TWI821223B - Negative photosensitive resin composition - Google Patents

Abstract

In order to be applicable to high-precision optical elements, the present invention provides a negative photosensitive resin composition, which has good adhesion between the partition wall and the substrate and can reduce residues in the opening, and can be used to manufacture, for example, quantum dot displays. , TFT arrays and thin film solar cells and other optical components. That is, a negative photosensitive resin composition is characterized by containing: an alkali-soluble resin, the main chain of which contains an aromatic ring, an acidic group and an vinyl double bond in the molecule, and an acid value of 40 mgKOH/g or more; light A free radical polymerization initiator; and, compound (I) represented by the following formula (I); [Chemical Formula 1] (R is a hydrogen atom or a methyl group, n is an integer above 2, X is an n-valent organic group, Q is -CH2- or a single bond; when Q is a single bond, the end of X bonded to Q does not contain - C(=O); the bases surrounded by n above 2 may be the same or different).

Description

Negative photosensitive resin composition

The present invention relates to a negative photosensitive resin composition used for manufacturing optical components such as quantum dot displays, TFT arrays and thin film solar cells.

Background technology In the manufacture of optical components such as quantum dot displays, TFT (Thin Film Transistor) arrays, and thin film solar cells, the inkjet (IJ) method is sometimes used to dot (dot) the organic layer or inorganic layer such as the light-emitting layer. A method of printing patterns into forms. In this method, partition walls are set along the contour of the point to be formed, and ink containing organic layer or inorganic layer material is injected into the partition surrounded by the partition walls (hereinafter also referred to as the opening), and then dried and/or Or heating, etc., to form the points of the desired pattern.

In the above content, when pattern printing is performed by the inkjet (IJ) method, in order to prevent the ink from mixing between adjacent dots and to apply the ink evenly when the dots are formed, the technology of making the partition walls with ink repellency is currently being studied. For example, Patent Document 1 describes a technology that uses partition walls in the production process of organic TFTs and further makes the partition walls liquid-repellent.

On the other hand, in recent years, regarding the formation of barrier ribs using negative photosensitive resin compositions, in order to obtain high-precision optical elements, it is required that the resulting barrier ribs have sufficient adhesion to the base material, and that the composition of the opening is required. There should be very little residue. Patent Document 2 discloses a photosensitive resin composition containing a compound having a (meth)allyl group, a compound having two or more mercapto groups, a photopolymerization initiator, and an alkali-soluble resin. It is particularly useful in color filters. This photosensitive resin composition is less likely to cause film loss in exposed areas during development, and has good sensitivity and adhesion.

However, even with the photosensitive resin composition disclosed in Patent Document 2, in view of the level required for high-precision optical devices in recent years, it is still unable to achieve both the adhesion to the substrate of the partition wall and the reduction of residue at the opening. Advanced technical documents patent documents

[Patent Document 1] International Publication No. 2010/058662 [Patent Document 2] Japanese Patent Application Publication No. 2010-39481

Summary of the invention The problem to be solved by the invention The present invention was made in view of the above-mentioned viewpoints, and in order to be applicable to high-precision optical elements, the purpose of the present invention is to provide a negative photosensitive resin composition that has good adhesion between the partition walls and the base material and can reduce residues in the openings. It can be used to manufacture optical components such as quantum dot displays, TFT arrays and thin film solar cells. means to solve problems

The present invention has the following aspects. [1] A negative photosensitive resin composition, characterized by containing: an alkali-soluble resin, which contains an aromatic ring on the main chain, has an acidic group and an vinyl double bond in the molecule, and has an acid value of 40 mgKOH/g or more; Photoradical polymerization initiator; and, compound (I) represented by the following formula (I);

[Chemical formula 1]

(However, in formula (I), R is a hydrogen atom or a methyl group, n is an integer above 2, X is an n-valent organic group, Q is -CH ₂ - or a single bond; when Q is a single bond, it is bonded to Q The end of X in the knot does not contain -C (=O); the groups surrounded by n above 2 may be the same or different).

[2] The negative photosensitive resin composition according to [1], wherein the compound (I) is a cyclic compound. [3] The negative photosensitive resin composition according to [1], wherein the compound (I) is an aliphatic heterocyclic compound. [4] The negative photosensitive resin composition according to any one of [1] to [3], wherein the total solid content of the negative photosensitive resin composition contains 5 to 80 mass % of the aforementioned alkali-soluble resin. [5] The negative photosensitive resin composition according to any one of [1] to [4], wherein the total solid content of the negative photosensitive resin composition contains 0.1 to 50 mass % of the aforementioned photoradical polymerization initiator agent. [6] The negative photosensitive resin composition according to any one of [1] to [5], wherein the total solid content of the negative photosensitive resin composition contains 1 to 50 mass % of the formula (I) described above. Show compound (I). [7] The negative photosensitive resin composition according to any one of [1] to [6], which further contains a thiol compound having two or more mercapto groups in one molecule.

[8] The negative photosensitive resin composition according to any one of [1] to [7], which further contains the aforementioned thiol compound in an amount relative to 1 mol of the negative photosensitive resin composition. The total solid content contains ethylenic double bonds and mercapto groups in an amount of 0.0001 to 1 mole. [9] The negative photosensitive resin composition according to any one of [1] to [8], which further contains an ink repellent agent. [10] The negative photosensitive resin composition according to [9], wherein the ink repellent agent has an vinyl double bond. [11] The negative photosensitive resin composition of [9] or [10], wherein the ink repellent agent has a fluorine content of 1 to 40 mass %. [12] The negative photosensitive resin composition according to any one of [9] to [11], wherein the total solid content in the negative photosensitive resin composition contains 0.01 to 15 mass of the aforementioned ink repellent agent. [13] The negative photosensitive resin composition according to any one of [1] to [12], which further contains a solvent. [14] The negative photosensitive resin composition according to any one of [1] to [136], wherein the water contact angle on the surface of the resin cured film formed using the negative photosensitive resin composition is 60 degrees or more. [15] The negative photosensitive resin composition according to any one of [1] to [13], wherein the surface of the resin cured film formed of the negative photosensitive resin composition is contacted with propylene glycol monomethyl ether acetate. The angle is more than 30 degrees. Invention effect

According to the present invention, it is possible to provide a negative photosensitive resin composition that is suitable for use in high-precision optical elements, has good adhesion between the partition walls and the base material, and can reduce residues in the openings, and can be used to manufacture, for example, quantum dot displays, Optical components such as TFT arrays and thin film solar cells.

Form used to implement the invention The meanings of terms used in this manual are as follows. "Acid value" means the number of milligrams of potassium hydroxide required to neutralize the resin acid in 1 g of the sample. The acid value can be measured according to the measurement method of JIS K 0070, and the unit is mgKOH/g. "(Meth)acrylyl" is the general term for "methacrylyl" and "acrylyl". (Meth)acrylic acid and (meth)acrylate are also allowed. "(Meth)allyl" is the collective name for "allyl" and "methallyl". "(iso)cyanurate" is the general term for "cyanurate" and "isocyanurate".

The basis represented by formula (x) is sometimes simply referred to as basis (x). In addition, the compound represented by formula (y) may be simply referred to as compound (y). Here, formula (x) and formula (y) represent arbitrary formulas. "Resin mainly composed of a certain component" or "resin mainly composed of a certain component" means that the content ratio of the component accounts for more than 50% by mass relative to the total amount of the resin.

"Side chain" means a group other than hydrogen atoms or halogen atoms bonded to the carbon atoms constituting the main chain in a polymer in which the main chain is composed of repeating units of carbon atoms. "Total solid content of the photosensitive resin composition" means the components contained in the photosensitive resin composition that form the cured film described below. It can be determined by heating the photosensitive resin composition at 140°C for 24 hours to remove the solvent residue. out. In addition, the total solid content can also be calculated from the feed amount.

A film composed of a cured product of a composition containing resin as the main component is called a "resin cured film". A film coated with a photosensitive resin composition on a substrate is called a "coating film", and a film that has been dried is called a "dried film". The film obtained by curing this "dry film" is a "resin cured film". In addition, "resin cured film" may be simply called "cured film." The resin cured film may be in the form of partition walls, and the partition walls may be formed into a shape that divides a predetermined area on the base material into a plurality of partitions. In the partition separated by the partition wall, that is, the opening surrounded by the partition wall, "ink" such as the following is injected to form "dots".

"Ink" is a general term for liquids that have optical and/or electrical properties after drying, hardening, etc. For optical components such as quantum dot displays, TFT arrays, thin film solar cells, and color filters, dot-forming inks are sometimes used to pattern-print dots used as various constituent elements using the inkjet (IJ) method. . “Printing ink” includes printing ink used for related purposes.

"Ink repellency" refers to the property of repelling the above-mentioned printing ink, which has water repellency and/or oil repellency. Ink repellency can be evaluated by, for example, the contact angle when dripping ink. "Ink affinity" is the opposite property to ink repellency, and can be evaluated by the contact angle when printing ink is dropped. Alternatively, the ink affinity can be evaluated based on a predetermined standard by evaluating the degree of ink spread when the ink is dropped (ink spreadability when wet).

A "spot" represents the smallest area in an optical element that can be photomodulated. For optical components such as quantum dot displays, TFT arrays, thin film solar cells and color filters, 1 dot = 1 pixel for white and black display, and 3 dots (R (red), G (green), B ( Blue) etc.) = 1 pixel. In this specification, "optical component" is used as a term including electronic components (electronics devices).

