Positive photosensitive resin composition

Abstract

The purpose of the present invention is to provide a positive photosensitive resin composition capable of forming a cured film, which is used in a liquid crystal display element, an organic EL display element or the like, has high hydrophobicity and high lipophobicity on the surface of the cured film, has little residue after formation of a pattern, does not overflow an organic functional ink in the pattern, and can satisfactorily wet and spread. The positive photosensitive resin composition contains the following component (A1), component (A2), component (B), component (C), component (D) and solvent (E). Component (A1): an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least (A1-I) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride Component (A2): an alkali-soluble resin having an N-hydroxyphenyl group and not having a carboxyl group Component (B): a surfactant Component (C): a 1, 2-quinonediazo compound Component (D): a crosslinking agent Component (E): a solvent Component (A1): an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least (A1-I) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride Component (A2): an alkali-soluble resin having an N-hydroxyphenyl group and not having a carboxyl group Component (A2).

Description

Technical Field

[0001] The present invention relates to a positive photosensitive resin composition and a cured film formed therefrom.

[0002] More specifically, the present invention relates to a positive photosensitive resin composition capable of forming a cured film, which is unlikely to generate residues when forming a pattern, has high hydrophobicity and oleophobicity on the surface of the cured film, does not allow the organic functional ink in the enclosed pattern to overflow, and wets and spreads well, and the cured film thereof, as well as various materials using the cured film. The positive photosensitive resin composition is particularly suitable for use as an interlayer insulating film in display elements such as liquid crystal displays, EL displays, and micro LED displays, as a light shielding material corresponding to an inkjet method, and as a spacer material. Background Art

[0003] Generally, display elements such as thin film transistor (TFT) type liquid crystal display elements and organic EL (electroluminescent) elements are provided with patterned electrode protection films, planarization films, insulating films, etc. As materials for forming these films, photosensitive resin compositions having characteristics such as a small number of steps for obtaining a desired pattern shape and sufficient planarity have been widely used.

[0004] In addition, in recent years, full-color display substrate manufacturing technology using inkjet in the manufacturing process of display display elements has also been actively studied. For example, regarding the production of color filters in liquid crystal display elements, compared with the previous printing method, electrodeposition method, dyeing method or pigment dispersion method, the following color filter and its manufacturing method have been proposed, that is, using a photosensitive resin layer that blocks light to pre-form partitions (hereinafter referred to as partitions) that define patterned pixels, and dripping ink drops into the openings surrounded by the partitions (Patent Document 1), etc. In addition, a method has been proposed in which a partition is pre-made in an organic EL display element, and ink that forms a light-emitting layer is dripped in the same way, thereby producing an organic EL display element (Patent Document 2).

[0005] However, when ink droplets are dropped surrounded by banks by the inkjet method, in order to prevent the ink droplets from exceeding the banks and overflowing into adjacent pixels, the substrate needs to be ink-philic (hydrophilic) and the bank surface needs to be hydrophobic.

[0006] On the other hand, in recent years, in the process of making a dam, the technology of using a grayscale mask or a halftone mask has also been actively studied. For example, with respect to the production of a color filter, in a lattice-shaped dam pattern, in order to form a lattice-shaped pattern in which the film thickness of the dam pattern in one direction is thinner than that of the dam pattern orthogonal thereto, a method of using a halftone mask has been proposed (Patent Document 3). In addition, in an organic EL display element, as a method of forming a linear dam pattern A and a dam pattern B for defining a pixel area arranged in a line and making B a thin film, an exposure method through a halftone mask has also been proposed (Patent Document 4). In such a technology, a photosensitive resin composition having sufficient flatness in the semi-exposed portion is required.

[0007] In order to achieve the above purpose, a negative photosensitive resin composition in which a fluorine-based surfactant or a fluorine-based polymer is blended into a photosensitive organic film has been proposed (Patent Document 5). However, it is difficult to improve the resolution, and a positive photosensitive resin needs to be used for high-definition display elements.

[0008] On the other hand, as a positive photosensitive resin composition, there is a positive photosensitive resin composition that can form a pattern with high sensitivity while maintaining the adhesion during development and can form a cured film with little residue in the pattern (Patent Document 6), but there is a problem that the residue does not completely disappear and the inkjet wettability and flatness of the half-exposed part are poor.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2000-187111

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 11-54270

[0013] Patent Document 3: Japanese Patent Application Publication No. 2009-258669

[0014] Patent Document 4: Japanese Patent No. 4495781

[0015] Patent Document 5: Japanese Patent Application Publication No. 2015-172742

[0016] Patent Document 6: Japanese Patent No. 6744577 Summary of the invention

[0017] Problems to be solved by the invention

[0018] The present invention has been completed in view of the above situation, and the problem to be solved is to provide a positive photosensitive resin composition that can form a cured film, which is used for liquid crystal display elements, organic EL display elements, etc. The surface of the cured film has high hydrophobicity and high oleophobicity, and there is almost no residue after pattern formation even when a low-concentration developer is used. It can take into account high inkjet wettability and high contact angle, and high flatness of the semi-exposed portion.

[0019] Means of solving the problem

[0020] The present inventors have conducted intensive studies to achieve the above-mentioned purpose, and as a result, found that by mixing different types of alkali-soluble polymers, that is, by further using an alkali-soluble resin having N-hydroxyphenyl groups in the conventional alkali-soluble polymers, the high-acidity carboxylic acid and the low-acidity large amount of phenol can weaken the penetration barrier effect of the alkali-insoluble group on the low-concentration developer, and develop while dissolving in the low-concentration developer, so that almost no residue is generated after pattern formation. Furthermore, it was found that by using a surfactant having a lyophobic group, a cured film having high hydrophobicity and high oleophobicity, high inkjet wettability and high contact angle, and high flatness of the semi-exposed portion can be formed, thereby completing the present invention.

[0021] The first embodiment of the present invention is a positive photosensitive resin composition capable of forming a cured film, comprising the following components (A1), (A2), (B), (C), (D) and (E) a solvent.

[0022] (A1) component: an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least (A1-I) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, (A2) component: an alkali-soluble resin having an N-hydroxyphenyl group and no carboxyl group, (B) component: a surfactant, (C) component: a 1,2-quinonediazide compound, (D) component: a crosslinking agent, and (E) a solvent;

[0023] The second embodiment of the present invention is the positive photosensitive resin composition according to the first embodiment, wherein the component (A1) is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least the compound (A1-I) and the following compounds (A1-II) and (A1-III),

[0024] (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group,

[0025] (A1-III) N-substituted maleimide compound;

[0026] The third embodiment of the present invention is the positive photosensitive resin composition according to the second embodiment, wherein the component (A1) is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least the compounds (A1-I), (A1-II), (A1-III) and the following (A1-IV),

[0027] (A1-IV) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group;

[0028] A fourth embodiment of the present invention is the positive photosensitive resin composition according to the third embodiment, wherein the monomer (A1-IV) having a phenolic hydroxyl group and a polymerizable unsaturated group is p-hydroxyphenyl (meth)acrylate;

[0029] A fifth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to fourth aspects, wherein the component (A1) is an alkali-soluble acrylic polymer having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene;

[0030] A sixth aspect of the present invention is a positive photosensitive resin composition according to any one of the first to fifth aspects, wherein the component (A2) is a polymer comprising a structural unit derived from at least one monomer selected from N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, or N-(hydroxyphenyl)maleimide;

[0031] A seventh aspect of the present invention is the positive photosensitive resin composition according to any one of the first to sixth aspects, wherein the component (A2) is an alkali-soluble resin having a number average molecular weight of 2,000 to 60,000 in terms of polystyrene;

[0032] The eighth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to seventh aspects, wherein the component (B) is a surfactant composed of a polymer having a lyophobic group;

[0033] A ninth aspect of the present invention is the positive photosensitive resin composition according to the eighth aspect, wherein the lyophobic group is at least one group selected from a fluoroalkyl group, a polyfluoroether group, and a polysiloxane group;

[0034] A tenth aspect of the present invention is the positive photosensitive resin composition according to the eighth aspect or the ninth aspect, wherein the monomer unit constituting the polymer having the lyophobic group is a monomer unit derived from an unsaturated hydrocarbon having the lyophobic group;

[0035] The 11th aspect of the present invention is the positive photosensitive resin composition according to any one of the 8th to 10th aspects, wherein the monomer unit constituting the polymer having the lyophobic group is a monomer unit derived from an alkoxysilane compound having the lyophobic group;

[0036] A twelfth aspect of the present invention is the positive photosensitive resin composition according to any one of the eighth to eleventh aspects, wherein the component (B) is a surfactant composed of a polymer having the lyophobic group and the thermosetting group;

[0037] A 13th aspect of the present invention is the positive photosensitive resin composition according to any one of the 1st to 12th aspects, wherein the component (D) is a crosslinking agent composed of a compound containing an epoxy group or a methoxymethyl group;

[0038] A fourteenth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to thirteenth aspects, wherein the composition comprises 0.05 to 20 parts by mass of the component (B) based on 100 parts by mass of the total of the components (A1) and (A2);

[0039] A fifteenth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to fourteenth aspects, wherein the composition comprises 5 to 100 parts by mass of the component (C) based on 100 parts by mass of the total of the components (A1) and (A2);

[0040] A sixteenth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to fifteenth aspects, wherein the composition comprises 5 to 50 parts by mass of the component (D) based on 100 parts by mass of the total of the components (A1) and (A2);

[0041] A seventeenth aspect of the present invention is a cured film formed from the positive photosensitive resin composition according to any one of the first to sixteenth aspects;

[0042] An eighteenth aspect of the present invention is a display element comprising the cured film according to the seventeenth aspect.

