KR102611589B1 - Negative photosensitive resin composition - Google Patents

Abstract

Provision of a negative photosensitive resin composition in which the resulting partition has high development adhesion, the upper surface has good ink repellency, and the development residue is sufficiently small in the opening for dot formation. Alkali-soluble resin (A) having a photocurable functional group, a crosslinking agent (B) containing a polyfunctional low molecular weight compound (B1) having an acidic group and two or more photocurable functional groups in one molecule, an acidic group and a fluorine atom and an acid value of 10 A negative photosensitive resin composition containing an ink repellent agent (C), a photoinitiator (D), and a solvent (E) of -100 mgKOH/g.

Description

Negative photosensitive resin composition

The present invention relates to a negative photosensitive resin composition.

In the production of optical elements such as organic EL (Electro-Luminescence) elements, quantum dot displays, TFT (Thin Film Transistor) arrays, and thin film solar cells, organic layers such as the light-emitting layer are used as dots, In some cases, pattern printing using the inkjet (IJ) method is used. In this method, a partition is formed along the outline of the dot to be formed, an ink containing the material of the organic layer is injected into a section (hereinafter also referred to as an “opening”) surrounded by the partition, and the ink is dried and/or Dots of the desired pattern are formed by heating, etc.

When performing pattern printing by the inkjet (IJ) method, the upper surface of the partition must have ink repellency to prevent mixing of ink between adjacent dots and to uniformly apply ink in dot formation. On the other hand, the opening for dot formation surrounded by the partition including the side of the partition needs to have ink affinity. Therefore, in order to obtain a partition having ink repellent properties on the upper surface, a negative photosensitive resin composition containing an ink repellent agent is used to create a dot pattern corresponding to the dot pattern by a photolithography method having each process of film formation, exposure, and development. A method of forming a partition is known.

In the formation of a partition using such a negative photosensitive resin composition, if a residue of the composition (hereinafter also referred to as “development residue”) exists in the opening after development, it is then supplied to the opening by the IJ method. There are cases where the ink does not spread sufficiently when wet. Additionally, as a method of reducing the development residue in the opening, there is a method of adjusting the negative photosensitive resin composition to a composition that is easy to remove with a developer, but the problem is that ink repellency of the upper surface of the partition cannot be sufficiently maintained in that method. There was.

For example, in Patent Document 1, (A) component; Ethylenically unsaturated compound, (B) component; Photopolymerization initiator, (C) component; An alkali-soluble binder having an ethylenically unsaturated group in the side chain, and (D) component; Liquid repellent consisting of a fluorine-based compound having an ethylenically unsaturated group in the side chain, component (E); A photosensitive composition for a barrier rib of an actively driven organic electroluminescent device containing a fluorine-based surfactant and/or a silicone-based surfactant is described.

In Patent Document 1, there is a description to the effect that developability can be improved by introducing carboxylic acid into components other than the alkali-soluble binder, for example, component (A) or component (D), and the examples show this. An example is shown. According to the examples, when carboxylic acid was introduced into component (A), developability and ink repellency were compatible, but when a liquid repellent containing carboxylic acid (component (D)) was used, developability was good. However, sufficient ink repellency is not obtained.

In this way, in Patent Document 1, it is stated that the ink repellency of the upper surface of the partition and the ink wettability of the opening are compatible depending on the composition, but the ink repellency of the upper surface of the partition and the ink wettability of the opening are not sufficient until they can sufficiently support higher-precision optical elements. ink wettability has not been achieved.

In addition, Patent Document 2 describes a technique for improving solubility in a developing solution by introducing an acidic group into the ink repellent agent suitable for a method of removing development residues by UV/O ₃ irradiation. . However, when the ink repellent agent according to Patent Document 2 was used for the negative photosensitive resin composition, it was difficult to say that it was sufficient in terms of ink repellency and development adhesion, similarly to the case of Patent Document 1.

Japanese Patent Publication No. 2011-165396 International Publication No. 2014/046210

The present invention has been made from the above viewpoint, and provides a negative photosensitive resin composition in which the resulting partition has high development adhesion, has good ink repellency on the upper surface, and has a sufficiently small development residue in the opening for dot formation. For the purpose.

The present invention has the following configuration.

[1] Alkali-soluble resin (A) having a photocurable functional group, a crosslinking agent (B) containing a polyfunctional low molecular weight compound (B1) having an acidic group and two or more photocurable functional groups in one molecule, and having an acidic group and a fluorine atom A negative photosensitive resin composition containing an ink repellent agent (C), a photoinitiator (D), and a solvent (E) whose acid value is 10 to 100 mgKOH/g.

[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 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 content of fluorine atoms in the ink repellent agent (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 agent (C) contains a photocurable functional group.

[6] The crosslinking agent (B) is a negative type according to any one of [1] to [5], further comprising a crosslinking agent (B2) having two or more photocurable functional groups in one molecule and no acidic group. Photosensitive resin composition.

[7] The negative described in [6], which contains the polyfunctional low molecular weight compound (B1) in a ratio of 10 to 90 parts by mass based on a total of 100 parts by mass of the polyfunctional low molecular weight compound (B1) and the crosslinking agent (B2). Type photosensitive resin composition.

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

1A is a process diagram schematically showing a method of manufacturing a partition according to an embodiment of the present invention.
1B is a process diagram schematically showing a method of manufacturing a partition according to an embodiment of the present invention.
1C is a process diagram schematically showing a method of manufacturing a partition according to an embodiment of the present invention.
1D is a process diagram schematically showing a method of manufacturing a partition according to an embodiment of the present invention.
Fig. 2A is a process diagram schematically showing a method of manufacturing an optical element according to an embodiment of the present invention.
Fig. 2B is a process diagram schematically showing a method of manufacturing an optical element according to an embodiment of the present invention.

In this specification, the following terms are used with the following meanings, respectively.

“(meth)acryloyl group” is a general term for “methacryloyl group” and “acryloyl group”. (meth)acryloyloxy group, (meth)acrylic acid, and (meth)acrylate also apply to this.

The group represented by the formula (x) may be simply described as group (x).

The compound represented by formula (y) may be simply described as compound (y).

Here, formula (x) and formula (y) represent arbitrary formulas.

“Resin mainly composed of a certain component” or “resin mainly composed of a certain component” means that the proportion of the component occupies 50% by mass or more with respect to the total amount of the resin.

“Side chain” refers to a group other than a hydrogen atom or halogen atom that is bonded to a carbon atom constituting the main chain in a polymer in which a repeating unit made of carbon atoms constitutes the main chain.

“Total solid content of the photosensitive resin composition” refers to the component that forms the cured film described later among the components contained in the photosensitive resin composition, and is obtained from the residue obtained by heating the photosensitive resin composition at 140°C for 24 hours and removing the solvent. Additionally, the total solid content can also be calculated from the injection amount.

A film made of a cured product of a composition containing resin as a main ingredient is called a “resin cured film.”

The film on which the photosensitive resin composition is applied is called a “coated film,” and the film on which the photosensitive resin composition is dried is called a “dried film.” The film obtained by curing the “dried film” is a “resin cured film.” Additionally, “resin cured film” is sometimes simply referred to as “cured film.”

The resin cured film may be in the form of a partition formed to divide a predetermined area into a plurality of partitions. For example, the following “ink” is injected into a section divided by a partition, that is, an opening surrounded by the partition, and a “dot” is formed.

“Ink” is a general term for liquids that have optical and/or electrical functions after drying, curing, etc. In organic EL devices, quantum dot displays, TFT arrays, and thin film solar cells, dots as various components are sometimes pattern-printed by the inkjet (IJ) method using ink for forming the dots. “Ink” includes ink used for these purposes.

“Ink repellency” refers to the property of repelling the ink, and has both water repellency and oil repellency. Ink repellency can be evaluated, for example, by the contact angle when ink is dropped. “Ink affinity” is a property that is opposite to ink repellency, and can be evaluated by the contact angle when ink is dropped in the same way as ink repellency. Alternatively, ink-philicity can be evaluated by evaluating the degree of wetting and spreading of the ink when the ink is dropped (wetting and spreading property of the ink) based on a predetermined standard.

“Dot” represents the minimum area in an optical element capable of light modulation. In organic EL devices, quantum dot displays, TFT arrays, and thin film solar cells, 1 dot = 1 pixel in the case of black-and-white display, and 3 dots (R (red), G (green), for example) in the case of color display. B (blue, etc.) = 1 pixel.

“Percent (%)” represents mass% unless otherwise specified.

Hereinafter, embodiments of the present invention will be described.

[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 crosslinker (B) containing a polyfunctional low molecular weight compound (B1) having an acidic group and two or more photocurable functional groups in one molecule. , an ink repellent agent (C) that has an acidic group and a fluorine atom and an acid value of 10 to 100 mgKOH/g, a photopolymerization initiator (D), and a 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 an ink repellent agent (C) having the above-mentioned predetermined acid value, thereby improving development adhesion. This height and the upper surface have good ink repellency, and a partition wall with sufficiently small development residue can be formed in the opening. When such a barrier rib is used in an optical element, for example, for an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell, dots can be formed with good precision due to good ink applicability by the IJ method, etc. and high-sensitivity optical elements can be manufactured.

In addition to the above essential components, the negative photosensitive resin composition of the present invention contains a crosslinking agent (B2) that does not have an acidic group and other optional components as needed. Below, each component is explained.

(Alkali soluble resin (A))

Alkali-soluble resin (A) is an alkali-soluble resin having a photocurable functional group. As the alkali-soluble resin (A), a photosensitive resin having an acidic group and an ethylenic double bond in one molecule is preferable. 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 by radicals generated from the photopolymerization initiator (D) and crosslinked by the crosslinking agent (B), It cures to form a cured film.

The exposed portion that has been sufficiently cured in this way cannot be easily removed with an alkaline developer (hereinafter also simply referred to as “developer”). In addition, the polyfunctional low molecular weight compound (B1) contained in the alkali-soluble resin (A) and the crosslinking agent (B) has an acidic group in the molecule, so that the unexposed portion of the uncured negative photosensitive resin composition is selectively treated with a developer. It can be removed. As a result, the cured film can be formed into a partition wall that divides a predetermined area into a plurality of partitions.

Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group, and these may be used individually or in combination of two or more types.