Unless otherwise specified, "%" means "mass %" and "part" means "mass parts". In addition, "~" indicating a numerical range is a range including the lower limit value and the upper limit value respectively.

[Negative photosensitive resin composition] The negative photosensitive resin composition of the present invention is characterized by containing: an alkali-soluble resin (hereinafter also referred to as alkali-soluble resin (A)), which contains an aromatic ring on the main chain and has an acidic group and an vinyl double bond in the molecule. , and the acid value is 40 or more; a photoradical polymerization initiator (hereinafter also referred to as a photopolymerization initiator (B)); and the compound (I) represented by the above formula (I).

Generally speaking, a negative photosensitive resin composition is cured by exposure to form a cured film. At this time, if a mask is used to form exposed portions and non-exposed portions of a predetermined shape on the substrate, the non-exposed portions will not be hardened and can be selectively removed from the substrate using an alkaline developer. As a result, the cured film can be formed into a partition wall shape that partitions a predetermined area into a plurality of partitions.

In the negative photosensitive resin composition of the present invention, in the above-mentioned exposed part, the alkali-soluble resin (A) and the compound (I) react and harden due to the free radicals generated by the photopolymerization initiator (B). A hardened film is formed on the base material. In the above reaction, compound (I) functions as a cross-linking agent. The inventors of the present case discovered that by combining the alkali-soluble resin (A) and the compound (I), and combining a cross-linking agent having a plurality of (meth)acrylyl groups that has been used as a cross-linking agent with the alkali-soluble resin (A ), the adhesion to the base material is improved and the pattern shape can be improved. On the other hand, since the non-exposed part has low affinity with the base material in an unhardened state, it is easy to remove when treated with a developer and Not easy to leave residue.

The negative photosensitive resin composition of the present invention may further contain an ink repellent agent, a thiol compound having two or more mercapto groups in one molecule (hereinafter also referred to as a thiol compound (C)), and compound (I) if necessary. Cross-linking agent with more than two ethylene double bonds in the molecule (hereinafter also referred to as cross-linking agent (D)), solvent, colorant, ultraviolet absorber and other optional ingredients. The negative photosensitive resin composition of the present invention may contain, as the alkali-soluble resin, a photosensitive resin having an acidic group and an vinyl double bond in one molecule other than the alkali-soluble resin (A).

(Alkali-soluble resin) The alkali-soluble resin mainly contains alkali-soluble resin (A). Alkali-soluble resin (A) is a photosensitive resin with an aromatic ring in the main chain, an acidic group and an vinyl double bond in the molecule, and an acid value of more than 40 mgKOH/g. Since the main chain of alkali-soluble resin (A) contains aromatic rings and its acid value is above 40 mgKOH/g, the negative photosensitive resin composition obtained by combining it with compound (I) has good developability and can achieve substrate density that takes into account the exposed part. Residues on adhesive and non-exposed parts are reduced. From the viewpoint of the residue, the acid value is preferably 45 mgKOH/g or more, and more preferably 50 mgKOH/g or more. From the viewpoint of adhesion to the base material, the upper limit of the acid value of the alkali-soluble resin (A) is preferably 100 mgKOH/g, and more preferably 80 mgKOH/g.

Examples of the aromatic ring contained in the main chain of the alkali-soluble resin (A) include divalent aromatic ring structures such as phenylene group, naphthylene group, and anthracenyl group. The carbon atoms in the aromatic ring can be replaced by heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms. The aromatic ring is preferably a phenyl group, and a biphenyl group formed by two phenyl groups bonded is particularly preferred.

The acidic group of the alkali-soluble resin (A) is preferably a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, etc., and two or more types may be used in combination. The acid value of the alkali-soluble resin (A) can be adjusted by the amount of introduced acidic groups.

The ethylenic double bonds of the alkali-soluble resin (A) are preferably (meth)acrylyl, (meth)allyl, allyl, vinyloxy, vinyloxyalkyl, etc., which have addition polymerizability. of double bonds, and more than two types can be used in combination. In addition, some or all of the hydrogen atoms in the ethylenic double bonds may be replaced by alkyl groups (preferably methyl groups).

Examples of alkali-soluble resin (A) include: resin (A1-1), whose main chain contains an aromatic ring, and has side chains with acidic groups and side chains with vinyl double bonds; resin (A1-2), It is one that introduces acidic groups and vinyl double bonds into an epoxy resin containing an aromatic ring in the main chain; and, monomer (A1-3), which has a side chain with an acidic group and a side chain with an vinyl double bond. chain, and the part that polymerizes to form the main chain contains aromatic rings, etc. Two or more of these may be used together.

The resin (A1-2) can be synthesized by reacting an epoxy resin containing an aromatic ring in the main chain with a compound having a carboxyl group and an vinyl double bond described later, and then reacting a polycarboxylic acid or an anhydride thereof. Specifically, an epoxy resin containing an aromatic ring in the main chain is reacted with a compound having a carboxyl group and an ethylene double bond, thereby introducing the ethylenic double bond into the epoxy resin. Next, a carboxyl group can be introduced by reacting an epoxy resin containing an aromatic ring in the main chain into which an ethylenic double bond has been introduced, and a polycarboxylic acid or its anhydride.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, cresol varnish type epoxy resin, phenol methane type epoxy resin, and ring having naphthalene skeleton. Oxygen resin, epoxy resin having a biphenyl skeleton represented by the following formula (A1-2a), epoxy resin represented by the following formula (A1-2b), epoxy having a biphenyl skeleton represented by the following formula (A1-2c) Resin etc.

[Chemical formula 2]

(In formula (A1-2a), v is an integer from 1 to 50 and preferably an integer from 2 to 10. The hydrogen atoms of the benzene ring can each be independently substituted by the following: alkyl group with 1 to 12 carbon atoms, halogen Phenyl in which atoms or part of the hydrogen atoms may be substituted by substituents).

[Chemical formula 3]

(In formula (A1-2b), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a chlorine atom or an alkyl group with 1 to 5 carbon atoms, and w is an integer from 0 to 10).

[Chemical formula 4]

(In formula (A1-2c), the hydrogen atoms of each benzene ring can be independently substituted by the following: an alkyl group with 1 to 12 carbon atoms, a halogen atom, or a phenyl group in which part of the hydrogen atoms can be substituted by a substituent. u is an integer from 0 to 10).

In addition, after reacting the epoxy resin represented by formulas (A1-2a) to (A1-2c) with a compound having a carboxyl and ethylenic double bond, and then reacting a polycarboxylic anhydride, the polycarboxylic anhydride is preferably dicarboxylic anhydride and tetracarboxylic anhydride. Mixture of carboxylic dianhydrides. Molecular weight can be controlled by changing the ratio of dicarboxylic anhydride to tetracarboxylic dianhydride.

Compounds with carboxyl and vinyl double bonds are preferably (meth)acrylic acid, ethylene acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid or their salts. Acrylic acid is especially preferred.

The mass average molecular weight (hereinafter also referred to as Mw) of the alkali-soluble resin (A) is preferably 1.5×10 ³ to 30×10 ³ . Mw is better than 2×10 ³ or more. On the other hand, it is more preferable that Mw is 15×10 ³ or less. In addition, the number average molecular weight (hereinafter also referred to as Mn) is preferably 500 to 20×10 ^3. Mn is more preferably 1.0×10 ³ or more. On the other hand, Mn is more preferably 10×10 ³ or less. If Mw and Mn If it is more than the lower limit of the said range, hardening will be sufficient during exposure, and if it is less than the upper limit of the said range, developability will be good.

In the total solid content of the negative photosensitive resin composition, the alkali-soluble resin content ratio is preferably 5 to 80%. The content ratio is preferably 10% or more. On the other hand, it is more preferable that the content ratio is 60% or less. When the content ratio is within the above range, the negative photosensitive resin composition has good photocurability and developability.

(Compound (I)) Compound (I) is represented by the following formula (I) and is a compound having n (n is 2 or more) ethylenic double bonds in the molecule and functioning as a cross-linking agent.

[Chemical formula 5] However, the definitions of each symbol in formula (I) are as above.

Compound (I) does not have a polar functional group at the end of the molecule, so its affinity with the substrate is not high. Therefore, it is easy to remove when treated with a developer, and residues are not likely to remain. Compound (I) has two or more CH ₂ =CR-Q- groups in the molecule, and does not contain ethylenic double bonds such as (meth)acrylyl groups except CH ₂ =CR-Q- groups. Two or more CH ₂ =CR-Q- groups may be the same or different.

R in the CH ₂ =CR-Q- group is preferably a hydrogen atom. Specifically, the CH ₂ =CR-Q- group is preferably CH ₂ =CH- or CH ₂ =CH-CH ₂ -. In the compound (I), n representing the number of CH ₂ =CR-Q- groups is preferably 3 or more from the viewpoint of adhesion to the base material. From the viewpoint of solubility in the developer, n is preferably 10 or less, and more preferably 6 or less.

In formula (I), X is an n-valent organic radical. For example, Amide bond, urethane bond, -S- and divalent amine group, and the hydrogen atom of the hydrocarbon group can be passed through hydroxyl group, epoxy group, glycidyl group, oxyethyl group, mercapto group, amine group, nitro group, carboxyl group , sulfonic acid group, phosphate group substitution. From the viewpoint of heat resistance, X is preferably an organic group that does not have an ethylenic double bond. When X is a chain hydrocarbon group, the number of carbon atoms in X is preferably 1 to 20, and more preferably 1 to 10.