[0043] A nineteenth aspect of the present invention is a display element comprising the cured film according to the seventeenth aspect as an image-forming bank.

[0044] Effects of the Invention

[0045] The positive photosensitive resin composition of the present invention has high hydrophobicity and high oleophobicity on the surface of the cured film, and even when a low-concentration developer is used, there is little residue after pattern formation, and a cured film with high inkjet wettability and a high contact angle can be formed. Moreover, a highly flat cured film can be formed on the semi-exposed portion. DETAILED DESCRIPTION

[0046] The photosensitive resin composition of the present invention is a positive photosensitive resin composition capable of forming a cured film, comprising the following components (A1), (A2), (B), (C), (D), and (E) a solvent.

[0047] Component (A1): an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least the following (A1-I); preferably, an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing the following compounds (A1-I), (A1-II) and (A1-III); more preferably, an alkali-soluble acrylic polymer obtained by copolymerizing the following (A1-I), (A1-II), (A1-III) and (A1-IV),

[0048] (A1-I) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A1-III) an N-substituted maleimide compound (however, N-(hydroxyphenyl)maleimide is (A1-IV)), (A1-IV) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group,

[0049] Component (A2): an alkali-soluble resin having an N-hydroxyphenyl group and having no carboxyl group,

[0050] (B) Ingredients: Surfactant,

[0051] (C) ingredient: 1,2-quinone diazine compound,

[0052] (D) ingredient: cross-linking agent,

[0053] (E) Solvent.

[0054] Hereinafter, each component will be described in detail.

[0055] <(A1)Component>

[0056] The component (A1) is an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least (A1-I) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride. Preferably, it is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least the monomers having a hydroxyalkyl group and a polymerizable unsaturated group (A1-I) and (A1-II) and an N-substituted maleimide compound (A1-III). More preferably, it is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least the monomers having a phenolic hydroxyl group and a polymerizable unsaturated group (A1-I), (A1-II), (A1-III), and (A1-IV).

[0057] The acrylic polymer is a polymer obtained by using a monomer having a polymerizable unsaturated group such as acrylate, methacrylate, styrene, or maleimide, that is, a polymerizable group having a C═C double bond in its structure.

[0058] The alkali-soluble acrylic polymer of the component (A1) may be any alkali-soluble acrylic polymer, and the main chain skeleton and side chain types constituting the acrylic polymer are not particularly limited.

[0059] If the number average molecular weight of the alkali-soluble acrylic polymer of the component (A1) is too large, exceeding 30,000, the flattening performance of the height difference is reduced. On the other hand, if the number average molecular weight is too small, less than 2,000, insufficient curing may occur during thermal curing, and the solvent resistance may be reduced. Therefore, the number average molecular weight is within the range of 2000 to 30,000.

[0060] As described above, the method for synthesizing the alkali-soluble acrylic polymer of the component (A1) is simple, for example, a method of polymerizing a monomer mixture containing (A1-I) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride. Depending on the situation, it is a method of copolymerizing a monomer mixture containing the above-mentioned (A1-I), (A1-II) monomers having a hydroxyalkyl group and a polymerizable unsaturated group and (A1-III) an N-substituted maleimide compound. In addition, depending on the situation, it is also a method of copolymerizing a monomer mixture containing the above-mentioned (A1-I), (A1-II), (A1-III) and (A1-IV) monomers having a phenolic hydroxyl group and a polymerizable unsaturated group.

[0061] Specific examples of the monomers constituting the component (A1) are given below, but the monomers are not limited to these.

[0062] Examples of the monomer having an unsaturated carboxylic acid as the component (A1-I) include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide. Examples of the monomer having an unsaturated carboxylic acid anhydride include maleic anhydride and itaconic anhydride.

[0063] Examples of the monomer (A1-II) having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone.

[0064] Examples of the (A1-III) N-substituted maleimide compound include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0065] The monomer having a phenolic hydroxyl group and a polymerizable unsaturated group as component (A1-IV) includes, for example, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, p-hydroxyphenyl acrylate, p-hydroxyphenyl methacrylate, etc. These monomers may be used alone or in combination of two or more. Among them, monomers selected from p-hydroxyphenyl acrylate and p-hydroxyphenyl methacrylate are preferred.

[0066] In addition, in the present invention, when obtaining the acrylic polymer of the component (A1), other monomers A copolymerizable with the above-mentioned monomers (A1-I), (A1-II), (A1-III) and (A1-IV) may be used in combination. Specific examples of other monomers A include acrylate compounds, methacrylate compounds, maleimide, acrylamide compounds, acrylonitrile and styrene compounds. Specific examples of other monomers A are given below, but are not limited to these.

[0067] Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracenyl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 8-methyl-8-tricyclodecyl acrylate and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, 2-(acryloyloxy)ethyl caprolactone, and poly(ethylene glycol)ethyl ether acrylate.

[0068] Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracenyl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 8-methyl-8-tricyclodecanyl methacrylate, 8-ethyl-8-tricyclodecanyl methacrylate, diethylene glycol monomethacrylate, 2-(methacryloyloxy)ethyl caprolactone, and poly(ethylene glycol)ethyl ether methacrylate.

[0069] Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide.

[0070] Examples of the styrene compound include styrenes having no hydroxyl group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

[0071] The method for obtaining the alkali-soluble acrylic polymer used in the present invention is not particularly limited, and it can be obtained, for example, by carrying out a polymerization reaction at a temperature of 50 to 110° C. in a solvent in which an alkali-soluble monomer (A1-I), preferably (A1-II), (A1-III), (A1-IV), and other copolymerizable monomers and, if necessary, a polymerization initiator are coexistent. The solvent used at this time is not particularly limited as long as it can dissolve the monomers constituting the alkali-soluble acrylic polymer and the alkali-soluble acrylic polymer having a specific functional group. Here, the specific functional group can include a carboxyl group, anhydride, and the like. Specific examples of the solvent used include the solvents described in the (E) solvent described later.

[0072] The alkali-soluble acrylic polymer having a specific functional group thus obtained is called a specific copolymer, and is usually in the form of a solution dissolved in a solvent.

[0073] In addition, the solution of the specific copolymer obtained as described above is put into ether, water, etc. under stirring to reprecipitate it, and the generated precipitate is filtered and washed, and then dried at room temperature or heated under normal pressure or reduced pressure to prepare a powder of the specific copolymer. Through this operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. In the case where the purification cannot be fully performed by one operation, the obtained powder is redissolved in a solvent and the above operation is repeated.

[0074] In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the (E) solvent described later and used in a solution state.

[0075] In the present invention, the acrylic polymer of the component (A1) may be a mixture of a plurality of specific copolymers.

[0076] <(A2) Component>

[0077] The component (A2) of the present invention is an alkali-soluble resin having an N-hydroxyphenyl group and no carboxyl group.

[0078] The alkali-soluble resin of the component (A2) may be any alkali-soluble resin having such a structure, and the types of the backbone and side chains constituting the polymer main chain of the resin are not particularly limited.

[0079] As for the component (A2), an alkali-soluble resin having a number average molecular weight in the range of 2,000 to 60,000 is preferred. If the number average molecular weight is too large, exceeding 60,000, it is easy to generate development residues and the sensitivity is greatly reduced. On the other hand, if the number average molecular weight is too small, less than 2,000, during development, a considerable amount of film reduction of the exposed part may occur, resulting in insufficient curing.

[0080] Examples of the alkali-soluble resin having an N-hydroxyphenyl group and having no carboxyl group as the component (A2) include acrylic resins and polymaleimide resins.

[0081] In the present invention, an alkali-soluble resin composed of a copolymer obtained by polymerizing a plurality of monomers may be used as the component (A2). In this case, the alkali-soluble resin of the component (A2) may be a blend of a plurality of copolymers.

[0082] That is, the copolymer is a copolymer comprising, as essential structural units, a monomer having an N-hydroxyphenyl group and having no carboxyl group and at least one monomer selected from monomers copolymerizable with these monomers and having no carboxyl group, and has a number average molecular weight of 2,000 to 60,000. If the number average molecular weight is too large than 60,000, residue may be generated.

[0083] The above-mentioned monomer having an N-hydroxyphenyl group and having no carboxyl group is not limited to a monomer having one N-hydroxyphenyl group, and may be a monomer having a plurality of N-hydroxyphenyl groups.

[0084] Specific examples of the above-mentioned monomers are given below, but the monomers are not limited to these.

[0085] Examples of the monomer having an N-hydroxyphenyl group and having no carboxyl group include N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide.

