WO2018116914A1 - Negative photosensitive resin composition - Google Patents

Abstract

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

Description

Negative photosensitive resin composition

The present invention relates to a negative photosensitive resin composition.

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

When pattern printing is performed by the inkjet (IJ) method, the upper surface of the partition wall needs to have ink repellency in order to prevent ink mixing between adjacent dots and to uniformly apply ink in dot formation. On the other hand, the dot forming opening surrounded by the partition including the partition side surface needs to have ink affinity. Therefore, in order to obtain a partition wall having ink repellency on the upper surface, a dot-type photolithography method having coating film formation, exposure, and development steps using a negative photosensitive resin composition containing an ink repellant is used. A method of forming a partition corresponding to a pattern is known.

In the partition formation using such a negative photosensitive resin composition, after development, if a residue of the composition (hereinafter, also referred to as “development residue”) is present in the opening, then the opening is formed by the IJ method. In some cases, wetting and spreading of the ink supplied to the ink is not sufficient. Further, 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 can be easily removed by the developer. However, in this method, the ink repellency on the upper surface of the partition wall is sufficiently maintained. There was a problem that it was not.

For example, in Patent Document 1, component (A); ethylenically unsaturated compound, component (B); photopolymerization initiator, component (C); an alkali-soluble binder having an ethylenically unsaturated group in the side chain, and ( D) component; a liquid repellent comprising a fluorine-based compound having an ethylenically unsaturated group in the side chain; (E) component; an active drive organic electroluminescence device containing a fluorine-based surfactant and / or a silicone-based surfactant The photosensitive composition for partition walls is described.

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

As described above, in Patent Document 1, the ink repellency on the upper surface of the partition wall and the ink wettability on the opening portion can be compatible by the composition. However, the ink repellency and the opening on the upper surface of the partition wall enough to cope with a higher-precision optical element. The ink wettability of the part has not been achieved.

Patent Document 2 discloses a technique for improving solubility in a developer by introducing an acidic group into an ink repellent agent suitable for a method of removing development residues by UV / O ₃ irradiation. Is described. However, when the ink repellent agent according to Patent Document 2 is used for the negative photosensitive resin composition, it is difficult to say that ink repellent property and development adhesion are sufficient as in the case of Patent Document 1.

JP 2011-165396 A International Publication No. 2014/046212

The present invention has been made from the above viewpoint, and the obtained partition wall has high development adhesiveness and good ink repellency on the upper surface, and the development residue is sufficiently small in the opening for forming dots. It aims at providing a type photosensitive resin composition.

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 A negative photosensitive resin composition comprising an ink repellent agent (C) having 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).
[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 fluorine atom content in the ink repellent agent (C) is from 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) further includes a crosslinking agent (B2) having two or more photocurable functional groups in one molecule and having no acidic group. The negative photosensitive resin composition in any one.
[7] The polyfunctional low molecular weight compound (B1) is contained at a ratio of 10 to 90 parts by mass with respect to 100 parts by mass in total of the polyfunctional low molecular weight compound (B1) and the crosslinking agent (B2). The negative photosensitive resin composition as described.

According to the present invention, there is provided a negative photosensitive resin composition in which the obtained partition wall has high development adhesiveness and good ink repellency on the upper surface, and development residue is sufficiently small in the opening for forming dots. it can.

It is process drawing which shows typically the manufacturing method of the partition of embodiment of this invention. It is process drawing which shows typically the manufacturing method of the partition of embodiment of this invention. It is process drawing which shows typically the manufacturing method of the partition of embodiment of this invention. It is process drawing which shows typically the manufacturing method of the partition of embodiment of this invention. It is process drawing which shows typically the manufacturing method of the optical element of embodiment of this invention. It is process drawing which shows typically the manufacturing method of the optical element of embodiment of this invention.

In the present specification, the following terms are respectively used with the following meanings.
“(Meth) acryloyl group” is a general term for “methacryloyl group” and “acryloyl group”. (Meth) acryloyloxy group, (meth) acrylic acid, and (meth) acrylate also conform to this.

The group represented by the formula (x) may be simply referred to as a group (x).
The compound represented by the formula (y) may be simply referred to as the compound (y).
Here, the expressions (x) and (y) indicate arbitrary expressions.

“A resin mainly composed of a certain component” or “a resin mainly composed of a certain component” means that the proportion of the component occupies 50% by mass or more based on the total amount of the resin.

The “side chain” is a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting the main chain in a polymer in which a repeating unit composed of carbon atoms constitutes the main chain.

The “total solid content of the photosensitive resin composition” refers to a component that forms a cured film described later among the components contained in the photosensitive resin composition, and the photosensitive resin composition is heated at 140 ° C. for 24 hours. Obtained from the residue from which the solvent has been removed. The total solid content can also be calculated from the charged amount.

A film made of a cured product of a composition containing resin as a main component is referred to as a “resin cured film”.
A film coated with the photosensitive resin composition is referred to as a “coating film”, and a film obtained by drying the film is referred to as a “dry film”. A film obtained by curing the “dry film” is a “resin cured film”. Further, the “resin cured film” may be simply referred to as “cured film”.

The resin cured film may be in the form of a partition formed in a shape that partitions a predetermined region into a plurality of sections. For example, the following “ink” is injected into the partitions partitioned by the partition walls, that is, the openings surrounded by the partition walls to form “dots”.

“Ink” is a general term for liquids having optical and / or electrical functions after drying, curing, and the like. In an organic EL element, a quantum dot display, a TFT array, and a thin film solar cell, dots as various constituent elements may be pattern-printed by an ink jet (IJ) method using the ink for forming the dots. “Ink” includes ink used in such applications.

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

The “dot” indicates a minimum area where light modulation is possible in the optical element. In an organic EL element, a quantum dot display, a TFT array, and a thin film solar cell, 1 dot = 1 pixel in the case of black and white display, for example, 3 dots (R (red), G (green), B in the case of color display. (Blue) etc. = 1 pixel.
“Percent (%)” represents mass% unless otherwise specified.
Embodiments of the present invention will be described below.

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

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 a combination of the ink repellent agent (C) having the predetermined acid value. By using it, it is possible to form a partition wall having high development adhesion and having a good ink repellency on the upper surface and sufficiently small development residue in the opening. If such a partition wall is used for an optical element, for example, an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell, the dot can be accurately formed due to good ink applicability by the IJ method or the like. A highly sensitive optical element that can be formed can be manufactured.

The negative photosensitive resin composition of the present invention contains a crosslinking agent (B2) having no acidic group and other optional components, if necessary, in addition to the above essential components. Hereinafter, each component will be described.

(Alkali-soluble resin (A))
The alkali-soluble resin (A) is an alkali-soluble resin having a photocurable functional group. As alkali-soluble resin (A), the photosensitive resin which has an acidic group and an ethylenic double bond in 1 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 is also crosslinked. It crosslinks with the agent (B) and cures to form a cured film.

The exposed portion sufficiently cured in this way is not easily removed with an alkaline developer (hereinafter also simply referred to as “developer”). Moreover, the non-exposure of the negative photosensitive resin composition which is not hardened because 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. The portion can be selectively removed with a developer. As a result, the cured film can be in the form of a partition that partitions a predetermined region into a plurality of sections.

Examples of the acidic group include a carboxy group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group. These may be used alone or in combination of two or more.

As the photocurable functional group, an ethylenic double bond is preferable. Examples of the ethylenic double bond include double bonds having an addition polymerization property such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, and a vinyloxyalkyl group. These may be used alone or in combination of two or more. In addition, some or all of the hydrogen atoms possessed by 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 a resin (A-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an acidic group in the epoxy resin. And a resin (A-2) having an ethylenic double bond introduced therein. These may be used alone or in combination of two or more. As such an alkali-soluble resin (A), those described in WO 2014/084279 can be used.

As alkali-soluble resin (A), peeling of the cured film at the time of development is suppressed, and a high-resolution dot pattern can be obtained, and the linearity of the pattern when the dots are linear is good. In view of the fact that a smooth cured film surface is easily obtained, it is preferable to use the resin (A-2). In addition, that the linearity of a pattern is favorable means that the edge of the partition obtained does not have a chip etc. and is linear.

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

Further, the unsaturated group-containing urethane resin as component (A) in JP-A-2001-33960, the polyurethane compound as component (E) in JP-A-2003-268067, and the reactivity as component (A) in JP-A-2010-280812. Examples thereof include urethane resins such as polyurethane compounds.