X From the viewpoint of reducing residue at the opening, a cyclic group is preferred. The term _" X" is a cyclic group means a group in which the atoms constituting the ring in

In the cyclic group, the ring constituting the skeleton (hereinafter simply referred to as a ring) is a hydrocarbon ring or a heterocyclic ring, and may be an aromatic ring or an aliphatic ring. From the perspective of reducing waste, the number of ring members is preferably 4 to 18. It is better if the number of ring members is 5 or more. On the other hand, it is better if the number of ring members is 12 or less. The ring can be a single ring or a structure formed by bonding multiple rings. When a plurality of rings are bonded, the total number of members of the plurality of rings should be within the above range. When X is a cyclic group, the ring is preferably an aliphatic ring, and an aliphatic heterocyclic ring is more preferred. Examples of heteroatoms include nitrogen atoms, oxygen atoms and sulfur atoms, and nitrogen atoms are preferred.

If imine (nadimide) ring, etc., and (iso)cyanuric acid ring is suitable.

Compound (I) may be exemplified by: (A) a compound (I) in which a CH ₂ =CR-Q- group is directly bonded to an atom constituting the main chain of a hydrocarbon group or a constituting atom of a ring; and (B) such as in CH ₂ =CR-Q- Compounds with reactive groups such as hydroxyl, epoxy, amine, carboxyl (except when Q is a single bond), isocyanate group and halogen atom at the terminal end, and compounds with more than 2 reactive groups Compound (I) obtained by reacting a compound with a reactive base (such as polyol, polycarboxylic acid or its anhydride, polyisocyanate, polyamine, etc.). In the case of (B) above, the compound having a hydroxyl group at the end of the CH ₂ =CR-Q- group refers to CH ₂ =CR-Q-OH, and the same applies to other groups. In the case of (B), the bonding end of the group X with the CH ₂ =CR-Q- group is composed of an ester bond, an ether bond, an amide bond, an ethyl urethane bond, or the like.

Specific examples of the compound (I) of the above (A) include triethylenecyclohexane, trimethyl(allyl)cyclohexane, (iso)tri(meth)allyl cyanurate, and di(methyl)cyclohexane. (iso)allyl monoepoxypropyl (iso)cyanurate, (iso)triethylene cyanurate, diallyl monoepoxypropyl (iso)cyanurate, ethoxy Tri(meth)allyl cyanurate (iso)cyanurate, 3,9-divinyl-2,4,8,10-tetraxaspiro[5.5]undecane and 3,9-divinyl (Meth)allyl-2,4,8,10-tetraxaspiro[5.5]undecane, etc.

Specific examples of the compound (I) having an ether bond at the end of the group methyl) allyl ester, neopenterythritol tetra(meth)allyl ester, di(trimethylol)propane tetra(meth)allyl ester, dineopenterythritol penta(meth)allyl ester, Dineopentyerythritol hexa(meth)allyl ester, diethylene glycol divinyl ether, trimethylolpropane triethylene ether, neopentylerythritol triethylene ether, neopentylerythritol tetraethylene ether, di(triethylene glycol) Hydroxymethyl)propane tetraethylene ether, dipenterythritol pentaethylene ether and dipenterythritol hexaethylene ether, etc.

Specific examples of the compound (I) in which the end of the group X is an ester bond include di(meth)allyl phthalate, di(meth)allyl isophthalate, and di(meth)allyl terephthalate. , Di(meth)allyl maleate, Di(meth)allyl fumarate, Di(meth)allyl endomethylene tetrahydrophthalanhydride, Trimellidine Tri(meth)allyl acid, divinyl phthalate, divinyl isophthalate, divinyl terephthalate, divinyl maleate, divinyl fumarate, diethylene Internal methylene tetrahydrophthalic anhydride and triethylene trimellitate, etc.

Among these, compound (I) is preferably a compound represented by any one of the following formulas (I-1) to (I-5), and compound (I-1) in which X is a cyclic group, compound (I- 2) and compound (I-3) are more preferred, and triallyl isocyanurate is particularly preferred. The compound in which X is a cyclic group has good diffusivity to the developer and can further reduce the residue at the opening. Furthermore, triallyl isocyanurate has high hydrophilicity, which can reduce the residue at the opening.

[Chemical formula 6]

(However, in formulas (I-1) to (I-5), R is a hydrogen atom or a methyl group, and Q is -CH ₂ - or a single bond).

Compound (I) can be used in combination of 2 or more types. In the total solid content of the negative photosensitive resin composition, the content ratio of compound (I) is preferably 1 to 50%. The content ratio is preferably 5% or more. On the other hand, it is more preferable that the content ratio is 40% or less. When the content ratio is within the above range, the negative photosensitive resin composition has good photocurability and developability, the resulting partition walls have substrate adhesion, and the residue at the opening can be sufficiently reduced. Furthermore, when used together with an ink repellent agent, the liquid repellency tends to be improved. In addition, the content ratio of the compound (I) is preferably 5 to 500% relative to 100% of the alkali-soluble resin. The content ratio is preferably 10% or more. On the other hand, it is more preferable that the content ratio is 100% or less.

(Photopolymerization initiator (B)) The photopolymerization initiator (B) in the present invention is not particularly limited as long as it is a compound that can generate radicals by active light and has a function as a photoradical polymerization initiator.

Examples of the photopolymerization initiator (B) include those described in WO2014/046209 such as [0130] and [0131] and in WO2014/069478 such as [0089] and [0090]. Specifically, they have disclosed diphenyl ketones, 9-oxosulfide esters, aminobenzoic acids, aliphatic amines, acetophenones and oxime esters.

Among the photopolymerization initiators (B), benzophenones and 9-oxosulfide If used together with other free radical initiators, aminobenzoic acids, aminobenzoic acids, and aliphatic amines can sometimes exhibit a sensitizing effect and are ideal. Specifically, it is better to use benzophenones in combination with benzophenones or 9-oxosulfide. It is better to use together with acetophenones. Two or more types of photopolymerization initiators (B) may be used in combination.

In the total solid content of the negative photosensitive resin composition, the content ratio of the photopolymerization initiator (B) is preferably 0.1 to 50%. A content ratio of 0.5% or more is more preferred, and 1% or more is particularly preferred. On the other hand, a content ratio of 30% or less is more preferred, and 15% or less is particularly preferred. If the content ratio is within the above range, the negative photosensitive resin composition will have good photocurability and developability.

(ink repellent) The ink repellent agent is an optional component contained in the negative photosensitive resin composition of the present invention. The ink repellent agent is preferably an ink repellent agent having fluorine atoms in the molecule (hereinafter also referred to as the ink repellent agent (E)). If the ink repellent (E) has a fluorine atom in the molecule, it will have excellent upward migration properties (upper migration properties) and repellent properties in the process of forming a cured film using a negative photosensitive resin composition containing it. Ink nature. By using the ink repellent agent (E), the upper portion of the cured film obtained including the upper surface becomes a layer in which the ink repellent agent (E) is hidden (hereinafter sometimes also referred to as the ink repellent layer), thereby imparting repellent properties to the upper surface of the cured film. Ink nature.

The fluorine atom content in the ink repellent agent (E) is preferably 1 to 40%. A content rate of more than 5% is more preferred, and a content rate of more than 10% is particularly preferred. On the other hand, a content rate of 35% or less is more preferred, and 32% or less is particularly preferred. If the fluorine atom content is more than the lower limit of the above range, good ink repellency can be imparted to the cured film surface, and if it is less than the upper limit, the compatibility with other components in the negative photosensitive resin composition is good.

In the ink repellent layer, when the ink repellent agent (E) itself is not reactive, photohardening components such as alkali-soluble resin (A) and compound (I) embedded in the negative photosensitive resin composition are polymerized and cross-linked. The form exists in the hardened resin obtained from the reaction.

From the perspective of improving the adhesion of the ink repellent agent (E) to the ink repellent layer, by providing the ink repellent agent (E) with an vinyl double bond, free radicals will damage the ink repellent agent (E) that migrates to the upper layer. The vinyl double bonds act, and the ink repellent agents (E) can (co)polymerize each other or the ink repellent agents (E) and other components containing the vinyl double bonds contained in the negative photosensitive resin composition to cause cross-linking. In addition, this reaction can be promoted by the thiol compound (C) (described later) optionally contained.

Thereby, when manufacturing the cured film which hardened the negative photosensitive resin composition, the fixability of the ink repellent agent (E) in the upper part of the cured film, ie, the ink repellent layer, can be improved. The negative photosensitive resin composition of the present invention, especially when it contains a thiol compound (C), can fully fix the ink repellent agent (E) even when the exposure amount during exposure is low. in the ink transfer layer.

As mentioned above, generally speaking, when radical polymerization of ethylenic double bonds occurs, the surfaces of the cured film and the partition wall that are in contact with the atmosphere are more likely to be hindered by oxygen, but the radical reaction caused by the thiol compound (C) is almost impossible. It will be hindered by oxygen, so it is especially beneficial to the fixation of ink repellent agent (E) under low exposure. Furthermore, during the manufacturing process of the partition wall, during development, the ink repellent agent (E) can be sufficiently prevented from being separated from the ink repellent layer and peeling off from the top surface of the ink repellent layer.

Examples of the ink repellent agent (E) include an ink repellent agent (E1) composed of a compound whose main chain is a hydrocarbon chain and whose side chain contains a fluorine atom. The ink repellent agent (E) may be a partially hydrolyzed condensate of a hydrolyzable silane compound. Two or more types of hydrolyzable silane compounds may be used in combination. Specific examples of the ink repellent agent (E) composed of a partially hydrolyzed condensate of a hydrolyzable silane compound include the following ink repellent agent (E2). The ink repellent agent (E1) and the ink repellent agent (E2) can be used alone or in combination. In the negative photosensitive resin composition of the present invention, ink repellent agent (E2) is particularly suitable from the viewpoint of excellent ultraviolet/ozone resistance.

