Positive photosensitive resin composition

Abstract

The present invention provides a positive photosensitive resin composition, which can be used for liquid crystal display elements, organic EL display elements, etc., and has a cured film surface with high hydrophobicity and high oleophobicity, less residue after pattern formation, and a cured film that does not overflow in the pattern after pattern formation and is well wetted and spread. The present invention is a positive photosensitive resin composition that can form a cured film, which contains the following (A) component, (B) component, (C) component, (D) component, (E) component and (F) solvent, but does not contain a photoacid generator, (A) component: at least one alkali-soluble polymer obtained by polymerizing a monomer mixture containing the following (A-I), (A-I): N-substituted maleimide compound, (B) component: surfactant, (C) component: compound having a vinyl ether group, (D) component: photosensitizer, (E) component: crosslinking agent, (F) solvent.

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 and a cured film thereof, which is capable of hardly generating residues when forming a pattern, and can form a cured film having high hydrophobicity and high oleophobicity on the surface of the cured film, and can form a cured film in which the organic functional ink does not overflow and is well wetted and spread in the pattern surrounded by the cured film, and various materials using the cured film. The positive photosensitive resin composition is particularly suitable for use as an interlayer insulating film in a display component such as a liquid crystal display, an EL display, or a micro-LED display, and as a light shielding material or a partition wall material for an inkjet method. Background Art

[0003] Generally speaking, display components such as thin film transistor (TFT) type liquid crystal display elements and organic EL (organic electroluminescence) components are provided with electrode protection films, planarization films, insulating films, etc. for forming patterns. As materials for forming these films, photosensitive resin compositions have been widely used in the past, which have the characteristics of having a small number of steps to obtain a desired pattern shape and having sufficient flatness.

[0004] In addition, in recent years, in the manufacturing steps of display display elements, the manufacturing technology of full-color display substrates using inkjet has also been actively explored. For example, regarding the production of color filters in liquid crystal display elements, a color filter and its manufacturing method (Patent Document 1) are proposed, which first forms a predetermined patterned pixel division (hereinafter referred to as a levee) with a photosensitive resin layer that can shield light, and then drips ink droplets into the opening surrounded by the levee, etc. In addition, for organic EL display elements, a method of manufacturing an organic EL display element by first making a levee and similarly dripping ink that becomes a light-emitting layer is also proposed (Patent Document 2).

[0005] However, when dropping ink droplets 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 must be ink-philic (hydrophilic) and the bank surface must be hydrophobic.

[0006] In order to achieve the above purpose, there is a proposal for a negative photosensitive resin composition (Patent Document 3) in which a fluorine-based surfactant or a fluorine-based polymer is blended into a photosensitive organic film. However, it is difficult to improve the resolution, and the application of positive photosensitive resins is required in the high-definition display components.

[0007] On the other hand, as a positive type, there is a positive type 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 4). However, in recent years, there is a demand for a higher hydrophobicity and higher oleophobicity of the bank surface and inkjet wettability.

[0008] [Prior art literature]

[0009] [Patent Document]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2000-187111

[0011] [Patent Document 2] Japanese Patent Application Laid-Open No. 11-54270

[0012] [Patent Document 3] Japanese Patent Application Publication No. 2015-172742

[0013] [Patent Document 4] Japanese Patent Application Laid-Open No. 6744577 Summary of the invention

[0014] [Problems to be Solved by the Invention]

[0015] The present invention is made in view of the above background, and the problem to be solved is to provide a positive photosensitive resin composition that can be used in liquid crystal display elements, organic EL display elements, etc., and the surface of the cured film has high hydrophobicity and high oleophobicity, and the organic functional ink droplets will not exceed the bank and overflow to the adjacent pixels but remain in the pattern after the pattern is formed, and there will be no cissing or unevenness and the cured film will be well wet and spread.

[0016] [Methods to solve the problem]

[0017] The present inventors have completed the present invention as a result of intensive studies to achieve the above-mentioned object.

[0018] A first aspect of the present invention is a positive photosensitive resin composition capable of forming a cured film, comprising the following components (A), (B), (C), (D), (E), and (F) a solvent, but does not contain a photoacid generator.

[0019] (A) component: at least one alkali-soluble polymer obtained by polymerizing a monomer mixture containing the following (AI),

[0020] (AI): N-substituted maleimide compound,

[0021] (B) ingredient: surfactant,

[0022] Component (C): a compound having a vinyl ether group,

[0023] (D) Ingredients: photosensitizer,

[0024] (E) component: cross-linking agent,

[0025] (F) Solvent.

[0026] A second aspect of the present invention is the positive photosensitive resin composition according to the first aspect, wherein the (AI) is N-methylmaleimide, N-phenylmaleimide or N-cyclohexylmaleimide.

[0027] A third aspect of the present invention is the positive photosensitive resin composition according to the first or second aspect, wherein the monomer mixture contains the following (A-II):

[0028] (A-II): A monomer having a hydroxyalkyl group and a polymerizable unsaturated group.

[0029] Aspect 4 of the present invention is the positive photosensitive resin composition according to any one of aspects 1 to 3, wherein the monomer mixture contains the following (A-III):

[0030] (A-III): A monomer having a phenolic hydroxyl group and a polymerizable unsaturated group.

[0031] A fifth aspect of the present invention is the positive photosensitive resin composition according to the fourth aspect, wherein the (A-III) is a monomer having an N-hydroxyphenyl group.

[0032] Aspect 6 of the present invention is the positive photosensitive resin composition according to any one of aspects 1 to 5, wherein the component (A) is an alkali-soluble polymer having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene.

[0033] Aspect 7 of the present invention is the positive photosensitive resin composition according to any one of aspects 1 to 6, wherein the component (B) is a surfactant composed of a polymer having a lyophobic group.

[0034] An eighth aspect of the present invention is the positive photosensitive resin composition according to the seventh aspect, wherein the lyophobic group is at least one group selected from a fluoroalkyl group, a polyfluoroether group, and a polysiloxane group.

[0035] A ninth aspect of the present invention is the positive photosensitive resin composition according to the seventh or eighth 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.

[0036] A tenth aspect of the present invention is the positive photosensitive resin composition according to any one of aspects 7 to 9, wherein the monomer unit constituting the polymer having the lyophobic group is a monomer unit derived from an alkoxysilane compound having the lyophobic group.

[0037] An eleventh aspect of the present invention is the positive photosensitive resin composition according to any one of aspects 7 to 10, wherein the component (B) is a surfactant composed of a polymer having the lyophobic group and a thermosetting group.