Specifically, a compound having a double bond and a hydroxyl group obtained by reacting a bifunctional epoxy resin and acrylic acid, a diol compound having a carboxyl group such as dimethylolpropionic acid, and a diisocyanate compound such as trimethylhexamethylene diisocyanate, an optional component And a resin obtained by reacting a polybasic acid anhydride such as glycidyl methacrylate or phthalic anhydride.

Examples of the bifunctional epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, epoxy resin having naphthalene skeleton, and biphenyl skeleton. And epoxy resin having fluorenyl substitution and bisphenol A type epoxy resin.

In particular, the use of a urethane-based resin is preferable because flexibility can be imparted, alkali resistance is good, and dispersion stability in the developer is also good.

Examples of the resin (A-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, epoxy resin having naphthalene skeleton, and biphenyl skeleton. An epoxy resin having an acidic group and an ethylenic double bond are preferably introduced into the epoxy resin having fluorenyl-substituted bisphenol A type epoxy resin and the epoxy resin described in JP-A-2006-84985.

Bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin having biphenyl skeleton, fluorenyl substituted bisphenol A type epoxy resin, and epoxy resin described in JP-A-2006-84985, respectively, have an acidic group and an ethylenic double bond. A resin into which is introduced is more preferable.

Of these, bisphenol A type epoxy resins, bisphenol F type epoxy resins, epoxy resins having a biphenyl skeleton, and fluorenyl-substituted bisphenol A type epoxy resins are particularly preferable. When these resins are used, the interaction with the photopolymerization initiator (D) is improved, and the adhesion with the substrate is improved.

The number of ethylenic double bonds in one molecule of the alkali-soluble resin (A) is preferably 3 or more on average, and particularly preferably 6 or more on average. When the number of ethylenic double bonds is at least the lower limit of the above range, the alkali solubility between the exposed and unexposed portions is likely to be different, and a fine pattern can be formed 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 , particularly preferably 2 × 10 ³ to 15 × 10 ³ . The number average molecular weight (Mn) is preferably 500 to 13 × 10 ³ , and particularly preferably 1.0 × 10 ³ to 10 × 10 ³ . When the mass average molecular weight (Mw) and the number average molecular weight (Mn) are not less than the lower limit of the above range, curing at the time of exposure is sufficient, and when it is not more than the upper limit of the above range, the developability is good.

In the present specification, the number average molecular weight (Mn) and the mass average molecular weight (Mw) are those measured by a gel permeation chromatography method using polystyrene as a standard substance unless otherwise specified.

The acid value of the alkali-soluble resin (A) is preferably 10 to 300 mgKOH / g, 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 is improved.

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

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

(Crosslinking agent (B))
The crosslinking agent (B) contains a polyfunctional low molecular weight compound (B1) having an acidic group and two or more photocurable functional groups in one molecule, preferably two or more in one molecule. It contains a crosslinking agent (B2) having a photocurable functional group and no acidic group (hereinafter also referred to as “non-acidic crosslinking agent (B2)”). Since the crosslinking agent (B) has two or more photocurable functional groups in one molecule, it 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 becomes a cured film sufficiently cured by crosslinking with the crosslinking agent (B) when the alkali-soluble resin (A) is polymerized by exposure.

<Polyfunctional low molecular weight compound (B1)>
The polyfunctional low molecular weight compound (B1) is a monomer having an acidic group and two or more photocurable functional groups in one molecule. The “low molecular weight compound” in the present invention means a concept opposite to a so-called high molecular substance (resin). In the present specification, “low molecular weight compound” is used in a concept including “monomer”, “dimer”, “trimer”, and “oligomer”. In the present specification, the “low molecular weight compound” means a compound having a mass average molecular weight (Mw) of 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. 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. When the mass average molecular weight (Mw) and the number average molecular weight (Mn) are in the above ranges, alkali solubility and developability are good.

The photocurable functional group possessed by the polyfunctional low molecular weight compound (B1) is preferably the same type of photocurable functional group as that possessed by the alkali-soluble resin (A). A double bond is preferred. The number of photocurable functional groups in one 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 coating film surface is improved, and the stability of ink repellency is improved on the upper surface of the obtained partition wall.

Examples of the acidic group possessed by the polyfunctional low molecular weight compound (B1) include a carboxy group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group. These may be used alone or in combination of two or more. Also good. The number of acidic groups in one molecule of the polyfunctional low molecular weight compound (B1) may be 1 or more, preferably 1 or 2, and more preferably 1.

Examples of the polyfunctional low molecular weight compound (B1) include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, a polyisocyanate compound and (meth) acryloyl containing Examples thereof include compounds in which an acidic group is introduced so that two or more unsaturated bonds (ethylenic double bonds) remain in an ethylenic compound having a urethane skeleton obtained by reacting with a hydroxy compound.

The polyfunctional low molecular weight compound (B1) is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an aromatic carboxylic acid anhydride or non-aromatic carboxylic acid is added to an unreacted hydroxy group of the aliphatic polyhydroxy compound. A polyfunctional low molecular weight compound having an acid group reacted with an acid anhydride is preferable, and a polyfunctional low molecular weight compound having an acid group reacted with a non-aromatic carboxylic acid anhydride is more preferable.

As an aliphatic polyhydroxy compound in an ester of an aliphatic polyhydroxy compound into which an acidic group is introduced and an unsaturated carboxylic acid, a compound having three or more hydroxy groups, for example, trimethylolpropane, trimethylolethane, pentaerythritol, Examples thereof include dipentaerythritol, tripentaerythritol, tetrapentaerythritol and the like. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, ilotonic acid, maleic acid and the like.

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

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

In the polyfunctional low molecular weight compound (B1), as a compound obtained by reacting an aromatic carboxylic acid anhydride with an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, for example, three hydroxy groups of pentaerythritol are acryloyloxy. For example, 2,2,2-triacryloyloxymethylethylphthalic acid having a structure in which the remaining one hydroxy group is ester-bonded to phthalic acid is exemplified.

As the polyfunctional low molecular weight compound (B1), a compound having a dipentaerythritol skeleton is preferable. As a compound having a dipentaerythritol skeleton, for example, five hydroxy groups of dipentaerythritol are substituted with (meth) acryloyloxy groups, and the remaining one hydroxy group is ester-bonded with, for example, succinic acid to form an acidic group. A compound in which is introduced is preferred.

The acid value of the polyfunctional low molecular weight compound (B1) is preferably 10 to 100 mgKOH / g, more preferably 20 to 95 mgKOH / g. When the acid value of the polyfunctional low molecular weight compound (B1) is not less than the above lower limit value, it is possible to obtain better solubility in a developing solution in the negative photosensitive composition, and it is not more than the above upper limit value. Manufacturing and handling properties become good, sufficient polymerizability can be secured, and curability such as surface smoothness of the resulting coating film becomes good.

In the negative photosensitive resin composition, the polyfunctional low molecular weight compound (B1) may be used alone or in combination of two or more. In addition, when using a polyfunctional low molecular weight compound (B1) as a 2 or more types of mixture, it is preferable that the acid value of a mixture exists in the said range.

<Non-acidic crosslinking agent (B2)>
In addition to the polyfunctional low molecular weight compound (B1), the crosslinking agent (B) has two or more photocurable functional groups in one molecule and does not have an acidic group, that is, a non-acidic crosslinking. An agent (B2) may be contained. By using a combination of the polyfunctional low molecular weight compound (B1) and the non-acidic crosslinker (B2), it becomes easy to adjust the acid value and the number of photocurable functional groups of the entire crosslinker (B), and negative photosensitive at the time of exposure. The effect of improving the curability of the photosensitive resin composition and the effect of improving the solubility of the negative photosensitive resin composition in the developer can be easily balanced.

As the photocurable functional group that the non-acidic crosslinking agent (B2) has two or more in one molecule, the same type of photocurable functional group as that of the alkali-soluble resin (A) is preferable, Specifically, an ethylenic double bond is preferable. The number of photocurable functional groups in one 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 coating film surface is improved, and the stability of ink repellency is improved on the upper surface of the obtained partition wall. In addition, the molecular weight of a non-acidic crosslinking agent (B2) can be made the same including a polyfunctional low molecular weight compound (B1) and a preferable aspect.

Specific examples of the non-acidic crosslinking agent (B2) include compounds having no acidic group in the polyfunctional low molecular weight compound (B1), and an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable.