<Ink repellent agent (E1)> The ink repellent agent (E1) is a compound whose main chain is a hydrocarbon chain and contains a side chain having a fluorine atom. The Mw of the ink repellent agent (E1) is preferably 100~1.0×10 ⁶ . Mw is preferably above 5.0×10 ³ . On the other hand, it is more preferable that Mw is 1.0×10 ⁵ or less. If Mw is above the lower limit, the ink repellent agent (E1) is likely to migrate upward when a negative photosensitive resin composition is used to form a cured film. If it is below the upper limit, the amount of residue at the opening will be reduced, which is preferable.

Specific examples of the ink repellent agent (E1) include those described in [0079] to [0102] in WO2014/046209 and [0144] to [0171] in WO2014/069478.

＜Ink repellent(E2)＞ The ink repellent agent (E2) is a partially hydrolyzed condensate of a hydrolyzable silane compound mixture (hereinafter also referred to as a mixture (M)). The mixture (M) contains a hydrolyzable silane compound (hereinafter also referred to as a hydrolyzable silane compound (s1)) having a fluoroalkylene group and/or a fluoroalkyl group and a hydrolyzable group bonded to a silicon atom as an essential component, and optionally It is selected to contain a hydrolyzable silane compound other than the hydrolyzable silane compound (s1). Examples of the hydrolyzable silane compound optionally contained in the mixture (M) include the following hydrolyzable silane compounds (s2) and (s3). The hydrolyzable silane compound optionally contained in the mixture (M) is particularly preferably the hydrolyzable silane compound (s2).

Hydrolyzable silane compound (s2): A hydrolyzable silane compound in which four hydrolyzable groups are bonded to a silicon atom. Hydrolyzable silane compound (s3): A hydrolyzable silane compound that has a group with an vinyl double bond and a group with a hydrolyzable group bonded to a silicon atom, and does not contain a fluorine atom. The mixture (M) may optionally contain one or more hydrolyzable silane compounds other than the hydrolyzable silane compounds (s1) to (s3).

Examples of other hydrolyzable silane compounds include: a hydrolyzable silane compound (s4) in which the only groups bonded to the silicon atom are a hydrocarbon group and a hydrolyzable group; a hydrolyzable silane compound (s5) having a mercapto group and a hydrolyzable group and not containing a fluorine atom; ), a hydrolyzable silane compound (s6) having an epoxy group and a hydrolyzable group and not containing a fluorine atom, a hydrolyzable silane compound (s7) having an oxyalkylene group and a hydrolyzable silicon group and not containing a fluorine atom, etc.

Examples of hydrolyzable silane compounds (s1) to (s3) and other hydrolyzable silane compounds include: those described in WO2014/046209 such as [0034] to [0072], and those in WO2014/069478 such as [0096] to [0136] wait. Specific examples of the compound (s1) include F(CF ₂ ) ₄ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , 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 . Specific examples of the compound (s2) include Si(OCH ₃ ) ₄ and Si(OCH ₂ CH ₃ ) ₄ . Specific examples of the compound (s3) include CH ₂ =CHCOO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ and CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ .

An example of the ink repellent agent (E2) is a partially hydrolyzed condensate of a mixture (M) containing an n1 compound (s1), an n2 compound (s2), and an n3 compound (s3). Here, n1 to n3 represent the molar fraction of each structural unit relative to the total molar amount of the structural units. n1>0, n2≧0, n3≧0 and n1+n2+n3=1.

n1:n2:n3 is consistent with the feed composition of the compounds (s1), (s2), (s3) in the mixture (M). Each ingredient is designed by Molbi based on the balance of effects of each ingredient. n1 is preferably 0.02~0.4 based on the amount that the fluorine atom content rate of the ink repellent agent (E1) will fall within the above-mentioned preferred range. n2 is preferably 0~0.98, especially 0.05~0.6. n3 is preferably 0~0.8, especially 0.2~0.5.

The Mw of the ink repellent agent (E2) is preferably above 500, preferably less than 1.0×10 ⁶ , and preferably below 5.0×10 ³ . If Mw is above the lower limit, the ink repellent agent (E2) is likely to migrate upward when a negative photosensitive resin composition is used to form a cured film. If it is less than the upper limit, the residue at the opening will be reduced, which is preferable. The Mw of the ink repellent agent (E2) can be adjusted by manufacturing conditions.

The ink repellent agent (E2) can be produced by subjecting the above mixture (M) to hydrolysis and condensation reactions by conventional methods. In this reaction, generally used 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 are preferably used as catalysts. In addition, alkali catalysts such as sodium hydroxide and tetramethylammonium hydroxide (TMAH) may also be used as needed. Common solvents can be used for the above reaction. The ink repellent agent (E2) obtained by the above reaction can also be blended into the negative photosensitive resin composition together with the solvent in the form of a solution.

In the total solid content of the negative photosensitive resin composition, the content ratio of the ink repellent agent (E) is preferably 0.01 to 15%. The content ratio is preferably 0.03% or more. On the other hand, the content ratio is more preferably 5% or less, and particularly preferably 1.5% or less. If the content ratio is more than the lower limit of the above range, the cured film formed of the negative photosensitive resin composition will have excellent ink repellency. If it is below the upper limit of the above range, the adhesion between the cured film and the base material will be good.

(thiol compound (C)) The thiol compound (C) optionally contained in the negative photosensitive resin composition of the present invention is a compound having two or more thiol groups in one molecule. If the negative photosensitive resin composition of the present invention contains a thiol compound (C), the thiol compound (C) will generate free radicals due to the free radicals generated by the photopolymerization initiator (B) during exposure and act on the alkali-soluble Ethylene double bonds such as resin (A) and compound (I) trigger a so-called ene-thiol reaction. This ene-thiol reaction is different from the free radical polymerization of general ethylenic double bonds. It is not hindered by oxygen and has a high degree of chain transfer. Moreover, it is also cross-linked during polymerization, so it becomes a hardened product. The shrinkage rate is also low, and it has the advantage of easily obtaining a uniform network.

When the negative photosensitive resin composition of the present invention contains a thiol compound (C), as mentioned above, it can be fully cured even under low exposure, so it has good developability and helps to achieve both substrate adhesion of the exposed part. Reduced residue on non-exposed parts. In addition, when the thiol compound (C) is contained, even the upper layer portion including the upper portion of the partition wall that is particularly susceptible to oxygen inhibition reaction can be sufficiently photocured. Therefore, when the negative photosensitive resin composition further contains an ink repellent agent, the thiol compound (C) helps impart good ink repellency to the upper surface of the partition wall.

The number of mercapto groups in the thiol compound (C) is preferably 2 to 10 per molecule, preferably 3 to 8, and more preferably 3 to 5. The molecular weight of the thiol compound (C) is not particularly limited. In the thiol compound (C), the mercapto group equivalent represented by [molecular weight/number of mercapto groups] (hereinafter also referred to as SH equivalent) is preferably 40 to 1,000, and more preferably 40 to 500 from the viewpoint of curability at low exposure. , 40~250 is especially good.

Examples of the thiol compound (C) include: ginseng (2-mercaptopropyloxyethyl)isocyanurate, neopentylerythritol (3-mercaptobutyrate), and trimethylolpropane Ginseng thioglycolate, neopentyl erythritol ginseng thioglycolate, neopentyl erythritol hexathioglycolate, trimethylolpropane ginseng (3-mercaptopropionate) ), neopenterythritol 4 (3-mercaptopropionate), ginseng-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, dipenterythritol hexa(3-mercapto) propionate), trimethylolpropane (3-mercaptobutyrate), neopenterythritol 4 (3-mercaptobutyrate), dineopenterythritol 6 (3-mercaptobutyrate), tris Hydroxymethylpropane (2-mercaptoisobutyrate), 1,3,5-hydroxymethyl (3-mercaptobutyryloxyethyl)-1,3,5-trihydroxy-2,4,6 (1H, 3H,5H)-triketone, trisphenolmethane (3-mercaptopropionate), trisphenolmethane (3-mercaptobutyrate), trishydroxymethylethane (3-mercaptobutyrate), 2,4,6-trimercapto-S-trimercapto and 1,4-bis(3-mercaptobutyloxy)butane, etc. Two or more types of thiol compounds (C) may be used in combination.

When the negative photosensitive resin composition contains a thiol compound (C), its content ratio is 0.0001 to 1 in terms of mercapto group per 1 mol of ethylenic double bonds contained in the total solid content of the negative photosensitive resin composition. The amount of mole is appropriate. A content ratio of 0.0005 mol or more is more preferred, and a content ratio of 0.001 mol or more is particularly preferred. On the other hand, it is more preferable that the content is 0.5 mol or less. If the content ratio is within the above range, the negative photosensitive resin composition will have good photocurability and developability even under low exposure. The content ratio of the thiol compound (C) in the total solid content is preferably 1 to 20%. The content ratio is preferably 3% or more. On the other hand, it is more preferable that the content ratio is 15% or less.

(Crosslinking agent (D)) The cross-linking agent (D) optionally contained in the negative photosensitive resin composition of the present invention is alkali-soluble resin (A), ink repellent agent (E) and compound (I) other than the alkali-soluble resin (A) and the compound (I). One molecule contains more than two ethylenes. Compounds with sexual double bonds. The negative photosensitive resin composition contains a cross-linking agent (D) in addition to the compound (I), whereby the curability of the negative photosensitive resin composition during exposure can be further improved, and a cured film can be formed efficiently .