[0038] Aspect 12 of the present invention is a positive photosensitive resin composition as described in any one of aspects 1 to 11, wherein the component (C) is at least one compound selected from cyclohexyl vinyl ether, octadecyl vinyl ether, tris[4-(vinyloxy)butyl]-1,2,4-benzenetricarboxylate, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,4-butanediol divinyl ether and triethylene glycol divinyl ether.

[0039] A thirteenth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to twelfth aspects, wherein the component (D) is a 1,2-quinonediazo compound.

[0040] 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 component (E) is a crosslinking agent composed of a compound containing an epoxy group or a methoxymethyl group.

[0041] Aspect 15 of the present invention is a positive photosensitive resin composition as described in any one of aspects 1 to 14, which contains 0.05 to 20 parts by mass of component (B), 0.1 to 80 parts by mass of component (C), 5 to 100 parts by mass of component (D), and 5 to 50 parts by mass of component (E), relative to 100 parts by mass of component (A).

[0042] A sixteenth aspect of the present invention is a cured film formed from the positive photosensitive resin composition according to any one of the first to fifteenth aspects.

[0043] A seventeenth aspect of the present invention is a display element comprising the cured film according to the sixteenth aspect.

[0044] An eighteenth aspect of the present invention is a display element comprising the cured film according to the sixteenth aspect as an image-forming bank.

[0045] [Effects of the invention]

[0046] The positive photosensitive resin composition of the present invention can form a cured film with high hydrophobicity and high oleophobicity on the surface, and the organic functional ink in the pattern after pattern formation does not overflow, and the cured film has no collapse and spreads well. DETAILED DESCRIPTION

[0047] The photosensitive resin composition of the present invention is a positive-type photosensitive resin composition capable of forming a cured film, comprising the following components (A), (B), (C), (D), (E) and (F) a solvent, and containing no photoacid generator.

[0048] Component (A) is at least one alkali-soluble polymer obtained by polymerizing a monomer mixture containing the following (AI). Preferably, component (A) is an alkali-soluble polymer obtained by copolymerizing a monomer mixture containing the following (AI) and a compound of the following (A-II). More preferably, component (A) is an alkali-soluble polymer obtained by copolymerizing the following (AI), the following (A-II) and the following (A-III);

[0049] (AI): N-substituted maleimide compounds,

[0050] (A-II): a monomer having a hydroxyalkyl group and a polymerizable unsaturated group,

[0051] (A-III): a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group,

[0052] (B) Ingredients: Surfactant,

[0053] Component (C): a compound having a vinyl ether group,

[0054] (D) Ingredients: photosensitizer,

[0055] (E) ingredient: cross-linking agent,

[0056] (F) Solvent.

[0057] Hereinafter, each component will be described in detail.

[0058] <(A)Component>

[0059] Component (A) is at least one alkali-soluble polymer obtained by polymerizing a monomer mixture containing at least (AI) described below. Preferably, it is at least one alkali-soluble polymer obtained by copolymerizing a monomer mixture containing at least (AI) described below and a compound of (A-II) described below. More preferably, component (A) is at least one alkali-soluble polymer obtained by copolymerizing at least (AI) described below, (A-II) described below, and (A-III) described below.

[0060] (AI): N-substituted maleimide compounds,

[0061] (A-II): a monomer having a hydroxyalkyl group and a polymerizable unsaturated group,

[0062] (A-III): A monomer having a phenolic hydroxyl group and a polymerizable unsaturated group.

[0063] The alkali-soluble polymer as the component (A) may be any polymer containing at least an alkali-soluble group and a structure derived from an N-substituted maleimide compound, and the main chain skeleton and side chain types constituting the polymer are not particularly limited.

[0064] As described above, the synthesis method of the alkali-soluble polymer as the component (A) is a simple method, for example, a method of polymerizing a monomer mixture containing (AI) an N-substituted maleimide compound. Depending on the case, it is a method of copolymerizing a monomer mixture containing the above (AI), (A-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A-III) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group.

[0065] Specific examples of the monomers constituting the component (A) are listed below, but the invention is not limited to these.

[0066] (AI)

[0067] Examples of the (AI)N-substituted maleimide compound include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide, and N-cyclohexylmaleimide is preferred.

[0068] (A-II)

[0069] Examples of the monomer (A-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.

[0070] (A-III)

[0071] (A-III) The monomer having a phenolic hydroxyl group and a polymerizable unsaturated group is not limited to one phenolic hydroxyl group, and may have a plurality of phenolic hydroxyl groups.

[0072] Specific examples of the above monomers are listed below, but the monomers are not limited to these.

[0073] Examples of the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group include p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, p-hydroxyphenyl acrylate, and p-hydroxyphenyl methacrylate.

[0074] Here, when the alkali-soluble polymer as the component (A) has a structural unit derived from N-hydroxyphenylmaleimide, the structural unit is not defined as being derived from the (AI) N-substituted maleimide compound but as being derived from the (A-III) monomer having a phenolic hydroxyl group and a polymerizable unsaturated group.

[0075] (Other monomers A)

[0076] In addition, in the present invention, when obtaining an alkali-soluble polymer as component (A), in addition to the above-mentioned monomers (AI), (A-II) and (A-III), other monomers A copolymerizable with the monomers (AI), (A-II) and (A-III) may be used in combination. Specific examples of other monomers A include acrylate compounds, methacrylate compounds, acrylamide compounds, acrylonitrile, styrene compounds and monomers having unsaturated carboxylic acids. Specific examples of other monomers A are listed below, but are not limited to these.

[0077] Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracenyl 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-tricyclodecanyl acrylate, 8-ethyl-8-tricyclodecanyl acrylate, diethylene glycol monoacrylate, 2-(acryloyloxy)ethyl caprolactone, and poly(ethylene glycol)ethyl ether acrylate.

[0078] Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracenyl 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, caprolactone 2-(methacryloyloxy)ethyl ester, and poly(ethylene glycol)ethyl ether methacrylate.

[0079] Examples of the acrylamide compound include N-methylacrylamide, N-methyl(methacrylamide), N,N-dimethylacrylamide, N,N-dimethyl(methacrylamide), N-methoxymethylacrylamide, N-methoxymethyl(methacrylamide), N-butoxymethylacrylamide, and N-butoxymethyl(methacrylamide).

[0080] Examples of the styrene compound include styrenes having no hydroxyl group, for example, styrene, α-methylstyrene, chlorostyrene, bromostyrene, and the like.

[0081] Examples of the monomer having an unsaturated carboxylic acid 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.

