100 mgKOH / g; photopolymerization Initiator (D); and solvent (E). [2] The negative photosensitive resin composition according to [1], wherein the polyfunctional low molecular weight compound (B1) has four or more photocurable functional groups. [3] The negative-type photosensitive resin composition according to [1] or [2], wherein the polyfunctional low-molecular-weight compound (B1) has a dipentaerythritol skeleton. [4] The negative photosensitive resin composition according to any one of [1] to [3], wherein the fluorine atom content rate in the ink repellent (C) is 5 to 55% by mass. [5] The negative photosensitive resin composition according to any one of [1] to [4], wherein the ink repellent (C) contains a photocurable functional group. [6] The negative photosensitive resin composition according to any one of [1] to [5], wherein the crosslinking agent (B) further contains a crosslinking agent (B2), and the crosslinking agent (B2) is The molecule has two or more photocurable functional groups and does not have an acidic group. [7] The negative photosensitive resin composition according to [6], which is a ratio of 10 to 90 parts by mass relative to 100 parts by mass of the polyfunctional low molecular weight compound (B1) and the crosslinking agent (B2) in total Contains the aforementioned polyfunctional low molecular weight compound (B1). Invention effect

According to the present invention, it is possible to provide a negative photosensitive resin composition which has high development adhesion of the partition wall and good ink repellency on the upper surface, and at the same time, the development residue in the opening for dot formation is sufficiently small.

Aspects for Implementing the Invention In this specification, the following terms are used in the following meanings. "(Meth) acrylfluorenyl" is a general term for "methacrylfluorenyl" and "acrylfluorenyl". (Meth) acrylic fluorenyloxy, (meth) acrylic and (meth) acrylic acid esters are all acceptable.

The base represented by the formula (x) may be described only as the base (x). The compound represented by formula (y) may be described only as compound (y). Here, expressions (x) and (y) represent arbitrary expressions.

"Resin mainly composed of a certain component" or "resin mainly composed of a certain component" means that the ratio of the component relative to the total amount of the resin accounts for 50% by mass or more.

"Side chain" means a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting a main chain in a polymer constituting a main chain composed of repeating units composed of carbon atoms.

"The all-solid content of the photosensitive resin composition" means a component that forms a cured film described later among the components contained in the photosensitive resin composition, and can be obtained by removing the solvent after heating the photosensitive resin composition at 140 ° C for 24 hours. Find the residue. The total solid content can also be calculated from the feed amount.

A film made of a hardened material of a resin-based composition is called a "resin hardened film". The film formed by applying the photosensitive resin composition is called a "coating film", and the film formed by drying it is called a "dry film". The film obtained by curing the "dry film" is a "resin cured film". In addition, the "resin cured film" may be simply referred to as a "cured film".

The resin-hardened film may be in the form of a partition wall, and the partition wall is formed so as to divide a predetermined area into a plurality of partitions. In the partition partitioned by the next wall, that is, the opening portion surrounded by the next wall, for example, the following "printing ink" can be injected to form a "dot".

"Ink" is a generic term for liquids that have optical and / or electrical functions after drying and hardening. In organic EL devices, quantum dot displays, TFT arrays, and thin-film solar cells, dots used as various constituent elements are sometimes pattern-printed by the inkjet (IJ) method using the ink for dot formation. "Ink" includes printing inks for related purposes.

"Ink repellency" means the nature of rejecting the above-mentioned printing ink, having both water repellency and oil repellency. The ink repellency can be evaluated, for example, by the contact angle when the ink is dripped. "Ink affinity" is the opposite of the ink repellency, and can be evaluated by the contact angle when the ink is dripped. In addition, the degree of wet spread of the printing ink when the printing ink is dropped (the wet spread of the printing ink) can be evaluated on a predetermined basis, thereby evaluating the ink affinity.

"Dot" means the smallest area of possible optical modulation in an optical element. For organic EL elements, quantum dot displays, TFT arrays, and thin-film solar cells, 1 point = 1 pixel in white and black display, and 3 points (R (red), G (green), B ( Blue) etc.) = 1 pixel. "Percentage (%)" indicates mass% unless otherwise specified. Embodiments of the present invention will be described below.

[Negative photosensitive resin composition] The negative photosensitive resin composition of the present invention includes: an alkali-soluble resin (A) having a photocurable functional group; and a cross-linking agent (B) containing a polyfunctional low-molecular-weight compound. (B1), the multifunctional low-molecular-weight compound (B1) has an acidic group and two or more photocurable functional groups in one molecule; an ink repellent (C), which has an acidic group and a fluorine atom, and has an acid value of 10 ~ 100 mgKOH / g; photopolymerization initiator (D); and solvent (E).

The negative photosensitive resin composition of the present invention contains a polyfunctional low-molecular-weight compound (B1) having an acidic group as a crosslinking agent (B), and is used in combination with the ink repellent (C) having a predetermined acid value as described above. It can form a partition wall with high development adhesion, good ink repellency on the upper surface, and sufficient development residue in the opening. If such a partition is used in an optical element, such as an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell, the dots can be formed with high accuracy due to good ink-coating properties using the IJ method. , And then can produce high-sensitivity optical elements.

In addition to the above-mentioned essential components, the negative photosensitive resin composition of the present invention may contain a cross-linking agent (B2) having no acidic group and other optional components as necessary. Hereinafter, each component is demonstrated.

(Alkali-soluble resin (A)) The alkali-soluble resin (A) is an alkali-soluble resin having a photocurable functional group. The alkali-soluble resin (A) is preferably a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. Since the alkali-soluble resin (A) has an ethylenic double bond in the molecule, the exposed portion of the negative photosensitive resin composition is polymerized due to free radicals generated from the photopolymerization initiator (D), and borrowed together The crosslinking agent (B) is crosslinked, and then cured to form a cured film.

As such, the sufficiently hardened exposure portion cannot be easily removed with an alkaline developer (hereinafter, also simply referred to as "developing solution"). In addition, since the molecules of the polyfunctional low-molecular-weight compound (B1) contained in the alkali-soluble resin (A) and the cross-linking agent (B) have acidic groups, the non-exposed portions of the uncured negative photosensitive resin composition can be developed. Liquid to be selectively removed. As a result, the cured film can be formed into a partition wall shape that divides a predetermined region into a plurality of partitions.

Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphate group. These may be used alone or in combination of two or more.

The photocurable functional group is preferably an ethylenic double bond. Examples of ethylenic double bonds include addition-polymerizable double bonds such as (meth) acrylfluorenyl, allyl, vinyl, vinyloxy, and vinyloxyalkyl. These may be used alone or in combination of two or more. In addition, part or all of the hydrogen atoms of the ethylenic double bond may be substituted with an alkyl group such as a methyl group.

The alkali-soluble resin (A) having an ethylene-based double bond may be, for example, a resin (A-1) having a side chain having an acidic group and a side chain having an ethylene-based double bond, and introducing an acidic group into an epoxy resin. Resin (A-2) made of ethylene double bond. These may be used individually by 1 type, and may use 2 or more types together. As the alkali-soluble resin (A), those described in the booklet No. WO2014 / 084279 can be used.

With regard to the alkali-soluble resin (A), the peeling of the cured film during development is suppressed to obtain a high-resolution dot pattern, the point that the linearity of the pattern is good when the dots are linear, and the smooth cured film is easily obtained. From the viewpoint of surface, resin (A-2) is preferably used. In addition, the good linearity of the pattern means that the edge of the obtained partition wall has a straight shape without a notch or the like.

Examples of the resin (A-1) include copolymers of acrylic acid, 2-hydroxymethacrylic acid ester, and other monomers with 2-propenyloxyethyl isocyanate.

In addition, examples include the unsaturated group-containing urethane resin (A) in Japanese Patent Application Laid-Open No. 2001-33960, the polyurethane compound (E) in Japanese Patent Application No. 2003-268067, and Japanese Patent Laid-Open A urethane-based resin such as a reactive polyurethane compound of (A) component in 2010-280812.

Specifically, for example, a compound having a double bond and a hydroxyl group formed by reacting a bifunctional epoxy resin with acrylic acid, a diol compound having a carboxyl group such as dimethylolpropionic acid, and trimethylhexamethylene Diisocyanate compounds such as diisocyanate, resins obtained by reacting diisocyanate compounds such as glycidyl methacrylate and polybasic acid anhydrides such as phthalic anhydride.

Examples of the aforementioned two-functional epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and phenol phenol methane epoxy resin. 2, epoxy resin with naphthalene skeleton, epoxy resin with biphenyl skeleton, and bisphenol A epoxy resin substituted with fluorenyl group.

In particular, when a urethane-based resin is used, it is possible to impart flexibility, to have good alkali resistance, and to improve dispersion stability to a developer, which is ideal.

As for the resin (A-2), p-bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and phenol phenol methane type ring Oxygen resin, epoxy resin with naphthalene skeleton, epoxy resin with biphenyl skeleton, bisphenol A type epoxy resin substituted with fluorenyl group, and epoxy resin contained in Japanese Patent Application Laid-Open No. 2006-84985 respectively introduce acidic groups A resin made of an ethylene-based double bond is preferred.

Para-bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, epoxy resin with biphenyl skeleton, bisphenol-A epoxy resin substituted with fluorenyl group, as described in Japanese Patent Application Publication 2006-84985 Oxygen resins are more preferably resins in which an acidic group and an ethylenic double bond are respectively introduced.

Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin having biphenyl skeleton, and bisphenol A type epoxy resin substituted with fluorenyl group are particularly preferable. If these resins are used, the interaction with the photopolymerization initiator (D) is improved, and the adhesion with the substrate is improved.

The number of ethylenic double bonds in the alkali-soluble resin (A) in one molecule is preferably 3 or more on average, and more preferably 6 or more on average. If the number of the ethylenic double bonds is above the lower limit of the above range, the alkali solubility of the exposed portion and the unexposed portion is liable to form a drop, and a fine pattern can be formed with less exposure.

The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1.0 × 10 ³ to 20 × 10 ³ , and more preferably 2 × 10 ³ to 15 × 10 ³ . In addition, the number average molecular weight (Mn) is preferably 500 to 13 × 10 ³ , and more preferably 1.0 × 10 ³ to 10 × 10 ³ . When the mass average molecular weight (Mw) and number average molecular weight (Mn) are above the lower limit of the above range, the curing is sufficient during exposure, and if it is below the upper limit of the above range, the developability is good.

In this specification, as long as the number average molecular weight (Mn) and the mass average molecular weight (Mw) are not particularly revealed, they refer to values measured by gel permeation chromatography with polystyrene as a standard substance.

The acid value of the alkali-soluble resin (A) is preferably 10 to 300 mgKOH / g, and particularly preferably 10 to 150 mgKOH / g. When the acid value of the alkali-soluble resin (A) is within the above range, the developability of the photosensitive composition for negative type is good.

The alkali-soluble resin (A) contained in the negative photosensitive resin composition may be used alone or in combination of two or more.

Of the all-solid content of the negative photosensitive resin composition, the content ratio of the alkali-soluble resin (A) is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass. When the content ratio is within the above range, the photo-curability and developability of the negative photosensitive resin composition are good.

(Crosslinking agent (B)) The crosslinking agent (B) contains a polyfunctional low-molecular-weight compound (B1) having an acidic group and two or more photocurable functional groups in one molecule, and more preferably containing one in one molecule. Crosslinking agent (B2) having two or more photocurable functional groups and having no acidic group (hereinafter also referred to as "non-acidic crosslinking agent (B2)"). The crosslinking agent (B) has two or more photocurable functional groups in one molecule, and reacts with the photocurable functional group of the alkali-soluble resin (A) through the action of the photopolymerization initiator (D). The negative-type photosensitive resin composition of the present invention containing these can be cross-linked with a cross-linking agent (B) when the alkali-soluble resin (A) is polymerized by exposure, and becomes a sufficiently hardened cured film.