The cross-linking agent (D) preferably has an ethylenic double bond in the (meth)acrylyl group. Specific examples of the cross-linking agent (D) include diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, and neopentyltetrahydrol. Alcohol tetra(meth)acrylate, di(trimethylol)propane tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, dineopenterythritol hexa(meth)acrylate , Ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone modified ginseng (2-hydroxyethyl) isocyanurate tri(meth)acrylate and urethane Ethyl acrylate, etc.

From the viewpoint of photoreactivity, it is preferable to have a plurality of ethylenic double bonds. For example, neopenterythritol tetra(meth)acrylate, di(trimethylol)propane tetra(meth)acrylate, dineopenterythritol hexa(meth)acrylate, dineopenterythritol Alcohol penta(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate and urethane acrylate, etc. Two or more types of cross-linking agents (D) may be used in combination.

When the negative photosensitive resin composition contains the cross-linking agent (D), its content ratio is preferably 1 to 2000%, more preferably 1 to 1000%, based on 100% of the compound (I). The content ratio of the cross-linking agent (D) in the total solid content is preferably 1 to 70%. The content ratio is more preferably 5% by mass or more. On the other hand, it is more preferable that the content ratio is 50% or less. In addition, the ratio of the total amount of the compound (I) and the cross-linking agent (D) is preferably 1 to 1400% relative to 100% of the alkali-soluble resin. The ratio of the total amount is better than 10%. On the other hand, the ratio of the total amount is more suitable to be 500%.

(solvent) The negative photosensitive resin composition of the present invention reduces the viscosity by containing a solvent, so that the negative photosensitive resin composition becomes easy to coat on the surface of the substrate. As a result, a negative photosensitive resin composition coating film with a uniform film thickness can be formed. As the solvent, conventional solvents can be used. Two or more solvents may be used in combination.

Examples of the solvent include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, and solvent naphtha. Among them, at least one solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates and alcohols is preferably selected from the group consisting of propylene glycol monomethyl At least one solvent from the group consisting of ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate and 2-propanol is more preferred.

The content ratio of the solvent in the negative photosensitive resin composition is preferably 50 to 99% relative to the total amount of the composition. A content ratio of 60% or more is more preferred, and 65% or more is particularly preferred. On the other hand, a content ratio of 95% or less is more preferred, and 90% or less is particularly preferred.

(colorant) The negative photosensitive resin composition of the present invention may contain a colorant when imparting light-shielding properties to a cured film (particularly, a partition wall), depending on the intended use. In the present invention, the coloring agent may include carbon black, nitrile black, anthraquinone black pigment, indole black pigment, perylene black pigment, etc. Specific examples include C.I. Pigment Black 1, 6, 7, 12, 20, 31, etc. Mixtures of organic pigments and/or inorganic pigments such as red pigments, blue pigments, and green pigments can also be used.

Two or more colorants may be used in combination. When the negative photosensitive resin composition of the present invention contains a colorant, the content ratio of the colorant in the total solid content is preferably 5 to 65%. The content ratio is preferably 10% or more. On the other hand, it is more preferable that the content ratio is 50% or less. If it is within the above range, the resulting negative photosensitive resin composition will have good sensitivity, and the formed partition wall will have excellent light-shielding properties.

(UV absorber) The negative photosensitive resin composition of the present invention may contain an ultraviolet absorber that absorbs in the ultraviolet region with a wavelength of 200 to 400 nm, especially a reactive ultraviolet absorber. Two or more types of ultraviolet absorbers may be used in combination. If the negative photosensitive resin composition of the present invention contains an ultraviolet absorber, the ultraviolet absorber will moderately absorb the light irradiated during exposure. Therefore, hardening near the substrate interface is suppressed, and it also helps to reduce development residue at the opening.

The reactivity of the ultraviolet absorber is preferably photoreactivity. If the ultraviolet absorber is reactive, when the negative photosensitive resin composition is cured, it can react with reactive components such as photocurable alkali-soluble resin (A) and compound (I), and be firmly fixed to the cured film. and next door. In this way, the overflow of the ultraviolet absorber from the cured film and the partition wall can be controlled to a low level. The UV absorber is preferably a compound with a benzyl ketone skeleton, a benzotriazole skeleton, a cyanoacrylate skeleton or a triskeleton skeleton, and the reactive group is preferably a group with an vinyl double bond, such as (methyl )acrylyl.

Two or more types of ultraviolet absorbers (preferably reactive ultraviolet absorbers) may be used in combination. When the negative photosensitive resin composition of the present invention contains an ultraviolet absorber, the content ratio of the ultraviolet absorber in the total solid content is preferably 0.01 to 20%. The content ratio is more preferably 0.1% or more, and even more preferably 0.5% or more. On the other hand, the content ratio is more preferably 15% or less, and particularly preferably 10% or less. When the content ratio is within the above range, the sensitivity of the negative photosensitive resin composition is good, the adhesion of the partition walls is improved, and the development residue is reduced. In addition, the content ratio of the ultraviolet absorber is preferably 0.1 to 300% relative to 100% of the alkali-soluble resin. The content ratio is preferably 0.8% or more. On the other hand, the content ratio is preferably 100% or less.

(other ingredients) The negative photosensitive resin composition of the present invention may further contain polymer dispersants, dispersion aids, silane coupling agents, microparticles, hardening accelerators, tackifiers, plasticizers, defoaming agents, leveling agents and anti-repellent agents as needed. Repellents and other additives may contain two or more types each.

The negative photosensitive resin composition of the present invention can be obtained by mixing a predetermined amount of each of the above components. The negative photosensitive resin composition of the present invention can be used to manufacture optical components such as quantum dot displays, TFT arrays, thin film solar cells, and color filters. Specifically, it is particularly effective when used in cured films and partition walls used to form optical components such as quantum dot displays, TFT arrays, and thin-film solar cells.

In the present invention, if a negative photosensitive resin composition containing an ink repellent is used, a cured film (especially a partition wall) with good ink repellency can be produced. In addition, when the ink repellent agent (E) is used, the ink repellent agent (E) is almost fully fixed in the ink repellent layer, and the ink repellent agent (E) is present in the partition wall below the ink repellent layer at a low concentration. Also, since the partition walls are sufficiently photohardened, they are not likely to migrate into the opening surrounded by the partition walls during development, so an opening can be obtained where the ink can be evenly applied.

[Manufacture of resin cured film and partition walls] When it is desired to use the negative photosensitive resin composition of the present invention to prepare a resin cured film, for example, the negative photosensitive resin composition of the present invention can be coated on the surface of a base material such as a substrate, and dried if necessary. It is produced by removing solvent, etc. and then exposure and hardening. The obtained resin cured film can be used in optical components, especially when used in quantum dot displays, TFT arrays and thin film solar cells.

The partition walls composed of the resin cured film using the negative photosensitive resin composition of the present invention are formed into a shape that divides the substrate surface into a plurality of partitions for dot formation. For example, partition walls can be produced as follows: In the process of producing the above-mentioned resin cured film, a coating film composed of a negative photosensitive resin composition is applied to a portion that will become a partition for dot formation before exposure. Mask is produced by developing after exposure. Through development, the portions that are masked but not exposed are removed, and openings corresponding to the partitions for dot formation are formed together with the partition walls. The partition wall according to the embodiment of the present invention can be particularly effective when used in optical components, especially quantum dot displays, TFT arrays and thin film solar cells.

In addition, it is advisable to remove volatile components such as solvents contained in the negative photosensitive resin composition from the coating film by drying before exposure. Examples of drying methods include heat drying, reduced pressure drying, and reduced pressure heat drying. Although it also depends on the type of solvent, the appropriate heating temperature for heat drying is 50~120°C. When the negative photosensitive resin composition contains an ink repellent agent, the ink repellent agent will migrate to the upper part of the dry film during the drying process.

The light irradiated during exposure can include: 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 such as excimer laser light; X-rays; and, electron beams, etc. The irradiation light is preferably light with a wavelength of 100~600nm, preferably 300~500nm, and especially light containing i-rays (365nm), h-rays (405nm) or g-rays (436nm). In addition, light below 330nm can also be cut off if necessary.

Exposure methods can include all-round exposure and scanning exposure. The same punishment can also be exposed multiple times. In this case, it does not matter whether the exposure conditions are the same or different a plurality of times. Regardless of any of the above exposure methods, for example, the exposure amount is 5~1,000mJ/ ^cm2 , preferably 5~500mJ/ ^cm2 , 5~300mJ/ ^cm2 better, 5~200mJ/cm2 cm ² is especially good, and 5~50mJ/cm ² is the best. In addition, the exposure amount can be appropriately optimized through the wavelength of the irradiation light, the composition of the negative photosensitive resin composition, and the thickness of the coating film.

The exposure time per unit area is not particularly limited and can be designed based on the exposure power of the exposure device used and the required exposure amount. In addition, when scanning exposure, the exposure time can be calculated from the scanning speed of light. The exposure time per unit area is usually about 1 to 60 seconds.

According to the negative photosensitive resin composition of the present invention, in the above-mentioned exposure part, the cross-linking of the alkali-soluble resin (A) caused by the compound (I) will be carried out simultaneously with the radical polymerization of the alkali-soluble resin (A) during exposure. Thus, according to the negative photosensitive resin composition of the present invention, the curing property of the alkali-soluble resin (A) in the cured film is improved, and a cured film with good adhesion to the substrate can be obtained. Alternatively, a cured film having curability equivalent to that of a conventional cured film even at a low exposure amount can be produced.