[0082] (A) As an alkali-soluble polymer of a component, an acrylic polymer, a polymaleimide type polymer, etc. are mentioned, for example.

[0083] The acrylic polymer refers to a polymer obtained using a monomer having a polymerizable unsaturated group such as acrylate, methacrylate, styrene, etc., and the polymaleimide polymer refers to a polymer obtained using a monomer having a polymerizable unsaturated group such as maleimide, that is, a polymerizable group containing a C=C double bond in the structure.

[0084] There is no particular limitation on the method for obtaining the alkali-soluble polymer used in the present invention, but it can be obtained, for example, by subjecting the N-substituted maleimide compound (AI), preferably (A-II), (A-III), copolymerizable monomers other than these, and a polymerization initiator added as desired to a coexistence of the compound, at a temperature of 50 to 110° C. The solvent used in this case is not particularly limited as long as it can dissolve the monomers and alkali-soluble polymer constituting the alkali-soluble polymer. As specific examples, the solvents described in the solvent (F) described later can be cited.

[0085] The alkali-soluble polymer obtained in this manner is usually in the form of a solution dissolved in a solvent.

[0086] In addition, the solution of the alkali-soluble polymer obtained as described above is put into ether or water under stirring to reprecipitate, and the generated precipitate is filtered and washed, and then dried at room temperature or by heating under normal pressure or reduced pressure to form a powder of the alkali-soluble polymer. By such an operation, the polymerization initiator or unreacted monomer coexisting with the alkali-soluble polymer can be removed, and as a result, a purified powder of the alkali-soluble polymer is obtained. In the case where the purification cannot be fully performed in one operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.

[0087] In the present invention, the powder of the alkali-soluble polymer may be used as it is, or the powder may be dissolved in, for example, the (F) solvent described later and used in the form of a solution.

[0088] Furthermore, in the present invention, the alkali-soluble polymer as the component (A) may be a mixture of a plurality of alkali-soluble polymers.

[0089] That is, the copolymer is a copolymer formed of an N-substituted maleimide compound and at least one monomer selected from monomers copolymerizable with these monomers as essential structural units. If the number average molecular weight exceeds 30,000, the flattening performance of the height difference is reduced. On the other hand, if the number average molecular weight is less than 2,000, it is too small, and the curing becomes insufficient during thermal curing and the solvent resistance is reduced. Therefore, the number average molecular weight is within the range of 2,000 to 30,000.

[0090] <(B) Ingredient>

[0091] The component (B) is a surfactant composed of a polymer having a lyophobic group.

[0092] The polymer refers to an acrylic polymer having a lyophobic group obtained by using a monomer having a polymerizable unsaturated group such as acrylate, methacrylate, styrene, maleimide, etc., that is, a polymerizable group containing an unsaturated hydrocarbon (C=C double bond) in the structure, or a polysiloxane obtained by hydrolysis and condensation of a multifunctional alkoxysilane monomer.

[0093] Examples of the liquid-repellent group include at least one group selected from a fluoroalkyl group, a polyfluoroether group, and a polysiloxane group.

[0094] Examples of the fluoroalkyl group include an Ra group consisting of a fluoroalkyl structure represented by the following formula 1.

[0095] -XY···Formula 1

[0096] 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. The total number of fluorine atoms in Formula 1 is 3 or more.

[0097] 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.

[0098] The number of carbon atoms in the fluoroalkyl group is not particularly limited as long as it is within the range that does not impair the liquid repellency, but is preferably 1 to 40, more preferably 1 to 30, and even more preferably 4 to 10.

[0099] 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.

[0100] The introduction of a fluoroalkyl group into the polymer of the component (B) of the present invention can be carried out by copolymerizing a monomer having a fluoroalkyl group. Alternatively, the polymer having a reactive site can be reacted with a compound having a fluoroalkyl group and a functional group reactive with the reactive site of the polymer.

[0101] Examples of the polyfluoroether group include an Rf group (a) consisting of a polyfluoroether structure represented by the following formula 2.

[0102] -(PO) n -Q···Formula 2

[0103] 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, each unit enclosed by n represents 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. The total number of fluorine atoms in Formula 2 is 2 or more.

[0104] As the form of P and Q in Formula 2, preferably, P is a fluorinated alkylene group having 1 to 10 carbon atoms after removing one hydrogen atom or a perfluorinated alkylene group having 1 to 10 carbon atoms, each unit enclosed by n represents the same group or different groups, and Q represents a fluorinated alkyl group having 1 to 20 carbon atoms after removing one hydrogen atom or a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0105] As the form of P and Q in Formula 2, it is more preferable that P is a perfluorinated alkylene group having 1 to 10 carbon atoms, each unit enclosed by n represents the same group or different groups, and Q represents a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0106] In Formula 2, n represents an integer of 2 to 50. n is preferably 2 to 30, and more preferably 2 to 15. If n is 2 or more, the liquid repellency is good. If n is 50 or less, when the polymer of component (B) is synthesized by copolymerization of the monomer having the Rf group (a) and other monomers, the compatibility of the monomers is good.

[0107] 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 of the component (B) can exhibit good liquid repellency.

[0108] Specific examples of P include -CF2-, -CF2CF2-,

[0109] -CF2CF2CF2-, -CF2CF(CF3)-, -CF2CF2CF2CF2-,

[0110] -CF2CF2CF(CF3)-, and CF2CF(CF3)CF2-.

[0111] Specific examples of Q include -CF3, -CF2CF3,

[0112] -CF2CHF2, -(CF2)2CF3, -(CF2)3CF3, -(CF2)4CF3,

[0113] -(CF2)5CF3, -(CF2)6CF3, -(CF2)7CF3, -(CF2)8CF3,

[0114] -(CF2)9CF3, and (CF2) 11 CF3, -(CF2) 15 CF3.

[0115] As a preferred embodiment of the Rf group (a) composed of the polyfluoroether structure represented by Formula 2, the Rf group (a) represented by Formula 3 can be cited.

[0116] -C p-1 F 2(p-1) -O-(C p F 2p -O) n-1 -C q F 2q+1 Formula 3

[0117] In Formula 3, p represents an integer of 2 or 3, each unit enclosed by n is the same group, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

[0118] Specifically, as the Rf group (a) represented by Formula 3, from the viewpoint of ease of synthesis,

[0119] Preferably, -CF2O(CF2CF2O) is mentioned. n-1 CF3 (n is 2 to 9),

[0120] -CF(CF3)O(CF2CF(CF3)O) n-1 C6F 13 (n is 2 to 6),

[0121] -CF(CF3)O(CF2CF(CF3)O) n-1 C3F7 (n is 2 to 6).