<Polyfunctional low molecular weight compound (B1)> The polyfunctional low molecular weight compound (B1) is a monomer having an acidic group and two or more photocurable functional groups in one molecule. In addition, the "low molecular weight compound" of the present invention means a concept with respect to a so-called polymer substance (resin). In the present specification, "low molecular weight compound" is used as a concept including "monomer", "dimer", "terpolymer" and "oligomer". In the present specification, the "low molecular weight compound" means a compound having a mass average molecular weight (Mw) of less than 1,000.

The mass average molecular weight (Mw) of the polyfunctional low molecular weight compound (B1) is preferably 300 or more and less than 1,000, and more preferably 500 or more and less than 800. The number average molecular weight (Mn) is preferably 300 or more and less than 1,000, and more preferably 500 or more and less than 800. When the mass average molecular weight (Mw) and number average molecular weight (Mn) are within the above ranges, alkali solubility and developability are good.

The photocurable functional group of the polyfunctional low molecular weight compound (B1) is preferably a photocurable functional group of the same type as the photocurable functional group of the alkali-soluble resin (A). Specifically, it is an ethylenic double bond. Better. The number of photocurable functional groups of the multifunctional low molecular weight compound (B1) in one molecule only needs to be two or more, and preferably three or more, more preferably four or more, and more preferably five or more. The greater the number of photocurable functional groups, the higher the hardenability of the coating film surface, and the better the ink repellency stability of the upper surface of the obtained partition wall.

Examples of the acidic group of the polyfunctional low molecular weight compound (B1) include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group. These may be used alone or in combination of two or more. The number of acidic groups in one molecule of the multifunctional low molecular weight compound (B1) need only be one or more, and preferably one or two, and more preferably one.

Examples of the polyfunctional low molecular weight compound (B1) include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, a polyisocyanate compound, and a (meth) acrylic acid-containing compound. An ethylenic compound having a urethane skeleton, which is a reaction of a hydroxy compound of a basic group, and a compound in which an acidic group is introduced such that two or more unsaturated bonds (ethylene double bonds) remain.

As for the polyfunctional low molecular weight compound (B1), the following polyfunctional low molecular weight compound is preferable: it is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an aromatic carboxylic acid anhydride or a non-aromatic carboxylic acid anhydride and Polyfunctional low-molecular-weight compounds having an acidic group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound; more preferably, polyfunctional low-molecular-weight compounds having an acidic group for non-aromatic carboxylic anhydride reaction.

To introduce an acidic group of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid ester, the aliphatic polyhydroxy compound may be, for example, a compound having three or more hydroxyl groups, such as trimethylolpropane, trimethylolethane, and Pentaerythritol, dinepentaerythritol, trinepentaerythritol, tetranepentaerythritol, etc. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, and the like.

Among the esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, neopentyl tetraol and / or dipentaerythritol are preferred, and dipentaerythritol is particularly preferred. The unsaturated carboxylic acid is preferably (meth) acrylic acid, more preferably acrylic acid.

Specific examples of the aromatic carboxylic acid anhydride used to introduce an acidic group to the above-mentioned esters include phthalic anhydride, and specific examples of the non-aromatic carboxylic acid anhydrides include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, and hexahydrogen. Phthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, among which succinic anhydride is preferred.

Among the polyfunctional low-molecular-weight compounds (B1), the compound that reacts an aromatic carboxylic anhydride and an aliphatic polyhydroxy compound with an ester of an unsaturated carboxylic acid can be exemplified by the substitution of three hydroxy groups of neopentyltetraol with propyleneoxy groups. And the remaining 1 hydroxyl group is 2,2,2-tripropenyloxymethylethylphthalic acid with a structure such as phthalic acid as an ester bond.

The polyfunctional low molecular weight compound (B1) is preferably a compound having a dipentaerythritol skeleton. For example, a compound having a dipentaerythritol skeleton is preferably the following compound: 5 hydroxyl groups of the dipentaerythritol are replaced with (meth) acryl fluorenyloxy groups, and the remaining 1 hydroxyl group is used as an ester with succinic acid, for example. A compound that is bonded to introduce an acidic group.

The polyfunctional low molecular weight compound (B1) preferably has an acid value of 10 to 100 mgKOH / g, and more preferably 20 to 95 mgKOH / g. If the polyvalent low-molecular-weight compound (B1) has an acid value above the above-mentioned lower limit, the negative-type photosensitive composition can have better solubility in the developer, and if it is below the above-mentioned upper limit, the manufacturing and handling properties are good. It can ensure sufficient polymerizability, and also has good hardenability such as surface smoothness of the obtained coating film.

In the negative photosensitive resin composition, the polyfunctional low molecular weight compound (B1) may be used alone or in combination of two or more. When the polyfunctional low molecular weight compound (B1) is used in the form of a mixture of two or more kinds, the acid value of the mixture is preferably within the above range.

<Non-acidic cross-linking agent (B2)> In addition to the polyfunctional low-molecular-weight compound (B1), the cross-linking agent (B) may contain two or more photo-hardenable functional groups in one molecule and no acidic groups. Crosslinker (B2), that is, non-acidic crosslinker (B2). By using a polyfunctional low molecular weight compound (B1) in combination with a non-acidic cross-linking agent (B2), the acid value and the number of photocurable functional groups of the entire cross-linking agent (B) can be easily adjusted, and the following two are easily obtained The balance of effects is the effect of improving the curability of the negative photosensitive resin composition upon exposure, and the effect of improving the solubility of the negative photosensitive resin composition on the developing solution.

The non-acidic crosslinking agent (B2) has two or more photocurable functional groups in one molecule, and the photocurable functional groups of the same type as the photocurable functional groups of the alkali-soluble resin (A). Preferably, specifically, an ethylenic double bond is preferred. The number of photohardenable functional groups in one molecule of the non-acidic cross-linking agent (B2) need only be two or more, and preferably three or more, more preferably four or more, and more preferably five or more. The greater the number of photocurable functional groups, the higher the hardenability of the coating film surface, and the better the ink repellency stability of the upper surface of the obtained partition wall. In addition, including the preferable aspect, the molecular weight of the non-acidic cross-linking agent (B2) can be made the same as that of the polyfunctional low-molecular-weight compound (B1).

As for the non-acidic cross-linking agent (B2), specifically, for example, a compound having no acidic group in the polyfunctional low molecular weight compound (B1), and an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid as should.

As for the non-acidic cross-linking agent (B2), more specifically, examples include: diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl tetraol Tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, bis (trimethylol) propane tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, di Neopentaerythritol hexa (meth) acrylate, trinepentaerythritol heptaacrylate, trinepentaerythritol octaacrylate, tetranepentaerythritol heptaacrylate, tetranepentaerythritol octaacrylate, tetraxin Pentaerythritol nine acrylate, tetranepentaerythritol decanoate, ethoxylated isotrimeric cyanate tri (meth) acrylate, gins- (2-propenyloxyethyl) isotrimeric cyanate Esters, ε-caprolactone modified ginseng- (2-propenyloxyethyl) isotricyanate, and HDI (hexamethylene diisocyanate) bonded to dipentaerythritol pentaacrylate Monomer (10-functional) with urethane skeleton, urethane acrylate, etc.

In the negative photosensitive resin composition, the non-acidic crosslinking agent (B2) may be used alone or in combination of two or more kinds.

The content of the cross-linking agent (B) in the all-solid content of the negative photosensitive resin composition is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass. The acid value of the cross-linking agent (B) is in the same range as the acid value of the polyfunctional low-molecular-weight compound (B1) when the cross-linking agent (B) is composed of only the polyfunctional low-molecular-weight compound (B1). The acid value of the cross-linking agent (B) When the cross-linking agent (B) contains both the polyfunctional low-molecular-weight compound (B1) and the non-acidic cross-linking agent (B2), it is preferably 10 to 80 mgKOH / g, 15 to 70 mgKOH / g is better.

The content ratio of the polyfunctional low molecular weight compound (B1) in the all-solid content of the negative photosensitive resin composition is preferably 5 to 80% by mass, and more preferably 7 to 60% by mass. When the content ratio of the polyfunctional low-molecular-weight compound (B1) is within the above range, the photo-curing property and developability of the negative photosensitive resin composition are good.

When the negative photosensitive resin composition contains a non-acidic cross-linking agent (B2) as the cross-linking agent (B), the non-acidic cross-linking agent (B2) in the total solid content of the composition contains 0.1 to 50 mass % Is preferable, and 1.0 to 40% by mass is more preferable.

At this time, the ratio of the polyfunctional low molecular weight compound (B1) is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the total of the polyfunctional low molecular weight compound (B1) and the non-acidic cross-linking agent (B2). 70 quality department is better. By setting the polyfunctional low-molecular-weight compound (B1) and the non-acidic cross-linking agent (B2) to the above ratio, the acid value and the number of photocurable functional groups of the entire cross-linking agent (B) can be easily adjusted, and the negative sensitivity is The resin composition can easily achieve a balance between photocurability and developability.

In addition, the cross-linking agent (B) may be a commercially available mixture of a polyfunctional low-molecular-weight compound (B1) and a non-acidic cross-linking agent (B2), such as dipentaerythritol hexaacrylate, dixin Succinate mixtures of pentaerythritol pentaacrylate and dinepentaerythritol pentaacrylate.

If necessary, such a mixture may be further used in combination with a monomer of the polyfunctional low molecular weight compound (B1) and / or a monomer of the non-acidic cross-linking agent (B2).

(Ink Repellent (C)) The ink repellent (C) has an acidic group and a fluorine atom, and has an acid value of 10 to 100 mgKOH / g. By having a fluorine atom, the ink repellent (C) has a property of moving toward the upper surface (upper surface migration) and ink repellency in the process of forming a cured film using a negative photosensitive resin composition containing the ink repellent (C). By using the ink-repellent agent (C), the upper layer portion including the upper surface of the obtained cured film becomes a layer in which the ink-repellent agent (C) exists secretly (hereinafter also referred to as "ink-repellent layer"), and the upper surface of the cured film is given. Repellency.

The ink repellent (C) is the same as other components such as the alkali-soluble resin (A) and the cross-linking agent (B) contained in the negative photosensitive resin composition because it has an acidic group and the acid value is above the lower limit. Good solubility for developer. Thereby, the negative photosensitive resin composition of a non-exposed part can be easily removed with a developing solution, and developability is favorable. On the other hand, since the acid value of the ink-repellent agent (C) is below the above-mentioned upper limit value, the ink-repellent layer formed on the upper layer portion of the cured film can be sufficiently adhered to the resin layer on the lower layer portion without being affected by the developer, It will remain after development and show high ink repellency.

The acid value of the ink repellent (C) is preferably 20 to 100 mgKOH / g, more preferably 25 to 80 mgKOH / g, and more preferably 30 to 60 mgKOH / g.

The fluorine atom content in the ink repellent (C) is from the viewpoint of the upper surface migration and ink repellency, preferably from 5 to 55 mass%, more preferably from 10 to 55 mass%, and more preferably from 12 to 40 mass%. Good, especially 14 to 30% by mass. If the fluorine atom content of the ink-repellent agent (C) is above the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film, and if it is below the upper limit, it is compatible with the negative photosensitive resin composition. The compatibility of other ingredients is good.