The photocurable functional group is preferably an ethylenic double bond. Examples of the ethylenic double bond include double bonds having addition polymerizability, such as (meth)acryloyl group, allyl group, vinyl group, vinyloxy group, and vinyloxyalkyl group. These may be used individually as one type or two or more types may be used in combination. Additionally, some or all of the hydrogen atoms of the ethylenic double bond may be substituted with an alkyl group such as a methyl group.

Examples of the alkali-soluble resin (A) having an ethylenic double bond include resin (A-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy resin into which an acidic group and an ethylenic double bond are introduced. Resin (A-2) etc. are mentioned. These may be used individually as one type or two or more types may be used in combination. As such an alkali-soluble resin (A), those described in specification WO2014/084279 can be used.

With the alkali-soluble resin (A), peeling of the cured film during development is suppressed, a high-resolution dot pattern can be obtained, the linearity of the pattern when the dots are straight is good, and the cured film surface is smooth. Because it is easy to obtain, it is preferable to use resin (A-2). In addition, good straightness of the pattern means that the edges of the obtained partitions are straight without any missing edges.

Examples of the resin (A-1) include those obtained by reacting 2-acryloyloxyethyl isocyanate with a copolymer of acrylic acid, 2-hydroxymethacrylate, and other monomers.

In addition, the unsaturated group-containing urethane resin as component (A) of Japanese Patent Application Publication No. 2001-33960, the polyurethane compound as component (E) of Japanese Patent Application Publication No. 2003-268067, and the (A) component of Japanese Patent Application Publication No. 2010-280812. and urethane-based resins such as phosphorus-reactive polyurethane compounds.

Specifically, a compound having a double bond and a hydroxyl group obtained by reacting a bifunctional epoxy resin with acrylic acid, a diol compound having a carboxyl group such as dimethylolpropionic acid, and a diisocyanate compound such as trimethylhexamethylene diisocyanate, and glycyrrhizate as an optional component. Resins obtained by reacting polybasic acid anhydrides such as dil methacrylate and phthalic anhydride can be mentioned.

Examples of the bifunctional epoxy resin include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, cresol novolac-type epoxy resin, trisphenolmethane-type epoxy resin, epoxy resin with a naphthalene skeleton, and An epoxy resin having a phenyl skeleton and a fluorenyl-substituted bisphenol A type epoxy resin are included.

In particular, the use of a urethane-based resin is preferable because flexibility can be provided, alkali resistance is improved, and dispersion stability to a developing solution is also improved.

Resin (A-2) includes bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, cresol novolak-type epoxy resin, trisphenolmethane-type epoxy resin, epoxy resin with a naphthalene skeleton, and biphenyl. Resins having an acidic group and an ethylenic double bond introduced into an epoxy resin having a skeleton, a fluorenyl-substituted bisphenol A type epoxy resin, and an epoxy resin described in Japanese Patent Application Publication No. 2006-84985, respectively, are preferred.

The bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, epoxy resin having a biphenyl skeleton, fluorenyl-substituted bisphenol A-type epoxy resin, and the epoxy resin described in Japanese Patent Application Publication No. 2006-84985 have an acidic group and an ethylenic double bond, respectively. A resin incorporating is more preferable.

Among them, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, epoxy resin having a biphenyl skeleton, and fluorenyl-substituted bisphenol A-type epoxy resin are particularly preferable. With these resins, interaction with the photopolymerization initiator (D) improves, and adhesion to the substrate improves.

The number of ethylenic double bonds that the alkali-soluble resin (A) has in one molecule is preferably 3 or more on average, and particularly preferably 6 or more on average. If the number of ethylenic double bonds is more than the lower limit of the above range, a difference is likely to occur in the alkali solubility of the exposed portion and the unexposed portion, and fine pattern formation is possible with a smaller exposure amount.

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

In this specification, unless otherwise specified, the number average molecular weight (Mn) and mass average molecular weight (Mw) refer to those measured by gel permeation chromatography using polystyrene as a standard material.

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 negative photosensitive composition becomes good.

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

The content rate of alkali-soluble resin (A) in the total solid in the negative photosensitive resin composition is preferably 5 to 80 mass%, and particularly preferably 10 to 60 mass%. When the content ratio is within the above range, the photocurability and developability of the negative photosensitive resin composition are good.

(Cross-linking 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 preferably further has two or more photocurable functional groups in one molecule, It contains a cross-linking agent (B2) that does not have an acidic group (hereinafter also referred to as “non-acidic cross-linking 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) by the action of the photopolymerization initiator (D). The negative photosensitive resin composition of the present invention containing these is crosslinked with a crosslinking agent (B) when the alkali-soluble resin (A) polymerizes through exposure, thereby forming a sufficiently cured cured film.

＜Multifunctional 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 term “low molecular weight compound” in the present invention means a concept relative to a so-called high molecular substance (resin). In this specification, “low molecular weight compound” is used as a concept including “monomer,” “dimer,” “trimer,” and “oligomer.” In addition, in this specification, “low molecular weight compound” refers to a compound whose mass average molecular weight (Mw) is less than 1000.

The mass average molecular weight (Mw) of the polyfunctional low molecular weight compound (B1) is preferably 300 or more and less than 1000, and more preferably 500 or more and less than 800. Moreover, the number average molecular weight (Mn) is preferably 300 or more and less than 1000, and particularly preferably 500 or more and less than 800. If 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), and specifically, an ethylenic double bond is preferable. The number of photocurable functional groups per molecule in the polyfunctional low molecular weight compound (B1) may be 2 or more, preferably 3 or more, more preferably 4 or more, and particularly preferably 5 or more. As the number of photocurable functional groups increases, the curability of the surface of the coating film improves, and the stability of ink repellency in the upper surface of the obtained partition becomes better.

Examples of the acidic group that the polyfunctional low molecular weight compound (B1) has include a carboxyl group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group, and these may be used individually or in combination of two or more types. The number of acidic groups in one molecule of the polyfunctional low molecular weight compound (B1) may be one or more, preferably 1 to 2, and more preferably 1.

Examples of the polyfunctional low molecular weight compound (B1) include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, esters of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, and polyisocyanate compounds and (meth)acryloyl. Examples include compounds in which an acidic group is introduced into an ethylenic compound having a urethane skeleton obtained by reacting a containing hydroxy compound, leaving at least two unsaturated bonds (ethylenic double bonds).

The polyfunctional low molecular weight compound (B1) is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and aromatic carboxylic acid anhydride or non-aromatic carboxylic acid anhydride is added to the unreacted hydroxy group of the aliphatic polyhydroxy compound. Polyfunctional low molecular weight compounds obtained by reacting with an acidic group are preferable, and polyfunctional low molecular weight compounds obtained by reacting a non-aromatic carboxylic acid anhydride with an acidic group are more preferable.

Examples of the aliphatic polyhydroxy compound in the ester of an unsaturated carboxylic acid and an aliphatic polyhydroxy compound introducing an acidic group include compounds having three or more hydroxy groups, such as trimethylolpropane, trimethylolethane, and pentaerythine. Litol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, etc. can be mentioned. Examples of unsaturated carboxylic acids include (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, etc.

In the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, the aliphatic polyhydroxy compound is preferably pentaerythritol and/or dipentaerythritol, and dipentaerythritol is particularly preferable. As the unsaturated carboxylic acid, (meth)acrylic acid is preferable and acrylic acid is more preferable.

Specific examples of the aromatic carboxylic acid anhydride used to introduce an acidic group into the ester include phthalic anhydride, and specific examples of the non-aromatic carboxylic acid anhydride include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, Examples include hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, and among these, succinic anhydride is preferable.

In the polyfunctional low molecular weight compound (B1), a compound obtained by reacting an aromatic carboxylic acid anhydride with an aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid, for example, three hydroxy groups of pentaerythritol are acryl Examples include 2,2,2-triacryloyloxymethylethylphthalic acid, which is substituted with a loyloxy group and the remaining hydroxy group is formed by an ester bond with phthalic acid.

As the polyfunctional low molecular weight compound (B1), a compound having a dipentaerythritol skeleton is preferable. Compounds having a dipentaerythritol skeleton include, for example, five hydroxy groups of dipentaerythritol being replaced with (meth)acryloyloxy groups, and the remaining one hydroxy group forming an ester bond with, for example, succinic acid. , compounds into which an acidic group is introduced are preferred.

The acid value of the polyfunctional low molecular weight compound (B1) is preferably 10 to 100 mgKOH/g, and more preferably 20 to 95 mgKOH/g. If the acid value of the polyfunctional low molecular weight compound (B1) is more than the above lower limit, better solubility in a developer solution can be obtained in the negative photosensitive composition, and if it is less than the above upper limit, manufacturing and handling properties become good, and sufficient polymerization is achieved. This ensures that the curability, such as surface smoothness, of the obtained coating film also improves.

In the negative photosensitive resin composition, the polyfunctional low molecular weight compound (B1) may be used individually or in combination of two or more types. In addition, when using the polyfunctional low molecular weight compound (B1) as a mixture of two or more types, it is preferable that the acid value of the mixture is within the above range.

＜Non-acidic crosslinking agent (B2)＞

In addition to the polyfunctional low molecular weight compound (B1), the crosslinking agent (B) may contain a crosslinking agent (B2) that has two or more photocurable functional groups in one molecule and does not have an acidic group, that is, a non-acidic crosslinking agent (B2). By using the polyfunctional low molecular weight compound (B1) and the non-acidic crosslinking agent (B2) in combination, it becomes easy to adjust the acid value and the number of photocurable functional groups of the entire crosslinking agent (B), and the negative photosensitive resin composition at the time of exposure It is easy to achieve a balance between the action of improving curability and the action of improving the solubility of the negative photosensitive resin composition in the developer.

The photocurable functional group that the non-acidic crosslinking agent (B2) has two or more in one molecule is preferably the same type of photocurable functional group as the photocurable functional group that the alkali-soluble resin (A) has, and specifically, the ethylenic double. Combination is preferred. The number of photocurable functional groups per molecule in the non-acidic crosslinking agent (B2) may be 2 or more, preferably 3 or more, more preferably 4 or more, and particularly preferably 5 or more. As the number of photocurable functional groups increases, the curability of the surface of the coating film improves, and the stability of ink repellency in the upper surface of the obtained partition becomes better. In addition, the molecular weight of the non-acidic crosslinking agent (B2) can be the same as that of the polyfunctional low molecular weight compound (B1), including preferred embodiments.

Specifically, the non-acidic crosslinking agent (B2) includes a compound that does not have an acidic group in the polyfunctional low molecular weight compound (B1), and an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable.