[0086] Examples of the monomer having no carboxyl group that is copolymerizable with the monomer having an N-hydroxyphenyl group and having no carboxyl group include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracenyl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 8-methoxybutyl methacrylate, and methacrylate. -Methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracene methyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, styrene, vinylnaphthalene, vinylanthracene, vinylbiphenyl, N-phenylma imide, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, hydroxystyrene, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6- lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate, 6,7-Epoxyheptyl ester, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyl Oxetane, 2-(acryloyloxymethyl)-4-trifluoromethyloxetane, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, 2-(0-(1'-methylpropyleneamino)carboxylamino)ethyl methacrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate, 3-acryloxytrimethoxysilane, 3-acryloxytriethoxysilane, 3-methacryloxytrimethoxysilane, and 3-methacryloxytriethoxysilane. ,

[0087] In the production of the alkali-soluble resin of the component (A2), the ratio of the monomer having an N-hydroxyphenyl group and not having a carboxyl group is preferably 10 to 90 mol%, more preferably 20 to 85 mol%, and most preferably 30 to 80 mol% of all the monomers used in the production of the alkali-soluble resin of the component (A2). When the ratio of the monomer having an N-hydroxyphenyl group and not having a carboxyl group is less than 10 mol%, the alkali solubility of the polymer is insufficient.

[0088] In the manufacture of the alkali-soluble resin as component (A2), the ratio of the monomer having no carboxyl group and copolymerizable with the above-mentioned monomer having N-hydroxyphenyl group and having no carboxyl group is preferably 80 wt % or less, more preferably 50 wt % or less, and further preferably 20 wt % or less. If it is more than 80 wt %, the essential components are relatively reduced, so it is difficult to fully obtain the effect of the present invention.

[0089] The method for obtaining the alkali-soluble resin as the component (A2) used in the present invention is not particularly limited, and can be obtained by, for example, carrying out a polymerization reaction at a temperature of 50 to 110° C. in a solvent in which a monomer having an N-hydroxyphenyl group and not having a carboxyl group, a copolymerizable monomer not having a carboxyl group other than the monomer, and a polymerization initiator are present when necessary. The solvent used at this time is not particularly limited as long as it is a solvent that can dissolve the monomer and the alkali-soluble resin constituting the alkali-soluble resin as the component (A2). As a specific example, the solvent described in the (E) solvent described later can be cited.

[0090] The alkali-soluble resin thus obtained is usually in the state of a solution dissolved in a solvent.

[0091] In addition, the solution of the alkali-soluble resin obtained as described above is put into ether, water, etc. under stirring to reprecipitate it, and the generated precipitate is filtered and washed, and then dried at room temperature or heated under normal pressure or reduced pressure to prepare a powder of the alkali-soluble resin. By such an operation, the polymerization initiator and unreacted monomer coexisting with the alkali-soluble resin can be removed, and as a result, a purified powder of the alkali-soluble resin can be obtained. In the case where the purification cannot be fully performed by one operation, the obtained powder is redissolved in a solvent and the above operation is repeated.

[0092] In the present invention, the powder of the alkali-soluble resin may be used as it is, or the powder may be dissolved in, for example, the (E) solvent described later and used in the state of a solution.

[0093] In the present invention, the alkali-soluble resin of the component (A2) may be a mixture of a plurality of alkali-soluble resins.

[0094] <(B) Ingredient>

[0095] The component (B) is a surfactant composed of a polymer having a lyophobic group.

[0096] The polymer refers to an acrylic polymer having a lyophobic group obtained by using a monomer having a polymerizable unsaturated group, i.e., a polymerizable group containing an unsaturated hydrocarbon (C=C double bond) in the structure, such as acrylate, methacrylate, styrene, maleimide, or a polysiloxane obtained by hydrolysis and condensation of a multifunctional alkoxysilane monomer.

[0097] Examples of the liquid-repellent group include at least one group selected from a fluoroalkyl group, a polyfluoroether group, and a polysiloxane group.

[0098] Examples of the fluoroalkyl group include an Ra group consisting of a fluoroalkyl structure represented by the following formula 1.

[0099] -XY···Formula 1

[0100] In Formula 1, X represents a single bond or a divalent saturated hydrocarbon group which may be substituted, and Y represents a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. However, the total number of fluorine atoms in Formula 1 is 3 or more.

[0101] When X is a divalent saturated hydrocarbon group, the number of carbon atoms is not particularly limited as long as it does not impair the liquid repellency, but is preferably 1 to 20, more preferably 1 to 10.

[0102] The number of carbon atoms in the fluoroalkyl group is not particularly limited as long as the liquid repellency is not impaired, but is preferably 1 to 40, more preferably 1 to 30, and even more preferably 4 to 10.

[0103] Examples of such fluoroalkyl groups include trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 3-perfluorobutyl-2-hydroxypropyl, 2-(perfluorohexyl)ethyl, 3-perfluorohexyl-2-hydroxypropyl, 2-(perfluorooctyl)ethyl, 3-perfluorooctyl-2-hydroxypropyl, 2-(perfluorodecyl)ethyl, 2-(perfluoro-3-methylbutyl)ethyl, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl, 2-(perfluoro-5-methylhexyl)ethyl, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl, 2-(perfluoro-7-methyloctyl)ethyl, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl.

[0104] In order to introduce a fluoroalkyl group into the polymer as the component (B) of the present invention, a monomer having a fluoroalkyl group may be copolymerized. Alternatively, a compound having a fluoroalkyl group and a functional group reactive with a reactive site of the polymer may be reacted with the polymer having the reactive site.

[0105] Examples of the polyfluoroether group include an Rf group (a) composed of a polyfluoroether structure represented by the following formula 2.

[0106] -(PO) n -Q…Formula 2

[0107] In Formula 2, P is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, n bracketed units represent the same group or different groups, Q represents a hydrogen atom (limited to the case where a fluorine atom is not bonded to the carbon atom adjacent to the oxygen atom adjacent to Q), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 to 50. However, the total number of fluorine atoms in Formula 2 is 2 or more.

[0108] As the scheme of P and Q in formula 2, it is preferred to cite the following: P is a fluorinated alkylene group having 1 to 10 carbon atoms and 1 hydrogen atom removed, or a perfluorinated alkylene group having 1 to 10 carbon atoms, the n enclosed units represent the same group or different groups, respectively, and Q represents a fluorinated alkyl group having 1 to 20 carbon atoms and 1 hydrogen atom removed, or a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0109] As a more preferred embodiment of P and Q in Formula 2, P is a perfluoroalkylene group having 1 to 10 carbon atoms, the n bracketed units each represent the same group or different groups, and Q represents a perfluoroalkyl group having 1 to 20 carbon atoms.

[0110] In Formula 2, n represents an integer of 2 to 50. n is preferably 2 to 30, and more preferably 2 to 15. When n is 2 or more, the liquid repellency is good. If n is 50 or less, when the polymer as the component (B) is synthesized by copolymerization of the monomer having the Rf group (a) and other monomers, the compatibility of the monomers becomes good.

[0111] The total number of carbon atoms in the Rf group (a) consisting of the polyfluoroether structure represented by Formula 2 is preferably 2 to 50, more preferably 2 to 30. Within this range, the polymer as the component (B) can exhibit good liquid repellency.

[0112] Specific examples of P include -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF(CF3)-, -CF2CF2CF2CF2-, -CF2CF2CF(CF3)-, and CF2CF(CF3)CF2-.

[0113] Specific examples of Q include -CF3, -CF2CF3, -CF2CHF2, -(CF2)2CF3, -(CF2)3CF3, -(CF2)4CF3, -(CF2)5CF3, -(CF2)6CF3, -(CF2)7CF3, -(CF2)8CF3, -(CF2)9CF3, and (CF2) 11 CF3, -(CF2) 15 CF3.

[0114] As a preferred embodiment of the Rf group (a) composed of the polyfluoroether structure represented by Formula 2, an Rf group (a) represented by Formula 3 is exemplified.

[0115] -C p-1 F 2(p-1) -O-(C p F 2p -O) n-1 -C q F 2q+1 ...Formula 3

[0116] In Formula 3, p represents an integer of 2 or 3, n bracketed units are the same group, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

[0117] As the Rf group (a) represented by Formula 3, specifically, preferably, from the viewpoint of ease of synthesis, the following are mentioned:

[0118] -CF2O(CF2CF2O) n-1 CF3 (n is 2 to 9),

[0119] -CF(CF3)O(CF2CF(CF3)O) n-1 C6F 13 (n is 2 to 6),

[0120] -CF(CF3)O(CF2CF(CF3)O) n-1 C3F7 (n is 2 to 6).

[0121] The Rf groups (a) in the polymer as the component (B) may all be the same or different.

[0122] Examples of the polysiloxane group include a group (b) having a polysiloxane structure represented by Formula 4. Hereinafter, the group (b) having a polysiloxane structure represented by Formula 4 is referred to as a pSi group (b).

[0123] -(SiR 1 R 2 -O)n-SiR 1 R 2 R 3 ...Formula 4

[0124] Among them, R 1 , R 2 R independently represents hydrogen, alkyl, cycloalkyl or aryl; 3 represents hydrogen or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200.

[0125] R 1 , R 2 Each siloxane unit may be the same or different. In view of the good liquid repellency of the polymer as component (B), R 1 , R 2 is hydrogen, methyl or phenyl, more preferably all siloxane units R 1 , R 2 is methyl. 3 It may also contain nitrogen atoms, oxygen atoms, etc.