The ink repellent (C) is preferably a compound having a photocurable functional group, particularly a compound having an ethylenic double bond. Since the ink-repellent agent (C) has an ethylenic double bond, the radicals will act on the ethylene-based double bond of the ink-repellent agent (C) that migrates to the upper surface, and the ink-repellent agents (C) and each other or the ink-repellent agent (C) Crosslinking by (co) polymerization with other components having an ethylenic double bond contained in the negative photosensitive resin composition.

This makes it possible to improve the fixability of the ink repellent agent (C) in the upper layer portion (that is, the ink repellent layer) of the cured film when the cured film obtained by curing the negative photosensitive resin composition is produced. With the negative-type photosensitive resin composition of the present invention, the ink repellent (C) can be sufficiently fixed in the ink repellent layer even when the exposure amount is low during exposure. When the ink repellent (C) has an ethylenic double bond, it is as described above. When the ink-repellent agent (C) does not have an ethylene-based double bond, the light-repellent component mainly composed of the alkali-soluble resin (A) existing around the ink-repellent agent (C) is sufficiently hardened, so that the ink-repellent agent (C) can be cured. Fully fixed.

The ink-repellent agent (C) includes, for example, an ink-repellent agent (C1), which is composed of a compound whose main chain is a hydrocarbon chain and has a side chain having an acidic group and a side chain containing a fluorine atom. The ink-repellent agent (C) may also be an ink-repellent agent (C2) composed of a partially hydrolyzed condensate of a hydrolyzable silane compound, which includes a hydrolyzable silane compound having an acidic group and a hydrolyzable silane having a fluorine atom. Compound.

The ink repellent (C1) and the ink repellent (C2) can be used alone or in combination. In the negative photosensitive resin composition of the present invention, an ink repellent (C1) is particularly preferably used from the viewpoint of exhibiting higher ink repellency. In addition, when UV / ozone resistance is sought, an ink repellent (C2) should be used.

<Ink Repellent (C1)> The repellent (C1) is a compound whose main chain is a hydrocarbon chain and has a side chain having an acidic group and a side chain containing a fluorine atom. The mass average molecular weight (Mw) of the ink repellent (C1) is preferably 1.0 × 10 ⁴ to 15 × 10 ^{4, more} preferably 1.2 × 10 ⁴ to 13 × 10 ^{4, and particularly} preferably 1.4 × 10 ⁴ to 12 × 10 ⁴ . When the mass average molecular weight (Mw) is at least the lower limit value, when the negative-type photosensitive resin composition is used to form a cured film, the ink repellent (C1) tends to migrate toward the upper surface. If it is below the upper limit value, it is preferable that the residue in the opening portion is small.

In the side chain having an acidic group, examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphate group. These may be used alone or in combination of two or more. The part of the ink repellent (C1) other than the acidic group in the side chain having an acidic group is not particularly limited.

The fluorine atom-containing side chain of the ink repellent (C1) is preferably one of the following: a side chain composed of a fluoroalkyl group which may contain an etheric oxygen atom and / or a fluoroalkyl group which may contain an etheric oxygen atom Side chain.

The fluoroalkyl group may be linear or branched. Specific examples of the fluoroalkyl group having no etheric oxygen atom include the following structures: -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ ,-(CF ₂ ) ₂ CF ₃ ,-(CF ₂ ) ₃ CF ₃ ,-(CF ₂ ) ₄ CF ₃ ,-(CF ₂ ) ₅ CF ₃ ,-(CF ₂ ) ₆ CF ₃ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₈ CF ₃ ,-( CF ₂ ) ₉ CF ₃ ,-(CF ₂ ) ₁₁ CF ₃ ,-(CF ₂ ) ₁₅ CF ₃ .

Specific examples of the fluoroalkyl group containing etheric oxygen atom are as follows: -CF (CF ₃ ) O (CF ₂ ) ₅ CF ₃ , -CF ₂ O (CF ₂ CF ₂ O) _r1 CF ₃ , -CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _r2 C ₆ F ₁₃ and -CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _r3 C ₃ F ₇ . In the above formula, r1 is an integer from 1 to 8, r2 is an integer from 1 to 4, and r3 is an integer from 1 to 5.

The hydrocarbon chain constituting the main chain of the ink-repellent agent (C1) can be specifically exemplified by the repeating of a main chain obtained by polymerizing a monomer having an ethylenic double bond, and repeating by -Ph-CH _2- (but "Ph" represents a benzene skeleton) A phenolic main chain composed of units and the like.

The ink repellent (C1) may further include one or more kinds of side chains selected from the group consisting of a side chain having an ethylene double bond and a side chain having an oxyalkylene group. It may contain an ethylenic double bond and an oxyalkylene group on one side chain. In addition, the acidic group-containing side chain may contain an ethylenic double bond and / or an oxyalkylene group.

In addition, the ink repellent (C1) may include a side chain such as a dimethylpolysiloxane chain, an alkyl group, an epoxypropyl group, an isofluorenyl group, an isocyanate group, and a trialkoxysilyl group.

When the main chain of the ink repellent (C1) is a phenolic main chain composed of repeating units of -Ph-CH _2- , it is usually used as the ink repellent (C1) as the benzene skeleton (Ph) that constitutes the main chain. ) A polymer in which a side chain having a fluorine atom and a side chain having an acidic group are bonded, and a side chain having an ethylene double bond and an oxyalkylene side chain are further optionally bonded. Each side chain can be bonded to the same benzene skeleton (Ph), or to different benzene skeletons (Ph). The number of side chains bonded to one benzene skeleton (Ph) is preferably one.

In addition, the adjustment of the acid value of the ink repellent (C1) can be easily performed by adjusting the proportion of the side chain having an acidic group introduced into the hydrocarbon chain main chain of the ink repellent (C1). Similarly, the adjustment of the fluorine atom content of the ink repellent (C1) can be easily performed by adjusting the proportion of the fluorine atom-containing side chain introduced into the hydrocarbon chain main chain of the ink repellent (C1).

<Ink Repellent (C2)> The ink repellent (C2) is a partially hydrolyzed condensate of a hydrolyzable silane compound mixture (hereinafter also referred to as "mixture (M)").

This mixture (M) contains the following hydrolyzable silane compounds as essential components: a hydrolyzable silane compound having a fluoroalkylene group and / or a fluoroalkyl group, and a group having a hydrolyzable group bonded to a silicon atom (hereinafter also referred to as Is a "hydrolyzable silane compound (s1)"); and a hydrolyzable silane compound (hereinafter also referred to as a hydrolyzable silane compound having an acidic group and a group having a hydrolyzable group bonded to a silicon atom and not containing a fluorine atom) "Hydrolyzable silane compound (s2)"); and optionally includes a hydrolyzable silane compound (s1) and a hydrolyzable silane compound other than the hydrolyzable silane compound (s2).

The hydrolyzable silane compound optionally contained in the mixture (M) is preferably a hydrolyzable silane compound (hereinafter also referred to as "hydrolyzable silane compound (s3)") having four hydrolyzable groups bonded to a silicon atom.

Specific examples of the hydrolyzable silane compound (s1) include the following compounds: F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , _{F (CF 2) 6 CH 2} CH 2 CH 2 Si (OCH 3) 3, F (CF 2) 8 CH 2 CH 2 Si (OCH 3) 3, F (CF 2) 3 OCF (CF 3) CF 2 O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₂ O (CF ₂ ) ₂ O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;

(CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₂ OCF ₂ (CF ₃ ) CFO (CF ₂ ) ₂ OCF (CF ₃ ) CF ₂ O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .

Among them, F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ and F (CF ₂ ) ₃ OCF (CF ₃ ) CF ₂ O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ Better.

The content ratio of the hydrolyzable silane compound (s1) in the mixture (M) is preferably a ratio such that the fluorine atom content ratio in the partially hydrolyzed condensate from the mixture becomes 5 to 55% by mass. It is more preferably 10 to 55 mass%, more preferably 12 to 40 mass%, and most preferably 15 to 30 mass%. If the content rate of the hydrolyzable silane compound (s1) is above the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film. If it is below the upper limit, it will be compatible with other hydrolyzable silane compounds in the mixture. Good compatibility.

The acidic group of the hydrolyzable silane compound (s2) is preferably a carboxyl group, a phenolic hydroxyl group, or a sulfonic acid group. Specific examples of the hydrolyzable silane compound (s2) include the following compounds:

(1) The compound represented by the following formula (c-2a), specifically, is the following formula (c-2a-1), the following formula (c-2a-2), the following formula (c-2a-3), The compounds represented by the following formulae (c-2a-4), (c-2a-5), and (c-2a-6).

[Chemical Formula 1]

R ²² is a formula: -R ²⁵ -COOH or -COO-R ²⁵ OOC- R ²⁵ -COOH (here, R ²⁵ represents a divalent hydrocarbon group having a carbon number of 1 to 10, a single bond or phenylene) base. When R ²² is -COO-R ²⁵ OOC-R ²⁵ -COOH, the solubility of the developer of the ink repellent (C2) is further improved, and the residue at the opening is reduced. The wet spread of the ink by the IJ method is better and even better. ideal.

R ²¹ is a group represented by -COOR ²⁴ (here, R ²⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), -COO- (C ₂ H ₄ O) _i- (C ₃ H ₆ O) _j -(C ₄ H ₈ O) _k -R ²⁸ (Here, R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, i represents 0 to 100, j represents 0 to 100, and k represents An integer from 0 to 100, i + j + k is 2 to 100. When there are several kinds of oxyalkylene units, the order is optional), or a phenyl group in which a hydrogen atom can be replaced with a hydrocarbon group having 1 to 10 carbon atoms . When R ²¹ is -COO- (C ₂ H ₄ O) _i- (C ₃ H ₆ O) _j- (C ₄ H ₈ O) _k -R ²⁸ , the dispersion stability and storage stability of the ink repellent (C2) Sex is improved and ideal.

Q ² is a divalent hydrocarbon group having 1 to 10 carbon atoms. X ² is a hydrolyzable group, and three X ² may be different from each other or may be the same. X ^{2 is} preferably methoxy or ethoxy. m is an integer of 0 or more, and n is an integer of 1 or more.

[Chemical Formula 2] [Chemical Formula 3] X ² , m, n, and i are the same as those in the formula (c-2a).

(2) A reactant of a cyclic carboxylic anhydride and a hydrolyzable silane compound having an amine group, specifically, a compound represented by the following formula (c-2b-1) and the following formula (c-2b-2), respectively.

[Chemical Formula 4] X ^{2 is the} same as the formula (c-2a).

(3) Compounds having an ethylenic double bond with a hydroxyl or carboxyl group and their derivatives and hydrogen-containing silanes, specifically, the following formulae (c-2c-1) and (c-2c- 2) The compound shown.

[Chemical Formula 5] X ^{2 has the} same formula (c-2a).

The content ratio of the hydrolyzable silane compound (s2) in the mixture (M) is such that the acid value of the partially hydrolyzed condensate obtained from the mixture becomes a ratio of 10 to 100 mgKOH / g. The acid value of the partially hydrolyzed condensate is preferably 20 to 100 mgKOH / g, more preferably 25 to 80 mgKOH / g, and more preferably 30 to 60 mgKOH / g.

When the content ratio of the hydrolyzable silane compound (s2) is at least the lower limit of the above range, the obtained negative photosensitive resin composition has good solubility in a developing solution. Thereby, the negative photosensitive resin composition in the non-exposed portion can be easily removed by the developer, and the developability is good. On the other hand, if the acid value of the ink repellent (C) is below the above-mentioned upper limit value, the ink repellent layer formed on the upper part of the cured film and the resin layer on the lower part can be sufficiently adhered without being affected by the developing solution. It will still remain afterwards and show high ink repellency.