More specifically, as non-acidic crosslinking agent (B2), diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol heptaacrylate, tetrapentaerythritol octaacrylate, tetrapenta Erythritol nonaacrylate, tetrapentaerythritol decaacrylate, ethoxylated iso HDI (hexamethylene diisocyanate) binds to tri (meth) acrylate of anuric acid, tris- (2-acryloyloxyethyl) isocyanurate, ε-caprolactone modified tris- (2-acryloyloxyethyl) isocyanurate, dipentaerythritol pentaacrylate And monomers having a urethane skeleton (10 functional) and urethane acrylate.

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

The content of the crosslinking agent (B) in the total solid content in the negative photosensitive resin composition is preferably 5 to 80% by mass, particularly preferably 10 to 60% by mass. Moreover, the acid value of a crosslinking agent (B) is the same range as the acid value of the said polyfunctional low molecular weight compound (B1), when a crosslinking agent (B) is comprised only with a polyfunctional low molecular weight compound (B1). is there. The acid value of the crosslinking agent (B) is preferably 10 to 80 mgKOH / g, and preferably 15 to 70 mgKOH / g when the crosslinking agent (B) contains both the polyfunctional low molecular weight compound (B1) and the non-acidic crosslinking agent (B2). g is more preferable.

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

When the negative photosensitive resin composition contains the 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 0.1. To 50% by mass is preferable, and 1.0 to 40% by mass is more preferable.

In this case, the ratio of the polyfunctional low molecular weight compound (B1) to the total 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 15 to 70 parts by mass. Part is more preferred. By adjusting the polyfunctional low molecular weight compound (B1) and the non-acidic crosslinking agent (B2) to the above ratio, the acid value and the number of photocurable functional groups of the entire crosslinking agent (B) can be easily adjusted, and the negative photosensitive resin. It is easy to balance the photocurability and developability of the composition.

In addition, as a crosslinking agent (B), what is marketed as a mixture of a polyfunctional low molecular weight compound (B1) and a non-acidic crosslinking agent (B2), for example, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipenta A succinic acid ester mixture of erythritol pentaacrylate may be used.

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

(Ink repellent (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 a property of transferring to the upper surface in the process of forming a cured film using the negative photosensitive resin composition containing the same (upper surface transfer property) and ink repellency. Have By using the ink repellent agent (C), the upper layer portion including the upper surface of the obtained cured film becomes a layer in which the ink repellent agent (C) is present densely (hereinafter also referred to as “ink repellent layer”). Ink repellency is imparted to the upper surface of the cured film.

The ink repellent agent (C) has an acidic group and has an acid value of not less than the above lower limit, so that the negative photosensitive resin composition contains an alkali-soluble resin (A), a crosslinking agent (B), etc. Like the component, it has good solubility in the developer. Thereby, the negative photosensitive resin composition in the non-exposed part can be easily removed with a developer, and the developability is good. On the other hand, when the acid value of the ink repellent agent (C) is not more than the above upper limit, the ink repellent layer formed on the upper layer portion of the cured film is sufficiently in close contact with the resin layer of the lower layer portion and is hardly affected by the developer. Without being received, it can remain after development and exhibit high ink repellency.

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

The content of fluorine atoms in the ink repellent agent (C) is preferably from 5 to 55% by mass, more preferably from 10 to 55% by mass, and further from 12 to 40% by mass from the viewpoints of upper surface migration and ink repellency. It is preferably 14 to 30% by mass. If the fluorine atom content of the ink repellent agent (C) is at least the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film, and if it is less than the upper limit, the negative photosensitive resin composition Compatibility with other components in the inside is improved.

Further, the ink repellent agent (C) is preferably a compound having a photocurable functional group, particularly an ethylenic double bond. Since the ink repellent agent (C) has an ethylenic double bond, radicals act on the ethylenic double bond of the ink repellent agent (C) transferred to the upper surface, and the ink repellent agent (C) or ink repellent Crosslinking by (co) polymerization with the agent (C) and other components having an ethylenic double bond contained in the negative photosensitive resin composition becomes possible.

Thereby, in the production of a cured film obtained by curing the negative photosensitive resin composition, the fixability in the upper layer portion 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 during 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 photocurable component mainly composed of the alkali-soluble resin (A) present around the ink repellent agent (C) is sufficiently cured. Thus, the ink repellent agent (C) can be sufficiently fixed.

Examples of the ink repellent agent (C) include an ink repellent agent (C1) made of a compound having a main chain of a hydrocarbon chain, a side chain having an acidic group, and a side chain containing a fluorine atom. As the ink repellent agent (C), an ink repellent agent (C2) composed of a partially hydrolyzed condensate of a hydrolyzable silane compound containing a hydrolyzable silane compound having an acidic group and a hydrolyzable silane compound having a fluorine atom is used. It may be used.

The ink repellent agent (C1) and the ink repellent agent (C2) are used alone or in combination. In the negative photosensitive resin composition of the present invention, it is particularly preferable to use the ink repellent agent (C1) from the viewpoint of developing higher ink repellency. In addition, when UV resistance / 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 having a main chain of a hydrocarbon chain, 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. ˜12 × 10 ⁴ is particularly preferred. When the mass average molecular weight (Mw) is at least the lower limit value, the ink repellent agent (C1) tends to shift to the upper surface when a cured film is formed using the negative photosensitive resin composition. The opening residue is less than the upper limit, which is preferable.

Examples of the acidic group in the side chain having an acidic group include a carboxy group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group. These may be used alone or in combination of two or more. In the ink repellent agent (C1), the portion other than the acidic group in the side chain having an acidic group is not particularly limited.

The side chain containing a fluorine atom in the ink repellent agent (C1) includes a side chain composed of a fluoroalkyl group which may contain an etheric oxygen atom and / or a fluoroalkyl group which may contain an etheric oxygen atom. Side chains having are preferred.

The fluoroalkyl group may be linear or branched.
Specific examples of the fluoroalkyl group not containing 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) _{r 2} 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 (C1), specifically, the main chain obtained by polymerization of a monomer having an ethylenic double bond, -Ph-CH 2 - _(where " Ph ”represents a benzene skeleton.) And a novolak-type main chain composed of repeating units.

The ink repellent agent (C1) can further contain one or more side chains 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. Moreover, the side chain containing the acidic group may contain an ethylenic double bond and / or an oxyalkylene group.

Further, the ink repellent agent (C1) can 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.

The main chain of the ink repellent (C1) is -Ph-CH 2 _- if the main chain of the novolak type comprising repeating units of, usually, a benzene skeleton (Ph) constituting the main chain, a side chain having a fluorine atom A polymer in which a side chain having an acidic group is bonded and a side chain having an ethylenic double bond and an oxyalkylene side chain are optionally bonded 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.

The acid value in the ink repellent agent (C1) can be easily adjusted by adjusting the ratio of the side chain having an acidic group introduced into the main chain of the hydrocarbon chain of the ink repellent agent (C1). Similarly, the fluorine atom content in the ink repellent agent (C1) can be easily adjusted by adjusting the proportion of side chains having fluorine atoms introduced into the main chain of the hydrocarbon chain of the ink repellent agent (C1). It can be done.

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

The mixture (M) is a hydrolyzable silane compound having a fluoroalkylene group and / or a fluoroalkyl group and a group in which a hydrolyzable group is bonded to a silicon atom (hereinafter referred to as “hydrolyzable silane compound (s1)”). And a hydrolyzable silane compound having a group having an acidic group and a group having a hydrolyzable group bonded to a silicon atom and not containing a fluorine atom (hereinafter referred to as “hydrolyzable silane compound (s2)”). Is also included as an essential component, and optionally includes a hydrolyzable silane compound other than the hydrolyzable silane compound (s1) and the hydrolyzable silane compound (s2).

The hydrolyzable silane compound optionally contained in the mixture (M) is a hydrolyzable silane compound in which four hydrolyzable groups are bonded to a silicon atom (hereinafter also referred to as “hydrolyzable silane compound (s3)”). .) Is preferred.

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 are Particularly preferred.

The content of the hydrolyzable silane compound (s1) in the mixture (M) is preferably such that the fluorine atom content in the partially hydrolyzed condensate obtained from the mixture is 5 to 55% by mass. More preferably, it is 10 to 55% by mass, still more preferably 12 to 40% by mass, and particularly preferably 15 to 30% by mass. When the content ratio of the hydrolyzable silane compound (s1) is not less than the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film. Compatibility with the decomposable silane compound is improved.

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

(1) A 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) A compound represented by the following formula (c-2a-4), the following formula (c-2a-5) and the following formula (c-2a-6).