[0126] As methods for introducing a pSi group (b) into a polymer serving as component (B), there can be listed methods of copolymerizing a monomer having a pSi group (b), various modification methods of reacting a compound having a pSi group (b) with a polymer having a reaction site, and a method of using a polymerization initiator having a pSi group (b).

[0127] Examples of monomers having a pSi group (b) include CH2=CHCOO(pSi), CH2=C(CH3)COO(pSi), etc., wherein pSi represents a pSi group (b). Monomers having a pSi group (b) may be used alone or in combination of two or more.

[0128] Examples of various modification methods for reacting a compound having a pSi group (b) with a polymer having a reactive site include the following methods.

[0129] A method of pre-copolymerizing a monomer having an epoxy group and then reacting a compound having a carboxyl group at one terminal and a pSi group at one terminal; a method of pre-copolymerizing a monomer having an epoxy group and then reacting a compound having an amino group at one terminal and a pSi group at one terminal; a method of pre-copolymerizing a monomer having an epoxy group and then reacting a compound having a mercapto group at one terminal and a pSi group at one terminal; and a method of pre-copolymerizing a monomer having an amino group and then reacting a compound having a carboxyl group at one terminal and a pSi group at one terminal.

[0130] In addition, there is a method of pre-copolymerizing a monomer having an amino group and then reacting a compound having an epoxy group at one end and a pSi group at one end; a method of pre-copolymerizing a monomer having a carboxyl group and then reacting a compound having an epoxy group at one end and a pSi group at one end; a method of pre-copolymerizing a monomer having a carboxyl group and then reacting a compound having an amino group at one end and a pSi group at one end; a method of pre-copolymerizing a monomer having a carboxyl group and then reacting a compound having an amino group at one end and a pSi group at one end; a method of pre-copolymerizing a monomer having a carboxyl group and then reacting a compound having a chlorosilyl group at one end and a pSi group at one end; and a method of pre-copolymerizing a monomer having a hydroxyl group and then reacting a compound having a chlorosilyl group at one end and a pSi group at one end.

[0131] As the polymerization initiator having a pSi group (b), a group having a divalent polysiloxane structure may be included in the main chain of the initiator molecule, or a group having a monovalent polysiloxane structure may be included in the terminal portion or side chain of the initiator molecule. As the initiator containing a group having a divalent polysiloxane structure in the main chain of the initiator molecule, compounds alternately containing a group having a divalent polysiloxane structure and an azo group may be cited. As commercially available products, VPS-1001 and VPS-0501 (made by Wako Pure Chemical Industries, Ltd.) may be cited.

[0132] In the polymer of the component (B), the amount of the lyophobic group introduced relative to the total repeating units is preferably 5 to 60 mol%. When it is less than 5 mol%, the lyophobic effect may not be exerted. When it is greater than 60 mol%, problems such as aggregation may occur.

[0133] For the polymer of (B) component, by copolymerizing the functional group with thermosetting property, it is possible to suppress the exudation and decomposition of (B) component to the opening portion during thermosetting. As the functional group with thermosetting property, as long as it is a group that forms a covalent bond by heating, there is no particular restriction, it can be a functional group that reacts with (A1) component, (A2) component, (D) component, or it can be a functional group that self-crosslinks between (B) component. As this functional group (thermosetting group) with thermosetting property, hydroxyl, carboxyl, amide group, amino, N- alkoxymethyl, N- hydroxymethyl, alkoxysilyl, epoxy group, oxetanyl, vinyl, mercapto, and blocked isocyanate group etc. can be listed.

[0134] (Method for producing acrylic polymer having a lyophobic group)

[0135] The method for producing the acrylic polymer having a lyophobic group as the above-mentioned (B) component is not particularly limited, and can be obtained by subjecting a monomer having a lyophobic group and free radical polymerizability, such as at least one of a monomer having a fluoroalkyl group, a monomer having a polyfluoroether group, and a monomer having a polysiloxane group, a monomer having a thermosetting group and free radical polymerizability, and, if necessary, monomers other than the above (hereinafter, also referred to as other monomers B) to polymerization reaction at a temperature of 50 to 110° C. in a solvent in the presence of a polymerization initiator. The solvent used at this time is not particularly limited as long as it is a solvent that can dissolve the monomers constituting the acrylic polymer having a lyophobic group as the (B) component and the acrylic polymer having a lyophobic group. As a specific example, the solvent described in the (E) solvent described later can be cited.

[0136] Specific examples of monomers having a lyophobic group and having radical polymerizability include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl acrylate, 2-(perfluorobutyl)ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2-(perfluorooctyl)ethyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, and acrylic acid. 2-(Perfluorodecyl)ethyl acrylate, 2-(Perfluorodecyl)ethyl methacrylate, 2-(Perfluoro-3-methylbutyl)ethyl acrylate, 2-(Perfluoro-3-methylbutyl)ethyl methacrylate, 3-(Perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 3-(Perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate, 2-(Perfluoro-5-methylhexyl)ethyl acrylate, 2-(Perfluoro-5-methylhexyl)ethyl methacrylate 2-(perfluoro-7-methyloctyl)ethyl acrylate, 2-(perfluoro-7-methyloctyl)ethyl methacrylate, 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl acrylate, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl methacrylate.

[0137] Specific examples of monomers having a thermosetting group and having radical polymerizability include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxyphenyl methacrylate, 2-Aminoethyl acrylate, 2-aminomethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl acrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3-(methacryloyloxymethyl)oxazoline cyclobutane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxymethyl)-4-trifluoromethyloxetane, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, methacrylate 2-(0-(1'-methylpropyleneamino)carboxyamino)ethyl ester, methacrylate 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl ester, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.

[0138] Specific examples of other monomers B include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracenyl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 8-methyl-8-tricyclodecanyl methacrylate, 8-ethyl-8-tricyclodecanyl methacrylate. , methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracene methyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, styrene, vinylnaphthalene, vinylanthracene, and vinylbiphenyl, etc.

[0139] The acrylic polymer having a lyophobic group thus obtained is usually in the state of a solution dissolved in a solvent.

[0140] In addition, the solution of the acrylic polymer having a lyophobic group obtained by the above operation is put into diethyl ether, water, etc. under stirring to reprecipitate, and the generated precipitate is filtered and washed, and then dried at room temperature or heated under normal pressure or reduced pressure to obtain a powder of the acrylic polymer having a lyophobic group. By such an operation, the polymerization initiator and unreacted monomer coexisting with the acrylic polymer having a lyophobic group can be removed, and as a result, a purified powder of the acrylic polymer having a lyophobic group can be obtained. In the case where the purification cannot be fully performed by one operation, the obtained powder is redissolved in a solvent and the above operation is repeated.

[0141] In the present invention, the powder of the acrylic polymer having a lyophobic group may be used as it is, or the powder may be redissolved in, for example, the (E) solvent described later and used in a solution state.

[0142] In the present invention, the acrylic polymer having a lyophobic group as the component (B) may be a mixture of a plurality of acrylic polymers having a lyophobic group.

[0143] (Method for Obtaining Polysiloxane)

[0144] The method for obtaining the polysiloxane of the component (B) is not particularly limited, but polysiloxane obtained by polycondensing an alkoxysilane having a lyophobic group, an alkoxysilane having a thermosetting group, and, if necessary, an alkoxysilane having another organic group is preferred.

[0145] Specific examples of alkoxysilane monomers having a lyophobic group include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, 2-(perfluorohexyl)ethyltrimethoxysilane, 2-(perfluorohexyl)ethyltriethoxysilane, 2-(perfluorobutyl)ethyltrimethoxysilane, and 2-(perfluorobutyl)ethyltriethoxysilane.

[0146] In the present invention, at least one kind of alkoxysilane having a liquid-repellent group may be used, and a plurality of kinds may be used as necessary.

[0147] Specific examples of the alkoxysilane monomer having a thermosetting group include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, trimethoxyvinylsilane, vinyltri(2-ethoxy)silane, vinyltri(2-methoxy)silane, meta-styryltriethoxysilane, meta-styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, diethoxy(3-glycidoxypropyl)methylsilane, 3-Glycidoxypropyl(dimethoxy)methylsilane, 3-Glycidoxypropyl(diethoxy)methylsilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(2-aminoethyl)propyldimethoxysilane, 3-(2-aminoethyl)propyldiethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl Trimethoxysilane, trimethoxy[3-(phenylamino)propyl]silane, 3-mercaptopropyl(dimethoxy)methylsilane, (3-mercaptopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane, 3-(triethoxysilyl)propyl isocyanate, 3-(triethoxysilyl)propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 2-(triethoxysilyl)ethyl methacrylate, 2-(trimethoxysilyl)ethyl methacrylate, Silane, 2-(trimethoxysilyl)ethyl acrylate, (triethoxysilyl)methyl methacrylate, (trimethoxysilyl)methyl methacrylate, (triethoxysilyl)methyl acrylate, (trimethoxysilyl)methyl acrylate, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N-1-phenylethyl-N'-triethoxysilylpropyl urea, (R)-N-1-phenylethyl-N-1-phenylethyl-N'-trimethoxysilylpropyl urea, 1-[3-(trimethoxysilyl)propyl]urea, and the like.

[0148] Furthermore, 3-glycidoxypropyl(dimethoxy)methylsilane, 3-glycidoxypropyl(diethoxy)methylsilane, 3-glycidoxypropyltrimethoxysilane, or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, which can undergo a thermal crosslinking reaction, is also preferably used.