[0122] The Rf groups (a) in the polymer of the component (B) may all be the same or different.

[0123] 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).

[0124] -(SiR 1 R 2 -O) n -SiR 1 R2 R 3 Formula 4

[0125] (Among them, R 1 , R 2 independently represent hydrogen, alkyl, cycloalkyl or aryl, R 3 represents hydrogen or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200).

[0126] R 1 , R 2 Each siloxy unit may be the same or different. In view of the good liquid repellency of the polymer of component (B), R 1 , R 2 When it is hydrogen, methyl or phenyl, it is further preferred that all R 1 , R 2 In the case of methyl. 3 Nitrogen atoms, oxygen atoms, etc. may also be contained.

[0127] Methods for introducing pSi groups (b) into the polymer of component (B) include a method of copolymerizing a monomer having a pSi group (b), various modification methods of reacting a polymer having a reaction site with a compound having a pSi group (b), a method of using a polymerization initiator having a pSi group (b), etc.

[0128] Examples of the monomer having a pSi group (b) include CH2=CHCOO(pSi), CH2=C(CH3)COO(pSi), etc., wherein pSi represents a pSi group (b). The monomer having a pSi group (b) may be used alone or in combination of two or more.

[0129] Examples of various modification methods for reacting a polymer having a reactive site with a compound having a pSi group (b) include the following methods.

[0130] The following methods are available: a method of first copolymerizing a monomer having an epoxy group and then reacting a compound having a carboxyl group at one end and a pSi group at one end; a method of first copolymerizing a monomer having an epoxy group and then reacting a compound having an amino group at one end and a pSi group at one end; a method of first copolymerizing a monomer having an epoxy group and then reacting a compound having a mercapto group at one end and a pSi group at one end; and a method of first copolymerizing a monomer having an amino group and then reacting a compound having a carboxyl group at one end and a pSi group at one end.

[0131] In addition, there are the following methods: a method of first 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 first 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 first 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 first copolymerizing a monomer having a carboxyl group and then reacting a compound having a chlorosilane group at one end and a pSi group at one end; and a method of first copolymerizing a monomer having a hydroxyl group and then reacting a compound having a chlorosilane group at one end and a pSi group at one end.

[0132] As the polymerization initiator having a pSi group (b), a group having a divalent polysiloxane structure in the main chain of the initiator molecule may be included, and a group having a monovalent polysiloxane structure at the terminal part or side chain of the initiator molecule may be included. As the initiator containing a group having a divalent polysiloxane structure in the main chain of the initiator molecule, compounds having a group having a divalent polysiloxane structure and an azo group alternately may be listed. As commercially available products, VPS-1001 and VPS-0501 (made by Wako Pure Chemical Industries, Ltd.) may be listed.

[0133] In the polymer of the component (B), the amount of the lyophobic group introduced is preferably 5 to 60 mol% relative to the total repeating units. When it is much less than 5 mol%, the lyophobic effect may not be achieved. When it is much greater than 60 mol%, problems such as aggregation may occur.

[0134] The polymer of component (B) can suppress the exudation or decomposition of component (B) to the opening during heat curing by copolymerizing the functional group with thermosetting property. As the functional group with thermosetting property, there is no particular limitation as long as it is a group that forms a covalent bond by heating, and it can be a functional group that reacts with component (A), component (C) or component (E), or it can be a functional group that self-crosslinks component (B). As such a functional group with thermosetting property (thermosetting group), hydroxyl, carboxyl, amido, amino, N-alkoxymethyl, N-hydroxymethyl, alkoxysilyl, epoxy, oxetane, vinyl, mercapto, and blocked isocyanate groups can be listed.

[0135] (Method for producing acrylic polymer having a lyophobic group)

[0136] The method for producing the acrylic polymer having a lyophobic group as the above-mentioned (B) component is not particularly limited, but it can be obtained by subjecting a free radical polymerizable monomer having a lyophobic group, for example, at least one of a monomer having a fluoroalkyl group, a monomer having a polyfluoroether group, and a monomer having a polysiloxane group, a free radical polymerizable monomer having a thermosetting group, and monomers other than the above added as desired (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. At this time, the solvent used is not particularly limited as long as it can dissolve the monomers and acrylic polymers constituting the acrylic polymer having a lyophobic group as the (B) component. As specific examples, the solvents described in the (F) solvent described later can be cited.

[0137] Specific examples of the radical polymerizable monomer having a lyophobic group 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, methacrylate, 3-Perfluorobutyl-2-hydroxypropyl ester, 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, propylene 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, etc.

[0138] Specific examples of the free radical polymerizable monomer having a thermosetting group 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-hydroxypropyl methyl acrylate ...phenyl methyl acrylate, 2-hydroxyphenyl methyl acrylate, 2-hydroxyphenyl methyl acrylate, 2-hydroxyphenyl methyl acrylate, 2-hydroxyphenyl methyl acrylate, 2-hydroxyphenyl methyl acrylate, 2-hydroxyphenyl methyl acrylate, 2-hydroxyphenyl acrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxyl-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-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-(methacryloyloxymethyl)oxyheterocyclic butane, 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-trifluoromethyloxetane, 2-(acryloyloxymethyl)-4-trifluoromethyloxetane Alkane, N-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, N-methoxymethyl acrylamide, N-methoxymethyl acrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, methacrylate 2-(0-(1'-methylpropyleneamino)carboxylamino)ethyl ester, methacrylate 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl ester, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.

[0139] Specific examples of other monomers B include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracenyl 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-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate. Acid esters, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracenyl acrylate, anthracenyl 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.

[0140] The acrylic polymer having a lyophobic group thus obtained is usually in the state of a solution dissolved in a solvent.

[0141] In addition, the solution of the acrylic polymer having a lyophobic group obtained as described above is put into ether or water or the like under stirring to reprecipitate, and the generated precipitate is filtered, washed, and then dried at room temperature or under heating under normal pressure or reduced pressure to form a powder of the acrylic polymer having a lyophobic group. By such an operation, the polymerization initiator or 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 in one operation, the obtained powder can be dissolved in a solvent again, and the above operation can be repeated.

[0142] 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 dissolved in, for example, a solvent (F) described later and used in the form of a solution.

[0143] Furthermore, 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.