R ²² represents 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 group represented by. When R ²² is —COO—R ²⁵ OOC—R ²⁵ —COOH, the solubility of the developer of the ink repellent agent (C2) is further improved, the residue of the opening is reduced, and the wettability of the ink by the IJ method is further increased. Good and preferable.

R ²¹ is -COOR ²⁴ (. ^{Wherein, R 24} is showing a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), a group represented _{by, -COO- (C 2 H 4 O} ) i - (C ₃ H ₆ O) _j- (C ₄ H ₈ O) _k -R ²⁸ (where R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent). , I represents an integer of 0 to 100, j represents an integer of 0 to 100, k represents an integer of 0 to 100, and i + j + k is 2 to 100. In the case of having a plurality of types of oxyalkylene groups, the order is arbitrary. ), Or a phenyl group in which a hydrogen atom may be substituted with a hydrocarbon group having 1 to 10 carbon atoms. When R ²¹ is —COO— (C ₂ H ₄ O) _i — (C ₃ H ₆ O) _j — (C ₄ H ₈ O) _k —R ²⁸ , the dispersion stability and storage of the ink repellent (C2) Stability is improved, which is preferable.

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

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

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

X ² is the same as in formula (c-2a).

(3) a reaction product of an ethylenic double bond, a compound having a hydroxyl group or a carboxy group and derivatives thereof, and hydrosilanes, specifically, the following formulas (c-2c-1) and (c-2c) -2) respectively.

X ² is the same as in formula (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 further preferably 30 to 60 mgKOH / g.

When the content ratio of the hydrolyzable silane compound (s2) is not less than the lower limit of the above range, the obtained negative photosensitive resin composition has good solubility in a developer. Thereby, the negative photosensitive resin composition in the non-exposed part can be easily removed with a developer, and the developability is good. On the other hand, when the acid value of the ink repellent agent (C) is not more than the above upper limit, the ink repellent layer formed on the upper layer portion of the cured film is sufficiently in close contact with the resin layer of the lower layer portion and is hardly affected by the developer. Without being received, it can remain after development and exhibit high ink repellency.

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

The content of the hydrolyzable silane compound (s3) in the mixture (M) is preferably 0.01 to 5 mol, particularly preferably 0.05 to 4 mol, relative to 1 mol of the hydrolyzable silane compound (s1). . When the content ratio is not less than the lower limit of the above range, the film forming property of the ink repellent agent (C2) is good, and when it is not more than the upper limit value, the ink repellent property of the ink repellent agent (C2) is good.

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

Hydrolyzable silane compound (s4): a hydrolyzable silane compound having 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.

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

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

The content of the hydrolyzable silane compound (s4) in the mixture (M) is preferably 0.1 to 5 mol, particularly 0.5 to 4 mol, relative to 1 mol of the hydrolyzable silane compound (s1). preferable. When the content ratio is equal to or more than the lower limit of the above range, the top transferability of the ink repellent agent (C2) is good, and the fixability of the ink repellent agent (C2) in the ink repellent layer including the top surface after shifting to the top surface. Further, the storage stability of the ink repellent agent (C2) is good. When the amount is not more than the upper limit, the ink repellency of the ink repellent agent (C2) is good.

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

The content of the hydrolyzable silane compound (s5) in the mixture (M) is preferably 0 to 2.0 mol, particularly 0 to 1.5 mol, per 1 mol of the hydrolyzable silane compound (s1). preferable. When the content ratio is equal to or more than the lower limit of the above range, the top transferability of the ink repellent agent (C2) is good, and the fixability of the ink repellent agent (C2) in the ink repellent layer including the top surface after shifting to the top surface. Further, the storage stability of the ink repellent agent (C2) is good. When the amount is not more than 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 the formula, Ph represents a phenyl group.

The content of the hydrolyzable silane compound (s6) in the mixture (M) is preferably 0 to 1.0 mol, particularly 0 to 0.08 mol, relative to 1 mol of the hydrolyzable silane compound (s1). preferable. Storage stability is favorable in a content rate being more than the lower limit of the said range. When it is at most the upper limit value, the ink applicability of the dot portion is good.

Other hydrolyzable silane compounds include an epoxy group and a hydrolyzable silyl group, a hydrolyzable silane compound (s7) containing no fluorine atom, an oxyalkylene group and a hydrolyzable silyl group, Hydrolyzable silane compound not containing fluorine atom (s8), having sulfide and hydrolyzable silyl group, hydrolyzable silane compound not containing fluorine atom (s9), having ureido group and hydrolyzable silyl group And hydrolyzable silane compound (s10) having no fluorine atom, hydrolyzable silane compound (s11) having an amino group and a hydrolyzable silyl group and not containing a fluorine atom.

Examples of the hydrolyzable silane compound (s7) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycol. Sidoxypropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane are used as the hydrolyzable silane compound (s8), for example, CH ₃ O (C ₂ H ₄ O) _k Si (OCH ₃ ) ₃ (poly Oxyethylene group-containing trimethoxysilane (here, k is, for example, about 10), hydrolyzable silane compound (s9), for example, bis (triethoxysilylpropyl) tetrasulfide, hydrolyzable silane compound ( s10), for example, 3-ureidopropyltriethoxysilane, water As a solution silane compound (s11), for example, N- phenyl-3-aminopropyltrimethoxysilane.

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

As an example of the ink repellent agent (C2), the hydrolyzable silane compound (s1) is n1, the hydrolyzable silane compound (s2) is n2, the hydrolyzable silane compound (s3) is n3, and the hydrolyzable silane compound (s4). ) Is n4, the hydrolyzable silane compound (s5) is n5, and the hydrolyzable silane compound (s6) is n6, and a partial hydrolysis condensate of the mixture (M) is included. Here, n1 to n6 represent the mole fraction of each structural unit relative 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 preparation composition of the hydrolyzable silane compounds (s1), (s2), (s3), (s4), (s5), and (s6) in the mixture (M). The molar ratio of each component is designed from the balance of the effect of each component.
n1 is preferably 0.02 to 0.4 in such an amount that the fluorine atom content in the ink repellent agent (C2) falls within the above-mentioned preferable range.
n2 is preferably 0.003 to 0.03 in such an amount that the acid value in the ink repellent agent (C2) falls within the above range.
n3 is preferably 0 to 0.98, particularly preferably 0.05 to 0.6.
n4 is preferably 0 to 0.4, particularly preferably 0 to 0.27.
n5 is preferably 0 to 0.1, particularly preferably 0 to 0.07.
n6 is preferably 0 to 0.2, 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 not less than the lower limit, the ink repellent agent (C2) is likely to shift to the upper surface when a cured film is formed using the negative photosensitive resin composition. When it is less than the upper limit, the opening residue is reduced, which is preferable. In addition, the mass average molecular weight (Mw) of the ink repellent agent (C2) can be adjusted by manufacturing conditions.

The ink repellent agent (C2) can be produced by subjecting the above-mentioned mixture (M) to hydrolysis and condensation reaction by a known method. This reaction is catalyzed by 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 Moreover, a well-known solvent can be used for the said reaction. The ink repellent agent (C2) obtained by the above reaction may be blended in a 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 a content ratio at which the surface satisfies the above characteristics in the partition obtained using the same. The content ratio depends on the type of the ink repellent agent (C) to be used, but specifically, 0.01 to 10% by mass is preferable, and 0.1 to 2% by mass is more preferable. When the content ratio is at least 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. Adhesiveness of a cured film and a base material becomes it favorable that it is below the upper limit of the said range.

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

Examples of the photopolymerization initiator (D) include α-diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like. Acyloin ethers; thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone; benzophenone, 4,4'-bis (dimethylamino) Benzophenones such as benzophenone and 4,4′-bis (diethylamino) benzophenone; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophene Non, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Acetophenones such as dimethylamino-1- (4-morpholinophenyl) -butan-1-one; quinones such as anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone; ethyl 2-dimethylaminobenzoate Aminobenzoic acids such as 4-dimethylaminobenzoic acid (n-butoxy) ethyl; halogen compounds such as phenacyl chloride and trihalomethylphenylsulfone; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. Acylphosphine oxides; di-t-butyl Peroxides such as oxides; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methylbenzoyl)- Oxime esters such as 9H-carbazol-3-yl] -1- (O-acetyloxime), aliphatics such as triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate Examples include amines.