[0149] In this case, various alkoxysilanes having an organic group containing a thermosetting group can be used.

[0150] Examples of alkoxysilanes having other organic groups include tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, Silane, alkyltrialkoxysilanes such as dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, and octadecyltriethoxysilane, trialkoxysilanes having an aromatic group such as phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, and benzyltriethoxysilane, dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, cyclohexyltriethoxysilane, and cyclohexyltrimethoxysilane.

[0151] The polysiloxane of the component (B) can be obtained by polycondensing an alkoxysilane containing a lyophobic group in an amount of preferably 5 to 70 mol % of all alkoxysilanes, an alkoxysilane containing a thermosetting group in an amount of preferably 10 to 95 mol % of all alkoxysilanes, and other alkoxysilanes as the remainder.

[0152] Considering the liquid repellency and solvent resistance of the coating, the content of the liquid repellent group-containing alkoxysilane is more preferably 10 to 60 mol %. The content of the thermosetting group-containing alkoxysilane is more preferably 30 to 80 mol % of the total alkoxysilane.

[0153] As a method for obtaining the polysiloxane of the above-mentioned (B) component, for example, a method of heating and polycondensing an alkoxysilane containing a lyophobic group, an alkoxysilane having a thermosetting group, other alkoxysilanes as necessary, and an organic solvent in the presence of an aqueous solution of tetraethylammonium hydroxide. Specifically, it is a method of mixing the above-mentioned various alkoxysilanes while heating a solution of an aqueous solution of tetraethylammonium hydroxide, after adding an aqueous solution of tetraethylammonium hydroxide to an organic solvent in advance. The amount of the above-mentioned aqueous solution of tetraethylammonium hydroxide is preferably 0.01 to 0.2 moles relative to 1 mole of all alkoxy groups possessed by the alkoxysilane used. The above-mentioned heating can be carried out at a liquid temperature preferably of 0 to 100°C. In addition, in order to prevent evaporation, volatilization, etc. of the liquid, it is preferably carried out under reflux in a container equipped with a reflux pipe for tens of minutes to more than ten hours.

[0154] When using a plurality of alkoxysilanes, they may be mixed in the form of a mixture in which the alkoxysilanes are premixed, or a plurality of alkoxysilanes may be mixed in sequence. When polycondensing the alkoxysilane, it is preferred that the concentration of all silicon atoms of the added alkoxysilane converted to oxide (hereinafter referred to as SiO2 conversion concentration) be heated in the range of 40 mass % or less, particularly preferably 10 to 30 mass %. By selecting any concentration within such a concentration range, the formation of gel can be suppressed, and a homogeneous solution containing polysiloxane can be obtained.

[0155] There is no particular limitation on the organic solvent (hereinafter also referred to as polymerization solvent) used when polycondensing the alkoxysilane, as long as it can dissolve the alkoxysilane having a lyophobic group, the alkoxysilane having a thermosetting group, and other alkoxysilanes as necessary, but solvent (E) is preferably used. Among them, alcohols or organic solvents having good compatibility with alcohols are used because alcohols are generated by the polycondensation reaction of the alkoxysilane.

[0156] Specific examples of the polymerization solvent include alcohols such as methanol, ethanol, propanol, and n-butanol, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl ether, and ethers such as tetrahydrofuran. In the present invention, a plurality of the organic solvents described above may be used in combination.

[0157] In the present invention, the specific polysiloxane solution obtained by the above method may be used directly in the photosensitive resin composition of the present invention, or may be concentrated, diluted by adding a solvent, or replaced with another solvent as needed.

[0158] The solvent (also referred to as an additional solvent) used when adding the above-mentioned solvent for dilution may be the solvent used in the polycondensation reaction or other solvents. There is no particular limitation on the additional solvent as long as it can uniformly dissolve the polysiloxane, and one or more kinds may be arbitrarily selected for use. As such an additional solvent, in addition to the solvent used in the above-mentioned polycondensation reaction, ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate or ethyl lactate, etc. may also be cited.

[0159] In the present invention, when a polymer other than polysiloxane is used in the photosensitive resin composition, alcohol generated during polycondensation of polysiloxane is preferably distilled off under normal pressure or reduced pressure before mixing the polymer other than polysiloxane.

[0160] In addition, as the polymer of component (B), in addition to the above-mentioned acrylic polymers and polysiloxanes having a lyophobic group, there can also be listed polymers obtained by introducing quinonediazide groups into polyamic acid, polyimide, polyamide, polyurea, polyurethane, phenolic resin, epoxy resin, polyester and acrylic polymers having a lyophobic group.

[0161] Examples of the polyamic acid, polyimide, polyamide and polyurea include polyamic acid obtained by reacting a diamine having a fluoroalkyl group or a fluoroalkoxy group and a diamine having a hydroxyl group with an acid dianhydride, polyimide obtained by imidizing a polyamic acid, polyamide obtained by reacting the above diamine with a dicarboxylic anhydride, or polyurea obtained by reacting the above diamine with a diisocyanate.

[0162] Examples of the polyurethane include polyurethanes obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group and a diol having an amino group with a diisocyanate.

[0163] Examples of the phenol resin include novolac resins obtained by polymerizing phenol having a fluoroalkyl group or a fluoroalkoxy group with formaldehyde.

[0164] Examples of the epoxy resin include epoxy resins obtained by reacting bisphenol A and / or bisphenol F having a fluoroalkyl group or a fluoroalkoxy group with a diglycidyl ether of the bisphenol A and / or bisphenol F.

[0165] Examples of the polyester include polyesters obtained by reacting a dicarboxylic acid having a fluoroalkyl group or a fluoroalkoxy group with a diol having a fluoroalkyl group or a fluoroalkoxy group.

[0166] The ratio of the component (B) to the component (A1) and the component (A2) is 0.05 to 20 parts by mass based on 100 parts by mass of the total of the components (A1) and (A2).

[0167] <(C) Ingredients>

[0168] The 1,2-quinonediazide compound as the component (C) may be a compound having either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group, wherein preferably 10 to 100 mol %, particularly preferably 20 to 95 mol % of these hydroxyl groups or amino groups (when having both hydroxyl groups and amino groups, the total amount thereof) are esterified or amidated with 1,2-quinonediazidesulfonic acid.

[0169] Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris(4-hydroxyphenyl)butane, 4,4-isopropylidene diphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenyl sulfone, 4,4-hexafluoroisopropylidene diphenol, 4,4',4"-trihydroxyphenylethane, 1,1,1-trihydroxyphenylethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1 Phenolic compounds such as 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, and 2,5-bis(2-hydroxy-5-methylbenzyl)methyl; and aliphatic alcohols such as ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.

[0170] Examples of the amino group-containing compound include anilines such as aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, and 4,4'-diaminodiphenyl ether, and aminocyclohexane.

[0171] Examples of compounds containing both a hydroxyl group and an amino group include aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4'-diamino-4"-hydroxytriphenylmethane, 4-amino-4',4"-dihydroxytriphenylmethane, bis(4-amino-3-carboxy-5-hydroxyphenyl)ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)propane, and 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane; and alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

[0172] These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

[0173] The content of component (C) in the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 8 to 80 parts by mass, and further preferably 10 to 60 parts by mass, relative to 100 parts by mass of the total of components (A1) and (A2). When it is less than 5 parts by mass, the difference in dissolution rate between the exposed part and the unexposed part of the positive photosensitive resin composition in the developer becomes smaller, and it is sometimes difficult to pattern by development. In addition, when it exceeds 100 parts by mass, the 1,2-quinonediazo compound may not be fully decomposed by short-time exposure, thereby reducing the sensitivity and generating residues between patterns.

[0174] <(D) Ingredient>

[0175] (D) component is a crosslinking agent, more specifically, a compound having a structure that can form a crosslinked structure by thermal reaction with the N-hydroxyphenyl group of the (A2) component. Specific examples are given below, but are not limited to these. For thermal crosslinking agents, for example, (D1) a crosslinking compound having two or more substituents selected from alkoxymethyl and hydroxymethyl, (D2) a substance selected from the crosslinking compound represented by the following formula (5), and (D3) a crosslinking agent having two or more isocyanate groups are preferred. These crosslinking agents can be used alone or in combination of two or more.

[0176] The crosslinkable compound having two or more substituents selected from alkoxymethyl and hydroxymethyl groups in the component (D1) undergoes a crosslinking reaction by a dehydration condensation reaction when exposed to a high temperature during thermal curing. Examples of such compounds include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine and phenolic plastic compounds.

[0177] Specific examples of the alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone. Examples of commercially available products include glycoluril compounds manufactured by Mitsui Science Corporation (trade names: SIMEIL (registered trademark) 1170, PAUDILIN (registered trademark) 1174), methylated urea resins (trade names: UFR (registered trademark) 65), butylated urea resins (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins manufactured by DIC Corporation (highly condensed type, trade names: BECCAMIN (registered trademark) J-300S, BECCAMIN P-955, BECCAMIN N).

[0178] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui Science Co., Ltd. (trade name: SIMEIL (registered trademark) 1123) and those manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicolack (registered trademark) BX-4000, Nicolack BX-37, Nicolack BL-60, Nicolack BX-55H).