Specific examples of the hydrolyzable silane compound (s3) include the following compounds: Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , partially hydrolyzed condensate of Si (OCH ₃ ) ₄ , and Si (OC ₂ H ₅ ) Partially hydrolyzed condensate of ₄ .

The content ratio of the hydrolyzable silane compound (s3) in the mixture (M) is preferably 0.01 to 5 moles, and more preferably 0.05 to 4 moles relative to 1 mole of the hydrolyzable silane compound (s1). If the content ratio is above the lower limit of the above range, the film repellency of the ink repellent (C2) is good, and if it is below the upper limit, the ink repellency of the ink repellent (C2) is good.

The mixture (M) may further optionally contain one or more types of hydrolyzable silane compounds other than the hydrolyzable silane compounds (s1) to (s3). Examples of the hydrolyzable silane compound preferably contained in the mixture (M) include the following hydrolyzable silane compound (s4), hydrolyzable silane compound (s5), and hydrolyzable silane compound (s6). The hydrolyzable silane compound further optionally contained in the mixture (M) is preferably a hydrolyzable silane compound (s4).

Hydrolyzable silane compound (s4): A hydrolyzable silane compound having a group having an ethylenic double bond and a group having a hydrolyzable group bonded to a silicon atom and not containing a fluorine atom.

Hydrolyzable silane compound (s5); a hydrolyzable silane compound with a mercapto group or a sulfide group and a hydrolyzable silicon group, and containing no fluorine atom. Hydrolyzable silane compound (s6); a hydrolyzable silane compound having only a hydrocarbon group and a hydrolyzable group as a group bonded to a silicon atom.

Specific examples of the hydrolyzable silane compound (s4) include the following compounds: CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , CH ₂ = CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ = CHCOO (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , [CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ ] CH ₃ Si (OCH ₃ ) ₂ , [CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ ] CH ₃ Si (OC ₂ H ₅ ) ₂ , CH ₂ = CHSi ( OCH ₃ ) ₃ and CH ₂ = CHC ₆ H ₄ Si (OCH ₃ ) ₃ .

The content ratio of the hydrolyzable silane compound (s4) in the mixture (M) is preferably 0.1 to 5 moles, and more preferably 0.5 to 4 moles relative to 1 mole of the hydrolyzable silane compound (s1). If the content ratio is above the lower limit of the above range, the upper surface of the ink repellent (C2) has good migration properties. In addition, after the upper surface migrates, the fixability of the ink repellent (C2) in the ink repellent layer including the upper surface is good. Good, in addition, the storage stability of the ink repellent (C2) was good. If it is below the upper limit, the ink repellency of the ink repellent (C2) is good.

Specific examples of the hydrolyzable silane compound (s5) include HS- (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , HS- (CH ₂ ) ₃ -Si (CH ₃ ) (OCH ₃ ) ₂ and [(1 , 2,3,4-tetrathiobutane-1,4-diyl) bis (trimethylene)] bis (triethoxysilane) ([(1,2,3,4-tetrathiabutane-1, 4-diyl) bis (trimethylene)] bis (triethoxysilane)).

The content ratio of the hydrolyzable silane compound (s5) in the mixture (M) is preferably 0 to 2.0 mol, and more preferably 0 to 1.5 mol, relative to 1 mol of the hydrolyzable silane compound (s1). If the content ratio is above the lower limit of the above range, the upper surface of the ink repellent (C2) has good migration properties. In addition, after the upper surface migrates, the fixability of the ink repellent (C2) in the ink repellent layer including the upper surface is good. Good. Furthermore, the storage stability of the ink repellent (C2) was good. If it is below the upper limit, the ink repellency of the ink repellent (C2) is good.

Specific examples of the hydrolyzable silane compound (s6) include the following compounds: (CH ₃ ) ₃ -Si-OCH ₃ , (CH ₃ CH ₂ ) ₃ -Si-OC ₂ H ₅ , (CH ₃ ) ₃ -Si- OC ₂ H ₅ , (CH ₃ CH ₂ ) ₃ -Si-OCH ₃ , (CH ₃ ) ₂ -Si- (OCH ₃ ) ₂ , (CH ₃ ) ₂ -Si- (OC ₂ H ₅ ) ₂ , (CH ₃ CH ₂ ) ₂ -Si- (OC ₂ H ₅ ) ₂ , (CH ₃ CH ₂ ) ₂ -Si- (OCH ₃ ) ₂ , Ph-Si (OC ₂ H ₅ ) ₃ , Ph-Si (OCH ₃ ) ₃ and C ₁₀ H ₂₁ -Si (OCH ₃ ) ₃ . In the formula, Ph represents a phenyl group.

The content ratio of the hydrolyzable silane compound (s6) in the mixture (M) is preferably 0 to 1.0 mol, and more preferably 0 to 0.08 mol, relative to 1 mol of the hydrolyzable silane compound (s1). When the content ratio is above the lower limit of the above range, storage stability is good. If it is below the upper limit, the ink coating properties of the dot portion are good.

Examples of other hydrolyzable silane compounds are: hydrolyzable silane compounds (s7) with epoxy groups and hydrolyzable silicon groups and containing no fluorine atom; hydrolyzability with oxyalkylene groups and hydrolyzable silicon groups without fluorine atom Silane compound (s8); hydrolyzable silane compound (s9) with sulfide and hydrolyzable silicon group and no fluorine atom; hydrolyzable silane compound (s10) with urea and hydrolyzable silicon group and no fluorine atom ; And a hydrolyzable silane compound (s11) having an amine group and a hydrolyzable silicon group and containing no fluorine atom;

Examples of the hydrolyzable silane compound (s7) include 2- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxy Propyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; hydrolyzable silane compounds (s8) For example, CH ₃ O (C ₂ H ₄ O) _k Si (OCH ₃ ) ₃ (trimethoxysilane containing polyoxyethylene) (for example, k is about 10); a hydrolyzable silane compound ( s9) can be exemplified by bis (triethoxysilylpropyl) tetrasulfide; hydrolyzable silane compound (s10) can be exemplified by 3-ureidopropyltriethoxysilane; hydrolyzable silane compound (s11) can be For example, N-phenyl-3-aminopropyltrimethoxysilane.

When the ink repellent (C2) contains a hydrolyzable silane compound (s8), the dispersion stability and storage stability of the ink repellent (C2) are particularly improved. When the ink repellent (C2) contains a hydrolyzable silane compound (s9), ink repellency is easily exhibited even at a low exposure amount, which is particularly preferable.

An example of the ink repellent (C2) is a partially hydrolyzed condensate such as a mixture (M), which contains the hydrolyzable silane compound (s1) of n1 and the hydrolyzable silane compound (s2 of n2) ), N3 hydrolyzable silane compound (s3), n4 hydrolyzable silane compound (s4), n5 hydrolyzable silane compound (s5), n6 hydrolyzable silane compound (s6). Here, n1 to n6 represent the mole fractions of each structural unit with respect to the total molar amount of the structural unit. n1> 0, n2> 0, n3 ≧ 0, n4 ≧ 0, n5 ≧ 0, n6 ≧ 0, n1 + n2 + n3 + n4 + n5 + n6 = 1.

n1: n2: n3 are consistent with the feed composition of the hydrolyzable silane compound (s1), (s2), (s3), (s4), (s5), (s6) in the mixture (M). The mole ratio of each component is designed by the effect balance of each component. To the extent that n1 in the ink repellent (C2) causes the fluorine atom content rate to fall within the above-mentioned preferred range, it is preferably 0.02 to 0.4. The amount of n2 in the ink repellent (C2) that causes the acid value to fall within the above range is preferably 0.003 to 0.03. n3 is preferably from 0 to 0.98, and more preferably from 0.05 to 0.6. n4 is preferably from 0 to 0.4, especially from 0 to 0.27. n5 is preferably 0 ~ 0.1, especially 0 ~ 0.07. n6 is preferably from 0 to 0.2, particularly from 0 to 0.15.

The mass average molecular weight (Mw) of the ink repellent (C2) is preferably 500 or more, more preferably less than 1 × 10 ⁶ , and particularly preferably 5 × 10 ³ or less. When the mass average molecular weight (Mw) is at least the lower limit value, the ink repellent (C2) tends to move toward the upper surface when a cured film is formed using a negative photosensitive resin composition. If it is less than the upper limit value, it is preferable that the residue at the opening portion is small. In addition, the mass average molecular weight (Mw) of the ink repellent (C2) can be adjusted by manufacturing conditions.

The ink repellent (C2) can be produced by subjecting the mixture (M) to a hydrolysis and condensation reaction in a conventional manner. In this reaction, basic catalysts such as sodium hydroxide and tetramethylammonium hydroxide (TMAH), inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or organic acids such as acetic acid, oxalic acid, and maleic acid can be used as the catalyst. In addition, a known solvent can be used for the above reaction. The ink repellent (C2) obtained by the above reaction can be blended with the solvent in the form of a solution to the negative photosensitive resin composition.

The content ratio of the ink-repellent agent (C) in the all-solid content of the negative photosensitive resin composition is set so that the surface of the partition wall obtained by using the ink-repellent agent satisfies the above characteristics. Although the content ratio varies depending on the type of the ink-repellent agent (C) used, specifically, it is preferably 0.01 to 10% by mass, and more preferably 0.1 to 2% by mass. If the content ratio is above the lower limit of the above range, the upper surface of the cured film formed of the negative photosensitive resin composition will have excellent ink repellency. When it is below the upper limit of the above range, the adhesion between the cured film and the substrate is good.

(Photopolymerization Initiator (D)) The photopolymerization initiator (D) of the present invention is not particularly limited as long as it is a compound having a function as a photopolymerization initiator. Compounds are preferred.

Examples of the photopolymerization initiator (D) include: α-diketones such as methyl phenylglyoxylate and 9,10-phenanthrenequinone; marionettes such as benzoin; benzoin methyl ether and benzoin Diethyl ethers such as diethyl ether and benzoin isopropyl ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthine Ketones, 2,4-diethylthioxanthone and other thioxanthones; diphenyl ketones, 4,4'-bis (dimethylamino) diphenyl ketones and 4,4'-bis (diethyl) Diphenyl ketones such as diphenyl ketone; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2 , 2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2- Phenylpropan-1-one and 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as phosphonophenyl) -butan-1-one; quinones such as anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone; ethyl 2-dimethylaminobenzoate Esters, 4-dimethylaminobenzoic acid (n-butoxy) ethyl esters and other amino benzoic acids; phenacyl chloride (phenacyl chloride), trihalomethylphenyl sulfonium and other halogen compounds; bis (2, 4,6-trimethylbenzylidene) -phenylphosphine oxide and other fluorenylphosphine oxides; peroxides such as di-tertiary butyl peroxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzylideneoxime) and ethyl ketone 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazole -3-yl] -1- (O-acetylamoxime) and other oxime esters; triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine and diethylamine Aliphatic amines such as ethyl methacrylate and the like.

Among the photopolymerization initiators (D), diphenyl ketones, aminobenzoic acids, and aliphatic amines may be used together with other radical-initiating groups to exhibit a sensitizing effect, which is ideal.

As for the photopolymerization initiator (D), 2-methyl-1- [4- (methylthio) phenyl] -2- Phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4- (Phenolinophenyl) -butan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzylideneoxime), ethyl ketone 1- [ 9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-acetamidooxime) or 2,4-diethylthioxanthone is should. Furthermore, combinations thereof with diphenyl ketones such as 4,4′-bis (diethylamino) diphenyl ketone are particularly preferred. The photopolymerization initiator (D) may be used individually by 1 type, and may use 2 or more types together.