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

Examples of the photopolymerization initiator (D) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) -butan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) or 2,4-diethylthioxanthone is preferred. Furthermore, combinations of these with benzophenones, for example, 4,4'-bis (diethylamino) benzophenone are particularly preferred. A photoinitiator (D) may be used individually by 1 type, or may use 2 or more types together.

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

(Solvent (E))
When the negative photosensitive resin composition of the present invention contains the solvent (E), the viscosity is reduced, and the negative photosensitive resin composition can be easily applied to the substrate surface. As a result, a coating film of a negative photosensitive resin composition having a uniform film thickness can be formed. A known solvent is used as the solvent (E). A solvent (E) may be used individually by 1 type, or may use 2 or more types together.

Examples of the solvent (E) include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, solvent naphtha, and water. Among these, at least one solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferable. Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol At least one selected from the group consisting of monoethyl ether acetate, N, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-n-butoxy-N, N-dimethylpropionamide and 2-propanol More preferred are seed solvents.

In particular, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, N, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, and 3-n-butoxy-N, N-dimethylpropionamide have a boiling point of 150 ° C. This is preferable because uneven coating and the like tend to be suppressed.

In addition, when a solvent (E) contains water, it is preferable that content of water is 10 mass% or less of the whole solvent (E). Within the above range, it is possible to reduce the unevenness of the pattern substrate comprising the partition formed from the cured film obtained from the negative photosensitive resin composition of the present invention. The water content is more preferably 1 to 10% by mass. 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 with respect to the total amount of the composition. The total amount of the alkali-soluble resin (A) and the crosslinking agent (B) is 100% by mass, preferably 0.1 to 3000% by mass, and more preferably 0.5 to 2000% by mass.

(Other ingredients)
(Thiol compound (G))
The thiol compound (G) optionally contained in the negative photosensitive resin composition of the present invention is a compound having two or more mercapto groups in one molecule. If the negative photosensitive resin composition of this invention contains a thiol compound (G), the radical of a thiol compound (G) will produce | generate by the radical produced | generated from the photoinitiator (D) at the time of exposure, and alkali-soluble resin ( A), a so-called ene-thiol reaction that acts on the ethylenic double bond of the other component contained in the crosslinking agent (B) or the negative photosensitive resin composition occurs. This ene-thiol reaction is different from the usual radical polymerization of ethylenic double bonds, and is not subject to reaction inhibition by oxygen, so it has high chain mobility and also undergoes crosslinking at the same time as polymerization. The shrinkage rate is low, and there is an advantage that a uniform network can be easily obtained.

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 amount as described above, and includes a partition upper surface that is particularly susceptible to reaction inhibition by oxygen. Since the photocuring is sufficiently performed also in the upper layer portion, it is possible to impart good ink repellency to the upper surface of the partition wall.

The mercapto group in the thiol compound (G) is preferably contained 2 to 10 in one molecule, more preferably 2 to 8 and even more preferably 2 to 5. From the viewpoint of storage stability of the negative photosensitive resin composition, 3 is particularly preferable.

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

Specific examples of the thiol compound (G) include tris (2-mercaptopropanoyloxyethyl) isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tristhioglycolate, pentaerythritol tristhioglycol. , Pentaerythritol tetrakisthioglycolate, dipentaerythritol hexathioglycolate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyl) Oxy) -ethyl] -isocyanurate, dipentaerythritol hexa (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobuty ), Pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), 1,3,5-tris (3- Mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, triphenolmethanetris (3-mercaptopropionate), triphenolmethanetris (3- Mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), 2,4,6-trimercapto-S-triazine and the like. A thiol compound (G) may be used individually by 1 type, or may use 2 or more types together.

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

(Phosphate compound (H))
The negative photosensitive resin composition of the present invention can optionally contain a phosphoric acid compound (H) in order to improve the adhesion of the obtained cured film to a substrate, a transparent electrode material such as ITO, and the like.

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

As a phosphoric acid compound having an ethylenically unsaturated double bond in the molecule, a phosphoric acid (meth) acrylate compound, that is, an O = P structure derived from at least phosphoric acid in the molecule and a (meth) acrylic acid compound A compound having a (meth) acryloyl group which is an ethylenically unsaturated double bond or a vinyl phosphate compound is preferred.

Examples of the phosphoric acid (meth) acrylate compound used in the present invention include mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate, and di (2-acryloyloxyethyl). Examples include acid phosphate, tris ((meth) acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) caproate acid phosphate, and the like.

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

The negative photosensitive resin composition of the present invention may contain, as the phosphoric acid compound (H), one kind of compound classified as such, or may contain two or more kinds.

When the negative photosensitive resin composition contains the phosphoric acid compound (H), the content is preferably 0.01 to 10% by mass with respect to the total solid content in the negative photosensitive resin composition, 0.1 to 5% by mass is particularly preferable. Further, 0.01 to 200% by mass is preferable and 0.1 to 100% by mass is more preferable with respect to 100% by mass of the alkali-soluble resin (A). When the content ratio of the phosphoric acid compound (H) is in the above range, the adhesion between the obtained cured film and the substrate is good.

The negative photosensitive resin composition in the present invention may further include a polymerization inhibitor, a thermal crosslinking agent, a polymer dispersant, a dispersion aid, a silane coupling agent, fine particles, a curing accelerator, a thickener, if necessary. You may contain 1 or more types of other additives chosen from the group which consists of a plasticizer, an antifoamer, a leveling agent, and a repellency inhibitor.

The negative photosensitive resin composition of the present invention can be obtained by mixing predetermined amounts of the above components. The negative photosensitive resin composition of the present invention is particularly effective when used for forming a cured film or a partition used for an optical element, for example, an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell. When the negative photosensitive resin composition of the present invention is used, the upper surface is a partition wall having good ink repellency and good development adhesion to the substrate, and a development residue is formed in the opening partitioned by the partition wall. A sufficiently small number of partition walls can be manufactured.

[Partition wall]
The partition according to the present invention is a partition made of a cured film of the above-described negative photosensitive resin composition of the present invention formed so as to partition the substrate surface into a plurality of sections for forming dots. The partition wall is, for example, applied to the surface of a substrate such as a substrate, the negative photosensitive resin composition of the present invention, dried as necessary to remove the solvent, etc. It is obtained by developing after masking, exposing. By development, an unexposed portion is removed by masking, and an opening corresponding to a dot forming section is formed together with a partition.

As described above, the partition wall of the embodiment according to the present invention is a partition wall having good ink repellency on the upper surface and good development adhesion to the substrate, and a development residue is present in the opening partitioned by the partition wall. There are few enough. As a result, when used in an optical element, particularly an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell manufactured by the IJ method, ink can be uniformly applied to the opening to form dots with high accuracy. A remarkable effect is exhibited.

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

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

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

In this drying process, the ink repellent agent (C) moves to the upper layer of the dry film. Even when the negative photosensitive resin composition does not contain the solvent (E), the upper surface transition of the ink repellent agent (C) is similarly achieved in the coating film.

Next, as shown in FIG. 1C, the dry film 22 is exposed to light through a photomask 30 having a masking portion 31 having a shape corresponding to the opening surrounded by the partition walls. The film after the dry film 22 is exposed is referred to as an exposure film 23. In the exposure film 23, the exposed portion 23 </ b> A is photocured, and the non-exposed portion 23 </ b> B is in the same state as the dry film 22.

As the light to be irradiated, excimer laser such as visible light; ultraviolet light; far ultraviolet light; KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, Kr ₂ excimer laser light, KrAr excimer laser light, and Ar ₂ excimer laser light. Examples include light; X-ray; electron beam.

The light to be irradiated is preferably light having a wavelength of 100 to 600 nm, more preferably light having a wavelength of 300 to 500 nm, particularly preferably light containing i-line (365 nm), h-line (405 nm) or g-line (436 nm). Moreover, you may cut light below 330 nm as needed.

The exposure method includes full-surface batch exposure, scan exposure, and the like. You may expose in multiple times with respect to the same location. At this time, the multiple exposure conditions may or may not be the same.

Exposure amount, In any of the above exposure method, for example, preferably 5 ~ 1,000mJ / cm ^2, more preferably 5 ~ 500mJ / cm ^2, more preferably ^{5 ~ 300mJ / cm 2, 5} ~ 200mJ / cm ² is particularly preferable, and 5 to 50 mJ / cm ² is most preferable. The exposure amount is appropriately optimized depending on the wavelength of light to be irradiated, the composition of the negative photosensitive resin composition, the thickness of the coating film, and the like.