[0179] Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine, etc. Examples of commercially available products include methoxymethyl melamine compounds manufactured by Mitsui Science (trade names: Smel (registered trademark) 300, Smel 301, Smel 303, Smel 350), butoxymethyl melamine compounds (trade names: Microte (registered trademark) 506, Microte 508), methoxymethyl melamine compounds manufactured by Sanhe Chemical (trade name: Nicoraku (registered trademark) MW-506, etc.), and methoxymethyl melamine compounds manufactured by Sanhe Chemical (trade name: Nicoraku (registered trademark) MW-506. 30. Nuclear MW-22, Nuclear MW-11, Nuclear MW-100LM, ニカラックMS-001、ニカラックMX-002、ニカラックMX-730、ニカラックMX-750, ニカラック MX-035), butoxymethyl melamine compound (trade name: ニカラック (registered trademark) MX-45, ニカラック MX-410, ニカラック MX-302), etc.

[0180] In addition, it can also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a hydroxymethyl group or an alkoxymethyl group. For example, a high molecular weight compound made from a melamine compound and a benzoguanamine compound described in U.S. Patent No. 6,323,310 can be cited. As a commercially available product of the above-mentioned melamine compound, a trade name: サイメル (registered trademark) 303 (Mitsui Saitek (KK) system) can be cited, and as a commercially available product of the above-mentioned benzoguanamine compound, a trade name: サイメル (registered trademark) 1123 (Mitsui Saitek (KK) system) can be cited.

[0181] Specific examples of phenolic plastic compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methylbenzyl alcohol), 4,4'-(1-methylethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6-bis(hydroxymethyl)phenol], 4,4'-methylenebis[2-methyl-6-methoxymethylphenol], 4,4'-methylenebis[2-methyl-6-methoxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol], 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol], and the like. It can also be obtained as a commercial product. Specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Organic Materials Industries, Ltd.).

[0182] As the component (D1), a polymer produced from an acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, or N-butoxymethylmethacrylamide, may be used.

[0183] Examples of such polymers include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, etc. The weight average molecular weight of such polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

[0184] These crosslinking compounds can be used alone or in combination of two or more.

[0185] When the component (D1) is selected as the crosslinking agent in the positive photosensitive resin composition of the present invention, the content is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the total of the components (A1) and (A2). When it is less than 5 parts by mass, sometimes the outgassing increases in the display element manufacturing process, or the components of the positive photosensitive resin composition are dissolved into other layers, or the element characteristics and reliability deteriorate. In addition, when it exceeds 50 parts by mass, there is a possibility that the storage stability is reduced, the adhesion during development is reduced, or the sensitivity is reduced.

[0186] The positive photosensitive resin composition of the present invention may contain a crosslinking compound having an epoxy group represented by formula (5) as component (D2).

[0187]

[0188] In the formula, k represents an integer of 2 to 10, m represents an integer of 0 to 4, and R 11 It represents a k-valent organic group.

[0189] Examples of commercially available products include エポリードGT-401, エポリードGT-403, エポリードGT-301, エポリードGT-302, and セロキサイド2021P, セロキサイド3000 (manufactured by ダイセル, trade name), デナコールEX-252 (ナガセケムッテク) which is an alicyclic epoxy resin (produced by DIC Corporation, trade name), Epicore 200, Epicore 400 (produced by DIC Corporation, trade name), Epicore 871, Epicore 872 (produced by Oil Chemical Industry Corporation, trade name), ED-5661, ED-5662 (produced by Celanese Codeng Corporation, trade name), etc. These crosslinking compounds may be used alone or in combination of two or more.

[0190] Among them, compounds having a cyclohexene oxide structure, Epore GT-401, Epore GT-403, Epore GT-301, Epore GT-302, Celocyside 2021P, and Celocyside 3000 are preferred from the perspective of process resistance such as heat resistance, solvent resistance, and resistance to long-term baking.

[0191] When the component (D2) is selected as the crosslinking agent, the content is 5 to 50 parts by mass, preferably 7 to 40 parts by mass, and more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the total of the components (A1) and (A2). When the content of the crosslinking compound is less than 5 parts by mass, the crosslinking density formed by the crosslinking compound is insufficient, so that sometimes the outgassing increases in the display element manufacturing process, the components of the positive photosensitive resin composition are dissolved into other layers, and the element characteristics and reliability deteriorate. On the other hand, when it exceeds 50 parts by mass, there are uncrosslinked crosslinking compounds, and the heat resistance, solvent resistance, and long-term sintering resistance after pattern formation are reduced. In addition, the storage stability of the photosensitive resin composition sometimes deteriorates.

[0192] <(E) Solvent>

[0193] The (E) solvent used in the present invention dissolves the (A1) component, the (A2) component, the (B) component, the (C) component and the (D) component, and dissolves other additives added as necessary, and the type and structure of the solvent are not particularly limited as long as it has such a dissolving ability.

[0194] Examples of such solvents (E) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2- Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0195] These solvents may be used alone or in combination of two or more.

[0196] Among these (E) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. are preferred in view of good coating properties and high safety. These solvents are generally used as solvents for photoresist materials.

[0197] <Other additives>

[0198] Furthermore, the positive photosensitive resin composition of the present invention may contain a rheology regulator, a pigment, a dye, a colorant, a storage stabilizer, a defoamer, an adhesion promoter, or a dissolution promoter such as a polyphenol or a polycarboxylic acid as necessary, unless the effects of the present invention are impaired.

[0199] <Positive photosensitive resin composition>

[0200] The positive photosensitive resin composition of the present invention is a positive photosensitive resin composition capable of forming a cured film, comprising the following components (A1), (A2), (B), (C), (D) and (E) solvent, and may further contain one or more of the other additives as required.

[0201] Component (A1): an alkali-soluble acrylic polymer obtained by copolymerizing at least the following (A1-I); preferably an alkali-soluble acrylic polymer obtained by copolymerizing at least the following (A1-I), the following (A1-II), and the following (A1-III); more preferably an alkali-soluble acrylic polymer obtained by copolymerizing at least the following (A1-I), the following (A1-II), the following (A1-III), and the following (A1-IV);

[0202] (A1-I) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride,

[0203] (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group,

[0204] (A1-III) N-substituted maleimide compound,

[0205] (A1-IV) A monomer having a phenolic hydroxyl group and a polymerizable unsaturated group.

[0206] (A2) component: an alkali-soluble resin having an N-hydroxyphenyl group and no carboxyl group;

[0207] (B) ingredient: surfactant;

[0208] (C) ingredient: 1,2-quinonediazide compound;

[0209] (D) component: a cross-linking agent;

[0210] (E) Solvent.

[0211] Among them, preferred examples of the positive photosensitive resin composition of the present invention are as follows.

[0212] A positive photosensitive resin composition comprising 0.05 to 20 parts by mass of a component (B), 5 to 100 parts by mass of a component (C), and 5 to 50 parts by mass of a component (D), based on 100 parts by mass of the total of components (A1) and (A2), wherein these components are dissolved in a solvent (E).

[0213] The solid content ratio in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, and is, for example, 1 to 80% by mass, and for example, 5 to 60% by mass, or 10 to 50% by mass. Here, the solid content refers to the components after removing the (E) solvent from all the components of the positive photosensitive resin composition.

[0214] The preparation method of the positive photosensitive resin composition of the present invention is not particularly limited. Examples of the preparation method include, for example, a method in which the component (B) (polymer) is dissolved in the solvent (E), and the alkali-soluble acrylic polymer (component (A1), the alkali-soluble resin (component (A2), the 1,2-quinonediazide compound (component (C), and the crosslinking agent (component (D)) are mixed in a predetermined ratio in the solution to form a uniform solution, or a method in which other additives are further added and mixed as needed at an appropriate stage of the preparation method.

[0215] When preparing the positive photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the (E) solvent may be used directly. In this case, when the (A1) component, the (A2) component, the (C) component, the (D) component, etc. are added to the solution of the (B) component as described above to form a uniform solution, the (E) solvent may be further added to adjust the concentration. In this case, the (E) solvent used in the formation of the copolymer and the (E) solvent used to adjust the concentration when preparing the positive photosensitive resin composition may be the same or different.

[0216] The prepared solution of the positive photosensitive resin composition is preferably filtered using a filter having a pore size of about 0.2 μm or the like before use.

[0217] <Coating film and cured film>

[0218] The positive photosensitive resin composition of the present invention is applied to a semiconductor substrate (e.g., a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate, etc.) by spin coating, flow coating, roller coating, slit coating, slit followed by spin coating, inkjet coating, etc., and then pre-dried using a hot plate or an oven, etc., to form a coating film. Then, the coating film is heat-treated to form a positive photosensitive resin film.

[0219] The conditions for the heat treatment include, for example, a heating temperature and a heating time appropriately selected from the range of 70° C. to 160° C. and a time of 0.3 to 60 minutes. The heating temperature and the heating time are preferably 80° C. to 140° C. and 0.5 to 10 minutes.

[0220] The film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 μm, for example, 0.2 to 10 μm, and further example, 0.3 to 5 μm.