As the non-acidic crosslinking agent (B2), more specifically, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate Latex, tetrapentaerythritol heptaacrylate, tetrapentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, ethoxylated isocyanuric acid tri(meth)acrylate, tris-( 2-acryloyloxyethyl)isocyanurate, ε-caprolactone modified tris-(2-acryloyloxyethyl)isocyanurate, dipentaerythritol pentaacrylate and HDI (hexamethylene diisocyanate) Examples include monomers having a bonded urethane skeleton (10 functional) and urethane acrylate.

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

The content rate of the crosslinking agent (B) in the total solid in the negative photosensitive resin composition is preferably 5 to 80 mass%, and particularly preferably 10 to 60 mass%. In addition, the acid value of the crosslinking agent (B) is in the same range as the acid value of the polyfunctional low molecular weight compound (B1) when the crosslinking agent (B) is composed only of the polyfunctional low molecular weight compound (B1). The acid value of the crosslinking agent (B) is preferably 10 to 80 mgKOH/g, and 15 to 70 mg when the crosslinking agent (B) contains both a polyfunctional low molecular weight compound (B1) and a non-acidic crosslinking agent (B2). KOH/g is more preferred.

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

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

In that case, the ratio of the polyfunctional low molecular weight compound (B1) to the total of 100 parts by mass of the polyfunctional low molecular weight compound (B1) and the non-acidic crosslinking agent (B2) is preferably 10 to 90 parts by mass, and is preferably 15 to 70 parts by mass. Addition is more desirable. By using the polyfunctional low molecular weight compound (B1) and the non-acidic crosslinking agent (B2) in the above ratio, it becomes easy to adjust the acid value and the number of photocurable functional groups of the entire crosslinking agent (B), and the photocurability and developability of the negative photosensitive resin composition are improved. Easy to maintain balance.

Additionally, as the crosslinking agent (B), a mixture of a polyfunctional low molecular weight compound (B1) and a non-acidic crosslinking agent (B2) is commercially available, such as dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate. and a mixture of succinic acid esters of dipentaerythritol pentaacrylate.

Additionally, if necessary, such a mixture may be used in combination with the polyfunctional low molecular weight compound (B1) and/or the non-acidic crosslinking agent (B2).

(Ink repellent agent (C))

The ink repellent agent (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 agent (C) has the property of transferring to the upper surface (top transfer property) and ink repellency in the process of forming a cured film using a negative photosensitive resin composition containing it. By using the ink repellent agent (C), the upper layer including the upper surface of the cured film obtained becomes a layer (hereinafter sometimes referred to as "ink repellent layer") in which the ink repellent agent (C) exists densely, and hardens. Ink repellency is provided to the upper surface of the membrane.

The ink repellent agent (C) has an acidic group and has an acid value equal to or higher than the above lower limit, so that it has good solubility in a developer, similar to other components such as the alkali-soluble resin (A) and the crosslinking agent (B) contained in the negative photosensitive resin composition. have As a result, the negative photosensitive resin composition in the non-exposed area can be easily removed with a developing solution, and developability is good. On the other hand, when the acid value of the ink repellent agent (C) is below the above upper limit, the ink repellent layer formed in the upper layer of the cured film is in sufficiently close contact with the resin layer in the lower layer and is hardly affected by the developer, and remains even after development, resulting in high ink repellent. It is possible to express sexuality.

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

The content of fluorine atoms in the ink repellent agent (C) is preferably 5 to 55% by mass, more preferably 10 to 55% by mass, and even more preferably 12 to 40% by mass from the viewpoint of top surface transferability and ink repellency. , 14 to 30 mass% is particularly preferable. If the content of fluorine atoms in the ink repellent agent (C) is more than the lower limit of the above range, good ink repellency can be provided to the upper surface of the cured film, and if it is less than the upper limit, compatibility with other components in the negative photosensitive resin composition is It gets better.

Moreover, the ink repellent agent (C) is preferably a compound having a photocurable functional group, especially an ethylenic double bond. Since the ink repellent agent (C) has an ethylenic double bond, a radical acts on the ethylenic double bond of the ink repellent agent (C) that has migrated to the upper surface, and the ink repellent agent (C) or the ink repellent agent (C) Crosslinking by (co)polymerization with other components having ethylenic double bonds contained in the negative photosensitive resin composition becomes possible.

Thereby, in manufacture of the cured film formed by hardening a negative photosensitive resin composition, fixation in the upper layer part of the cured film of the ink repellent agent (C), that is, the ink repellent layer, can be improved. In the negative photosensitive resin composition of the present invention, the ink repellent agent (C) can be sufficiently fixed to the ink repellent layer even when the exposure amount at the time of exposure is low. The case where the ink repellent agent (C) has an ethylenic double bond is as described above. When the ink repellent agent (C) does not have an ethylenic double bond, the ink repellent agent (C) is sufficiently cured by curing the photocurable component mainly composed of the alkali-soluble resin (A) present around the ink repellent agent (C). (C) can be sufficiently established.

Examples of the ink repellent agent (C) include ink repellent agent (C1), which consists 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. As the ink repellent agent (C), you may use an ink repellent agent (C2) consisting of a partial hydrolysis condensate of a hydrolysable silane compound containing a hydrolysable silane compound having an acidic group and a hydrolysable silane compound having a fluorine atom.

Ink repellent agent (C1) and ink repellent agent (C2) are used individually or in combination. In the negative photosensitive resin composition of the present invention, it is particularly preferable to use an ink repellent agent (C1) from the viewpoint of expressing higher ink repellency. Additionally, when ultraviolet ray/ozone resistance is required, it is preferable to use an ink repellent agent (C2).

＜Ink repellent agent (C1)＞

The ink repellent agent (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 agent (C1) is preferably 1.0 × 10 ⁴ to 15 × 10 ⁴ , more preferably 1.2 × 10 ⁴ to 13 × 10 ⁴ , and 1.4 × 10 ⁴ to 12 × 10 ⁴ is particularly preferred. When the mass average molecular weight (Mw) is more than the lower limit and a cured film is formed using a negative photosensitive resin composition, the ink repellent agent (C1) is likely to transfer to the upper surface. If it is below the upper limit, the amount of residue in the opening decreases and is therefore preferable.

Examples of the acidic group in the side chain having an acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group, and these may be used individually or in combination of two or more types. In the ink repellent agent (C1), parts other than the acidic group in the side chain having an acidic group are not particularly limited.

The side chain containing the fluorine atom of the ink repellent agent (C1) includes a side chain consisting of a fluoroalkyl group that may contain an etheric oxygen atom and/or a fluoroalkyl group that may contain an etheric oxygen atom. Having a side chain is preferred.

The fluoroalkyl group may be linear or branched.

Specific examples of fluoroalkyl groups that do not contain an 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 an etheric oxygen atom include the following structures.

-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 of 1 to 8, r2 is an integer of 1 to 4, and r3 is an integer of 1 to 5.

The hydrocarbon chain constituting the main chain of the ink repellent agent (C1), specifically, the main chain obtained by polymerization of a monomer having an ethylenic double bond, -Ph-CH ₂ - (where "Ph" represents the benzene skeleton A novolak-type main chain composed of repeating units (shown), etc. can be mentioned.

The ink repellent agent (C1) may further contain at least one type of side chain selected from the group consisting of a side chain having an ethylenic double bond and a side chain having an oxyalkylene group. One side chain may contain an ethylenic double bond and an oxyalkylene group. Additionally, the side chain containing the acidic group may contain an ethylenic double bond and/or an oxyalkylene group.

Additionally, the ink repellent agent (C1) may contain side chains such as a dimethyl silicone chain, an alkyl group, a glycidyl group, an isobornyl group, an isocyanate group, and a trialkoxysilyl group.

When the main chain of the ink repellent agent (C1) is a novolak-type main chain composed of repeating units of -Ph-CH ₂ -, usually the side having a fluorine atom in the benzene skeleton (Ph) constituting the main chain A polymer in which a side chain having an acidic group is bonded to a chain, and a side chain having an ethylenic double bond and an oxyalkylene side chain are optionally bonded together is used as the ink repellent agent (C1). Each side chain may be bonded to the same benzene skeleton (Ph) or may be bonded to a different benzene skeleton (Ph). The number of side chains bonded to one benzene skeleton (Ph) is preferably one.

In addition, adjustment of the acid value in ink repellent agent (C1) can be easily performed by adjusting the ratio of the side chain which has an acidic group introduced into the main chain of the hydrocarbon chain of ink repellent agent (C1). Similarly, adjustment of the content of fluorine atoms in the ink repellent agent (C1) is easily carried out by adjusting the ratio of the side chain having a fluorine atom introduced into the main chain of the hydrocarbon chain of the ink repellent agent (C1). can do.

＜Ink repellent agent (C2)＞

The ink repellent agent (C2) is a partial hydrolysis condensate of a hydrolyzable silane compound mixture (hereinafter also referred to as “mixture (M)”).

The mixture (M) is a hydrolysable silane compound (hereinafter also referred to as “hydrolysable silane compound (s1)”) having a fluoroalkyl group and/or a fluoroalkyl group and a group in which a hydrolyzable group is bonded to a silicon atom, and A hydrolysable silane compound (hereinafter also referred to as “hydrolysable silane compound (s2)”) containing a group having an acidic group and a hydrolysable group bonded to a silicon atom and containing no fluorine atom as an essential component, and optionally hydrolysable silane Includes hydrolysable silane compounds other than compound (s1) and hydrolysable silane compound (s2).

As the hydrolysable silane compound optionally contained in the mixture (M), a hydrolysable silane compound in which four hydrolysable groups are bonded to a silicon atom (hereinafter also referred to as “hydrolysable silane compound (s3)”) is preferable.

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 Particularly desirable.

The content of the hydrolyzable silane compound (s1) in the mixture (M) is preferably such that the content of fluorine atoms in the partially hydrolyzed condensate obtained from the mixture is 5 to 55% by mass. More preferably, it is 10 to 55 mass%, further preferably 12 to 40 mass%, and particularly preferably 15 to 30 mass%. If the content ratio of the hydrolysable silane compound (s1) is more than the lower limit of the above range, good ink repellency can be provided to the upper surface of the cured film, and if it is less than the upper limit, compatibility with other hydrolysable silane compounds in the mixture is good. It becomes.

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

(1) Compound represented by the following formula (c-2a), specifically, the following formula (c-2a-1), the following formula (c-2a-2), the following formula (c-2a-3), the following formula Compounds represented by (c-2a-4), (c-2a-5), and (c-2a-6), respectively.