The content ratio of the photopolymerization initiator (D) in the all-solid content of the negative photosensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 15% by mass. When the content ratio is within the above range, the photo-curability and developability of the negative photosensitive resin composition are good.

(Solvent (E)) The negative photosensitive resin composition of the present invention can reduce the viscosity by containing the solvent (E), so that the negative photosensitive resin composition can be easily applied to the surface of the substrate. As a result, a negative-type photosensitive resin composition coating film having a uniform film thickness can be formed. As the solvent (E), a conventional solvent can be used. The solvent (E) may be used singly or in combination of two or more kinds.

Examples of the solvent (E) include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, Solvent naphthas, and water. Among them, at least one solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferred, and is selected from the group consisting of propylene glycol alone Methyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, N, N-dimethylisobutylamidamine, 3-methoxy- At least one solvent in the group consisting of N, N-dimethylpropanamide, 3-n-butoxy-N, N-dimethylpropanamide, and 2-propanol is more preferable.

Among them, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, N, N-dimethylisobutylamidamine, 3-methoxy-N, N-dimethylpropylamine , 3-n-butoxy-N, N-dimethylpropanamide has a boiling point of 150 ° C or higher, and the phenomenon of uneven coating tends to be suppressed, which is particularly desirable.

When the solvent (E) contains water, the water content is preferably 10% by mass or less of the entire solvent (E). If it is in the said range, the unevenness of the pattern substrate which consists of the partition wall formed from the hardened film of the negative photosensitive resin composition of this invention can be reduced. In addition, the water content is more preferably 1 to 10% by mass. If it is in the said range, the dispersion stability of a composition will be favorable.

The content of the solvent (E) in the negative photosensitive resin composition is preferably 10 to 99% by mass, more preferably 20 to 95% by mass, and even more preferably 50 to 90% by mass relative to the total amount of the composition. In addition, it is preferably 0.1 to 3000% by mass, and more preferably 0.5 to 2000% by mass, relative to 100% by mass of the alkali-soluble resin (A) and the crosslinking agent (B) in total.

(Other components) (Mercaptan compound (G)) The thiol compound (G) optionally contained in the negative photosensitive resin composition of the present invention is a compound having two or more mercapto groups in one molecule. If the negative photosensitive resin composition of the present invention contains a thiol compound (G), it is alkali-soluble resin due to free radicals generated from the photopolymerization initiator (D) and free radicals of the thiol compound (G) during exposure. (A), the cross-linking agent (B), and the ethylenic double bonds of other components contained in the negative photosensitive resin composition act to cause a so-called ene-thiol reaction. This ene-thiol reaction is different from the radical polymerization of general ethylenic double bonds, and is not inhibited by the reaction caused by oxygen. Therefore, it has a high chain transferability, and it is also crosslinked at the same time during polymerization. The shrinkage rate is also low, which has the advantage of obtaining a uniform network.

When the negative-type photosensitive resin composition of the present invention contains a thiol compound (G), it can be sufficiently cured even at a low exposure amount as described above. In particular, even when the The upper layer can still be sufficiently light-hardened, and can impart good ink repellency to the upper surface of the partition.

The thiol group in the thiol compound (G) should preferably contain 2 to 10 molecules, and preferably 2 to 8 molecules, more preferably 2 to 5 molecules. From the viewpoint of storage stability of the negative photosensitive resin composition, three are particularly preferred.

The molecular weight of the thiol compound (G) is not particularly limited. In the thiol compound (G), the thiol equivalent represented by [Molecular Weight / Mercapto Number] is preferably from 40 to 1,000, more preferably from 40 to 500, and more preferably from 40 to 250 from the viewpoint of hardenability at low exposure. It's better.

Specific examples of the thiol compound (G) include ginseng (2-mercaptopropionyloxyethyl) isotricyanate, neopentaerythritol (3-mercaptobutyrate), and trimethylolpropane. Acetate, neopentaerythritol thioglycolate, neopentaerythritol thioglycolate, dinepentaerythritol hexamercaptoacetate, trimethylolpropane ginseng (3-mercaptopropionate), Neopentaerythritol (3-mercaptopropionate), ginseng-[(3-mercaptopropionyloxy) -ethyl] -isotricyanate, dipentaerythritol hexa (3-mercaptopropionic acid) (Ester), trimethylolpropane ginseng (3-mercaptobutyrate), neopentaerythritol (3-mercaptobutyrate), dinepentaerythritol hexa (3-mercaptobutyrate), trimethylol Propane ginseng (2-mercaptoisobutyrate), 1,3,5-ginseng (3-mercaptobutyryloxyethyl) -1,3,5-tris -2,4,6 (1H, 3H, 5H) -trione, trisphenol methane (3-mercaptopropionate), trisphenol methane (3-mercaptobutyrate), trimethylolethane (3-mercaptobutyrate) and 2,4,6-trimercapto-S-tri Wait. The thiol compound (G) may be used individually by 1 type, and may use 2 or more types together.

When the negative photosensitive resin composition contains a thiol compound (G), its content ratio is 1 mol, and the mercapto group is 0.0001 to 1 mol relative to the ethylenic double bond of the all-solid component in the negative photosensitive resin composition. The amount is appropriate, more preferably 0.0005 to 0.5 mole, especially 0.001 to 0.5 mole. The alkali-soluble resin (A) is preferably 0.1 to 1200% by mass, and more preferably 0.2 to 1000% by mass, with respect to 100% by mass of the alkali-soluble resin (A). If the content ratio of such a thiol compound (G) is within the above range, the photo-curability and developability of the negative photosensitive resin composition are good even at a low exposure amount.

(Phosphoric acid compound (H)) The negative-type photosensitive resin composition of the present invention may optionally include a phosphoric acid compound (H) in order to improve the adhesion of the obtained cured film to a substrate and a transparent electrode material such as ITO.

The phosphoric acid compound (H) is not particularly limited as long as it can improve the adhesion of the cured film to the substrate and the transparent electrode material, but it is preferably a phosphoric acid compound having an ethylenically unsaturated double bond in the molecule. .

The phosphate compound having an ethylenically unsaturated double bond in the molecule is preferably one of the following: a phosphoric acid (meth) acrylate compound, that is, at least an O = P structure derived from phosphoric acid and a (meth) acrylic compound derived from the molecule (Meth) acrylfluorenyl compounds of ethylenically unsaturated double bonds; and vinyl phosphate compounds.

Examples of the (meth) acrylic acid phosphate compound used in the present invention include mono (2- (meth) acryloxyethyl) acid phosphate and bis (2- (meth) acryloxyethyl) acid. Phosphate, bis (2-propenyloxyethyl) acid phosphate, ginseng ((meth) propenyloxyethyl) acid phosphate, mono (2-methacryloxyethyl) ) Caproate acid phosphate and the like.

In addition to the phosphoric acid compound (H), in addition to a phosphoric acid compound having an ethylenically unsaturated double bond in the molecule, phenylphosphonic acid or the like can also be used.

In the negative photosensitive resin composition of the present invention, as the phosphoric acid compound (H), a single type of compound classified as such a compound may be contained, or two or more kinds may be contained.

When the negative photosensitive resin composition contains a phosphoric acid compound (H), its content ratio is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass, relative to the total solids content in the negative photosensitive resin composition. The alkali-soluble resin (A) is preferably 0.01 to 200% by mass, and more preferably 0.1 to 100% by mass. If the content ratio of such a phosphoric acid compound (H) is in the said range, the adhesiveness of the obtained cured film and a base material etc. will be favorable.

The negative photosensitive resin composition of the present invention may further contain, if necessary, a member selected from the group consisting of a polymerization inhibitor, a thermal cross-linking agent, a polymer dispersant, a dispersion auxiliary agent, a silane coupling agent, fine particles, a hardening accelerator, and a thickener Agent, plasticizer, defoamer, leveling agent, and anti-repelling agent in the group of one or more other additives.

The negative photosensitive resin composition of the present invention is obtained by mixing a predetermined amount of each of the above components. The negative photosensitive resin composition of the present invention is particularly effective in forming a cured film and a partition wall for forming an optical element such as an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell. If the negative photosensitive resin composition of the present invention is used, a partition wall having good ink repellency on the upper surface and good development adhesion to the substrate can be manufactured, and the development residue in the opening portion partitioned by the partition wall is sufficiently small.

[Partition Wall] The partition wall of the present invention is a partition wall composed of the hardened film of the negative photosensitive resin composition of the present invention described above, and is formed in a shape that divides the substrate surface into a plurality of partitions for dot formation. For example, the partition wall is prepared in the following manner: The negative photosensitive resin composition of the present invention is coated on the surface of a substrate such as a substrate, and if necessary, the solvent is dried and removed, and then the partitions for the dot formation are formed. After partially applying a mask and exposing, development is performed. By the development, the unexposed portion is removed due to the mask, and an opening portion and a partition wall corresponding to the dot formation partition are formed together.

As described above, the partition wall of the embodiment of the present invention is a partition wall with a good ink repellency on the upper surface and good development adhesion to the substrate, and the development residue in the opening portion partitioned by the partition wall is small enough. Therefore, when used for optical elements, especially organic EL elements produced by the IJ method, quantum dot displays, TFT arrays, or thin-film solar cells, the ink can be evenly applied to the openings and dots can be formed with high accuracy. Significant effect.

Hereinafter, an example of a method for manufacturing a partition wall according to an embodiment of the present invention will be described with reference to FIGS. 1A to 1D. However, the method for manufacturing a partition wall is not limited to the following. In addition, the following manufacturing method is demonstrated as the form which contains a solvent (E) in a negative photosensitive resin composition.

As shown in FIG. 1A, a negative photosensitive resin composition is coated on the entire main surface on one side of the substrate 1 to form a coating film 21. At this time, the entire ink repellent (C) was dissolved in the coating film 21 and dispersed uniformly. In addition, in FIG. 1A, the ink repellent (C) is schematically shown, and does not actually exist in such a particle shape.

Next, as shown in FIG. 1B, the coating film 21 is dried to form a dry film 22. Examples of the drying method include heating drying, drying under reduced pressure, and drying under reduced pressure. Although it depends on the type of the solvent (E), the heating temperature during heating and drying is preferably 50 to 120 ° C.

During this drying process, the ink repellent (C) will move toward the upper layer portion of the drying film. In addition, even when the negative photosensitive resin composition does not contain the solvent (E), the ink repellent (C) can be shifted on the upper surface inside the coating film.

Next, as shown in FIG. 1C, the dry film 22 is irradiated with light through a mask 30 having a mask portion 31 having a shape corresponding to an opening portion surrounded by a partition wall, and exposed. The film after the dry film 22 is exposed is referred to as an exposure film 23. In the exposure film 23, the exposed portion 23A is light-hardened, and the non-exposed portion 23B is in the same state as the dry film 22.

The irradiated light may be: visible light; ultraviolet light; far ultraviolet light; KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, Kr ₂ excimer laser light, KrAr excimer laser light, and Ar ₂ excimer Excimer laser light, such as laser light; X-rays; electron rays, etc.

The light to be irradiated is preferably a light having a wavelength of 100 to 600 nm, more preferably a light of 300 to 500 nm, and particularly a light including an i-ray (365 nm), an h-ray (405 nm) or a g-ray (436 nm). In addition, light below 330 nm can be cut if necessary.