[0221] A mask having a predetermined pattern is mounted on the coating film obtained above, and the film is irradiated with light such as ultraviolet rays and developed with an alkaline developer to wash out the exposed portion, thereby obtaining a relief pattern with sharp edges.

[0222] In addition, the positive photosensitive resin film formed from the positive photosensitive resin composition of the present invention can also be applied to grayscale masks and halftone masks. Simply by attaching a grayscale mask or halftone mask having a predetermined pattern on the obtained coating film, irradiating it with light such as ultraviolet rays, and developing it with an alkaline developer, a lyophilic portion and a lyophobic portion having sufficient flatness can be formed using a single material.

[0223] As the alkaline developer that can be used, there can be mentioned aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine, etc. Moreover, surfactants etc. may be added to these developers.

[0224] Among the above, a 0.1-3 mass % aqueous solution of tetramethylammonium hydroxide is generally used as a developer for photoresists, and the use of this alkaline developer in the photosensitive resin composition of the present invention can also be well developed without causing problems such as swelling. By preferably using a 0.2-2.38 mass % aqueous solution, a relief pattern can be obtained more effectively.

[0225] As a developing method, any of a flooding method, a dipping method, a shaking dipping method, etc. can be used. The developing time in this case is usually 15 to 180 seconds.

[0226] After development, the positive photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, thereby obtaining a film having a pattern formed thereon.

[0227] Next, the patterned film is post-baked for thermal curing. Specifically, it is heated using a hot plate or an oven, thereby obtaining a film having excellent heat resistance, transparency, planarization properties, low water absorption, chemical resistance, etc. and having a good relief pattern.

[0228] As the post-baking, a method of treating the substrate at a heating temperature selected from the temperature range of 140° C. to 270° C. for 5 to 30 minutes on a hot plate or for 15 to 90 minutes in an oven is generally used.

[0229] Then, by this post-baking, a targeted cured film having a good pattern shape can be obtained.

[0230] As described above, the positive photosensitive resin composition of the present invention can form a coating film having high storage stability, sufficiently high sensitivity, extremely small film reduction in unexposed portions during development, and having a fine pattern.

[0231] In addition, the coating film (cured film) obtained in this way has the characteristic of having almost no pattern residue. Therefore, it is suitable for use as a light shielding material or spacer material corresponding to the inkjet method together with various films in liquid crystal displays and organic EL displays, such as interlayer insulating films, protective films, insulating films, etc.

[0232] Example

[0233] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[0234] In addition, in the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

[0235] (1) Ultraviolet irradiation device

[0236] Device: PLA-600FA manufactured by Canon Corporation

[0237] (2) Development device

[0238] Device: AD-1200 manufactured by Takizawa Industry Co., Ltd.

[0239] (3) Gel Permeation Chromatography (GPC)

[0240] Device: Made by Shimadzu Corporation

[0241] Column: Shodex (registered trademark) GPC K-803L, GPC K-804L manufactured by Showa Denko K.K.

[0242] Column temperature: 40°C

[0243] Eluent: Tetrahydrofuran

[0244] The number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) are shown as polystyrene-equivalent values.

[0245] (4) Residue evaluation

[0246] Equipment: Scanning electron microscope S-4800 manufactured by Hitachi High-Tech Nolodike Co., Ltd.

[0247] (5) Contact angle evaluation

[0248] Device: Drop Master manufactured by Kyowa Interface Science Co., Ltd.

[0249] (6) Wettability evaluation

[0250] Device: Inkjet Designer manufactured by Kurakusun Technology Co., Ltd.

[0251] (7) Flatness evaluation of the semi-exposed part

[0252] Equipment: Olympus Corporation semiconductor automatic inspection microscope MX61A

[0253] In addition, the abbreviations have the following meanings.

[0254] MMA: Methyl Methacrylate

[0255] HEMA: 2-Hydroxyethyl Methacrylate

[0256] HPMA: 4-Hydroxyphenyl Methacrylate

[0257] CHMI: N-cyclohexylmaleimide

[0258] MAA: Methacrylic acid

[0259] AIBN: α,α'-azobisisobutyronitrile

[0260] QD: A compound synthesized by the condensation reaction of 1 mol of 4,4'-[4-(4-hydroxyphenyl)butane-2,2-diyl]diphenol and 2 mol of 1,2-naphthoquinone-2-diazo-5-sulfonyl chloride

[0261] GT-401: Butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) ester-modified ε-caprolactone [Epol GT-401 manufactured by Daicel Corporation]

[0262] 2021P: 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate [Dicel Co., Ltd. Celocyside 2021P]

[0263] PFHMA: 1H,1H,2H,2H-tridecafluorooctyl methacrylate

[0264] KBM-503: 3-methacryloxypropyltrimethoxysilane [KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.]

[0265] NHPMA: N-(4-hydroxyphenyl)methacrylamide

[0266] PFHTMOS: Trimethoxy(1H,1H,2H,2H-tridecafluorooctyl)silane

[0267] KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane [KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.]

[0268] 35wt%TEAHaq.: 35wt% tetraethylammonium hydroxide aqueous solution

[0269] 15JWET: Ion-exchange resin made by Alontron Co., Ltd. 15JWET

[0270] KC Flock: KC Flock W-100GK manufactured by Nippon Paper Industries, Ltd.

[0271] PGME: Propylene glycol monomethyl ether

[0272] PGMEA: Propylene glycol monomethyl ether acetate

[0273] MeOH: Methanol

[0274] DMI: 1,3-dimethyl-2-imidazolidinone

[0275] 2,3-BD: 2,3-Butanediol

[0276] DPM: Dipropylene glycol monomethyl ether

[0277] TMAH: Tetramethylammonium hydroxide

[0278] [Synthesis example 1]

[0279] MAA 6.0 g, CHMI 16.0 g, HEMA 10.0 g, HPMA 2.0 g, MMA 6.0 g, AIBN 2.5 g as a free radical polymerization initiator, were subjected to polymerization reaction at 60°C to 100°C in PGME 63.6 g as a solvent, thereby obtaining a solution of an alkali-soluble acrylic polymer component (specific copolymer) having an Mn of 3,600 and an Mw of 8,600 (specific copolymer concentration: 40% by mass). (A1-1)

[0280] [Synthesis example 2]

[0281] MAA 7.8 g, CHMI 20.4 g, HEMA 14.7 g, MMA 14.8 g, AIBN 3.8 g as a radical polymerization initiator, were subjected to polymerization reaction in PGMEA 92.3 g as a solvent at a temperature of 60°C to 100°C, thereby obtaining a solution of an alkali-soluble acrylic polymer component (specific copolymer) having an Mn of 4,400 and an Mw of 7,700 (specific copolymer concentration: 40% by mass). (A1-2)

[0282] [Synthesis example 3]

[0283] 3.00 g of NHPMA, 0.98 g of HEMA, 2.34 g of CHMI, and 0.12 g of AIBN were dissolved in 24.20 g of PGME solvent and reacted at 90° C. for 20 hours to obtain an alkali-soluble resin solution (solid content: 21% by mass) (A2-1). The obtained alkali-soluble resin had an Mn of 6,200 and an Mw of 9,900.

[0284] [Synthesis Example 4]

[0285] 3.00 g of NHPMA, 1.11 g of HEMA, 3.04 g of CHMI, and 0.14 g of AIBN were dissolved in 27.30 g of PGME solvent and reacted at 90° C. for 20 hours to obtain an alkali-soluble resin solution (solid content: 21% by mass) (A2-2). The obtained alkali-soluble resin had an Mn of 5,600 and an Mw of 9,300.

[0286] [Synthesis example 5]

[0287] PFHTMOS 2.34 g, KBM-303 2.29 g, 35 wt% TEA Haq. 0.24 g, water 0.49 g, and MeOH 0.54 g were dissolved in a solvent of PGMEA 15.54 g, and stirred at 40°C for 4 hours. Then, 15JWET 0.93 g washed with a mixed solvent of PGMEA and MeOH was added, and stirred at 25°C for 1 hour. Then, the waste 15JWET was filtered out using a membrane filter equipped with KC Flock to obtain a polysiloxane solution (B1). The obtained polysiloxane had an Mn of 2,300 and an Mw of 2,700.

[0288] [Synthesis example 6]

[0289] 5.00 g of PFHMA, 3.83 g of KBM-503, 1.51 g of HEMA, and 0.52 g of AIBN were dissolved in 25.32 g of PGME solvent and reacted at 80° C. for 20 hours to obtain an acrylic polymer solution having a lyophobic group (solid content 30% by mass) (B2). The obtained acrylic polymer having a lyophobic group had an Mn of 4,800 and an Mw of 6,700.

[0290] [Synthesis Example 7]

[0291] An organic functional ink was obtained by the same method as Comparative Example 1-2 of International Publication No. 2019 / 124413, except that the solid concentration was set to 1.7% by mass.

[0292] [Examples 1 to 6, Comparative Examples 1 to 5]

[0293] The following components were mixed as described in Table 1 to prepare a positive photosensitive resin composition. In the table, [parts] represent [parts by mass], and the values ​​in the table were adjusted according to the solid ratio.