[Formula 1]

R ²² has the formula: -R ²⁵ -COOH or -COO-R ²⁵ OOC-R ²⁵ -COOH (where R ²⁵ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, a single bond, or a phenylene group). It is a flag that represents. When R ²² is -COO-R ²⁵ OOC-R ²⁵ -COOH, the solubility of the ink repellent agent (C2) in the developer is further improved, residues in openings are reduced, and the wet and spreadability of the ink in the IJ method is further improved. desirable.

R ²¹ is a group represented by -COOR ²⁴ (where 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 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, i is 0 to 100, and j is 0 to 100. , k each represents an integer of 0 to 100, and I + j + k is 2 to 100. When having multiple types of oxyalkylene group units, the order is arbitrary.), or the hydrogen atom has 1 to 1 carbon atom. It is a phenyl group that may be substituted with a 10 hydrocarbon group. 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 agent (C2) This improvement is desirable.

Q ² is a divalent hydrocarbon group having 1 to 10 carbon atoms.

X ² is a hydrolyzable group, and the three X ² may be different from each other or may be the same. X ² is preferably a methoxy group or an ethoxy group.

m is an integer greater than 0, and n is an integer greater than 1.

[Formula 2]

[Formula 3]

X ² , m, n and i are the same as equation (c-2a).

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

[Formula 4]

X ² is the same as equation (c-2a).

(3) A reactant of a compound having an ethylenic double bond, a hydroxyl group or a carboxyl group, and a derivative thereof, and hydrosilanes, specifically, the formula (c-2c-1) below and the formula (c-2c-2) below: Each compound represents.

[Formula 5]

X ² is the same as equation (c-2a).

The content ratio of the hydrolyzable silane compound (s2) in the mixture (M) is such that the acid value in the partially hydrolyzed condensate obtained from the mixture is 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 still more preferably 30 to 60 mgKOH/g.

If the content rate of the hydrolyzable silane compound (s2) is more than the lower limit of the above range, the resulting negative photosensitive resin composition has good solubility in the developer. As a result, the negative photosensitive resin composition in the non-exposed area can be easily removed with a developing solution, and developability is good. On the other hand, when the acid value of the ink repellent agent (C) is below the above upper limit, the ink repellent layer formed in the upper layer of the cured film is in sufficiently close contact with the resin layer in the lower layer and is hardly affected by the developer, and remains even after development, resulting in high ink repellent. It is possible to express sexuality.

Specific examples of the hydrolyzable silane compound (s3) include the following compounds.

Si(OCH ₃ ) ₄ , Si(OC ₂ H ₅ ) ₄ ,

Partial hydrolysis condensate of Si(OCH ₃ ) ₄ ,

Partial hydrolysis condensate of Si(OC ₂ H ₅ ) ₄ .

The content ratio of the hydrolysable silane compound (s3) in the mixture (M) is preferably 0.01 to 5 moles, and particularly preferably 0.05 to 4 moles, per 1 mole of the hydrolysable silane compound (s1). If the content ratio is more than the lower limit of the above range, the film-forming property of the ink repellent agent (C2) is good, and if it is less than the upper limit, the ink repellent property of the ink repellent agent (C2) is good.

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

Hydrolysable silane compound (s4); A hydrolysable silane compound that has a group having an ethylenic double bond and a group in which a hydrolyzable group is bonded to a silicon atom, and does not contain a fluorine atom.

Hydrolysable silane compound (s5); A hydrolysable silane compound that has a mercapto group, a sulfide group, or a hydrolyzable silyl group and does not contain a fluorine atom.

Hydrolysable silane compound (s6); A hydrolysable 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 ,

CH ₂ =CHC ₆ H ₄ Si(OCH ₃ ) ₃ .

The content ratio of the hydrolysable silane compound (s4) in the mixture (M) is preferably 0.1 to 5 mol, and particularly preferably 0.5 to 4 mol, per 1 mol of the hydrolysable silane compound (s1). If the content ratio is more than the lower limit of the above range, the transfer property of the ink repellent agent (C2) to the top surface is good, and the fixation property of the ink repellent agent (C2) in the ink repellent layer including the top surface after transfer to the top surface is good. , In addition, the storage stability of the ink repellent agent (C2) is good. If it is below the upper limit, the ink repellency of the ink repellent agent (C2) is good.

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

The content ratio of the hydrolysable silane compound (s5) in the mixture (M) is preferably 0 to 2.0 mol, and particularly preferably 0 to 1.5 mol, per 1 mol of the hydrolysable silane compound (s1). If the content ratio is more than the lower limit of the above range, the transfer property of the ink repellent agent (C2) to the top surface is good, and the fixation property of the ink repellent agent (C2) in the ink repellent layer including the top surface after transfer to the top surface is good. , In addition, the storage stability of the ink repellent agent (C2) is good. If it is below the upper limit, the ink repellency of the ink repellent agent (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 , C ₁₀ H ₂₁ -Si(OCH ₃ ) ₃ .

In addition, Ph in the formula represents a phenyl group.

The content ratio of the hydrolysable silane compound (s6) in the mixture (M) is preferably 0 to 1.0 mol, and particularly preferably 0 to 0.08 mol, per 1 mole of the hydrolysable silane compound (s1). If the content ratio is more than the lower limit of the above range, storage stability is good. If it is below the upper limit, ink applicability to the dot portion is good.

Other hydrolysable silane compounds include a hydrolysable silane compound (s7) that has an epoxy group and a hydrolysable silyl group and does not contain a fluorine atom, and a hydrolysable silane compound that has an oxyalkylene group and a hydrolysable silyl group and does not contain a fluorine atom. Compound (s8), a hydrolysable silane compound (s9) having a sulfide and a hydrolysable silyl group and not containing a fluorine atom, a hydrolysable silane compound (s10) having a ureido group and a hydrolysable silyl group and not containing a fluorine atom , a hydrolyzable silane compound (s11) that has an amino group and a hydrolyzable silyl group and does not contain a fluorine atom.

As the hydrolyzable silane compound (s7), for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane is a hydrolyzable silane compound (s8), for example, CH ₃ O(C ₂ H ₄ O) _k Si (OCH ₃ ) ₃ (polyoxyethylene group-containing trimethoxysilane) (where k is, for example, about 10), as a hydrolyzable silane compound (s9), for example, bis(triethoxysilylpropyl) Tetrasulfide, as a hydrolyzable silane compound (s10), for example, 3-ureidopropyltriethoxysilane, as a hydrolyzable silane compound (s11), for example, N-phenyl-3-aminopropyltrime Toxisilane may be mentioned.

In particular, when the ink repellent agent (C2) contains a hydrolyzable silane compound (s8), the dispersion stability and storage stability of the ink repellent agent (C2) improve, and this is preferable. In particular, when the ink repellent agent (C2) contains a hydrolyzable silane compound (s9), ink repellency becomes easy to develop even at a low exposure amount, so it is preferable.

As an example of the ink repellent agent (C2), n1 is the hydrolysable silane compound (s1), n2 is the hydrolysable silane compound (s2), n3 is the hydrolysable silane compound (s3), n4 is the hydrolysable silane compound (s4), and a partial hydrolysis condensate of the mixture (M) containing n5 as the hydrolyzable silane compound (s5) and n6 as the hydrolyzable silane compound (s6). Here, n1 to n6 represent the mole fraction of each structural unit with respect to the total molar amount of the structural units. n1 > 0, n2 > 0, n3 ≥ 0, n4 ≥ 0, n5 ≥ 0, n6 ≥ 0, n1 + n2 + n3 + n4 + n5 + n6 = 1.

n1:n2:n3 corresponds to the injection composition of the hydrolysable silane compounds (s1), (s2), (s3), (s4), (s5), and (s6) in the mixture (M). The molar ratio of each component is designed based on the balance of the effects of each component.

n1 is preferably 0.02 to 0.4 in an amount in which the content of fluorine atoms in the ink repellent agent (C2) falls within the above preferable range.

n2 is preferably 0.003 to 0.03 in the amount in which the acid value in the ink repellent agent (C2) falls within the above range.

n3 is preferably 0 to 0.98, and particularly preferably 0.05 to 0.6.

n4 is preferably 0 to 0.4, and particularly preferably 0 to 0.27.

n5 is preferably 0 to 0.1, and particularly preferably 0 to 0.07.

n6 is preferably 0 to 0.2, and particularly preferably 0 to 0.15.

The mass average molecular weight (Mw) of the ink repellent agent (C2) is preferably 500 or more, preferably less than 1×10 ⁶ , and particularly preferably 5×10 ³ or less. When the mass average molecular weight (Mw) is more than the lower limit and a cured film is formed using a negative photosensitive resin composition, the ink repellent agent (C2) is likely to transfer to the upper surface. If it is less than the upper limit, the amount of residue in the opening decreases and is therefore preferable. In addition, the mass average molecular weight (Mw) of the ink repellent agent (C2) can be adjusted according to production conditions.

Ink repellent agent (C2) can be manufactured by hydrolyzing and condensing the above-mentioned mixture (M) by a known method. In this reaction, alkali 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 catalysts. Additionally, known solvents can be used in the above reaction. The ink repellent agent (C2) obtained by the above reaction may be blended with the negative photosensitive resin composition in the form of a solution together with a solvent.

The content ratio of the ink repellent agent (C) in the total solid content in the negative photosensitive resin composition is set to a content ratio at which the surface satisfies the above-mentioned characteristics in the partition wall obtained by using this. Although the content ratio may vary depending on the type of ink repellent agent (C) to be used, specifically, 0.01 to 10 mass% is preferable and 0.1 to 2 mass% is more preferable. If the content ratio is more than the lower limit of the above range, the upper surface of the cured film formed from the negative photosensitive resin composition has excellent ink repellency. If it is below the upper limit of the above range, the adhesion between the cured film and the base material becomes good.

(Photopolymerization initiator (D))

The photopolymerization initiator (D) in the present invention is not particularly limited as long as it is a compound that has a function as a photopolymerization initiator, and a compound that generates radicals by light is preferable.