[0144] (Method for Obtaining Polysiloxane)

[0145] The method for obtaining the polysiloxane of the component (B) is not particularly limited, but preferably the polysiloxane is obtained by polycondensing an alkoxysilane having a lyophobic group, an alkoxysilane having a thermosetting group, and an alkoxysilane having another organic group which is added as desired.

[0146] 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.

[0147] In the present invention, at least one kind of alkoxysilane having a liquid-repellent group may be used, but a plurality of kinds may be used as necessary.

[0148] Specific examples of the alkoxysilane monomer having a thermosetting group include allyl triethoxysilane, allyl trimethoxysilane, diethoxymethyl vinyl silane, dimethoxymethyl vinyl silane, triethoxy vinyl silane, trimethoxy vinyl silane, vinyl tri(2-ethoxy) silane, vinyl tri(2-methoxy) silane, m-phenylvinyl triethoxy silane, m-phenylvinyl trimethoxy silane, p-phenylvinyl triethoxy silane, p-phenylvinyl trimethoxy silane, 3-(N-phenylvinylmethyl-2-aminoethylamino)propyl trimethoxy silane, diethoxy(3-(glycidoxy)propyl)methyl Silane, 3-(glycidoxy)propyl(dimethoxy)methylsilane, 3-(glycidoxy)propyl(diethoxy)methylsilane, 3-(glycidoxy)propyltrimethoxysilane, 3-(glycidoxy)propyltriethoxysilane, 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 silane, 3-aminopropyltrimethoxysilane, 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 Acid ester, ethyl 2-(triethoxysilyl)acrylate, ethyl 2-(trimethoxysilyl)acrylate, methyl (triethoxysilyl)methacrylate, methyl (trimethoxysilyl)methacrylate, methyl (triethoxysilyl)acrylate, methyl (trimethoxysilyl)acrylate, methyl (trimethoxysilyl)acrylate, γ-ureidopropyl triethoxysilane, γ-ureidopropyl trimethoxysilane, γ-ureidopropyl tripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropyl urea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropyl urea, 1-[3-(trimethoxysilyl)propyl]urea, and the like.

[0149] Furthermore, 3-(glycidoxy)propyl(dimethoxy)methylsilane, 3-(glycidoxy)propyl(diethoxy)methylsilane, 3-(glycidoxy)propyltrimethoxysilane, or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, which can induce a crosslinking reaction by heat, is preferably used.

[0150] In this case, various alkoxysilanes having an organic group having a thermosetting group may be used.

[0151] Examples of alkoxysilanes having other organic groups include tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, and dodecyltrimethoxysilane. Alkyltrialkoxysilanes such as alkyltriethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, trialkoxysilanes having an aromatic group such as phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrimethoxysilane, etc.

[0152] The polysiloxane of the component (B) preferably contains 5 to 70 mol % of alkoxysilanes containing a lyophobic group, preferably 10 to 95 mol % of alkoxysilanes containing a thermosetting group, and the remainder is obtained by polycondensing other alkoxysilanes.

[0153] Considering the liquid repellency and solvent resistance of the film, the content of the alkoxysilane containing a liquid repellent group is more preferably 10 to 60 mol %. The content of the alkoxysilane containing a thermosetting group is more preferably 30 to 80 mol % of the total alkoxysilane.

[0154] As a method for obtaining the polysiloxane of the above-mentioned (B) component, there can be cited, for example, a method of heating and polycondensing an alkoxysilane containing a lyophobic group, an alkoxysilane having a thermosetting group, other alkoxysilanes as needed, and an organic solvent in the presence of an aqueous solution of tetraethylammonium hydroxide. Specifically, a method of preliminarily adding an aqueous solution of tetraethylammonium hydroxide to an organic solvent to form a solution of an aqueous solution of tetraethylammonium hydroxide, and then mixing the above-mentioned various alkoxysilanes while heating the solution. The amount of the above-mentioned aqueous solution of tetraethylammonium hydroxide is preferably 0.01 to 0.2 moles relative to 1 mole of the total alkoxy group amount of the alkoxysilane used. The above-mentioned heating is preferably carried out at a liquid temperature of 0 to 100°C. In addition, in order not to cause 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.

[0155] When using multiple alkoxysilanes, they can be mixed as a mixture of pre-mixed alkoxysilanes, or multiple alkoxysilanes can be mixed in sequence. When the alkoxysilane is polycondensed, it is preferred that the concentration of all silicon atoms of the added alkoxysilane converted into oxides (hereinafter referred to as SiO2 conversion concentration) is 40% by mass or less, and it is particularly preferred to heat in the range of 10 to 30% by mass. By selecting an arbitrary concentration within such a concentration range, the formation of gel can be suppressed, and a homogeneous solution containing polysiloxane can be obtained.

[0156] The organic solvent (hereinafter also referred to as polymerization solvent) used when the alkoxysilane is polycondensed is not particularly limited as long as it can dissolve the alkoxysilane having a lyophobic group, the alkoxysilane having a thermosetting group, and other alkoxysilanes as required, but it is preferred to use solvent (E). Among them, since alcohol is generated by the polycondensation reaction of alkoxysilane, alcohols or organic solvents with good compatibility with alcohols are used.

[0157] 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 may be mixed and used.

[0158] 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 the specific polysiloxane solution obtained by the above method may be concentrated or diluted with a solvent or used in place of another solvent as needed.

[0159] The solvent used when adding the solvent for dilution (also referred to as an additional solvent) may be the solvent used for the polycondensation reaction or other solvents. The additional solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one or more kinds may be arbitrarily selected for use. As such an additional solvent, in addition to the solvent used in the 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 be cited.

[0160] Furthermore, in the present invention, when a polymer other than polysiloxane is used in the photosensitive resin composition, it is preferred to distill off alcohol generated during the polycondensation reaction of polysiloxane under normal pressure or reduced pressure before mixing the polymer other than polysiloxane.

[0161] In addition, as the polymer of the component (B), in addition to the above-mentioned acrylic polymers and polysiloxanes having a lyophobic group, there can be listed polyamic acid, polyimide, polyamide, polyurea, polyurethane, phenolic resin, epoxy resin, polyester and a polymer obtained by introducing a quinone diazide group into an acrylic polymer having a lyophobic group.

[0162] 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 diamine with a dicarboxylic anhydride, or polyurea obtained by reacting the diamine with a diisocyanate.

[0163] 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.

[0164] Examples of the phenol resin include novolac resins obtained by polymerizing phenol having a fluoroalkyl group or a fluoroalkoxy group with formaldehyde.

[0165] 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 glycidyl ether of the bisphenol A and / or bisphenol F.

[0166] 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.