[0294] [Evaluation of residue in opening portion]

[0295] The positive photosensitive resin composition was applied on the ITO-glass using a spin coater and pre-baked on a hot plate at 100°C for 120 seconds to form a coating film with a thickness of 1.15 μm. The coating film was irradiated with a light intensity of 5.5 mW / cm at 365 nm for a certain period of time through a mask with a 10 μm line and space pattern. 2of ultraviolet rays. Then, after developing by immersing in a 0.40% TMAH aqueous solution for 60 seconds, it was washed with ultrapure water for 30 seconds. Next, the coating film formed with the line and space pattern was heated at a temperature of 230°C for 30 minutes, thereby post-baking and curing it. The opening residue of the cured line and space pattern was observed using a scanning electron microscope S-4800 manufactured by Hitachi High-Tech Nologi, and evaluated according to the following standards. It should be noted that, assuming the actual specifications, at least B is required, preferably A.

[0296] A: There is no residue in the pattern, very good

[0297] B: No residue in the pattern, good

[0298] C: There are residues in the pattern

[0299] [Evaluation of inkjet wettability]

[0300] After applying the positive photosensitive resin composition on the ITO-glass using a spin coater, it was pre-baked on a hot plate at 100°C for 120 seconds to form a coating film with a thickness of 1.15 μm. The coating film was irradiated with a light intensity of 5.5 mW / cm at 365 nm for a certain period of time through a mask with a plurality of rectangular patterns with a long side of 160 μm and a short side of 80 μm. 2 of ultraviolet rays. Then, after developing by immersing in a 0.40% TMAH aqueous solution for 60 seconds, it was washed with ultrapure water for 30 seconds. Next, the coating film formed with the rectangular pattern was heated at a temperature of 230°C for 30 minutes, thereby post-baking and curing it. A certain number of sprays (about 3pL per spray) of the organic functional ink prepared in Synthesis Example 7 was sprayed on the opening part of the cured rectangular pattern, and the organic functional film was naturally dried to form an organic functional film. The appearance of the organic functional film was observed using an optical microscope and evaluated according to the following standards. It should be noted that, assuming the actual specifications, it is required to be at least B, preferably A.

[0301] A: No pinholes or overflow after spraying twice, good

[0302] B: No pinholes or overflow after 6 sprays, good

[0303] C: Pinholes or overflow even after 6 sprays

[0304] [Evaluation of contact angle]

[0305] After the positive photosensitive resin composition is coated on a silicon wafer using a spin coater, it is pre-baked on a hot plate at a temperature of 100°C for 120 seconds to form a coating film with a film thickness of 1.15 μm. After the coating film is developed by immersing it in a 0.40% TMAH aqueous solution for 60 seconds, it is washed with ultrapure water for 30 seconds. Then, it is heated at a temperature of 230°C for 30 minutes, and then post-baked to solidify it. 1 μL of anisole is attached to the cured coating film, and the contact angle θ is measured at 5 locations after 7 seconds. The average value is used as the contact angle value and evaluated according to the following standards. It should be noted that, assuming the actual specifications, it is required to be at least B, preferably A.

[0306] A: θ≥53°

[0307] B: 50°≤θ<53°

[0308] C: θ<50°

[0309] [Evaluation of Flatness of Half-Exposure Part]

[0310] After applying the positive photosensitive resin composition on the ITO-glass using a spin coater, it was pre-baked on a hot plate at 100°C for 120 seconds to form a coating film with a film thickness of 1.15 μm. The coating film was irradiated with a light intensity of 5.5 mW / cm at 365 nm for a certain time through a halftone mask with a transmittance of 50% and a plurality of rectangular patterns with a long side of 50 μm and a short side of 30 μm so that the film thickness of the rectangular pattern becomes a thin film thinner than 1.15 μm. 2 Then, the film was immersed in a 0.40% TMAH aqueous solution for 60 seconds for development and then washed with ultrapure water for 30 seconds. Next, the coating film with the rectangular pattern was heated at a temperature of 230°C for 30 minutes, thereby post-baking and curing. The surface of the cured rectangular pattern was observed using an optical microscope and evaluated according to the following standards.

[0311] A: No peeling, unevenness, good

[0312] C: Peeling or unevenness occurs

[0313] Table 1

[0314]

[0315] Table 2

[0316] Residue Inkjet Wettability Contact angle Flatness of half-exposed part Example 1 A A A A Example 2 A A A A Example 3 A A A A Example 4 A A A A Example 5 A A A A Example 6 A A B A Comparative Example 1 c c C A Comparative Example 2 A C C A Comparative Example 3 B C C A Comparative Example 4 A C C A Comparative Example 5 C A A C

[0317] As shown in Table 2, the cured films (Examples 1 to 6) produced using the positive photosensitive compositions respectively mixed with A1-1 or A1-2 as the alkali-soluble acrylic polymer A1, A2-1 or A2-2 as the alkali-soluble resin A2, and B1 and B2 as the surfactants showed excellent residue, inkjet wettability and contact angle, and excellent flatness of the half-exposed portion.

[0318] On the other hand, the cured films formed of the positive photosensitive compositions of Comparative Examples 1 and 3, which used A1-1 and A1-2 as the alkali-soluble acrylic polymer A1 and did not use the alkali-soluble resin A2, showed poor inkjet wettability or contact angle. Also, the cured film formed of the positive photosensitive composition of Comparative Example 5, which used A1-2 as the alkali-soluble acrylic polymer A1 and did not use the alkali-soluble resin A2, showed excellent inkjet wettability and contact angle, but poor residue and flatness of the half-exposed portion. Next, Comparative Examples 2 and 4, which used A1-1 as the alkali-soluble acrylic polymer A1 and A2-1 as the alkali-soluble resin A2 and did not add a surfactant, showed excellent residue but poor inkjet wettability and contact angle.

[0319] As shown in the above results of the examples, by preparing a positive photosensitive composition composed of an alkali-soluble acrylic polymer A1 and an alkali-soluble resin A2, a surfactant, a cross-linking agent, and a photosensitizer, a cured film that satisfies the requirements of residue, inkjet wettability, contact angle, and flatness of the semi-exposed portion can be obtained for the first time.

Claims

1. A positive photosensitive resin composition capable of forming a cured film, comprising the following components (A1), (A2), (B), (C), (D) and (E) a solvent; (A1) component: an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least (A1-I) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, Component (A2): an alkali-soluble resin having an N-hydroxyphenyl group and having no carboxyl group, (B) ingredient: surfactant, (C) ingredient: 1,2-quinone diazine compound, (D) component: cross-linking agent, (E) Solvent.

2. The positive photosensitive resin composition according to claim 1, wherein the component (A1) is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least the compound (A1-I) and the following compounds (A1-II) and (A1-III); (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A1-III) N-substituted maleimide compound.

3. The positive photosensitive resin composition according to claim 2, wherein the component (A1) is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least the compounds (A1-I), (A1-II), (A1-III) and the following (A1-IV); (A1-IV) A monomer having a phenolic hydroxyl group and a polymerizable unsaturated group. 4 . The positive photosensitive resin composition according to claim 3 , wherein the monomer (A1-IV) having a phenolic hydroxyl group and a polymerizable unsaturated group is p-hydroxyphenyl (meth)acrylate. 5 . The positive photosensitive resin composition according to claim 1 , wherein the component (A1) is an alkali-soluble acrylic polymer having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene. 6 . The positive photosensitive resin composition according to claim 1 , wherein the component (A2) is a polymer comprising a structural unit derived from at least one monomer selected from N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, or N-(hydroxyphenyl)maleimide. 7 . The positive photosensitive resin composition according to claim 1 , wherein the component (A2) is an alkali-soluble resin having a number average molecular weight of 2,000 to 60,000 in terms of polystyrene. 8 . The positive photosensitive resin composition according to claim 1 , wherein the component (B) is a surfactant composed of a polymer having a lyophobic group. 9 . The positive photosensitive resin composition according to claim 8 , wherein the lyophobic group is at least one group selected from the group consisting of a fluoroalkyl group, a polyfluoroether group, and a polysiloxane group. 10 . The positive photosensitive resin composition according to claim 8 , wherein the monomer unit constituting the polymer having the lyophobic group is a monomer unit derived from an unsaturated hydrocarbon having the lyophobic group. 11 . The positive photosensitive resin composition according to claim 8 , wherein the monomer unit constituting the polymer having the lyophobic group is a monomer unit derived from an alkoxysilane compound having the lyophobic group. 12 . The positive photosensitive resin composition according to claim 8 , wherein the component (B) is a surfactant composed of a polymer having the lyophobic group and a thermosetting group. 13 . The positive photosensitive resin composition according to claim 1 , wherein the component (D) is a crosslinking agent composed of a compound containing an epoxy group or a methoxymethyl group. 14 . The positive photosensitive resin composition according to claim 1 , further comprising 0.05 to 20 parts by mass of component (B) based on 100 parts by mass of the total of component (A1) and component (A2). 15 . The positive photosensitive resin composition according to claim 1 , comprising 5 to 100 parts by mass of component (C) based on 100 parts by mass of the total of component (A1) and component (A2). 16 . The positive photosensitive resin composition according to claim 1 , comprising 5 to 50 parts by mass of component (D) based on 100 parts by mass of the total of component (A1) and component (A2). 17 . A cured film formed from the positive photosensitive resin composition according to claim 1 . 18 . A display element comprising the cured film according to claim 17 . 19 . A display element comprising the cured film according to claim 17 as an image-forming bank.

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