Examples of the photopolymerization initiator (D) include α-diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acylophosphones such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; Thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, and 2,4-diethylthioxanthone; Benzophenones, such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone; Acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one Acetophenones such as; Quinones such as anthraquinone, 2-ethylanthraquinone, camphor quinone, and 1,4-naphthoquinone; Aminobenzoic acids such as 2-dimethylaminobenzoic acid ethyl and 4-dimethylaminobenzoic acid (n-butoxy)ethyl; Halogen compounds such as phenacyl chloride and trihalomethylphenylsulfone; Acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Peroxides such as di-t-butyl peroxide; 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-1-(O-acetyloxime) and other oxime esters, triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacryl. Aliphatic amines such as latex, etc. can be mentioned.

Among the photopolymerization initiators (D), benzophenones, aminobenzoic acids, and aliphatic amines are preferred because they may exhibit a sensitizing effect when used together with other radical initiators.

As the photopolymerization initiator (D), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morph Polinophenyl)-butan-1-one, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone 1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), or 2,4-diethylthioxanthone is preferred. Additionally, a combination of these with benzophenones, such as 4,4'-bis(diethylamino)benzophenone, is particularly preferred. The photopolymerization initiator (D) may be used individually or in combination of two or more types.

The content rate of the photopolymerization initiator (D) in the total solid in the negative photosensitive resin composition is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%, and particularly preferably 1 to 15 mass%. . When the content ratio is within the above range, the photocurability and developability of the negative photosensitive resin composition are good.

(Solvent (E))

The viscosity of the negative photosensitive resin composition of the present invention is reduced by containing the solvent (E), and it becomes easy to apply the negative photosensitive resin composition to the surface of the base material. As a result, a coating film of the negative photosensitive resin composition with a uniform film thickness can be formed. As the solvent (E), a known solvent is used. The solvent (E) may be used individually or in combination of two or more types.

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 preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, di Ethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide And at least one solvent selected from the group consisting of 2-propanol is more preferable.

In particular, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-dimethyl Propionamide has a boiling point of 150°C or higher and tends to suppress coating unevenness, etc., so it is preferred.

Additionally, when the solvent (E) contains water, the water content is preferably 10% by mass or less of the entire solvent (E). If it is within the above range, the unevenness of the patterned substrate consisting of a partition formed from a cured film obtained from the negative photosensitive resin composition of the present invention can be reduced. Moreover, it is more preferable that the water content is 1 to 10 mass%. If it is within the above range, the dispersion stability of the composition is good.

The content ratio 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 particularly preferably 50 to 90% by mass, relative to the total amount of the composition. . Moreover, with respect to a total of 100 mass% of alkali-soluble resin (A) and crosslinking agent (B), 0.1 to 3000 mass% is preferable, and 0.5 to 2000 mass% is more preferable.

(Other ingredients)

(Thiol compound (G))

The thiol compound (G) that the negative photosensitive resin composition of the present invention optionally contains is a compound having two or more mercapto groups in one molecule. When the negative photosensitive resin composition of the present invention contains a thiol compound (G), radicals of the thiol compound (G) are generated by radicals generated from the photopolymerization initiator (D) during exposure, thereby forming an alkali-soluble resin (A), A so-called en-thiol reaction occurs that acts on the ethylenic double bond of the crosslinking agent (B) or other components contained in the negative photosensitive resin composition. This N-thiol reaction, unlike conventional radical polymerization of ethylenic double bonds, is not inhibited by oxygen, so it has high chain mobility, and crosslinking is carried out simultaneously with polymerization, so it can be used as a cured product. It has the advantage of having a low shrinkage rate and making it easy to obtain a uniform network.

When the negative photosensitive resin composition of the present invention contains a thiol compound (G), it can be sufficiently cured even at a low exposure dose as described above, and includes the upper surface of the partition which is particularly susceptible to reaction inhibition by oxygen. Since photocuring is sufficiently performed also in the upper layer, it becomes possible to provide good ink repellency to the upper surface of the partition.

The number of mercapto groups in the thiol compound (G) is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 5 mercapto groups per molecule. From the viewpoint of storage stability of the negative photosensitive resin composition, three are particularly preferable.

The molecular weight of the thiol compound (G) is not particularly limited. In the thiol compound (G), the mercapto group equivalent expressed as [molecular weight/number of mercapto groups] is preferably 40 to 1,000, more preferably 40 to 500, from the viewpoint of curability at low exposure doses, and 40 ~250 is particularly preferred.

The thiol compound (G) specifically includes tris(2-mercaptopropanoyloxyethyl)isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tristioglycolate, Pentaerythritol tristioglycolate, pentaerythritol tetrachistioglycolate, dipentaerythritol hexathioglycolate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercapto) propionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, dipentaerythritol hexa(3-mercaptopropionate), trimethylolpropane tris(3-mercapto butyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptobutyrate), trimethylolpropane tris (2-mercaptoisobutylate), 1,3 ,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, triphenolmethanetris(3-mercaptopro) cypionate), triphenolmethanetris(3-mercaptobutylate), trimethylolethantris(3-mercaptobutylate), 2,4,6-trimercapto-S-triazine, etc. The thiol compound (G) may be used individually or in combination of two or more types.

When the negative photosensitive resin composition contains a thiol compound (G), the content ratio is an amount such that the mercapto group is 0.0001 to 1 mole with respect to 1 mole of the ethylenic double bond of the total solid content in the negative photosensitive resin composition. is preferable, 0.0005 to 0.5 mol is more preferable, and 0.001 to 0.5 mol is particularly preferable. Moreover, regarding 100 mass % of alkali-soluble resin (A), 0.1-1200 mass % is preferable, and 0.2-1000 mass % is more preferable. If the content ratio of such a thiol compound (G) is within the above range, the photocurability and developability of the negative photosensitive resin composition are good even at a low exposure amount.

(Phosphoric acid compound (H))

The negative photosensitive resin composition of the present invention may optionally contain a phosphoric acid compound (H) in order to improve adhesion to the substrate in the resulting cured film or transparent electrode materials such as ITO.

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

Phosphoric acid compounds having an ethylenically unsaturated double bond in the molecule include phosphoric acid (meth)acrylate compounds, that is, at least an O=P structure derived from phosphoric acid and an ethylenically unsaturated double bond derived from a (meth)acrylic acid-based compound in the molecule. Compounds having a (meth)acryloyl group and vinyl phosphate compounds are preferable.

Phosphoric acid (meth)acrylate compounds used in the present invention include mono(2-(meth)acryloyloxyethyl)acid phosphate, di(2-(meth)acryloyloxyethyl)acid phosphate, and di(2). -acryloyloxyethyl) acid phosphate, tris ((meth)acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) caproate acid phosphate, etc.

Additionally, as the phosphoric acid compound (H), in addition to phosphoric acid compounds having an ethylenically unsaturated double bond in the molecule, phenylphosphonic acid and the like can be used.

The negative photosensitive resin composition of the present invention is a phosphoric acid compound (H) and may contain one type of compound classified as this, or two or more types thereof.

When the negative photosensitive resin composition contains a phosphoric acid compound (H), the content ratio is preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass, relative to the total solid content in the negative photosensitive resin composition. . Moreover, about 100 mass % of alkali-soluble resin (A), 0.01-200 mass % is preferable, and 0.1-100 mass % is more preferable. If the content ratio of this phosphoric acid compound (H) is within the above range, the adhesiveness between the obtained cured film and the base material, etc. is good.

The negative photosensitive resin composition in the present invention further contains, if necessary, a polymerization inhibitor, a thermal crosslinking agent, a polymer dispersant, a dispersing aid, a silane coupling agent, fine particles, a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent and a cratering agent. It may contain one or more other additives selected from the group consisting of inhibitors.

The negative photosensitive resin composition of the present invention is obtained by mixing predetermined amounts of each of the above components. The negative photosensitive resin composition of the present invention can be particularly effective when used in the formation of a cured film or barrier rib used in an optical device, such as an organic EL device, quantum dot display, TFT array, or thin film solar cell. By using the negative photosensitive resin composition of the present invention, it is possible to manufacture a partition wall that has good ink repellency on the upper surface and good development adhesion to the substrate, and has a sufficiently small development residue in the opening divided by the partition wall. possible.

[septum]

The partition wall according to the present invention is a partition wall made of a cured film of the negative photosensitive resin composition of the above-mentioned invention formed in a form that divides the substrate surface into a plurality of sections for dot formation. For the partition, for example, the negative photosensitive resin composition of the present invention is applied to the surface of a substrate such as a substrate, dried as necessary to remove solvents, etc., and then masked to the portion that becomes the division for dot formation. , obtained by exposure and development. By development, the unexposed portion is removed by masking, and an opening corresponding to the section for dot formation is formed together with the partition wall.

As described above, the partition wall of the embodiment related to the present invention is a partition wall that has good ink repellency on the upper surface and good development adhesion to the substrate, and the development residue is sufficiently small in the opening divided by the partition wall. As a result, when used in optical elements, especially organic EL elements manufactured by the IJ method, quantum dot displays, TFT arrays, or thin film solar cells, ink can be uniformly applied to the openings to form dots with good precision. Yes, it has a remarkable effect.

Hereinafter, an example of a method of manufacturing a partition according to an embodiment related to the present invention will be described using FIGS. 1A to 1D, but the method of manufacturing a partition is not limited to the following. In addition, the following manufacturing method is demonstrated as a negative photosensitive resin composition containing a solvent (E).

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

Next, as shown in FIG. 1B, the coating film 21 is dried to form a dry film 22. Drying methods include heat drying, reduced pressure drying, and reduced pressure heat drying. Although it may vary depending on the type of solvent (E), in the case of heat drying, the heating temperature is preferably 50 to 120°C.

In this drying process, the ink repellent agent (C) migrates to the upper layer of the dried film. Moreover, even when the negative photosensitive resin composition does not contain a solvent (E), transfer of the ink repellent agent (C) to the upper surface within a coating film is achieved in the same way.

Next, as shown in FIG. 1C, the dried film 22 is exposed by irradiating light through a photomask 30 having a masking portion 31 of a shape corresponding to an opening surrounded by a partition. The film after exposing the dry film 22 is called the exposed film 23. In the exposed film 23, the exposed portion 23A is photocured, and the non-exposed portion 23B is in the same state as the dried film 22.

The light to be irradiated is visible light; UV-rays ; Far ultraviolet rays; Excimer laser light such as 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 laser light; X-ray; Electron beams, etc. can be mentioned.

The light to be irradiated is preferably light with a wavelength of 100 to 600 nm, more preferably light with a wavelength of 300 to 500 nm, and includes the i-line (365 nm), the h-line (405 nm), or the g-line (436 nm). Light that produces light is particularly preferable. Additionally, light of 330 nm or less may be cut as needed.