Development is performed using an alkali developer to form partition walls and openings. According to the negative photosensitive resin composition of the present invention, the non-exposed portion can be easily removed, and the residue in the opening can be reduced. In addition, the hardened part that is the exposed part is resistant to erosion and peeling caused by alkali developer during development. Therefore, the exposed part is not easily affected even if it is developed for a long time, which is helpful for removing residues in the opening.

In addition, when the negative photosensitive resin composition contains an ink repellent agent, the uppermost layer including the partition wall will form an ink repellent layer, and the lower side of the ink repellent layer is mainly composed of alkali-soluble resin (A), compound (I) and optionally The thiol compound (C), the cross-linking agent (D), or other photo-hardening components contained therein undergo photo-hardening to form a layer containing almost no ink repellent agent.

After development, the partition walls can be further heated. The appropriate heating temperature is 130~250℃. Through heating, the hardening of the partition wall will become stronger. In addition, when an ink repellent is included, the ink repellent will be more firmly fixed on the ink repellent layer. In addition, in order to ensure the ink affinity of the opening, after the above heating, in order to remove the development residue of the negative photosensitive resin composition that may be present in the opening, the substrate with the partition wall can be subjected to ultraviolet/ozone treatment. .

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

It is preferable that the partition wall formed of the negative photosensitive resin composition of the present invention has less unevenness in the edge portion and has excellent linearity when the width is formed as described above. This enables high-precision pattern formation even with fine patterns. If such high-precision pattern formation can be performed, it will be particularly useful as a partition wall for quantum dot displays, TFT arrays, and thin-film solar cells.

When pattern printing is performed by the IJ method, the partition wall of the present invention can be used as a partition wall having its opening as an ink injection region. When the partition wall has ink repellency, if the partition wall is formed and used so that its opening coincides with the desired ink injection area, since the upper surface of the partition wall has good ink repellency, it can prevent ink from exceeding the partition wall and being injected into the undesired opening. That is, the area where printing ink is injected (contamination). In addition, the opening surrounded by the partition wall has good wet diffusion properties of the ink, so that the ink can be printed evenly on the desired area without causing spacing.

The surface water contact angle of the resin cured film obtained by using the negative photosensitive resin composition of the present invention is preferably above 60 degrees, and more preferably above 80 degrees. When the negative photosensitive resin composition contains an ink repellent agent, the water contact angle is easily within the above range, especially above 80 degrees. In addition, the surface propylene glycol monomethyl ether acetate (PGMEA) contact angle of the above-mentioned resin cured film should be more than 30 degrees, and more preferably more than 40 degrees. Especially when the negative photosensitive resin composition contains an ink repellent agent, it is easy to keep the PGMEA contact angle within the above range. When a high PGMEA contact angle is required, the negative photosensitive resin composition should contain an ink repellent agent.

In addition, the resin cured film is formed on the base material and can be used directly. In this aspect, the surface of the resin cured film means the upper surface of the resin cured film. The ink-repellent property of the resin cured film surface can still be expressed equally on the partition wall. That is to say, no matter whether the ink used in the IJ method is water-based or oil-based, the upper surface of the partition wall has sufficient properties to repel the ink. At the same time, the contamination and repelling phenomenon of the ink in the opening can be fully suppressed.

Here, the contact angle was measured in accordance with JIS R3257 "Wetness test method of substrate glass surface" by placing water droplets or PGMEA droplets on three places on the surface of the cured film, and using the lying drop method for each water droplet or PGMEA droplet. The droplet size was 2 μL/drop, and the measurement was performed at 20°C. The contact angle is calculated from the average of 3 measured values.

If the partition wall of the present invention is used, as described above, pattern printing by the IJ method can be performed accurately. Therefore, the partition wall of the present invention is very useful as an optical element having partition walls (located between dots adjacent to a plurality of dots on the surface of a substrate formed by the IJ method), especially partition walls of quantum dot displays, TFT arrays and thin film solar cells. .

[Optical components] Optical elements having partition walls formed using the negative photosensitive resin composition of the present invention, especially quantum dot displays, TFT arrays or thin film solar cells, are as mentioned above. Since the residue in the openings separated by the partition walls is reduced, the printing ink can be Moisturizes and spreads evenly without deviation. Furthermore, the partition walls have excellent substrate adhesion. If the adhesion between the partition wall and the base material is insufficient, for example, the ink may spread beyond the opening and cause problems.

The base material forming the partition wall can be appropriately selected from various inorganic materials and organic materials according to the type of optical element. The partition wall is made of inorganic oxides such as glass, alumina, tantalum oxide and titanium oxide, inorganic nitrides such as silicon nitride and aluminum nitride, polyimide, polyamide, polyester, polyacrylate, and photofree radicals. Base materials composed of polymeric and photocationic polymerization photocurable resins, copolymers containing acrylonitrile, polyvinylphenol, polyvinyl alcohol, varnish resins and organic compounds such as cyanoethyl polytriglycose and other insulating materials Excellent adhesion, in addition to Al, Au, Ag, Pt, Pd, Cu, Cr, Mo, In, Zn, Mg, etc. and alloys or oxides containing the same, or carbon nanotubes Substrates made of conductive materials such as organic conductors, tin-doped indium oxide (ITO), and zinc-doped indium oxide (IZO) also have excellent adhesion.

The optical element having the partition wall of the present invention is an optical element having dots, especially a quantum dot display, a TFT array, or a thin film solar cell. The dots are formed with high accuracy due to improved adhesion to the partition wall substrate and reduced residue at the opening.

For example, a quantum dot display can be manufactured as follows, but is not limited thereto. A film of a translucent electrode such as ITO is formed on a translucent substrate such as glass by sputtering or the like. The translucent electrode can be patterned if necessary. Next, the negative photosensitive resin composition of the present invention is used, and then the partition walls are formed into a grid shape in plan view along the outline of each point by a photolithography method including coating, exposure and development. Secondly, if necessary, apply the charge injection material solution and/or the charge transport material solution in the dots by the IJ method and dry them, and then apply the electroluminescent nanoparticle solution and let them dry to make a module. Thereby, a quantum dot display with excellent color reproducibility can be produced.

The so-called TFT array element refers to an element in which a plurality of points are arranged in an array shape in a plan view, and a pixel electrode and a TFT used as a switching element for driving the pixel electrode are provided at each point, and an inorganic semiconductor layer or an organic semiconductor layer is used as the element including the TFT. The semiconductor layer of the channel layer. For example, the organic TFT array element can be provided on a liquid crystal element as a TFT array substrate. For example, the TFT array can be manufactured as follows, but is not limited thereto. Gate electrodes of aluminum and its alloys are formed on transparent substrates such as glass by sputtering. The gate electrode can be patterned as desired.

Next, a gate insulating film such as silicon nitride is formed using a plasma CVD method or the like. The source and drain can also be formed on the gate insulating film. For example, vacuum evaporation and sputtering can be used to form metal films of aluminum, gold, silver, copper or alloys thereof to form source and drain electrodes.

Methods for patterning the source and drain electrodes include: after forming a metal thin film, apply photoresist, expose and develop, leaving the photoresist remaining in the part where the electrode is to be formed, and then remove the exposed metal with phosphoric acid or aqua regia, etc. How to remove photoresist. In addition, when forming a metal film such as gold, there is also the following method: apply photoresist in advance, expose, and develop, leaving the photoresist in the portion where the electrode is not to be formed. After the metal film is formed, the photoresist and the metal film are removed together. In addition, metal nanocolloids such as silver or copper can also be used to form the source and drain by inkjet or other techniques.

Next, the negative photosensitive resin composition of the present invention is used to form the partition walls into a grid shape in plan view along the outline of each point by a photolithography method including coating, exposure, and development. Then, a semiconductor solution is applied in the dots using the IJ method, and the solution is allowed to form a semiconductor layer. As the semiconductor solution, an organic semiconductor solution and an inorganic coating-type oxide semiconductor solution may be used. The source electrode and the drain electrode can also be formed using inkjet or other techniques after the semiconductor layer is formed. Finally, a transparent electrode such as ITO is formed by a sputtering method, and a protective film such as silicon nitride is formed. Example

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Examples 1 to 17 are examples, and Examples 18 to 20 are comparative examples.

Each characteristic was measured by the following method. [Number average molecular weight (Mn), mass average molecular weight (Mw)] Polystyrene was used as a standard material by gel permeation chromatography. The gel permeation chromatography used was HPLC-8220GPC (manufactured by Tosoh Corporation). The column is connected to three Shodex LF-604 tubes. The detector uses an RI detector. EasiCal PS1 (manufactured by Polymer Laboratories) was used as the standard material. Furthermore, during the measurement, the column was maintained at 37°C, tetrahydrofuran was used as the eluent, the flow rate was set to 0.2 mL/min, and 40 μL of a 0.5% tetrahydrofuran solution of the measurement sample was injected.

[Fluorine atom content] Calculated by ¹⁹ F NMR measurement using 1,4-bis(trifluoromethyl)benzene as a standard material. [Acid value] Calculate the acid value theoretically from the blending ratio of raw materials.

The abbreviations of each compound used in the following examples are shown below. (Alkali-soluble resin (A)) A1: Resin obtained by reacting cresol varnish type epoxy resin with acrylic acid and 1,2,3,6-tetrahydrophthalic anhydride, and then purifying the resin into which acrylic and carboxyl groups have been introduced using hexane (alkali-soluble resin (A1), acid value 80mgKOH/g). When manufacturing a negative photosensitive resin composition, a composition of alkali-soluble resin (A1) (solid content 70%, PGMEA 30%) is used.