The exposure time per unit area is not particularly limited, and is designed from the exposure power of the exposure apparatus to be used and the required exposure amount. In the case of scan exposure, the exposure time is determined from the light scanning speed. The exposure time per unit area is usually about 1 to 60 seconds.

Next, as shown in FIG. 1D, development using an alkali developer is performed to form the partition wall 4 composed only of a portion corresponding to the exposed portion 23A of the exposed film 23. The opening 5 surrounded by the partition wall 4 is a portion where the non-exposed portion 23B exists in the exposure film 23, and FIG. 1D shows a state after the non-exposed portion 23B is removed by development. In the negative photosensitive resin composition, all of the alkali-soluble resin (A), the cross-linking agent (B), and the ink repellent agent (C) have an acidic group. Dissolution and removal with a liquid are easily performed, and the composition hardly remains in the opening 5. On the other hand, since the partition 4 which is a cured product of the negative photosensitive resin composition is excellent in development adhesion, it is sufficiently adhered to the substrate 1 even after development.

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, the ink repellent agent (C) is present in a high concentration as it is in the uppermost layer 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 contained, and other photocuring components are strongly photocured to cause the ink repellent agent. (C) is fixed to the ink repellent layer.

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

In any of the above cases, the ink repellent layer 4A has an ink-repellent layer on the lower side of the ink-repellent layer 4A, in which mainly the alkali-soluble resin (A) and the thiol compound (G) optionally contained, and other photocurable components are photocured. A layer 4B containing almost no agent (C) is formed.

Conventionally, when the ink repellent agent has an acid group, the ink repellent layer formed on the uppermost layer of the partition wall is easily removed during development. In the present invention, by using the ink repellent agent (C) whose acid value is regulated within a predetermined range, it is easy to dissolve and remove with an alkaline developer in the non-exposed area at the time of development. The ink repellent layer 4 </ b> A formed in the upper layer can remain without being substantially affected by the alkaline developer. Further, since the ink repellent agent (C) is sufficiently fixed to the partition including the ink repellent layer 4A and the lower layer 4B, it hardly migrates to the opening during development.

The partition 4 may be further heated after development. The heating temperature is preferably 130 to 250 ° C. The partition 4 is hardened by heating. Further, the ink repellent agent (C) is more firmly fixed in the ink repellent layer 4A.

The cured resin film and the partition wall 4 according to the present invention thus obtained have good ink repellency on the upper surface even when the exposure is performed at a low exposure amount. In the partition 4, the ink repellent (C) hardly exists in the opening 5 after development, and the uniform coating property of the ink in the opening 5 can be sufficiently secured.

For the purpose of more reliably obtaining the ink affinity of the opening 5, in order to remove the development residue and the like of the negative photosensitive resin composition that may exist in the opening 5 after the heating, The substrate 1 with the partition walls 4 may be subjected to ultraviolet / 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. The distance between adjacent partition walls (pattern width) is preferably 300 μm or less, and particularly preferably 100 μm or less. The height of the partition wall is preferably 0.05 to 50 μm, particularly preferably 0.2 to 10 μm.

The partition formed from the negative photosensitive resin composition of the present invention has few irregularities in the edge portion when formed to the above width, and is excellent in linearity. The high linearity in the partition walls is particularly remarkable when a 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, even a fine pattern can be formed with high accuracy. If such a highly accurate pattern can be formed, it is particularly useful as a partition for an organic EL element.

The partition according to the present invention can be used as a partition having the opening as an ink injection region when pattern printing is performed by the IJ method. When pattern printing is performed by the IJ method, if the partition wall according to the present invention is formed so that its opening coincides with a desired ink injection region, the partition top surface has good ink repellency. Ink can be prevented from being injected into an undesired opening, that is, an ink injection region beyond the partition. In addition, since the opening surrounded by the partition wall has good ink wetting and spreading properties, it is possible to print the ink uniformly without causing white spots or the like in a desired region.

If the partition wall according to the present invention is used, pattern printing by the IJ method can be performed precisely as described above. Therefore, the partition according to the present invention is an optical element having a partition located between a plurality of adjacent dots on the surface of a substrate on which dots are formed by the IJ method, particularly an organic EL element, a quantum dot display, a TFT array, or a thin film. It is useful as a partition for solar cells.

[Optical element]
As an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell as an optical element according to the present invention, an organic EL having a plurality of dots and a partition wall according to the present invention located between adjacent dots on the substrate surface It is an element, a quantum dot display, a TFT array, or a thin film solar cell. In the optical element (organic EL element, quantum dot display, TFT array, or thin film solar cell) according to the present invention, the dots are preferably formed by the IJ method.

The organic EL element has a structure in which a light emitting layer of an organic thin film is sandwiched between an anode and a cathode, and the partition wall according to the present invention is a partition use separating an organic light emitting layer, a partition use separating an organic TFT layer, and a coating type oxide semiconductor. It can be used for separating partition applications.

In addition, the organic TFT array element is a semiconductor layer including a plurality of dots arranged in a matrix in plan view, each pixel having a pixel electrode and a TFT as a switching element for driving it, and including a TFT channel layer. An element in which an organic semiconductor layer is used. The organic TFT array element is provided as a TFT array substrate in, for example, an organic EL element or a liquid crystal element.

Referring to the optical element of the embodiment according to the present invention, for example, an organic EL element, an example in which dots are formed in the opening by the IJ method using the partition obtained above will be described below. In addition, the formation method of the dot in optical elements, such as an organic EL element concerning this invention, is not limited to the following.

2A and 2B schematically show a method of manufacturing an organic EL element using the partition walls 4 formed on the substrate 1 shown in FIG. 1D. Here, the partition 4 on the substrate 1 is formed such that the opening 5 matches the dot pattern of the organic EL element 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 wall 4 and a predetermined amount of ink 10 is injected into the opening 5. As the ink, known inks for organic EL elements are appropriately selected and used in accordance with the function of dots.

Next, depending on the type of the ink 10 used, for example, a process such as drying and / or heating is performed to remove or cure the solvent, and as shown in FIG. The organic EL element 12 in which 11 is formed is obtained.

An optical element (an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell) according to an embodiment of the present invention uses a partition wall according to the present invention, so that ink is formed in an opening partitioned by the partition wall in the manufacturing process. Is an optical element (an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell) having dots formed with high accuracy.

In addition, although an organic EL element can be manufactured as follows, for example, it is not limited to this.
A light-transmitting electrode such as tin-doped indium oxide (ITO) is formed on a light-transmitting substrate such as glass by a sputtering method or the like. The translucent electrode is patterned as necessary.

Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice pattern in plan view along the outline of each dot by a photolithography method including coating, exposure and development. Next, the materials for the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking layer, and the electron injection layer are respectively applied and dried in the dot formation openings by the IJ method. Laminate. The kind and number of organic layers formed in the opening for forming dots are appropriately designed. Finally, a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by vapor deposition or the like.

Further, the quantum dot display can be manufactured, for example, as follows, but is not limited thereto.

A light-transmitting electrode such as ITO is formed on a light-transmitting substrate such as glass by a sputtering method or the like. The translucent electrode is patterned as necessary. Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice shape in plan view along the outline of each dot by photolithography including coating, exposure and development. Next, the materials for the hole injection layer, the hole transport layer, the quantum dot layer, the hole blocking layer, and the electron injection layer are applied and dried in the dot formation openings by the IJ method. Laminate sequentially. The kind and number of organic layers formed in the opening for forming dots are appropriately designed. Finally, a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by vapor deposition or the like.

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

A negative photosensitive resin composition of the present invention is used for a translucent substrate such as glass, and partition walls are formed in a lattice shape in plan view along the outline of each dot. Next, a nanoparticle solution that converts blue light to green light, a nanoparticle solution that converts blue light to red light, and a blue color ink if necessary are dried in the dot formation opening by the IJ method. To make a module. A liquid crystal display having excellent color reproducibility can be obtained by using a light source that emits blue light as a backlight and using the module as a color filter alternative.

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

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 over the gate insulating film. The source electrode and the drain electrode can be produced by forming a metal thin film such as aluminum, gold, silver, copper, or an alloy thereof by, for example, vacuum deposition or sputtering. As a method of patterning the source electrode and the drain electrode, after forming a metal thin film, a resist is coated, exposed and developed to leave the resist in a portion where the electrode is to be formed, and then exposed with phosphoric acid or aqua regia. There is a method of removing the metal and finally removing the resist.