Exposure methods include full surface exposure, scan exposure, and the like. The exposure may be divided into multiple times for the same point. At this time, the exposure conditions for multiple exposures may or may not be the same.

In any of the above exposure methods, the exposure amount is preferably, for example, 5 to 1,000 mJ/cm2, more preferably 5 to 500 mJ/cm2, more preferably 5 to 300 mJ/cm2, and 5 to 200 mJ. /cm2 is particularly preferable, and 5 to 50 mJ/cm2 is most preferable. In addition, the exposure amount becomes appropriately desirable depending on the wavelength of the light to be irradiated, the composition of the negative photosensitive resin composition, the thickness of the coating film, etc.

The exposure time per unit area is not particularly limited and is designed based on the exposure power of the exposure device used and the required exposure amount. Additionally, in the case of scan exposure, the exposure time is obtained from the scanning speed of light. The exposure time per unit area is usually about 1 to 60 seconds.

Next, as shown in FIG. 1D, development using an alkaline developer is performed to form the partition 4 consisting only of the portion corresponding to the exposed portion 23A of the exposure film 23. The opening 5 surrounded by the partition 4 is a portion of the exposure film 23 where the non-exposed portion 23B existed, and FIG. 1D shows the state after the non-exposed portion 23B is removed by development. there is. In the negative photosensitive resin composition, the alkali-soluble resin (A), the crosslinking agent (B), and the ink repellent agent (C) all have an acidic group, so they can be dissolved and removed by an alkaline developer in the non-exposed area 23B. is easily implemented, and the composition hardly remains in the opening 5. On the other hand, the partition wall 4, which is a cured product of the negative photosensitive resin composition, has excellent development adhesion and is sufficiently adhered to the substrate 1 even after development.

Moreover, in the partition 4 shown in FIG. 1D, the uppermost layer including the upper surface is the ink repellent layer 4A. When the ink repellent agent (C) does not have a side chain having an ethylenic double bond, at the time of exposure, the ink repellent agent (C) exists in a high concentration in the uppermost layer as is and becomes an ink repellent layer. At the time of exposure, the alkali-soluble resin (A) present around the ink repellent agent (C), the thiol compound (G) optionally further contained, and other photocurable components are strongly photocured to form the ink repellent agent (C). ) settles in the ink repellent layer.

When the ink repellent agent (C) has a side chain having an ethylenic double bond, the ink repellent agent (C) may be combined with each other and/or the alkali-soluble resin (A), the thiol compound (G) optionally contained, or other It is photocured together with a photocuring component to form an ink repellent layer (4A) to which the ink repellent agent (C) is firmly bonded.

In any of the above cases, on the lower side of the ink repellent layer 4A, mainly the alkali-soluble resin (A) and the optionally contained thiol compound (G) and other photocurable components are photocured, and the ink repellent agent (C ) A layer (4B) containing little is formed.

Conventionally, when the ink repellent agent had an acidic group, the problem was that the ink repellent layer formed on the uppermost layer of the partition was easily removed during development. In the present invention, by using an ink repellent agent (C) whose acid value is within a predetermined range, the repellent formed on the uppermost layer of the partition 4 is easily dissolved and removed by an alkaline developer in the non-exposed area during development. The ink layer 4A was able to remain almost unaffected by the alkaline developer. Moreover, since the ink repellent agent (C) is sufficiently fixed to the partition containing the ink repellent layer 4A and its lower layer 4B, it rarely migrates to the opening during development.

After development, the partition wall 4 may be further heated. The heating temperature is preferably 130 to 250°C. By heating, the partition wall 4 is hardened to become stronger. Additionally, the ink repellent agent (C) settles more firmly within the ink repellent layer 4A.

The resin cured film and partition wall 4 according to the present invention obtained in this way have good ink repellency on the upper surface even when exposure is performed at a low exposure amount. In addition, in the partition 4, there is almost no case where the ink repellent agent (C) is present in the opening 5 after development, and uniform coating of ink in the opening 5 can be sufficiently ensured. .

In addition, for the purpose of more reliably obtaining the ink-philicity of the opening 5, in order to remove development residues of the negative photosensitive resin composition that may be present in the opening 5 after the heating, a partition ( 4) The formed substrate 1 may be subjected to ultraviolet ray/ozone treatment.

For example, the width of the partition formed from the negative photosensitive resin composition of the present invention is preferably 100 μm or less, and particularly preferably 20 μm or less. In addition, the distance (width of the pattern) between adjacent partitions is preferably 300 μm or less, and particularly preferably 100 μm or less. The height of the partition is preferably 0.05 to 50 μm, and particularly preferably 0.2 to 10 μm.

The partition formed from the negative photosensitive resin composition of the present invention has few irregularities at the edges when formed with the above width and is excellent in straightness. In addition, the high linearity in the partition is particularly remarkable when resin (A-2), in which an acidic group and an ethylenic double bond are introduced into an epoxy resin, is used as the alkali-soluble resin. As a result, high-precision pattern formation is possible, even if it is a fine pattern. If such high-precision pattern formation can be performed, it is particularly useful as a partition for organic EL elements.

The partition according to the present invention can be used as a partition whose opening serves as an ink injection area when performing pattern printing by the IJ method. When performing pattern printing by the IJ method, if the partition wall according to the present invention is formed and used so that its opening coincides with the desired ink injection area, the upper surface of the partition wall has good ink repellency, so that unwanted particles exceeding the partition wall are formed and used. It is possible to suppress ink from being injected into the opening, that is, the ink injection area. Additionally, since the opening surrounded by the partition has good wettability and spreadability of the ink, it becomes possible to uniformly print the ink in the desired area without causing discoloration or the like.

Using the partition according to the present invention, pattern printing by the IJ method can be performed precisely as described above. Therefore, the barrier rib related to the present invention is an optical element having a barrier rib located between a plurality of dots and adjacent dots on the surface of a substrate where the dots are formed by the IJ method, especially an organic EL device, a quantum dot display, a TFT array, or a thin film solar panel. It is useful as a barrier in a battery.

[Optical elements]

The organic EL element, quantum dot display, TFT array or thin film solar cell as an optical element related to the present invention includes an organic EL element having a plurality of dots on the surface of a substrate and a partition wall according to the present invention located between adjacent dots, These are quantum dot displays, TFT arrays or thin film solar cells. In the optical element (organic EL element, quantum dot display, TFT array or thin film solar cell) related to the present invention, the dots are preferably formed by the IJ method.

An organic EL device is a structure in which a light-emitting layer of an organic thin film is sandwiched between an anode and a cathode, and the barrier wall related to the present invention can be used as a barrier wall to block an organic light-emitting layer, a partition wall to block an organic TFT layer, a partition wall to block a coated oxide semiconductor, etc. You can.

In addition, an organic TFT array element means that a plurality of dots are arranged in a matrix in plan view, a TFT is formed in each dot as a pixel electrode and a switching element for driving the pixel electrode, and the semiconductor layer including the channel layer of the TFT is an organic TFT array element. This is a device that uses a semiconductor layer. The organic TFT array element is provided as a TFT array substrate in, for example, an organic EL element or a liquid crystal element.

Regarding the optical element of the embodiment related to the present invention, for example, an organic EL element, an example of forming a dot in an opening by the IJ method using the barrier rib obtained above will be described below. In addition, the method of forming dots in optical elements such as organic EL elements related to the present invention is not limited to the following.

FIGS. 2A and 2B schematically show a method of manufacturing an organic EL device using the partition 4 formed on the substrate 1 shown in FIG. 1D. Here, the partition 4 on the substrate 1 is formed so that the opening 5 matches the dot pattern of the organic EL device to be manufactured.

As shown in FIG. 2A, ink 10 is dropped from the inkjet head 9 into the opening 5 surrounded by the partition 4, and a predetermined amount of ink 10 is injected into the opening 5. As the ink, a known ink for organic EL elements is appropriately selected and used according to the function of the dot.

Next, depending on the type of ink 10 used, treatment such as drying and/or heating is performed, for example, to remove the solvent or to cure the ink 10, and as shown in FIG. 2B, the ink 10 adjacent to the partition wall 4 is treated. An organic EL device 12 in which the desired dots 11 are formed is obtained.

The optical element (organic EL element, quantum dot display, TFT array, or thin film solar cell) of the embodiment related to the present invention uses the partition wall according to the present invention, so that ink is not uneven in the opening divided by the partition wall during the manufacturing process. It is possible to uniformly wet and spread without spreading, thereby creating an optical device (organic EL device, quantum dot display, TFT array or thin film solar cell) with dots formed with good precision.

In addition, the organic EL element can be manufactured as follows, for example, but is not limited to this.

A translucent electrode such as tin-doped indium oxide (ITO) is deposited on a translucent substrate such as glass by a sputtering method or the like. This translucent electrode is patterned as required.

Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a grid shape in plan view along the outline of each dot by a photolithography method including application, exposure, and development. Next, materials for the hole injection layer, hole transport layer, light-emitting layer, hole blocking layer, and electron injection layer are applied and dried in the opening for dot formation by the IJ method, and these layers are sequentially stacked. The type and number of organic layers formed in the opening for dot formation are 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.

Additionally, the quantum dot display can be manufactured as follows, for example, but is not limited to this.

A translucent electrode such as ITO is deposited on a translucent substrate such as glass by a sputtering method or the like. This translucent electrode is patterned as required. Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a grid shape in plan view along the outline of each dot by a photolithography method including application, exposure, and development. Next, materials for the hole injection layer, hole transport layer, quantum dot layer, hole blocking layer, and electron injection layer are respectively applied and dried in the opening for dot formation by the IJ method, and these layers are sequentially stacked. The type and number of organic layers formed in the opening for dot formation are 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.

Additionally, the optical element of the embodiment related to the present invention can also be applied to, for example, a blue light conversion type quantum dot display manufactured as follows.

Using the negative photosensitive resin composition of the present invention on a translucent substrate such as glass, partition walls are formed in a grid shape in plan view along the outline of each dot. Next, into the opening for dot formation, a nanoparticle solution that converts blue light into green light by the IJ method, a nanoparticle solution that converts blue light into red light, and blue color ink as necessary are applied and dried, Create a module. By using a light source that produces blue color as a backlight and using the module as a replacement for a color filter, a liquid crystal display with excellent color reproducibility is obtained.

The TFT array can be manufactured as follows, for example, but is not limited to this.