A2: Resin obtained by reacting bisphenol A-type epoxy resin with acrylic acid and 1,2,3,6-tetrahydrophthalic anhydride, and then purifying the resin into which acrylic and carboxyl groups have been introduced using hexane (alkali-soluble resin (A2), acid value 50mgKOH/g). When manufacturing a negative photosensitive resin composition, a composition of alkali-soluble resin (A2) (solid content 70%, PGMEA 30%) is used.

A-R-1: After flowing nitrogen into a 1L flask equipped with a stirrer, reflux cooler, titration funnel and stirrer at a rate of 0.02L/min to form a nitrogen atmosphere, add 305 parts of PGMEA and heat to 70°C while stirring. Next, a solution dissolved in 60 parts of methacrylic acid, 240 parts of 3,4-epoxytricyclo[5.2.1.02.6]decyl acrylate and 140 parts of PGMEA was prepared, and the solution was titrated using a titration funnel over 4 hours. Insulate it in a flask at 70°C. On the other hand, using another titration funnel, a solution in which 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of PGMEA was titrated into the flask over 4 hours. .

After the titration of the solution of the polymerization initiator is completed, the solution is kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a resin (A-R-1) with an Mw of 12,800, a dispersion of 2.5, and an acid value of 34 mgKOH/g. When manufacturing the negative photosensitive resin composition, a composition of alkali-soluble resin (A-R-1) (solid content 33%, PGMEA 67%) is used.

A-R-2: Resin obtained by reacting cresol varnish type epoxy resin with acrylic acid and 1,2,3,6-tetrahydrophthalic anhydride, and then purifying the resin into which acrylic and carboxyl groups have been introduced using hexane (alkali Soluble resin (A-R-2), acid value 30mgKOH/g). When manufacturing a negative photosensitive resin composition, a composition of alkali-soluble resin (A-R-2) (solid content 70%, PGMEA 30%) is used.

(Compound (I)) I-11: triallyl isocyanurate (a compound in which R is H and Q is -CH ₂ - in the above formula (I-1)). I-21: 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane (a compound in which R is H and Q is a single bond in the above formula (I-2)) . I-31: 1,3,4-trivinylcyclohexane (a compound in which R at positions 1, 3, and 4 is H and Q is a single bond in the above formula (I-3)). I-41: Neopenterythritol triallyl ether (a compound in which Y is H, R is H and Q is -CH ₂ - in the above formula (I-4)). I-42: Neopenterythritol tetraethylene ether (a compound in which Y is a CH ₂ =CR-Q- group, R is H and Q is a single bond in the above formula (I-4)).

(Photopolymerization initiator (B)) B-1: 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌linylpropan-1-one EAB: 4,4'-bis(diethylamino)diphenylketone.

(thiol compound (C)) C-1: 1,3,5-shen(3-mercaptobutyryloxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione. (Crosslinking agent (D)) DPHA: dipenterythritol hexaacrylate.

(Ink repellent agent (E)) The following raw material compounds were used and synthesized as follows. MEK: 2-butanone. X-8201: Methacrylate containing dimethyl polysiloxy chain (manufactured by Shin-Etsu Chemical Industry Co., Ltd., X-24-8201). C6FMA: CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ (CF ₂ ) ₆ F. MAA: methacrylic acid. 2-HEMA: 2-hydroxyethylmethyl acrylate. AOI: 2-propylene oxyethyl isocyanate. DBTDL: dibutyltin dilaurate. BHT: 2,6-bis(tertiary butyl)p-cresol. Compound (s1-1) equivalent to compound (s1): F(CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₃ ) ₃ (produced according to a common method). Compound (s2-1) corresponding to compound (s2): Si(OC ₂ H ₅ ) ₄ . Compound (s3-1) equivalent to compound (s3): CH ₂ =CHCOO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ .

[Synthesis of ink repellent agent (E1-1)] Feed MEK (420.0g), X-8201 (27.0g), C6FMA (66.6g), MAA (14.4g), 2-HEMA (72.0g) and 2 into an autoclave with a mixer and an internal volume of 1L. , 2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile) (1.4g) was polymerized at 30°C for 24 hours while stirring in a nitrogen atmosphere to prepare a copolymer. 1 solution. Heptane was added to the MEK solution of the obtained copolymer 1 for reprecipitation and purification, and after vacuum drying, 148.7 g of copolymer 1 was obtained. Mn is 17320 and Mw is 51200.

Copolymer 1 (50.0g), AOI (21.7g), DBTDL (0.087g), BHT (1.1g) and MEK (128.1g) were fed into a glass flask with a thermometer, stirrer and heating device and a content of 300mL. ), and reacted at 40° C. for 48 hours while stirring to prepare a solution of polymer (E1-1). Heptane was added to the MEK solution of the obtained polymer (E1-1) for reprecipitation and purification, and after vacuum drying, 64.1 g of the polymer (E1-1) was obtained. Mn is 36520, Mw is 68610, and the fluorine atom content is 14.7%.

[Synthesis of ink repellent agent (E1-2)] Feed MEK (420.0g), C6FMA (93.6g), MAA (14.4g), 2-HEMA (72.0g) and 2,2'-azobis ( 4-Methoxy-2,4-dimethylvaleronitrile) (2.9 g) was polymerized at 30° C. for 24 hours while stirring in a nitrogen atmosphere to prepare a solution of copolymer 2. Heptane was added to the MEK solution of the obtained copolymer 2 for reprecipitation and purification, and after vacuum drying, 150.3 g of copolymer 2 was obtained. Mn is 12370 and Mw is 37660.

Copolymer 2 (50.0g), AOI (21.7g), DBTDL (0.087g), BHT (1.1g) and MEK (128.1g) were fed into a glass flask with a thermometer, a stirrer and a heating device and a content of 300mL. ), and reacted at 40° C. for 48 hours while stirring to obtain a solution of polymer (E1-2). Heptane was added to the MEK solution of the obtained polymer (E1-2) for reprecipitation and purification, and after vacuum drying, 63.8 g of the polymer (E1-2) was obtained. Mn is 18460, Mw is 48890, and the fluorine atom content is 20.7%.

[Synthesis of ink repellent agent (E2-1)] Put 15.0g of compound (s1-1), 20.0g of compound (s2-1) and 27.0g of compound into a ^1,000cm3 three-necked flask equipped with a stirrer. (s3-1), a hydrolyzable silane compound mixture is obtained. Next, 284.3 g of IPA (2-propanol) was added to the mixture to prepare a raw material solution.

30.0 g of 1% hydrochloric acid aqueous solution was titrated into the obtained raw material solution. After the titration is completed, stir at 40°C for 5 hours to prepare an IPA solution of the ink repellent agent (E2-1) (concentration of the ink repellent agent (E2-1): 10%, also referred to as the ink repellent agent ((E2-1) below). )) solution). In addition, after the reaction, the components of the reaction solution were measured using a gas chromatograph to confirm that each compound used as a raw material was below the detection limit. In addition, the Mn of the obtained ink repellent agent (E2-1) was 1200, Mw was 1310, and the fluorine atom content was 21.0%.

(UV absorber) UVA-1: 2,4-dihydroxydiphenylketone. UVA-2: 2-(2’-hydroxy-5’-methacryloxyethylphenyl)-2H-benzotriazole. Surfactant: BYK302 (manufactured by BYK Japan KK) (solvent) PGME: propylene glycol monomethyl ether. EDM: diethylene glycol ethyl methyl ether PGMEA: propylene glycol monomethyl ether acetate

[Example 1] (Production of negative photosensitive resin composition) The alkali-soluble resin (A), compound (I), photopolymerization initiator (B), thiol compound (C), and cross-linking agent shown in Table 1 (D), the reactive ultraviolet absorber, surfactant and solvent were put into a 200 cm ³ stirring container to form the composition in Table 1, and stirred for 3 hours to prepare negative photosensitive resin composition 1.

(Manufacture of cured film) A square glass substrate with a side length of 10 cm was ultrasonically cleaned with ethanol for 30 seconds, and then UV/O ₃ treated for 5 minutes. UV/O ₃ treatment uses PL2001N-58 (manufactured by SEN ENGINEERING Co., Ltd.) as a UV/O ₃ generation device. The converted optical power (light output) of 254nm is 10mW/cm ² .

The negative photosensitive resin composition 1 was applied to the surface of the glass substrate obtained above using a spinner, and then dried on a hot plate at 100° C. for 2 minutes to form a dry film with a thickness of 2.4 μm. The entire dry film obtained was irradiated with UV light from an ultra-high-pressure mercury lamp with an exposure power (exposure output) of 300 mW/cm ² converted to 365 nm. In this method, the irradiation time is adjusted so that the exposure amount is 50 mJ/cm ² to produce a cured film. In addition, in either case, light below 330nm is intercepted during exposure.

Next, the glass substrate after the above-mentioned exposure treatment was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds, rinsed with water, and then dried. Next, it was placed on a hot plate and heated at 230° C. for 60 minutes, thereby obtaining a cured film without openings.