[0167] The ratio of the component (B) to the component (A) is 0.05 to 20 parts by mass of the component (B) relative to 100 parts by mass of the total of the components (A).

[0168] <(C) Ingredients>

[0169] The compound having a vinyl ether group as the component (C) may be any compound having one or more vinyl ether groups in one molecule, and its type and structure are not particularly limited.

[0170] Examples of the compound having one vinyl ether group in one molecule include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, diethylene glycol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether and octadecyl vinyl ether.

[0171] Examples of the compound having two or more vinyl ether groups in one molecule include compounds represented by formula (5) and formula (6).

[0172]

[0173] (wherein n is an integer from 2 to 10, k is an integer from 1 to 10, R 3 represents an n-valent organic group).

[0174]

[0175] (wherein m represents an integer from 2 to 10).

[0176] n in formula (5) represents the number of vinyl ether groups in one molecule, and n is more preferably an integer of 2 to 4. m in formula (6) also represents the number of vinyl ether groups in one molecule, and m is more preferably an integer of 2 to 4.

[0177] Specific examples of the compounds represented by formula (5) and formula (6) include bis(4-(vinyloxymethyl)cyclohexylmethyl)glutarate, divinyl adipate, bis(4-(vinyloxy)butyl)phthalate, bis(4-(vinyloxy)butyl isophthalate, tris[4-(vinyloxy)butyl]-1,2,4-benzenetricarboxylate, tris[4-(vinyloxy)butyl]-1,3,5-benzenetricarboxylate and 1,4-cyclohexanedimethanol divinyl ether.

[0178] In addition, among the compounds having two or more vinyl ether groups in one molecule, examples of compounds other than the compounds represented by formula (5) and formula (6) include 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

[0179] In addition, the compound of component (C) is used in an amount of 0.1 to 80 parts by mass, preferably 0.5 to 40 parts by mass, relative to 100 parts by mass of the alkali-soluble polymer as component (A). If the amount of the compound of component (C) is too small to reach the lower limit of the range, the film in the unexposed part is significantly reduced, and there is a situation where the relief shape of the pattern is defective or the hydrophobicity is reduced. On the other hand, if the amount of the compound of component (C) is too large to exceed the upper limit of the range, the sensitivity of the film is greatly reduced, and residues between the patterns are generated after development.

[0180] <(D) Ingredient>

[0181] As the photosensitizer of the component (D), 1,2-quinonediazide compounds can be cited. As the 1,2-quinonediazide compound, a compound having either a hydroxyl group or an amino group, or having both a hydroxyl group and an amino group can be used, and preferably 10 to 100 mol%, particularly preferably 20 to 95 mol% of these hydroxyl groups or amino groups (in the case of having both hydroxyl groups and amino groups, the total amount thereof) are esterified or amidated with 1,2-quinonediazidesulfonic acid.

[0182] 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-methyl Phenolic compounds such as 2,5-bis(2-hydroxy-5-methylbenzyl)methyl and the like; 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.

[0183] Examples of the amino group-containing compound include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminobiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, anilines such as 4,4'-diaminodiphenyl ether, and aminocyclohexane.

[0184] Furthermore, 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.

[0185] These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

[0186] The content of the component (D) 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 component (A). When it is less than 5 parts by mass, the difference in dissolution rate of the exposed part and the unexposed part of the positive photosensitive resin composition in the developer becomes small, and there is a case where patterning by development is difficult. In addition, if it exceeds 100 parts by mass, there is a case where the sensitivity is reduced because the 1,2-quinonediazide compound cannot be fully decomposed under short-time exposure, or a case where residues are generated between patterns.

[0187] <(E) Ingredient>

[0188] (E) component is a crosslinking agent, more specifically, a compound having a structure that can form a crosslinked structure by thermally reacting with the phenolic hydroxyl group of component (A-III). Specific examples are listed below but are not limited to these. The thermal crosslinking agent, for example, is preferably (E1) a crosslinking compound having two or more substituents selected from alkoxymethyl and hydroxymethyl, or (E2) a crosslinking compound selected from the following formula (7) and (E3) a crosslinking agent having two or more isocyanate groups. These crosslinking agents can be used alone or in combination of two or more.

[0189] The crosslinkable compound having two or more substituents selected from alkoxymethyl and hydroxymethyl groups as the component (E1) undergoes a crosslinking reaction by a dehydration condensation reaction when exposed to a high temperature during thermal curing. Examples of such compounds include compounds such as alkoxymethylated acetylene urea, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenolic plastic compounds.

[0190] Specific examples of the alkoxymethylated acetylene carbamide include 1,3,4,6-tetrakis(methoxymethyl)acetylene carbamide, 1,3,4,6-tetrakis(butoxymethyl)acetylene carbamide, 1,3,4,6-tetrakis(hydroxymethyl)acetylene carbamide, 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 acetylene urea compounds manufactured by Mitsui Cytec Co., Ltd. (trade names: CYMEL (registered trademark) 1170, Powderlink (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-based resins manufactured by DIC Corporation (highly condensed type, trade names: BECKAMINE (registered trademark) J-300S, BECKAMINE P-955, BECKAMINE N).

[0191] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui CyteC Co., Ltd. (trade name: CYMEL (registered trademark) 1123), and those manufactured by Sanwa Chemical Co., Ltd. (trade names: NIKALAC (registered trademark) BX-4000, NIKALAC BX-37, NIKALAC BL-60, and NIKALAC BX-55H).

[0192] Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Examples of commercially available products include methoxymethyl-type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade names: CYMEL (registered trademark) 300, CYMEL 301, CYMEL 303, CYMEL 350), butoxymethyl-type melamine compounds (trade names: Mycoat (registered trademark) 506, Mycoat 508), methoxymethyl-type melamine compounds manufactured by Sanwa Chemical Co., Ltd. (trade names: NIKALAC (registered trademark) MW-30, NIKALAC MW-22, NIKALAC MW-11, NIKALAC MW-100LM, NIKALAC MS-001, NIKALAC MX-002, NIKALAC MX-730, NIKALAC MX-750, NIKALAC MX-035), butoxymethyl-type melamine compounds (trade names: NIKALAC (registered trademark) MX-45, NIKALAC MX-410, NIKALAC MX-302), etc.

[0193] In addition, it may be a compound obtained by condensing a melamine compound, a urea compound, an acetylene urea compound and a benzoguanamine compound in which the hydrogen atoms of such an amino group are replaced by a hydroxymethyl group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound as described in U.S. Patent No. 6,323,310 may be cited. Commercially available products of the melamine compound include trade names: CYMEL (registered trademark) 303 (manufactured by MitsuiCytec (Strain)), and commercially available products of the benzoguanamine compound include trade names: CYMEL (registered trademark) 1123 (manufactured by MitsuiCytec (Strain)).