Exposure methods can include full exposure and scan exposure. You can also expose the same spot several times. At this time, the exposure conditions for multiple times may be the same or different.

Whether the exposure amount is under any of the above exposure methods, for example, it is preferably 5 to 1,000 mJ / cm ² , more preferably 5 to 500 mJ / cm ² , and more preferably 5 to 300 mJ / cm ² , and 5 to 200 mJ / cm ^{2 is} particularly preferred, 5 to 50 mJ / cm ^{2 is the} best. In addition, the exposure amount can be appropriately optimized depending on the wavelength of the light to be irradiated, the composition of the negative photosensitive resin composition, and the thickness of the coating film.

The average exposure time per unit area is not particularly limited, and can be designed by the exposure power and necessary exposure amount of the exposure device used. In the case of scanning exposure, the exposure time can be obtained from the scanning speed of light. The average exposure time per unit area is usually about 1 to 60 seconds.

Next, as shown in FIG. 1D, development is performed using an alkaline developer to form a partition wall 4 composed of only a portion corresponding to the exposure portion 23A of the exposure film 23. The opening portion 5 surrounded by the partition wall 4 is a part of the exposure film 23 where the non-exposed portion 23B was once present. The state after the non-exposed portion 23B is removed by development is shown in FIG. In the negative photosensitive resin composition, any of the alkali-soluble resin (A), the cross-linking agent (B), and the ink repellent (C) has an acidic group, so that the non-exposed portion 23B can be made alkaline. The developer is easily dissolved and removed, and the composition hardly remains in the opening 5. On the other hand, since the partition wall 4 of the cured product of the negative photosensitive resin composition has excellent development adhesion, it can be sufficiently adhered to the substrate 1 after development.

In addition, the uppermost layer including the upper surface of the partition wall 4 shown in FIG. 1D is an ink repellent layer 4A. When the ink-repellent agent (C) does not have a side chain having an ethylenic double bond, the ink-repellent agent (C) is directly present in the upper layer at a high concentration and becomes an ink-repellent layer during exposure. At the time of exposure, the alkali-soluble resin (A) existing around the ink repellent (C), the thiol compound (G) which can be optionally contained, and other photo-hardening components will strongly photo-harden and cause The ink repellent (C) is fixed on the ink repellent layer.

When the ink-repellent agent (C) has a side chain having an ethylene-based double bond, the ink-repellent agent (C) may mutually and / or with the alkali-soluble resin (A), the thiol compound (G) and The other light-hardening components are light-hardened together to form an ink-repellent layer 4A to which the ink-repellent agent (C) is strongly bonded.

In either case, the main alkali-soluble resin (A), the thiol compound (G) optionally contained, and other light-hardening components will be light-hardened under the ink repellent layer 4A, forming almost no Layer 4B of the ink repellent (C).

In the past, when the ink repellent had an acidic base, the ink repellent layer formed on the uppermost layer of the partition wall was easily removed during development, which was a problem. In the present invention, by using the ink repellent (C) whose acid value has been set within a predetermined range, the non-exposed portion is easily dissolved and removed with an alkaline developer during development, and at the same time, it is formed on the uppermost layer of the partition wall 4 The ink-repellent layer 4A can be left hardly affected by the alkaline developer. In addition, since the ink repellent (C) can be sufficiently fixed to the partition wall including the ink repellent layer 4A and the lower layer 4B, it hardly migrates to the opening portion during development.

After development, the partition wall 4 can be further heated. The heating temperature is preferably 130 ~ 250 ° C. By heating, the hardening of the partition wall 4 becomes stronger. In addition, the ink repellent (C) can be more firmly fixed in the ink repellent layer 4A.

The thus obtained resin hardened film and the partition wall 4 have good ink repellency even when exposed at a low exposure amount. In addition, the partition wall 4 has almost no ink repellent (C) in the opening portion 5 after development, and it is possible to sufficiently ensure the uniform coatability of the printing ink in the opening portion 5.

In addition, in order to more surely obtain the ink affinity of the opening 5, after the heating, in order to remove the development residue and the like of the negative photosensitive resin composition that may exist in the opening 5, a partition wall may be attached. The substrate 1 of 4 is subjected to ultraviolet / ozone treatment.

The width of the partition wall formed of the negative photosensitive resin composition of the present invention is, for example, preferably 100 μm or less, and particularly preferably 20 μm or less. In addition, the distance (pattern width) between adjacent partition walls is preferably 300 μm or less, and more preferably 100 μm or less. The height of the next wall should be 0.05 ~ 50μm, especially 0.2 ~ 10μm.

The partition wall formed of the negative photosensitive resin composition of the present invention has less unevenness in the edge portion when forming the width, and has excellent linearity. In addition, in terms of the high linearity of the partition wall, it is particularly remarkable when a resin (A-2) having an acidic group and an ethylenic double bond introduced into the epoxy resin is used as the alkali-soluble resin. With this, it is possible to form a high-precision pattern even with a fine pattern. The formation of such a high-precision pattern is particularly useful when used as a partition for an organic EL element.

The partition wall of the present invention can be used as a partition wall in which an opening is set as a printing ink injection area when pattern printing is performed by the IJ method. When pattern printing is performed by the IJ method, if the partition wall of the present invention is formed so that its opening is consistent with the desired ink injection area and then used, the upper surface of the partition wall has good ink repellency, which can prevent the printing ink from exceeding the partition wall. The undesired opening is the ink injection area. In addition, the openings surrounded by the partition wall have good wet-diffusion properties of the printing ink, so that the printing ink can be printed uniformly, and whitening does not occur in the desired area.

By using the partition wall of the present invention, pattern printing can be performed delicately by the IJ method as described above. Therefore, the partition wall of the present invention is very useful as a partition wall of an optical element (especially an organic EL element and a quantum dot display, a TFT array, or a thin-film solar cell). The optical element has a majority on the surface of the substrate on which dots are formed by the IJ method. The point is next door between adjacent points.

[Optical Element] An organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell, which is an optical element of the present invention, has a plurality of dots on the surface of the substrate and the adjacent organic EL element and quantum of the present invention located between adjacent dots. Dot display, TFT array or thin film solar cell. In the optical element (organic EL element, quantum dot display, TFT array, or thin-film solar cell) of the present invention, the dots are preferably formed by the IJ method.

The organic EL element has a structure in which an anode and a cathode are used to hold a thin film light-emitting layer. The partition wall of the present invention can be used to partition an organic light-emitting layer, to partition an organic TFT layer, and to partition a coated oxide semiconductor.

In addition, the organic TFT array element is an element described as follows: a plurality of dots are arranged in a matrix in a plan view, each dot is provided with a pixel electrode and a TFT for driving a switching element thereof, and an organic semiconductor layer is used as a channel of the TFT. Layer of semiconductor layer. For example, the organic TFT array element is provided as a TFT array substrate on an organic EL element, a liquid crystal element, or the like.

The following will describe an example in which an optical element such as an organic EL element according to an embodiment of the present invention is formed by using the partition wall obtained above and forming a dot by an IJ method on an opening. In addition, the dot formation method in the optical element such as the organic EL element of the present invention is not limited to the following.

2A and 2B schematically show a method for manufacturing an organic EL element using the partition wall 4 formed on the substrate 1 shown in FIG. 1D described above. Here, the partition wall 4 on the substrate 1 has been formed so that the opening portion 5 is consistent with the dot pattern of the organic EL element to be manufactured.

As shown in FIG. 2A, the printing ink 10 is dropped from the inkjet head 9 to the opening portion 5 surrounded by the partition wall 4, and a predetermined amount of the printing ink 10 is injected into the opening portion 5. As far as printing ink is concerned, the conventional printing ink used for organic EL elements can be selected and used in accordance with the function of dots.

Next, depending on the type of printing ink 10 used, for example, drying and / or heating are performed in order to remove the solvent or harden, as shown in FIG. 2B, the desired point 11 is formed in a form adjacent to the partition wall 4. Organic EL element 12.

The optical element (organic EL element, quantum dot array, TFT array, or thin-film solar cell) according to the embodiment of the present invention can use the partition wall of the present invention to uniformly wet and spread the ink in the opening without unevenness during the manufacturing process. This makes it an optical element (organic EL element, quantum dot display, TFT array, or thin-film solar cell) with dots formed with high accuracy.

In addition, for example, the organic EL element can be manufactured as described below, but is not limited thereto. A light-transmitting electrode such as tin-doped indium oxide (ITO) is formed on a light-transmitting substrate such as glass by a sputtering method or the like. This translucent electrode can be patterned as needed.

Next, using the negative-type photosensitive resin composition of the present invention, the partition wall is formed into a grid pattern in plan view along the outline of each point by a photolithography method including coating, exposure, and development. Next, the materials for the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking layer, and the electron injection layer are respectively coated and dried in the openings for dot formation by the IJ method, and these layers are sequentially laminated. The type and number of organic layers formed in the dot-forming openings can be appropriately designed. Finally, a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by a vapor deposition method or the like.

In addition, for example, the quantum dot display may be manufactured as described below, but is not limited thereto.

A light-transmitting electrode such as ITO is formed on a light-transmitting substrate such as glass by a sputtering method. This translucent electrode is patterned as needed. Next, using the negative-type photosensitive resin composition of the present invention, the partition wall is formed into a grid pattern in plan view along a contour of each point by a photolithography method including coating, exposure, and development. Next, the materials for the hole injection layer, the hole transport layer, the quantum dot layer, the hole blocking layer, and the electron injection layer were respectively coated and dried in the opening for dot formation by the IJ method, and these layers were sequentially laminated. The type and number of organic layers formed in the dot-forming openings can be appropriately designed. Finally, a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by a vapor deposition method or the like.

In addition, the optical element according to the embodiment of the present invention can be manufactured, for example, by the following method, and can also be applied to a blue light conversion type quantum dot display.

The negative photosensitive resin composition of the present invention is used on a light-transmitting substrate such as glass, and the partition wall is formed into a grid pattern in plan view along the outline of each point. Next, a nano particle solution capable of converting blue light to green light, a nano particle solution capable of converting blue light to red light, and a blue printing ink, as required, are applied to the opening for dot formation by the IJ method and dried. To make modules. By using a light source with a blue color as a backlight and using the aforementioned module instead of a color filter, a liquid crystal display with excellent color reproducibility can be obtained.

For example, the TFT array can be manufactured as described below, but is not limited thereto. A gate electrode such as aluminum or an alloy thereof is formed on a light-transmitting substrate such as glass by a sputtering method or the like. The gate can be patterned as required.

Next, a gate insulating film such as silicon nitride is formed by a plasma CVD method. Source and drain electrodes can also be formed on the gate insulating film. For example, the source and drain electrodes can be made by vacuum evaporation and sputtering to form metal films such as aluminum, gold, silver, copper, and alloys thereof. The method of patterning the source and drain electrodes is as follows: After forming a metal film, apply a photoresist, and expose and develop the photoresist so that the photoresist remains on the part where the electrode is to be formed. Then, the exposed metal is removed with phosphoric acid and aqua regia, etc. , And finally remove the photoresist.

In addition, when a metal film such as gold has been formed, the following methods are also available: coating the photoresist in advance and exposing and developing it so that the photoresist remains on the part where the electrode is not intended to be formed. The film is removed together. In addition, metal nano colloids such as silver or copper can also be used to form the source and drain electrodes by inkjet or other methods. Next, using the negative-type photosensitive resin composition of the present invention, the partition wall is formed into a grid pattern in plan view along a contour of each point by a photolithography method including coating, exposure, and development.