In addition, when a metal thin film such as gold is formed, a resist is applied in advance, exposed and developed to leave the resist in a portion where it is not desired to form an electrode, and after forming the metal thin film, the photoresist is applied together with the metal thin film. There is also a technique to remove. Further, the source electrode and the drain electrode may be formed by a method such as ink jet using a metal nanocolloid such as silver or copper. Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice pattern in plan view along the outline of each dot by photolithography including coating, exposure and development.

Next, a semiconductor solution is applied in the dot forming opening 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 coating type oxide semiconductor solution can also be used. The source electrode and the drain electrode may be formed by using a method such as inkjet after forming the semiconductor layer. Finally, a transparent electrode such as ITO is formed by sputtering or the like, and a protective film such as silicon nitride is formed.

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

Each measurement was performed by the following method.
[Number average molecular weight (Mn) and mass average molecular weight (Mw)]
Gel permeation chromatography (GPC) of a plurality of types of monodisperse polystyrene polymers with different degrees of polymerization, which is commercially available as a standard sample for molecular weight measurement, is a commercially available GPC measurement device (manufactured by Tosoh Corporation, device name: HLC-8320GPC). It measured using. A calibration curve was prepared based on the relationship between the molecular weight of polystyrene and the retention time (retention time).

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

[PGMEA contact angle]
According to JIS R3257 “Test method for wettability of substrate glass surface”, PGMEA droplets were placed at three locations on the measurement surface on the substrate by the sessile drop method, and each PGMEA droplet was measured. The droplet was 2 μL / droplet, and the measurement was performed at 20 ° C. The contact angle was determined from the average value of three measured values (n = 3). PGMEA is an abbreviation for propylene glycol monomethyl ether acetate.

Abbreviations of the compounds used in each example are as follows.
(Alkali-soluble resin (A))
A-1: A resin solution obtained by reacting a cresol novolac type epoxy resin with acrylic acid and then with 1,2,3,6-tetrahydrophthalic anhydride to purify a resin into which an acryloyl group and a carboxy group have been introduced with hexane ( Solid content 70% by mass, acid value 60 mgKOH / g, mass average molecular weight 9.2 × 10 ³ ).
A-2: RE-310S (manufactured by Nippon Kayaku Co., Ltd., bifunctional bisphenol-A type epoxy resin, epoxy equivalent: 184.0 g / equivalent) described in Example 1 (paragraph 0045) in JP-A-2003-268067 A polyurethane compound solution obtained by reacting with acrylic acid, then with dimethylolpropionic acid and trimethylhexamethylene diisocyanate, and finally with glycidyl methacrylate (solid content 65 mass%, acid value 79.32 mg KOH / g).

(Polyfunctional low molecular weight compound (B1))
B1-1: 2,2,2-triacryloyloxymethylethylphthalic acid (acid value 87 mg KOH / g, molecular weight 446).
B1-2: Succinic acid ester of dipentaerythritol pentaacrylate (acid value 92 mg KOH / g, molecular weight 612).
(Non-acidic crosslinking agent (B2))
B2-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

(Ink repellent agent (C1) raw material)
_{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

(Ink repellent (C2) raw material)
Compound (cx-1) corresponding to compound (s1): F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (produced by a known method).

Compound (cx-21) corresponding to compound (s2), raw material of compound (cx-22) AC: acrylic acid MMA: methyl methacrylate AIBN: azobisisobutyronitrile V-65: (2,2′-azobis) (2,4-dimethylvaleronitrile))
3-mercatopropyltrimethoxysilane 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: ethyl diglycol acetate.
E-4: DMIB: N, N-dimethylisobutyramide.

[Synthesis of ink repellent agent (C)]
Ink repellent agents (C1-1), ink repellent agents (C2-1) to (C2-3) and ink repellent agents (Cf-1) to (Cf-3) for comparative examples used in Examples are as follows. Synthesized as follows.

(Synthesis Example 1: Synthesis of ink repellent agent (C1-1))
In an autoclave with an internal volume of 1,000 cm ³ 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, and 5.5 of polymerization initiator V-65. 0 g and 4.7 g of n-DM were charged, polymerized at 50 ° C. for 24 hours with stirring under a nitrogen atmosphere, and further heated at 70 ° C. for 5 hours to inactivate the polymerization initiator, A solution was obtained. 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 above copolymer solution, 33.5 g of BEI, 0.13 g of DBTDL, and 1.5 g of TBQ were charged in an autoclave having an internal volume of 300 cm ³ equipped with a stirrer, The reaction was carried out at 24 ° C. for 24 hours to synthesize a crude polymer. Hexane was added to the obtained crude polymer solution for purification by reprecipitation, followed by vacuum drying to obtain 65.6 g of an ink repellent agent (C1-1). Thereafter, it is diluted with PGMEA, and the PGMEA solution of the ink repellent agent (C1-1) (ink repellent agent (C1-1) concentration: 10 mass%, hereinafter also referred to as “ink repellent agent (C1-1) solution”). Got.

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%), and a C = C content of 3. It was 79 (mmol / g) and acid value 35.7 (mgKOH / g).

(Synthesis Example 2: Synthesis of hydrolyzable silane compound (cx-21))
In a 50 cm ³ three-necked flask equipped with a stirrer and a thermometer, 0.40 g of 3-mercaptopropyltrimethoxysilane, 2.06 g of MMA, 1.48 g of AC, 0.05 g of V-65, PGME 35.59 g was added and stirred at 60 ° C. for 12 hours. By gas chromatography, the disappearance of the peaks of the starting 3-mercaptopropyltrimethoxysilane, MMA and AC was confirmed, and a PGME solution (concentration: 10% by mass) of the hydrolyzable silane compound (cx-21) was obtained.

(Synthesis Example 3: Preparation of ink repellent agent (C2-1))
In a 50 cm ³ 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), compound (cx-4) ) 0.63 g was added to obtain a hydrolyzable silane compound mixture. Subsequently, 6.67g of PGME was put into this mixture, and it was set as the raw material solution.

0.76 g of 1% hydrochloric acid aqueous solution was dropped into the obtained raw material solution. After completion of the dropping, 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 “ink repellent agent (C2-1)”. Also referred to as a “solution”.

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 (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%), and C = C. The content was 2.69 (mmol / g) and the acid value was 32.8 (mgKOH / g).

(Synthesis Example 4: Preparation of ink repellent (C2-2) solution)
In a 50 cm ³ 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), compound (cx-4) ) 0.44 g, compound (cx-6) 0.05 g, and compound (cx-51) 0.22 g were added to obtain a hydrolyzable silane compound mixture. Subsequently, 6.37g of PGME was put into this mixture, and it was set as the raw material solution.

0.85 g of 1% hydrochloric acid aqueous solution was dropped into the obtained raw material solution. After completion of the dropping, 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 “ink repellent agent (C2-2)”. Also referred to as a “solution”.

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 (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%), and a content of C = C. The acid value was 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 cm ³ 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, 31. 50 g was added and stirred at 60 ° C. for 12 hours. By gas chromatography, the disappearance of peaks of the starting materials 3-mercaptopropyltrimethoxysilane, MMA and AC was confirmed, and a PGME solution (concentration: 10% by mass) of the hydrolyzable silane compound (cx-22) was obtained.

(Synthesis Example 6: Preparation of ink repellent (C2-3) solution)
In a 50 cm ³ 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), compound (cx-4) ) 0.21 g, compound (cx-6) 0.06 g, and compound (cx-52) 0.33 g were added to obtain a hydrolyzable silane compound mixture. Subsequently, 6.88g of PGME was put into this mixture, and it was set as the raw material solution.

0.47 g of 1% hydrochloric acid aqueous solution was dropped into the obtained raw material solution. After the completion of dropping, 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 “ink repellent agent (C2-3)”. Also referred to as a “solution”.

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 (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%), and C = C. The content was 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 cm ³ 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 0.36 g of compound (cx-4). 40 g was added to obtain a hydrolyzable silane compound mixture. Next, 4.22 g of PGME was added to this mixture to prepare a raw material solution.

0.53 g of 1% hydrochloric acid aqueous solution was dropped into the obtained raw material solution. After completion of dropping, the mixture was stirred at 40 ° C. for 5 hours, and the PGME solution of the ink repellent agent (Cf-1) (ink repellent agent (Cf-1) concentration: 10% by mass, hereinafter, “ink repellent agent (Cf-1) Also referred to as a “solution”.