[0194] 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.).

[0195] Furthermore, as the component (E1), a polymer produced using an acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, or N-butoxymethylmethacrylamide, can be used.

[0196] 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 these polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

[0197] These crosslinking compounds can be used alone or in combination of two or more.

[0198] When the content of component (E1) is selected as the crosslinking agent in the positive photosensitive resin composition of the present invention, it 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 component (A). When it is less than 5 parts by mass, there is a situation where outgassing increases in the display component manufacturing step, or components of the positive photosensitive resin composition are eluted into other layers, or component characteristics or reliability deteriorate. In addition, if it exceeds 50 parts by mass, the storage stability is reduced, or the adhesion during development is reduced, and there is a possibility of reduced sensitivity.

[0199] The positive photosensitive resin composition of the present invention may contain a crosslinking compound having an epoxy group represented by formula (7) as component (E2).

[0200]

[0201] (wherein, k represents an integer of 2 to 10, m represents an integer of 0 to 4, R 11 represents an organic group with a valence of k).

[0202] Examples of commercially available products include EPOLEAD GT-401, EPOLEAD GT-403, EPOLEAD GT-301, EPOLEAD GT-302, CELLOXIDE 2021P, CELLOXIDE 3000 (trade names manufactured by Daicel Corporation), DENACOL EX-252 (trade name manufactured by Nagase ChemteX Corporation), EPICLON 200, EPICLON 400 (these are trade names manufactured by DIC Corporation), EPIKOTE 871, EPIKOTE 872 (these are trade names manufactured by Yuka Shell Epoxy Corporation), ED-5661, ED-5662 (these are trade names manufactured by Celanese Coating Corporation), etc. These crosslinking compounds may be used alone or in combination of two or more.

[0203] Among these, compounds having a cyclohexene oxide structure, EPOLEAD GT-401, EPOLEAD GT-403, EPOLEAD GT-301, EPOLEAD GT-302, CELLOXIDE 2021P, and CELLOXIDE 3000 are preferred from the viewpoint of process resistance such as heat resistance, solvent resistance, and long-term baking resistance.

[0204] When the component (E2) is selected as the crosslinking agent, the content thereof 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 component (A). When the content of the crosslinking compound is less than 5 parts by mass, the density of the crosslinks formed by the crosslinking compound is insufficient, so there is an increase in outgassing in the display component manufacturing step, or the components of the positive photosensitive resin composition are eluted into other layers, or the component characteristics or reliability are deteriorated. On the other hand, when the content exceeds 50 parts by mass, there is an uncrosslinked crosslinking compound, and the heat resistance, solvent resistance, and resistance to long-term firing after the pattern is formed are reduced. In addition, the storage stability of the photosensitive resin composition is deteriorated.

[0205] <(F)Solvent>

[0206] The (F) solvent used in the present invention is a solvent that can dissolve the (A) component, the (B) component, the (C) component, the (D) component and the (E) component, and can dissolve other additives that are added as desired. The type and structure of the solvent are not particularly limited as long as it has such a dissolving ability.

[0207] Examples of such solvents (F) 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-butanone, 2-heptanone, 3-methyl-2-pentanone, 2-heptan ... lactone, ethyl 2-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, etc.

[0208] These solvents may be used alone or in combination of two or more.

[0209] Among these (F) 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 from the viewpoint of good coating properties and high safety. These solvents can be solvents generally used for photoresist materials.

[0210] <Other additives>

[0211] 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.

[0212] <Photoacid generator>

[0213] The photoacid generator is a reagent described in Japanese Patent Application Laid-Open No. 2012-220860 or International Publication No. WO2007 / 132892, except for 1,2-quinonediazide compounds.

[0214] <Positive photosensitive resin composition>

[0215] 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 (A), (B), (C), (D), (E) and (F) a solvent, and does not contain a photoacid generator, and may further contain one or more of the other additives as desired.

[0216] Component (A): an alkali-soluble polymer obtained by polymerizing at least the following (AI); preferably an alkali-soluble polymer obtained by copolymerizing at least the following (AI) and the following (A-II); more preferably an alkali-soluble polymer obtained by copolymerizing at least the following (AI), the following (A-II) and the following (A-III);

[0217] (AI): N-substituted maleimide compounds,

[0218] (A-II): a monomer having a hydroxyalkyl group and a polymerizable unsaturated group,

[0219] (A-III): a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group,

[0220] (B) Ingredients: Surfactant,

[0221] Component (C): a compound having a vinyl ether group,

[0222] (D) Ingredients: photosensitizer,

[0223] (E) component: cross-linking agent,

[0224] (F) Solvent.

[0225] Among them, preferred examples of the positive photosensitive resin composition of the present invention are as follows.

[0226] A positive photosensitive resin composition containing 0.05 to 20 parts by mass of the component (B), 0.1 to 80 parts by mass of the component (C), 5 to 100 parts by mass of the component (D), and 5 to 50 parts by mass of the component (E) based on 100 parts by mass of the component (A), wherein these components are dissolved in a solvent (F).

[0227] 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, but is, for example, 1 to 80% by mass, and also, for example, 5 to 60% by mass, or 10 to 50% by mass. Here, the solid content refers to the components after removing the (F) solvent from all the components of the positive photosensitive resin composition.

[0228] The preparation method of the positive photosensitive resin composition of the present invention is not particularly limited, but examples thereof include a method of dissolving component (B) (polymer) in solvent (F), and mixing an alkali-soluble polymer as component (A), a compound having a vinyl ether group as component (C), a photosensitizer as component (D), and a cross-linking agent as component (E) in a specified ratio in the solution to form a uniform solution, or a method of further adding and mixing other additives as needed at an appropriate stage of the preparation method.

[0229] When preparing the positive photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the (F) solvent may be used directly. In this case, when, for example, the (A) component, the (C) component, the (D) component, the (E) component, etc. are added to the solution of the (B) component in the same manner as described above to form a uniform solution, the (F) solvent may be further added for the purpose of concentration adjustment. In this case, the (F) solvent used in the formation of the copolymer may be the same as or different from the (F) solvent used for concentration adjustment when preparing the positive photosensitive resin composition.

[0230] Then, 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.