Next, a semiconductor solution was applied to the opening for dot formation by the IJ method, and the solution was dried to form a semiconductor layer. The semiconductor solution may be an organic semiconductor solution or an inorganic coated oxide semiconductor solution. The source electrode and the drain electrode can be formed by a method such as inkjet after the formation of the semiconductor layer. Finally, a light-transmitting electrode such as ITO is formed by a sputtering method or the like, and then a protective film such as silicon nitride is formed. Examples

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Examples 1 to 9 are examples, and examples 10 to 16 are comparative examples.

Each measurement was performed by the following method. [Number average molecular weight (Mn) and mass average molecular weight (Mw)] A variety of monodisperse polystyrene polymers having different degrees of polymerization on the market were used as standard samples for measuring molecular weight, and a commercially available GPC measuring device (TOSOH) was used. (Manufactured by CORPORATION, device name: HLC-8320GPC) was subjected to gel permeation chromatography (GPC) measurement. A calibration curve was made based on the relationship between the molecular weight of polystyrene and the retention time.

For each sample, it was diluted to 1.0% by mass with tetrahydrofuran and passed through a filter of 0.5 μm, and then the GPC was measured using the apparatus described above. Using the calibration curve described above, the GPC spectrum was analyzed by a computer, and the number average molecular weight (Mn) and mass average molecular weight (Mw) of the sample were obtained.

[PGMEA contact angle] Each PGMEA droplet was measured by placing the PGMEA droplets on three measurement surfaces on the substrate by using the lye drop method and in accordance with JIS R3257 "Test method for wettability of the substrate glass surface". The droplet was set to 2 μL / drop, and the measurement was performed at 20 ° C. The contact angle was calculated from the average value (n = 3) of the three measured values. In addition, PGMEA is an abbreviation of propylene glycol monomethyl ether acetate.

The abbreviations of the compounds used in each example are as follows. (Alkali-soluble resin (A)) A-1: Resin solution, which is made by reacting cresol novolac epoxy resin with acrylic acid, 1,2,3,6-tetrahydrophthalic anhydride, and then introducing the acrylic fluorenyl group A resin obtained with a carboxyl group was purified by hexane (solid content: 70% by mass, acid value: 60mgKOH / g, mass average molecular weight: 9.2 × 10 ³ ). A-2: Polyurethane compound solution described in Example 1 of Japanese Patent Application Laid-Open No. 2003-268067 (paragraph number 0045) is RE-310S (manufactured by Nippon Kayaku Co., Ltd., bifunctional bisphenol-A type) Epoxy resin, epoxy equivalent weight: 184.0g / equivalent) The reaction with acrylic acid, dimethylolpropionic acid, trimethylhexamethylene diisocyanate, and finally reaction with epoxypropyl methacrylate (solid Ingredient 65% by mass, acid value 79.32mgKOH / g).

(Polyfunctional low molecular weight compound (B1)) B1-1: 2,2,2-tripropenyloxymethyl ethyl phthalic acid (acid value: 87 mgKOH / g, molecular weight: 446). B1-2: succinic acid ester of dinepentaerythritol pentaacrylate (acid value: 92 mgKOH / g, molecular weight: 612). (Non-acidic cross-linking agent (B2)) B2-1: a mixture of dipentaerythritol hexaacrylate and dinepentaerythritol pentaacrylate.

(Raw material for ink repellent (C1)) C6FMA: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ F MAA: methacrylic acid 2-HEMA: 2-hydroxyethyl methacrylate V- 65: (2,2'-azobis (2,4-dimethylvaleronitrile)) n-DM: n-dodecyl mercaptan BEI: 1,1- (bispropenyloxymethyl) ethyl Isocyanate DBTDL: dibutyltin dilaurate TBQ: tertiary butyl p-benzoquinone MEK: 2-butanone

(Raw material for ink repellent (C2)) Compound (cx-1) equivalent to compound (s1): F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (manufactured by a conventional method).

Compound (cx-21) equivalent to compound (s2), raw material of compound (cx-22) AC: acrylic MMA: methyl methacrylate AIBN: azobisisobutyronitrile V-65: (2,2'- Azobis (2,4-dimethylvaleronitrile)) 3-mercaptopropyltrimethoxysilane PGME: propylene glycol monomethyl ether

Compound (cx-3) equivalent to compound (s3): Si (OC ₂ H ₅ ) ₄ . Compound (cx-4) equivalent to compound (s4): CH ₂ = CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ . Compound (cx-51) equivalent to compound (s5): SH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ . Compound (cx-52) equivalent to compound (s5): [(1,2,3,4-tetrathiobutane-1,4-diyl) bis (trimethylene)] bis (triethoxy Silane) Compound (cx-6) equivalent to compound (s6): (CH ₃ ) ₃ SiOCH ₃ .

(Photopolymerization initiator (D)) D-1: 2-methyl-1- [4- (methylthio) phenyl] -2- Phenylpropan-1-one. D-2: 4,4'-bis (diethylamino) diphenyl ketone.

(Solvent (E)) E-1: PGME: propylene glycol monomethyl ether. E-2: PGMEA: propylene glycol monomethyl ether acetate. E-3: EDGAC: ethyl diethylene glycol acetate. E-4: DMIB: N, N-dimethylisobutylamidamine.

[Synthesis of Ink Repellent (C)] The ink repellent (C1-1), ink repellents (C2-1) to (C2-3), and ink repellent for comparative examples ( Cf-1) ~ (Cf-3).

(Synthesis Example 1: Synthesis of Ink Removal Agent (C1-1)) 411,000 g of MEK, 81.0 g of C6FMA, 18.0 g of MAA, and 81.0 g were fed into an autoclave equipped with a stirrer with an internal volume of 1,000 cm ³ . 2-HEMA, 5.0 g of polymerization initiator V-65 and 4.7 g of n-DM, while stirring in a nitrogen environment, polymerized at 50 ° C for 24 hours, and heated at 70 ° C for 5 hours to polymerize The initiator is deactivated to obtain a copolymer solution. The number average molecular weight of the copolymer was 5,540, and the mass average molecular weight was 13,200.

Next, an autoclave with an internal volume of 300 cm ³ equipped with a stirrer was fed with 130.0 g of the above-mentioned copolymer solution, 33.5 g of BEI, 0.13 g of DBTDL, and 1.5 g of TBQ, and stirred at 40 ° C while stirring. After reacting for 24 hours, a crude polymer was synthesized. Hexane was added to the obtained crude polymer solution for reprecipitation and purification, and then dried under vacuum to obtain 65.6 g of an ink repellent (C1-1). Thereafter, it was diluted with PGMEA to prepare a PGMEA solution of the ink repellent (C1-1) (concentration of the ink repellent (C1-1): 10% by mass, hereinafter also referred to as the "ink repellent (C1-1) solution") .

The number average molecular weight (Mn) of the ink repellent (C1-1) is 7,540, the mass average molecular weight (Mw) is 16,200, the fluorine atom content rate is 14.1 (mass%), the C = C content is 3.79 (mmol / g), and The acid value was 35.7 (mgKOH / g).

(Synthesis Example 2: Synthesis of Hydrolyzable Silane Compound (cx-21)) A 50 cm ³ three-neck flask equipped with a stirrer and a thermometer was charged with 0.40 g of 3-mercaptopropyltrimethoxysilane and 2.06 g of MMA. , 1.48 g of AC, 0.05 g of V-65, and 35.59 g of PGME, and stirred at 60 ° C. for 12 hours. It was confirmed by gas chromatography that the peaks of 3-mercaptopropyltrimethoxysilane, MMA, and AC of the raw materials disappeared, and a PGME solution (concentration: 10% by mass) of a hydrolyzable silane compound (cx-21) was prepared.

(Synthesis Example 3: Preparation of Ink Removal Agent (C2-1)) A 50 cm ³ three-necked flask equipped with a stirrer was charged with 0.35 g of compound (cx-1) and 1.03 g of a PGME solution of compound (cx-21). 0.55 g of compound (cx-3) and 0.63 g of compound (cx-4) to obtain a hydrolyzable silane compound mixture. Then, 6.67 g of PGME was added to the mixture to prepare a raw material solution.

The obtained raw material solution was titrated with 0.76 g of a 1% aqueous hydrochloric acid solution. After the titration was completed, the mixture was stirred at 40 ° C. for 5 hours to obtain a PGME solution of the ink repellent (C2-1) (concentration of the ink repellent (C2-1): 10% by mass, hereinafter also referred to as “ink repellent (C2- 1) Solution ").

After the reaction was completed, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (C2-1) was 1,105, the mass average molecular weight (Mw) was 2,082, the fluorine atom content rate was 18.2 (mass%), and the C = C content was 2.69 (mmol / g) The acid value was 32.8 (mgKOH / g).

(Synthesis Example 4: Preparation of Ink Repellent (C2-2) Liquid) A 50 cm ³ three-necked flask equipped with a stirrer was charged with 0.38 g of compound (cx-1) and a PGME solution of compound (cx-21) 1.09. g, compound (cx-3) 0.59 g, compound (cx-4) 0.44 g, compound (cx-6) 0.05 g, and compound (cx-51) 0.22 g to obtain a hydrolyzable silane compound mixture. Then, 6.37 g of PGME was added to the mixture to prepare a raw material solution.

The obtained raw material solution was titrated with 0.85 g of a 1% aqueous hydrochloric acid solution. After the titration was completed, the mixture was stirred at 40 ° C. for 5 hours to obtain a PGME solution of the ink repellent (C2-2) (the concentration of the ink repellent (C2-2): 10% by mass, hereinafter also referred to as “ink repellent (C2- 2) Solution ").

After the reaction was completed, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (C2-2) was 945, the mass average molecular weight (Mw) was 1,944, the fluorine atom content rate was 18.2 (mass%), and the C = C content was 1.73 (mmol / g) And the acid value was 31.6 (mgKOH / g).

(Synthesis Example 5: Synthesis of Hydrolyzable Silane Compound (cx-22)) A 50 cm ³ three-necked flask equipped with a stirrer and a thermometer was charged with 0.40 g of 3-mercaptopropyltrimethoxysilane and 1.00 g of MMA. , 2.20 g of AC, 0.03 g of AIBN, and 31.50 g of PGME, and stirred at 60 ° C. for 12 hours. It was confirmed by gas chromatography that the peaks of 3-mercaptopropyltrimethoxysilane, MMA, and AC of the raw materials disappeared, and a PGME solution (concentration: 10% by mass) of a hydrolyzable silane compound (cx-22) was prepared.

(Synthesis Example 6: Preparation of Ink Repellent (C2-3) Liquid) A 50 cm ³ three-necked flask equipped with a stirrer was charged with 0.38 g of compound (cx-1) and 0.90 of a PGME solution of compound (cx-22). g, compound (cx-3) 0.28 g, compound (cx-4) 0.21 g, compound (cx-6) 0.06 g, and compound (cx-52) 0.33 g to obtain a hydrolyzable silane compound mixture. Then, 6.88 g of PGME was added to the mixture to prepare a raw material solution.

0.47 g of a 1% hydrochloric acid aqueous solution was titrated to the obtained raw material solution. After the titration was completed, stirring was performed at 40 ° C for 5 hours to obtain a PGME solution of the ink repellent (C2-3) (concentration of the ink repellent (C2-3): 10% by mass, hereinafter also referred to as "ink repellent (C2- 3) Solution ").

After the reaction was completed, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (C2-3) was 1,330, the mass average molecular weight (Mw) was 2,980, the fluorine atom content rate was 23.1 (mass%), and the C = C content was 1.05 (mmol / g) And the acid value was 50.3 (mgKOH / g).