A gate electrode, such as aluminum or an alloy thereof, is deposited on a light-transmitting substrate, such as glass, by a sputtering method or the like. This gate electrode is patterned as needed.

Next, a gate insulating film such as silicon nitride is formed by a plasma CVD method or the like. A source electrode and a drain electrode may be formed on the gate insulating film. The source electrode and drain electrode can be manufactured by, for example, forming a metal thin film of aluminum, gold, silver, copper, or their alloys by vacuum deposition or sputtering. A method of patterning the source and drain electrodes includes forming a metal thin film, applying resist, exposing and developing, leaving a resist in the area where the electrode is to be formed, and then exposing the exposed metal with phosphoric acid or aqua regia, etc. There is a method to remove the resist at the end.

In addition, when forming a metal thin film such as gold, a resist is applied in advance, exposed and developed to leave a resist in the area where an electrode is not to be formed, and then after forming the metal thin film, the photoresist is applied together with the metal thin film. There is also a method to remove . Additionally, the source electrode and drain electrode may be formed by a method such as inkjet using metal nanocolloids such as silver or copper. Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a grid shape in plan view along the outline of each dot by a photolithographic method including application, exposure, and development.

Next, a semiconductor solution is applied into the opening for dot formation by the IJ method and the solution is dried to form a semiconductor layer. As this semiconductor solution, an organic semiconductor solution or an inorganic coated oxide semiconductor solution can also be used. The source electrode and drain electrode may be formed using a method such as inkjet after forming the semiconductor layer. Finally, it is formed by forming a translucent electrode such as ITO by a sputtering method and forming a protective film such as silicon nitride.

Example

The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In addition, 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)]

Gel permeation chromatography (GPC) of multiple types of commercially available monodisperse polystyrene polymers with different degrees of polymerization was used as a standard sample for molecular weight measurement using a commercially available GPC measurement device (manufactured by Tosoh Corporation, device name: HLC-8320GPC). Measured. A calibration curve was prepared based on the relationship between the molecular weight and retention time of polystyrene.

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

[PGMEA contact angle]

By a static method, in accordance with JIS R 3257 "Method for testing wettability of glass surface of substrate", PGMEA droplets were placed on three points of the measurement surface on the substrate, and each PGMEA drop was measured. The number of droplets was 2 μl/drop, and the measurement was performed at 20°C. The contact angle was determined from the average of 3 measurements (n = 3). Additionally, PGMEA is an abbreviation for propylene glycol monomethyl ether acetate.

The abbreviations of the compounds used in each example are as follows.

(Alkali soluble resin (A))

A-1: A resin solution in which a cresol novolak-type epoxy resin was reacted with acrylic acid and then 1,2,3,6-tetrahydrophthalic anhydride, and the resin into which acryloyl and carboxyl groups were introduced was purified with hexane (solid content: 70 Mass %, acid value 60 mgKOH/g, mass average molecular weight 9.2 × 10 ³ ).

A-2: RE-310S (Nippon Chemical Co., Ltd., difunctional bisphenol-A type epoxy resin, epoxy equivalent weight: 184.0 g/equivalent), described in Example 1 (paragraph number 0045) in Japanese Patent Application Publication No. 2003-268067. A polyurethane compound solution obtained by reacting with acrylic acid, then dimethylolpropionic acid, trimethylhexamethylene diisocyanate, and finally with glycidyl methacrylate (solid content: 65% by mass, acid value: 79.32 mgKOH/g).

(Multifunctional low molecular weight compound (B1))

B1-1: 2,2,2-triacryloyloxymethylethylphthalic acid (acid value 87 mgKOH/g, molecular weight 446).

B1-2: Succinic acid ester of dipentaerythritol pentaacrylate (acid value 92 mgKOH/g, molecular weight 612).

(Non-acidic cross-linking agent (B2))

B2-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

(Raw material of ink repellent agent (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-(bisacryloyloxymethyl)ethyl isocyanate.

DBTDL: dibutyltin dilaurate

TBQ: t-butyl-p-benzoquinone

MEK: 2-butanone

(Raw material of ink repellent agent (C2))

Compound (cx-1) corresponding to compound (s1): F(CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₃ ) ₃ (prepared by a known method).

Raw materials for compound (cx-21) and compound (cx-22) corresponding to compound (s2)

AC: Acrylic acid

MMA: Methyl methacrylate

AIBN: Azobisisobutyronitrile

V-65: (2,2'-azobis(2,4-dimethylvaleronitrile))

3-Mercaptopropyltrimethoxysilane

PGME: propylene glycol monomethyl ether

Compound (cx-3) corresponding to compound (s3): Si(OC ₂ H ₅ ) ₄ .

Compound (cx-4) corresponding to compound (s4): CH ₂ =CHCOO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ .

Compound (cx-51) corresponding to compound (s5): SH(CH ₂ ) ₃ Si(OCH ₃ ) ₃ .

Compound (cx-52) corresponding to compound (s5): [(1,2,3,4-tetrathiabutane-1,4-diyl)bis(trimethylene)]bis(triethoxysilane)

Compound (cx-6) corresponding to compound (s6): (CH ₃ ) ₃ SiOCH ₃ .

(Photopolymerization initiator (D))

D-1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.

D-2: 4,4'-bis(diethylamino)benzophenone.

(Solvent (E))

E-1: PGME: propylene glycol monomethyl ether.

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

E-3: EDGAC: Ethyldiglycol acetate.

E-4: DMIB: N,N-dimethylisobutylamide.

[Synthesis of ink repellent agent (C)]

Ink repellent agents (C1-1), ink repellent agents (C2-1) to (C2-3) used in the examples, and ink repellent agents (Cf-1) to (Cf-3) for comparative examples were prepared as follows. synthesized.

(Synthesis Example 1: Synthesis of ink repellent (C1-1))

In an autoclave with an internal volume of 1,000 cm3 equipped with a stirrer, 415.1 g of MEK, 81.0 g of C6FMA, 18.0 g of MAA, 81.0 g of 2-HEMA, 5.0 g of polymerization initiator V-65 and 4.7 g of n-DM. was injected and polymerized at 50°C for 24 hours while stirring in a nitrogen atmosphere, and further heated at 70°C for 5 hours to inactivate the polymerization initiator to obtain a copolymer solution. The copolymer had a number average molecular weight of 5,540 and a mass average molecular weight of 13,200.

Next, 130.0 g of the solution of the copolymer, 33.5 g of BEI, 0.13 g of DBTDL, and 1.5 g of TBQ were charged into an autoclave with an internal volume of 300 cm3 equipped with a stirrer and reacted at 40° C. for 24 hours while stirring. to synthesize the crude polymer. After adding hexane to the solution of the obtained crude polymer and purifying it by reprecipitation, it was vacuum dried and 65.6 g of ink repellent agent (C1-1) was obtained. After that, it was diluted with PGMEA to produce a PGMEA solution of the ink repellent agent (C1-1) (Ink repellent agent (C1-1) concentration: 10% by mass, hereinafter also referred to as “ink repellent agent (C1-1) solution”) got it

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

(Synthesis Example 2: Synthesis of hydrolyzable silane compound (cx-21))

In a 50 cm3 three-necked flask equipped with a stirrer and thermometer, add 0.40 g of 3-mercaptopropyltrimethoxysilane, 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. By gas chromatography, the peak disappearance of the raw materials 3-mercaptopropyltrimethoxysilane, MMA, and AC was confirmed, and a PGME solution (concentration: 10% by mass) of the hydrolysable silane compound (cx-21) was obtained.

(Synthesis Example 3: Preparation of ink repellent agent (C2-1))

In a 50 cm3 three-necked flask equipped with a stirrer, 0.35 g of compound (cx-1), 1.03 g of PGME solution of compound (cx-21), 0.56 g of compound (cx-3), and 0.63 g of compound (cx-4). was added, and a hydrolyzable silane compound mixture was obtained. Next, 6.67 g of PGME was added to this mixture to serve as a raw material solution.

To the obtained raw material solution, 0.76 g of 1% hydrochloric acid aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40°C for 5 hours to prepare a PGME solution of the ink repellent agent (C2-1) (ink repellent agent (C2-1) concentration: 10% by mass, hereinafter referred to as “ink repellent agent (C2-1) solution. 」) was obtained.

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

(Synthesis Example 4: Preparation of ink repellent (C2-2) liquid)

In a 50 cm3 three-necked flask equipped with a stirrer, 0.38 g of compound (cx-1), 1.09 g of PGME solution of compound (cx-21), 0.59 g of compound (cx-3), and 0.44 g of compound (cx-4). , 0.05 g of compound (cx-6) and 0.22 g of compound (cx-51) were added to obtain a hydrolyzable silane compound mixture. Next, 6.37 g of PGME was added to this mixture to serve as a raw material solution.

To the obtained raw material solution, 0.85 g of 1% hydrochloric acid aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40°C for 5 hours to prepare a PGME solution of the ink repellent agent (C2-2) (ink repellent agent (C2-2) concentration: 10% by mass, hereinafter referred to as “ink repellent agent (C2-2) solution. 」) was obtained.

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

(Synthesis Example 5: Synthesis of hydrolyzable silane compound (cx-22))

In a 50 cm3 three-necked flask equipped with a stirrer and thermometer, 0.40 g of 3-mercaptopropyltrimethoxysilane, 1.00 g of MMA, 2.20 g of AC, 0.03 g of AIBN, and 31.50 g of PGME were added, and 60 g It was stirred at ℃ for 12 hours. By gas chromatography, the disappearance of the peaks of the raw materials 3-mercaptopropyltrimethoxysilane, MMA, and AC was confirmed, and a PGME solution (concentration: 10% by mass) of the hydrolysable silane compound (cx-22) was obtained.

(Synthesis Example 6: Preparation of ink repellent (C2-3) liquid)

In a 50 cm3 three-necked flask equipped with a stirrer, 0.38 g of compound (cx-1), 0.90 g of PGME solution of compound (cx-22), 0.28 g of compound (cx-3), and 0.21 g of compound (cx-4). , 0.06 g of compound (cx-6) and 0.33 g of compound (cx-52) were added to obtain a hydrolyzable silane compound mixture. Next, 6.88 g of PGME was added to this mixture to serve as a raw material solution.

To the obtained raw material solution, 0.47 g of 1% hydrochloric acid aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40°C for 5 hours to prepare a PGME solution of the ink repellent agent (C2-3) (ink repellent agent (C2-3) concentration: 10% by mass, hereinafter referred to as “ink repellent agent (C2-3) solution. 」) was obtained.