(Production of pattern film 1) (for evaluation of Cu adhesion) A substrate having a Cu layer on a glass substrate was used, and the above-mentioned negative photosensitive resin composition 1 was applied on the Cu layer using a spinner, and then Dry on a hot plate at 100°C for 2 minutes to form a dry film with a film thickness of 2.4 μm. Through the photomask, the entire surface of the obtained dry film was irradiated with UV light from an ultra-high-pressure mercury lamp (exposure amount: 50mJ/cm ² ) with an exposure power (exposure output) of 300mW/cm ² converted to 365nm. Cut off light below 330nm during exposure. In addition, let the distance between the dry film and the photomask be 50 μm. Use a photomask with a line width/space design of 20μm/50μm, 10μm/50μm, 8μm/50μm, 6μm/50μm, or 4μm/50μm.

Next, the above-exposed glass substrate was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds to develop, and then the non-exposed parts were washed away with water and then dried. Next, it was placed on a hot plate and heated at 230° C. for 60 minutes, thereby producing a patterned film 1 having five lines with widths of 20 μm, 10 μm, 8 μm, 6 μm, and 4 μm at intervals of 50 μm as a cured film.

(Production of pattern film 2) (for evaluation of organic film adhesion) Use a spinner to apply DL-1000 (positive polyimide photoresist, manufactured by Toray Industries, Inc.) on the glass substrate, and then dry it on a hot plate at 110°C for 2 minutes to form a film thickness of 2.0 μm dry film. Immerse in 2.38% tetramethylammonium hydroxide aqueous solution for 40 seconds to develop and then dry. Then, it was placed on a hot plate and heated at 220° C. for 60 minutes, thereby producing a glass substrate with an organic film attached to the entire surface.

The above-mentioned negative photosensitive resin composition 1 was applied to the organic film of the obtained glass substrate with an organic film using a spinner, and then dried on a hot plate at 100° C. for 2 minutes to form a dry film with a film thickness of 2.4 μm. Through the photomask, the entire dry film obtained was irradiated with UV light (exposure amount: 50mJ/cm2) from an ultra-high-pressure mercury lamp with an exposure power (exposure output) of 300mW/cm2 at 365nm. Cut off light below 330nm during exposure. In addition, let the distance between the dry film and the photomask be 50 μm. Use a photomask with a line width/space design of 20μm/50μm, 10μm/50μm, 8μm/50μm, 6μm/50μm, or 4μm/50μm.

Next, the above-exposed glass substrate was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds to develop, and then the non-exposed parts were washed away with water and then dried. Next, it was placed on a hot plate and heated at 230° C. for 60 minutes, thereby producing a patterned film 2 having five lines with widths of 20 μm, 10 μm, 8 μm, 6 μm, and 4 μm at intervals of 50 μm as a cured film.

(Manufacture of pattern film 3) (with ITO glass; for analysis of XPS residue) Use a substrate with an ITO layer on a glass substrate, use a spinner to apply the above-mentioned negative photosensitive resin composition 1 on the ITO layer, and then dry it on a hot plate at 100°C for 2 minutes to form a film thickness of 2.4 μm. of dry film. Through a photomask with an opening pattern (a grid-like pattern with a light-shielding part of 100 μm × 200 μm and a light-transmitting part of 20 μm), the entire surface of the obtained dry film was irradiated with an ultra-high-pressure mercury lamp with an exposure power (exposure output) of 300 mW/cm2 converted to 365 nm. UV light (exposure is 50mJ/cm2). Cut off light below 330nm during exposure. In addition, let the distance between the dry film and the photomask be 50 μm.

Next, the above-exposed glass substrate was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds to develop, and then the non-exposed parts were washed away with water and then dried. Next, it was placed on a hot plate and heated at 230° C. for 60 minutes, thereby producing a pattern film 3 having a pattern corresponding to the opening pattern of the photomask as a cured film.

(evaluation) The following evaluation was performed about the obtained negative photosensitive resin composition 1, the cured film, and the pattern films 1 to 3. The evaluation results are shown in Table 1 together with the composition of the negative photosensitive resin composition 1. ＜Thickness of hardened film＞ Measurement was performed using a laser microscope (manufactured by KEYENCE CORPORATION., device name: VK-8500).

＜Ink repellency＞ The water contact angle and the PGMEA contact angle on the surface of the cured film obtained above were measured by the following method to evaluate the ink repellency.

In accordance with JIS R3257 "Method for wettability test of substrate glass surface", water droplets or PGMEA droplets are placed on three places on the surface of the cured film, and each water droplet or PGMEA droplet is measured using the lying drop method. The droplet volume was 2 μL/droplet, and the measurement was performed at 20°C. The contact angle was determined from the average of 3 measured values.

＜Tight adhesion＞ Using pattern film 1 and pattern film 2, the adhesion of the following (1) and (2) was tested. (1)Copper <Development time (60 seconds) residual resolution> Regarding the pattern film 1, the peeling resistance to long-term development was evaluated based on the following criteria. ◎: At least a line with a line width of 10μm remains. ○: At least a line with a line width of 20 μm remains. ×: Line portions are peeled off in all line width/space samples.

(2)Organic film <Development time (60 seconds) residual resolution> Regarding the pattern film 2, the peeling resistance to long-term development was evaluated based on the following criteria. ◎: At least a line with a line width of 10μm remains. ○: At least a line with a line width of 20 μm remains. ×: Line portions are peeled off in all line width/space samples.

＜Residues at the opening＞ Surface analysis was performed using X-ray photoelectron spectroscopy (XPS) under the following conditions on the central portion of the opening of the ITO substrate with the pattern film 3 . The opening surface C/In value measured by XPS (the ratio of the indium atom concentration to the carbon atom concentration) is less than 5.0 as "◎", those between 5.0 and 8.0 are "○", and those above 8.0 are "×".

[Conditions of XPS] Device: Quantera-SXM manufactured by ULVAC-PHI, Inc. X-ray source: Al Kα, X-ray beam size: about 20 μmφ, measurement area: about 20 μmφ, Detection angle: 45° from the sample surface, measurement peak: F1s. Measurement time (measured as Acquired Time): within 5 minutes. Analysis software: MultiPak

[Examples 2~20] In Example 1, except that the negative photosensitive resin composition was changed to the composition shown in Table 1 or Table 2, a negative photosensitive resin composition, partition walls and a cured film were produced in the same manner, and the same process as in Example 1 was performed. Evaluation. The evaluation results of each example are shown in Tables 1 and 2 together with the composition of the negative photosensitive resin composition. In addition, in Table 1 and Table 2, the blank column means the blending amount "0".

[Table 1] (Solid content)

[Table 2]

As can be seen from Table 1 and Table 2, the partition walls obtained using the negative photosensitive resin compositions of Examples 1 to 17 of the Examples have good adhesion to the base material, and at the same time, the residue at the opening is reduced.

In addition, the entire contents of the specification, patent scope, drawings and abstract of Japanese Patent Application No. 2017-236753 filed on December 11, 2017 are quoted here and incorporated into the disclosure content of the specification of the present invention.

(without)

Claims (13)

A negative photosensitive resin composition, characterized in that it contains: an alkali-soluble resin, the acid value of which is 40 mgKOH/g or more, and is bound to bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolac type ring Oxygen resin, cresol varnish type epoxy resin, phenol methane type epoxy resin or epoxy resin with biphenyl skeleton are introduced with acidic groups and vinyl double bonds; photoradical polymerization initiator; and selected from the following formula At least one compound among the compounds represented by (I-1), formula (I-2), formula (I-3), formula (I-4) and formula (I-5);

(In formulas (I-1) ~ (I-5), R is a hydrogen atom or methyl group, Q is -CH ₂ - or a single bond, n1 is an integer from 2 to 6, Y is a hydrogen atom or -Q-CR =CH ₂ ). The negative photosensitive resin composition of claim 1, wherein the total solid content of the negative photosensitive resin composition contains 5 to 80 mass % of the aforementioned alkali-soluble resin. The negative photosensitive resin composition of claim 1 or 2, wherein the total solid content of the negative photosensitive resin composition contains 0.1 to 50 mass % of the aforementioned photoradical polymerization initiator. The negative photosensitive resin composition of claim 1 or 2, wherein the total solid content of the negative photosensitive resin composition contains 1 to 50 mass % selected from the aforementioned formula (I-1), the aforementioned formula (I- 2), at least one compound among the compounds represented by the aforementioned formula (I-3), the aforementioned formula (I-4) and the aforementioned formula (I-5). For example, the negative photosensitive resin composition of claim 1 or 2 further contains a thiol compound having more than two mercapto groups in one molecule. The negative photosensitive resin composition of claim 5 further contains the aforementioned thiol compound in the following amounts: ethylenic double bonds, mercapto groups per 1 mol of the total solid content of the negative photosensitive resin composition It is an amount of 0.0001~1 mole. For example, the negative photosensitive resin composition of claim 1 or 2 further contains an ink repellent agent. The negative photosensitive resin composition of claim 7, wherein the ink repellent agent has an vinyl double bond. The negative photosensitive resin composition of claim 7, wherein the ink repellent agent has a fluorine content of 1 to 40 mass %. Such as the negative photosensitive resin composition of claim 7, which The total solid content of the neutral negative photosensitive resin composition contains 0.01 to 15% by mass of the aforementioned ink repellent agent. For example, the negative photosensitive resin composition of claim 1 or 2 further contains a solvent. The negative photosensitive resin composition of claim 1 or 2, wherein the water contact angle on the surface of the resin cured film formed using the negative photosensitive resin composition is 60 degrees or more. The negative photosensitive resin composition of claim 1 or 2, wherein the propylene glycol monomethyl ether acetate contact angle on the surface of the resin cured film formed using the negative photosensitive resin composition is 30 degrees or more.