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 (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%), and C = C. The content was 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 cm ³ 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 and 0.21 g of compound (cx-51) were added to obtain a hydrolyzable silane compound mixture. Next, 7.52 g of PGME was added to this mixture to prepare a raw material solution.

0.81 g of 1% hydrochloric acid aqueous solution was dropped into the obtained raw material solution. After completion of dropping, the mixture was stirred at 40 ° C. for 5 hours, and the PGME solution of the ink repellent agent (Cf-2) (ink repellent agent (Cf-2) concentration: 10% by mass, hereinafter, “ink repellent agent (Cf-2) Also referred to as a “solution”.

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 (Cf-2) has 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. It was 76 (mmol / g). Since the ink repellent agent (Cf-2) has no acidic group, the acid value is 0 (mgKOH / g).

(Synthesis Example 9: Preparation of ink repellent agent (Cf-3))
In a 50 cm ³ 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 and 0.34 g of compound (cx-52) were added to obtain a hydrolyzable silane compound mixture. Subsequently, 6.43g of PGME was put into this mixture, and it was set as the raw material solution.

0.50 g of 1% hydrochloric acid aqueous solution was dropped into the obtained raw material solution. After completion of dropping, the mixture was stirred at 40 ° C. for 5 hours, and a PGME solution of the ink repellent agent (Cf-3) (ink repellent agent (Cf-3) concentration: 10% by mass, hereinafter “ink repellent agent (Cf-3)” Also referred to as a “solution”.

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 (Cf-3) has 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 C = C. The content was 1.19 (mmol / g). Since the ink repellent agent (Cf-3) has no acidic group, the acid value is 0 (mgKOH / g).

[Example 1: Production of negative photosensitive resin composition and production of cured film (partition)]
(Manufacture of negative photosensitive resin composition)
0.25 g of the (C1-1) solution obtained in Synthesis Example 1 above, 16.07 g of A-1 (solid content is 11.25 g, the rest is EDGAC as a solvent), 6.25 g of B1-1, B2 -1 g of 5.00 g, D-1.50 g, D-2 0.75 g, E-1 70.18 g were placed in a 200 cm ³ stirring vessel and stirred for 5 hours to give negative photosensitivity. A resin composition was produced. Table 1 shows the solid content concentration (% by mass) of the negative photosensitive resin composition, the composition (% by mass) of the solid content in the negative photosensitive resin composition, the composition of the solvent (% by mass), and the multifunctional low The ratio (mass%) of the polyfunctional low molecular weight compound (B1) with respect to the sum total of a molecular weight compound (B1) and a non-acidic crosslinking agent (B2) is shown.

(Manufacture of cured film 1)
A 10 cm square ITO substrate (indium-tin-oxide formed on a glass substrate) was ultrasonically cleaned with ethanol for 30 seconds, and then subjected to UV / O ₃ treatment for 5 minutes. For the UV / O ₃ treatment, PL2001N-58 (manufactured by Sen Engineering Co., Ltd.) was used as a UV / O ₃ generator. The optical power (optical output) in terms of 254 nm was 10 mW / cm ² . Note was also used the device in all the UV / O ₃ treatment follows.

The negative photosensitive resin composition was applied to the cleaned ITO substrate surface using a spinner and then dried on a hot plate at 100 ° C. for 2 minutes to form a dry film having a thickness of 2.4 μm. . A photomask having an opening pattern (opening portions (exposure portions) 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, The exposure power (exposure output) in terms of 365 nm is 25 mW / through 18, 20, 30, 40, 50 μm × 1000 μm (a pattern having a spacing of 50 μm is repeated in a range of 20 mm × 20 mm). The entire surface was irradiated with UV light from an ultra-high 4 pressure mercury lamp of cm ² . During the exposure, light of 330 nm or less was cut. The distance between the dry film and the photomask was 50 μm. In each example, the exposure conditions were an exposure time of 6 seconds and an exposure amount of 150 mJ / cm ² .

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

(Manufacture of cured film 2)
Similarly, a dry film of the negative photosensitive resin composition is formed on the surface of the ITO substrate in the same manner as described above, and a photomask (the size of the light shielding part: 100 μm × 200 μm and the width of the opening (exposed part): 20 μm. The dried film is exposed under the same exposure conditions as above using an exposure pattern of 20 m × 20 mm, and the exposure amount is 150 mJ / cm ^2. Development was performed under the same conditions, and heating was performed on a hot plate at 230 ° C. for 60 minutes to obtain an ITO substrate with a cured film 2 in a pattern in which a dot portion (100 μm × 200 μm) was surrounded by a partition having a line width of 20 μm.

[Examples 2 to 16]
A negative photosensitive resin composition, a cured resin film, and a partition wall were produced 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 carried out on the negative photosensitive resin compositions, resin cured films and partition walls obtained in Examples 1 to 16. The results are shown in the lower column of Table 1 or Table 2.

<Ink repellency on top of partition wall>
The PGMEA contact angle on the upper surface of the partition wall obtained by the resin cured film 1 with an exposure amount of 150 mJ / cm ² was measured by the above method.

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

<IJ applicability>
20 pl of 1% TPD (triphenyldiamine) cyclohexylbenzene solution was dropped into the inside of the dots surrounded by the partition walls by the ITO substrate with the cured resin film 2 using an IJ apparatus (manufactured by LaboJET 500 Microjet). The spread of the dried material inside the dots after drying was confirmed. The determination was based on the following criteria.

○: Spreads uniformly within the dot, and the material reaches the partition wall.
X: Not spread within the dot.

<Development adhesion>
Photomask having an opening pattern of the cured resin film 1 (opening portions (exposure portions) are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20 , 30, 40, 50 μm × 1000 μm), the partition walls obtained with an exposure amount of 150 mJ / cm ² were observed with a microscope, and judged according to the following criteria:

○: A line with a mask width of less than 10 μm remains.
Δ: A line of 10 μm or more and less than 20 μm remains.
X: A line of 20 μm or more and 50 μm or less remains.
XX: No line pattern.

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

The negative photosensitive resin composition of the present invention can be suitably used as a composition for forming barrier ribs when performing pattern printing by the IJ method in organic EL elements, quantum dot displays, TFT arrays, or thin film solar cells. it can.

The barrier ribs according to the present invention include barrier ribs (banks) for pattern printing of organic layers such as light emitting layers by the IJ method in organic EL elements, or quantum dot layers and hole transport layers in quantum dot displays by the IJ method. Can be used as partition walls (banks) for pattern printing. The partition according to the present invention can also be used as a partition for pattern printing of a conductor pattern or a semiconductor pattern by the IJ method in a TFT array. The partition according to the present invention can be used as a partition for pattern printing of an organic semiconductor layer, a gate electrode, a source electrode, a drain electrode, a gate wiring, a source wiring, and the like forming a channel layer of a TFT by an IJ method.

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 21 ... Coating film, 22 ... Dry film, 23 ... Exposure film | membrane, 23A ... Exposure part, 23B ... Non-exposure part, 4 ... Partition, 4A ... Ink-repellent layer, 5 ... Opening part, 31 ... Masking part, DESCRIPTION OF SYMBOLS 30 ... Photomask, 9 ... Inkjet head, 10 ... Ink, 11 ... Dot, 12 ... Organic EL element.

Claims (7)

1. Alkali-soluble resin (A) having photocurable functional group (A), crosslinker (B) containing acidic group and polyfunctional low molecular weight compound (B1) having two or more photocurable functional groups in one molecule, acidic group And a negative photosensitive resin composition comprising an ink repellent (C) having a fluorine atom and an acid value of 10 to 100 mgKOH / g, a photopolymerization initiator (D), and a solvent (E).
2. The negative photosensitive resin composition according to claim 1, wherein the polyfunctional low molecular weight compound (B1) has four or more photocurable functional groups.
3. The negative photosensitive resin composition according to claim 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 claims 1 to 3, wherein the content of fluorine atoms in the ink repellent agent (C) is 5 to 55 mass%.
5. The negative photosensitive resin composition according to claim 1, wherein the ink repellent agent (C) contains a photocurable functional group.
6. 6. The crosslinking agent (B) according to any one of claims 1 to 5, further comprising a crosslinking agent (B2) having two or more photocurable functional groups in one molecule and having no acidic group. The negative photosensitive resin composition as described.
7. The negative according to claim 6, comprising 10 to 90 parts by mass of the polyfunctional low molecular weight compound (B1) with respect to 100 parts by mass in total of the polyfunctional low molecular weight compound (B1) and the crosslinking agent (B2). Type photosensitive resin composition.

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