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

(Synthesis Example 7: Preparation of ink repellent agent (Cf-1))

In a 50 cm3 three-necked flask equipped with a stirrer, 0.22 g of compound (cx-1), 4.27 g of compound (cx-22), 0.36 g of compound (cx-3), and 0.40 g of compound (cx-4) were added, A hydrolyzable silane compound mixture was obtained. Next, 4.22 g of PGME was added to this mixture to serve as a raw material solution.

To the obtained raw material solution, 0.53 g of 1% hydrochloric acid aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40°C for 5 hours to prepare a PGME solution of the ink repellent agent (Cf-1) (ink repellent agent (Cf-1) concentration: 10% by mass, hereinafter referred to as “ink repellent agent (Cf-1) solution. 」) was obtained.

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

(Synthesis Example 8: Preparation of ink repellent agent (Cf-2))

In a 50 cm3 three-necked flask equipped with a stirrer, 0.38 g of compound (cx-1), 0.55 g of compound (cx-3), 0.41 g of compound (cx-4), 0.12 g of compound (cx-6), compound ( cx-51) 0.21 g was added to obtain a hydrolyzable silane compound mixture. Next, 7.52 g of PGME was added to this mixture to serve as a raw material solution.

To the obtained raw material solution, 0.81 g of 1% hydrochloric acid aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40°C for 5 hours to prepare a PGME solution of the ink repellent agent (Cf-2) (ink repellent agent (Cf-2) concentration: 10% by mass, hereinafter referred to as “ink repellent agent (Cf-2) solution. 」) was obtained.

Additionally, after completion of the reaction, the components of the reaction solution were measured using gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit. The obtained ink repellent agent (Cf-2) had a number average molecular weight (Mn) of 678, a mass average molecular weight (Mw) of 745, a fluorine atom content of 20.0 (mass%), and a C=C content of 1.76 (mmol/g). . Additionally, since the ink repellent agent (Cf-2) does not have an acidic group, its acid value is 0 (mgKOH/g).

(Synthesis Example 9: Preparation of ink repellent agent (Cf-3))

In a 50 cm3 three-necked flask equipped with a stirrer, 0.38 g of compound (cx-1), 0.31 g of compound (cx-3), 0.23 g of compound (cx-4), 0.06 g of compound (cx-6), compound ( cx-52) 0.34 g was added to obtain a hydrolyzable silane compound mixture. Next, 6.43 g of PGME was added to this mixture to serve as a raw material solution.

To the obtained raw material solution, 0.50 g of 1% hydrochloric acid aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40°C for 5 hours to prepare a PGME solution of the ink repellent agent (Cf-3) (ink repellent agent (Cf-3) concentration: 10% by mass, hereinafter referred to as “ink repellent agent (Cf-3) solution. 」) was obtained.

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

[Example 1: Preparation of negative photosensitive resin composition and preparation of cured film (partition wall)]

(Manufacture of negative photosensitive resin composition)

0.25 g of the (C1-1) solution obtained in Synthesis Example 1, 16.07 g of A-1 (solid content is 11.25 g, the remainder is EDGAC as a solvent), 6.25 g of B1-1, 5.00 g of B2-1, D 1.50 g of -1, 0.75 g of D-2, and 70.18 g of E-1 were placed in a 200 ㎤ stirring container and stirred for 5 hours to prepare a negative photosensitive resin composition. In Table 1, the solid content concentration (mass %) of the negative photosensitive resin composition, the solid content composition (mass %) in the negative photosensitive resin composition, the solvent composition (mass %), and the ratio with the polyfunctional low molecular weight compound (B1). The ratio (mass %) of the polyfunctional low molecular weight compound (B1) to the total of the acidic crosslinking agent (B2) is shown.

(Manufacture of cured film 1)

An ITO substrate measuring 10 cm by 10 cm (Indium-Tin-Oxide film formed on a glass substrate) was ultrasonic cleaned with ethanol for 30 seconds, followed by UV/O ₃ treatment for 5 minutes. For UV/O ₃ treatment, PL2001N-58 (manufactured by Sen Engineering Company) was used as a UV/O ₃ generator. The optical power (light output) converted to 254 nm was 10 mW/cm2. In addition, this device was used for all UV/O ₃ treatments below.

After applying the negative photosensitive resin composition to the cleaned ITO substrate surface using a spinner, it was dried on a hot plate at 100°C for 2 minutes to form a dried film with a thickness of 2.4 μm. For the obtained dried film, a photomask having an opening pattern (openings (exposed areas) of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, respectively Patterns of 30, 40, 50 ㎛ × 1000 ㎛ (the spacing between patterns is 50 ㎛) are repeated in the range of 20 ㎜ The entire surface was irradiated with UV light from an ultra-high 4-pressure mercury lamp at mW/cm2. During exposure, light of 330 nm or less was cut. Additionally, the distance between the dry film and the photomask was set to 50 ㎛. In each example, the exposure conditions were that the exposure time was 6 seconds and the exposure amount was 150 mJ/cm2.

Next, the ITO substrate after the exposure treatment was developed by immersing it in a 0.4% by mass tetramethylammonium hydroxide aqueous solution for 40 seconds, and the non-exposed portion was washed with water and dried. Next, an ITO substrate on which a cured film (partition) 1 having a pattern corresponding to the opening pattern of the photomask was formed was obtained by heating at 230°C for 60 minutes on a hot plate.

(Manufacture of cured film 2)

Additionally, in the same manner as above, a dried film of the negative photosensitive resin composition was formed on the surface of the ITO substrate, and a photomask (size of the light-shielding portion: 100 μm × 200 μm, width of the opening (exposed portion): 20 μm, and a grid pattern was applied). (repeated in the range of 20 mm First, by heating at 230°C for 60 minutes, an ITO substrate was obtained with the cured film 2 formed in a pattern surrounding the dot portion (100 μm x 200 μm) with a partition wall having a line width of 20 μm.

[Examples 2 to 16]

In Example 1, the negative photosensitive resin composition, the resin cured film, and the partition were manufactured in the same manner as in Example 1, except that the negative photosensitive resin composition was changed to the composition shown in Table 1 or Table 2.

(evaluation)

The following evaluation was performed on the negative photosensitive resin composition, cured resin 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＞

In the resin cured film 1, the PGMEA contact angle on the upper surface of the partition obtained at an exposure dose of 150 mJ/cm2 was measured by the above method.

◎: Contact angle 40° or more

○: Contact angle 30° or more but less than 40°

×: Contact angle less than 30°

＜IJ applicability＞

In the ITO substrate on which the resin cured film 2 was formed, 20 pl of a cyclohexylbenzene solution of 1% TPD (triphenyldiamine) was added dropwise to the inside of a dot surrounded by a partition using an IJ device (LaboJET 500 manufactured by Micro Jet). The diffusion of the dried material inside the dot after drying was confirmed. In addition, the judgment was made based on the following criteria.

○: The material is spread uniformly within the dot, and the material reaches the partition wall.

×: Not spread within the dot.

＜Development adhesion＞

A photomask having an opening pattern of the resin cured film 1 (openings (exposed areas) are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, respectively. The partition wall obtained at an exposure dose of 150 mJ/cm2 (30, 40, 50 ㎛

○: A line with a mask width of less than 10 μm remains.

△: A line of 10 μm or more and less than 20 μm remains.

×: A line of 20 μm or more and 50 μm or less remains.

××: No line pattern.

As is clear from Table 1, in the negative photosensitive resin compositions of Examples 1 to 9 corresponding to the Examples, by selecting the crosslinking agent (B) and the ink repellent agent (C), the liquid repellency of the upper part of the partition is good, and the partition wall is The IJ applicability within the dots surrounded by is good, and a high-definition partition pattern can be formed.

The negative photosensitive resin composition of the present invention can be preferably used as a composition for forming partition walls when pattern printing by the IJ method is performed in organic EL devices, quantum dot displays, TFT arrays, or thin film solar cells. .

The barrier wall related to the present invention is a barrier wall (bank) for pattern printing an organic layer such as a light emitting layer by the IJ method in an organic EL device, or a barrier wall (bank) for pattern printing a quantum dot layer, hole transport layer, etc. by the IJ method in a quantum dot display. It can be used as a partition wall (bank), etc. The partition according to the present invention can also be used as a partition for pattern printing a conductor pattern or semiconductor pattern in a TFT array by the IJ method. The barrier wall related to the present invention can be used, for example, as a barrier wall for pattern printing the organic semiconductor layer, gate electrode, source electrode, drain electrode, gate wiring, and source wiring forming the channel layer of the TFT by the IJ method. .

One ; Board
21 ; paint film
22 ; dry film
23 ; exposure film
23A ; exposure department
23B ; Non-exposed section
4 ; septum
4A; Ink repellent layer
5 ; opening
31 ; Masking part
30 ; photomask
9 ; inkjet head
10 ; ink
11 ; dot
12 ; Organic EL device.

Claims (7)

Alkali-soluble resin (A) having a photocurable functional group, a crosslinking agent containing a polyfunctional low molecular weight compound (B1) having an acidic group and three or more photocurable functional groups in one molecule and having a mass average molecular weight (Mw) of 300 or more and less than 1000 ( B), a negative photosensitive resin composition containing an ink repellent agent (C), a photopolymerization initiator (D), and a solvent (E) which has an acidic group and a fluorine atom and has an acid value of 10 to 100 mgKOH/g. According to claim 1,
The polyfunctional low molecular weight compound (B1) is a negative photosensitive resin composition having four or more photocurable functional groups. According to claim 1,
The polyfunctional low molecular weight compound (B1) is a negative photosensitive resin composition having a dipentaerythritol skeleton. According to claim 1,
The negative photosensitive resin composition where the content of fluorine atoms in the ink repellent agent (C) is 5 to 55% by mass. According to claim 1,
The said ink repellent agent (C) is a negative photosensitive resin composition containing a photocurable functional group. The method according to any one of claims 1 to 5,
A negative photosensitive resin composition in which the crosslinking agent (B) further contains a crosslinking agent (B2) that has two or more photocurable functional groups in one molecule and no acidic group. According to claim 6,
A negative photosensitive resin composition containing the polyfunctional low molecular weight compound (B1) in a ratio of 10 to 90 parts by mass based on a total of 100 parts by mass of the polyfunctional low molecular weight compound (B1) and the crosslinking agent (B2).