(Synthesis Example 7: Preparation of Ink Repellent (Cf-1)) A 50 cm ³ three-necked flask equipped with a stirrer was charged with 0.22 g of compound (cx-1), 4.27 g of compound (cx-22), and ( cx-3) 0.36 g and compound (cx-4) 0.40 g to obtain a hydrolyzable silane compound mixture. Then, 4.22 g of PGME was added to the mixture to prepare a raw material solution.

0.53 g of a 1% aqueous hydrochloric acid solution was titrated on the obtained raw material solution. After the completion of the titration, the mixture was stirred at 40 ° C for 5 hours to obtain a PGME solution of the ink repellent (Cf-1) (concentration of the ink repellent (Cf-1): 10% by mass, hereinafter also referred to as "ink repellent (Cf- 1) Solution ").

After the reaction was completed, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (Cf-1) was 1,130, the mass average molecular weight (Mw) was 2,170, the fluorine atom content rate was 11.4 (mass%), and the C = C content was 1.76 (mmol / g) And the acid value was 227.1 (mgKOH / g).

(Synthesis Example 8: Preparation of Ink Repellent (Cf-2)) A 50 cm ³ three-necked flask equipped with a stirrer was charged with 0.38 g of compound (cx-1), 0.55 g of compound (cx-3), and compound ( cx-4) 0.41 g, compound (cx-6) 0.12 g, and compound (cx-51) 0.21 g to obtain a hydrolyzable silane compound mixture. Then, 7.52 g of PGME was added to the mixture to prepare a raw material solution.

The obtained raw material solution was titrated with 0.81 g of a 1% aqueous hydrochloric acid solution. After the completion of the titration, the mixture was stirred at 40 ° C. for 5 hours to obtain a PGME solution of the ink repellent (Cf-2) (concentration of the ink repellent (Cf-2): 10% by mass, hereinafter also referred to as “ink repellent (Cf- 2) Solution ").

After the reaction was completed, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (Cf-2) was 678, the mass average molecular weight (Mw) was 745, the fluorine atom content rate was 20.0 (mass%), and the C = C content was 1.76 (mmol / g) . In addition, since the ink repellent (Cf-2) has no acidic group, the acid value is 0 (mgKOH / g).

(Synthesis Example 9: Preparation of Ink Repellent (Cf-3)) A 50 cm ³ three-necked flask equipped with a stirrer was charged with 0.38 g of compound (cx-1), 0.31 g of compound (cx-3), and compound ( cx-4) 0.23 g, compound (cx-6) 0.06 g, and compound (cx-52) 0.34 g, to obtain a hydrolyzable silane compound mixture. Then, 6.43 g of PGME was added to the mixture to prepare a raw material solution.

The obtained raw material solution was titrated with 0.50 g of a 1% aqueous hydrochloric acid solution. After the completion of the titration, stirring was performed at 40 ° C for 5 hours to obtain a PGME solution of the ink repellent (Cf-3) (concentration of the ink repellent (Cf-3): 10% by mass, hereinafter also referred to as "ink repellent (Cf- 3) Solution ").

After the reaction was completed, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (Cf-3) was 1,030, the mass average molecular weight (Mw) was 1,520, the fluorine atom content rate was 24.3 (mass%), and the C = C content was 1.19 (mmol / g) . In addition, since the ink repellent (Cf-3) does not have an acidic group, the acid value is 0 (mgKOH / g).

[Example 1: Production of negative photosensitive resin composition and production of cured film (partition wall)] (Production of negative photosensitive resin composition) 0.25 g of the (C1-1) solution obtained in the above Synthesis Example 1 and 16.07 g-1 (solid content is 11.25g, the remainder is the solvent EDGAC), 6.25g B1-1, 5.00g B2-1, 1.50g D-1, 0.75g D-2, and 70.18g E -1 was put into a 200 cm ³ stirring container and stirred for 5 hours to prepare a negative photosensitive resin composition. The solid content concentration (mass%) of the negative photosensitive resin composition, the solid content composition (mass%), the solvent composition (mass%) of the negative photosensitive resin composition, and the polyfunctional low molecular weight compound ( B1) The ratio (mass%) of the polyfunctional low-molecular-weight compound (B1) in total with the non-acidic crosslinking agent (B2) is shown in Table 1.

(Production of hardened film 1) A 10 cm square ITO substrate (indium-tin-oxide film formed on a glass substrate) was ultrasonically washed with ethanol for 30 seconds, and then subjected to UV / O ₃ treatment for 5 minutes. The UV / O ₃ processing system uses PL2001N-58 (manufactured by SEN Engineering Co., Ltd.) as a UV / O ₃ generating device. The optical power (light output) in terms of 254 nm was 10 mW / cm ² . In addition, all the following UV / O ₃ processes also use this device.

The surface of the washed ITO substrate was coated with the negative photosensitive resin composition using a spinner, and then dried on a hot plate at 100 ° C for 2 minutes to form a dry film having a film thickness of 2.4 μm. Through the mask with the opening pattern (the openings (exposure parts) are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 30, 40, 50μm × 1000μm (interval between the patterns is 50 m) of the repeated pattern in the range of 20mm × 20mm person), a full illumination of the resulting dried film of 365nm in terms of exposure power (exposure output) of 25mW / cm ² ultra high pressure mercury lamp 4 UV light. Cut light below 330nm during exposure. In addition, the distance between the dry film and the photomask was set to 50 μm. In each example, the exposure conditions were set to an exposure time of 6 seconds and an exposure amount of 150 mJ / cm ² .

Next, the ITO substrate after the exposure treatment was immersed in a 0.4 mass% tetramethylammonium hydroxide aqueous solution for 40 seconds to develop, and the non-exposed portion was rinsed with water and dried. Next, it was heated on a hot plate at 230 ° C. for 60 minutes, thereby preparing an ITO substrate with a cured film (partition wall) 1 having a pattern corresponding to the opening pattern of the photomask.

(Production of cured film 2) In addition, a dry film of the above-mentioned negative photosensitive resin composition was formed on the surface of the ITO substrate in the same manner as described above, and a photomask (size of light-shielding portion: 100 μm × 200 μm and width of opening portion (exposed portion): A 20 μm grid pattern is repeated within a range of 20 mm × 20 mm), the dried film is exposed under the same exposure conditions as described above at an exposure of 150 mJ / cm ² , and then developed under the same conditions as the above development conditions at 230 The substrate was heated on a hot plate at 60 ° C for 60 minutes to prepare an ITO substrate with a cured film 2. The cured film was obtained in a pattern surrounded by dots (100 μm × 200 μm) with a line width of 20 μm.

[Examples 2 to 16] In the above Example 1, except that the negative photosensitive resin composition was changed to the composition shown in Table 1 or Table 2, a negative photosensitive resin composition, a resin cured film, and a partition wall were produced in the same manner. .

(Evaluation) The following evaluations were performed with respect to the negative photosensitive resin composition, resin cured film, and partition wall obtained in Examples 1 to 16. The results are shown in the lower column of Table 1 or Table 2.

<Ink Repellency of the Upper Surface of the Partition Wall> The PGMEA contact angle of the upper surface of the partition wall prepared by using the above resin cured film 1 and an exposure amount of 150 mJ / cm ² was measured by the above method.

◎: Contact angle 40 ° or more ○: Contact angle 30 ° or more and less than 40 ° ×: Contact angle less than 30 °

<IJ coatability> A ring of 1% TPD (triphenyldiamine) at 20 pl was titrated with an IJ device (LaboJET 500, manufactured by MICROJET CORPORATION) inside the point surrounded by the partition wall in the ITO substrate with resin cured film 2 described above. Hexylbenzene solution. Check the spread of the dried material inside the spot after drying. The determination is based on the following criteria.

○: The material diffuses uniformly to the edge of the partition wall within the point. X: It does not spread in a point.

<Development Adhesiveness> The photomasks (openings (exposure parts) each having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 , 12, 14, 16, 18, 20, 30, 40, 50 μm × 1000 μm,) and a partition wall made with an exposure of 150 mJ / cm ² and judged based on the following criteria

○: Lines smaller than 10 μm in width of the mask remain. Δ: Lines of 10 μm or more and less than 20 μm remain. ×: Lines of 20 μm or more and 50 μm or less remain. ××: wireless pattern.

[Table 1]

[Table 2]

As can be clearly seen from Table 1, the negative photosensitive resin composition corresponding to Examples 1 to 9 of the Example makes the liquid repellency of the upper part of the partition wall good by selecting the crosslinking agent (B) and the ink repellent (C). In the point surrounded by the partition wall, the IJ coating property is good, and a high-definition partition wall pattern can be formed. Industrial availability

In the case of an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell, the negative photosensitive resin composition of the present invention can be suitably used as a composition for forming a partition wall when a pattern is printed by the IJ method.

The partition wall of the present invention can be used in an organic EL device as a bank for printing an organic layer such as a light-emitting layer in an IJ method pattern, or can be used in a quantum dot display as: for printing a quantum dot layer in an IJ method pattern. And the bank of the hole transport layer. The partition wall of the present invention can also be used in a TFT array as a partition wall for printing a conductor pattern or a semiconductor pattern in an IJ method pattern. For example, the partition wall of the present invention can be used as a partition wall for forming an organic semiconductor layer, a gate electrode, a source electrode, a drain electrode, a gate wiring, and a source wiring of a TFT channel layer by IJ pattern printing.

1‧‧‧ substrate

21‧‧‧coating film

22‧‧‧ dry film

23‧‧‧ exposure film

23A‧‧‧Exposure Department

23B‧‧‧Unexposed

4‧‧‧ next door

4A‧‧‧Ink layer

5‧‧‧ opening

31‧‧‧Mask

30‧‧‧Mask

9‧‧‧ inkjet head

10‧‧‧Ink

11 o'clock

12‧‧‧Organic EL element

FIG. 1A is a flowchart schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention. FIG. 1B is a flowchart schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention. FIG. 1C is a flowchart schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention. FIG. 1D is a flowchart schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention. FIG. 2A is a flowchart schematically showing a method for manufacturing an optical element according to an embodiment of the present invention. FIG. 2B is a flowchart schematically showing a method for manufacturing an optical element according to an embodiment of the present invention.

Claims (7)

A negative photosensitive resin composition comprising: an alkali-soluble resin (A) having a photocurable functional group; a cross-linking agent (B) comprising a polyfunctional low-molecular-weight compound (B1), the polyfunctional low-molecular-weight compound (B1) an acidic group and two or more photocurable functional groups in one molecule; an ink repellent (C), which has an acidic group and a fluorine atom, and has an acid value of 10 to 100 mgKOH / g; a photopolymerization initiator ( D); and solvent (E). The negative photosensitive resin composition according to claim 1, wherein the polyfunctional low molecular weight compound (B1) has four or more photocurable functional groups. The negative photosensitive resin composition according to claim 1 or 2, wherein the polyfunctional low-molecular-weight compound (B1) has a dipentaerythritol skeleton. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the fluorine atom content rate in the ink repellent (C) is 5 to 55% by mass. The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the ink repellent (C) contains a photocurable functional group. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the cross-linking agent (B) further includes a cross-linking agent (B2), and the cross-linking agent (B2) has two in one molecule. The above photo-curable functional group does not have an acidic group. For example, the negative photosensitive resin composition according to claim 6, which contains the above-mentioned polyimide in a proportion of 10 to 90 parts by mass relative to 100 parts by mass of the polyfunctional low molecular weight compound (B1) and the cross-linking agent (B2) in total Functional low molecular weight compound (B1).