[0231] <Coating film and cured film>

[0232] 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, roll coating, slit coating, slit coating followed by spin coating, inkjet coating, etc., and then pre-dried by a hot plate or oven to form a coating film. Thereafter, the coating film is heat treated to form a positive photosensitive resin film.

[0233] As the conditions for this heat treatment, 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 are adopted. The heating temperature and the heating time are preferably 80° C. to 140° C. and 0.5 to 10 minutes.

[0234] 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, or further, for example, 0.3 to 5 μm.

[0235] The coating film obtained above is mounted with a mask having a predetermined pattern and irradiated with light such as ultraviolet rays, and then developed with an alkaline developer to wash away the exposed portion to obtain a relief pattern with a sharp edge surface.

[0236] 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. On the above-obtained coating film, a grayscale mask or halftone mask having a specified pattern is mounted and irradiated with light such as ultraviolet rays, and it can be developed only with an alkaline developer to form a lyophilic part and a lyophobic part with sufficient flatness with a single material.

[0237] As the alkaline developer that can be used, there can be cited alkaline aqueous solutions such as aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, etc., aqueous solutions of tertiary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc., and aqueous solutions of amines such as ethanolamine, propylamine, ethylenediamine, etc. Furthermore, surfactants and the like may be added to these developers.

[0238] Among the above, 0.1-3 mass % aqueous solution of tetramethylammonium hydroxide is generally used as a developer for photoresists. In the photosensitive resin composition of the present invention, the use of this alkaline developer can also develop well without causing problems such as swelling. It is preferred to use a 0.2-2.38 mass % aqueous solution, thereby more effectively obtaining a relief pattern.

[0239] As a developing method, a coating method, an immersion method, a shaking immersion method, etc. can be used. The developing time in this case is usually 15 to 180 seconds.

[0240] 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 patterned film.

[0241] Next, the pattern-formed film is post-baked for thermal curing, specifically, heated using a hot plate, an oven, etc., thereby obtaining a film having excellent heat resistance, transparency, planarization properties, low water absorption, chemical resistance, etc., and having a good relief pattern.

[0242] The post-baking method generally employs a method in which a heating temperature selected from the range of 140° C. to 270° C. is used and the treatment is performed on a hot plate for 5 to 30 minutes or in an oven for 15 to 90 minutes.

[0243] Then, through this post-baking, a target cured film having a good pattern shape can be obtained.

[0244] As described above, the positive photosensitive resin composition of the present invention can form a coating film having high storage stability, sufficiently high sensitivity, very little film reduction in unexposed areas during development, excellent inkjet wettability and contact angle, and fine patterns.

[0245] 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 a partition material such as a dam for inkjet printing together with various films in liquid crystal displays or organic EL displays, such as interlayer insulating films, protective films, insulating films, etc.

[0246] Example

[0247] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0248] In addition, the apparatus and conditions used for the preparation of samples and the analysis of physical properties in Examples are as follows.

[0249] (1) Ultraviolet irradiation device

[0250] Device: PLA-600FA manufactured by Corinno Co., Ltd.

[0251] (2) Development device

[0252] Device: AD-1200 manufactured by Takizawa Industry Co., Ltd.

[0253] (3) Gel Permeation Chromatography (GPC)

[0254] Device: Made by Shimadzu Corporation

[0255] Column: Shodex (registered trademark) GPCK-803L, GPCK-804L manufactured by Showa Denko K.K.

[0256] Column temperature: 40℃

[0257] Solvent: Tetrahydrofuran

[0258] 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.

[0259] (4) Contact angle evaluation

[0260] Device: Drop Master manufactured by Kyowa Interface Science Co., Ltd.

[0261] (5) Wettability evaluation

[0262] Device: Inkjet Designer manufactured by CLUSTERTECHNOLOGY Co., Ltd.

[0263] In addition, the abbreviations have the following meanings.

[0264] MMA: Methyl Methacrylate

[0265] HEMA: 2-Hydroxyethyl Methacrylate

[0266] HPMA: 4-Hydroxyphenyl Methacrylate

[0267] CHMI: N-cyclohexylmaleimide

[0268] MAA: Methacrylic acid

[0269] AIBN: α,α'-azobisisobutyronitrile

[0270] QD1: A compound synthesized by the condensation reaction of 1 mol of 4,4'-[4-(4-hydroxyphenyl)butane-2,2-diyl]biphenol and 2 mol of 1,2-naphthoquinone-2-diazo-5-sulfonyl chloride

[0271] QD2: A compound synthesized by the condensation reaction of 1 mol of α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 2 mol of 1,2-naphthoquinone-2-diazo-5-sulfonyl chloride

[0272] GT-401: Butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone [EPOLEAD GT-401 manufactured by Daicel Corporation]

[0273] 2021P: 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate [CELLOXIDE 2021P manufactured by Daicel Corporation]

[0274] NHPMA: N-(4-hydroxyphenyl)methacrylamide

[0275] PFHTMOS: Trimethoxy(1H,1H,2H,2H-tridecafluoro-n-octyl)silane

[0276] PFBTMOS: Trimethoxy (1H,1H,2H,2H-nonafluorohexyl) silane

[0277] KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane [KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.]

[0278] 35wt%TEAHaq.: 35wt%tetraethylammonium hydroxide solution

[0279] 15JWET: Amberlyst ion exchange resin manufactured by Organo Co., Ltd.

[0280] KC FLOCK: KC FLOCK W-100GK manufactured by Nippon Paper Industries, Ltd.

[0281] CHDVE: 1,4-cyclohexanedimethanol divinyl ether

[0282] TrisVE: Tris[4-(vinyloxy)butyl]-1,2,4-benzenetricarboxylate

[0283] CHVE: Cyclohexyl vinyl ether

[0284] BDVE: 1,4-Butanediol divinyl ether

[0285] TEGDVE: triethylene glycol divinyl ether

[0286] OdVE: Octadecyl vinyl ether

[0287] CHMVE: 1,4-cyclohexanedimethanol monovinyl ether

[0288] PGME: Propylene glycol monomethyl ether

[0289] PGMEA: Propylene glycol monomethyl ether acetate

[0290] MeOH: Methanol

[0291] TMAH: Tetramethylammonium hydroxide

[0292] [Synthesis example 1]

[0293] MAA 6.0g, CHMI 16.0g, HEMA 10.0g, HPMA 2.0g and MMA 6.0g were used, and AIBN 2.5g was used as a free radical polymerization initiator, and these were polymerized at a temperature of 60°C to 100°C in a solvent of PGME 63.6g, thereby obtaining a solution of an alkali-soluble polymer component with Mn 3,600 and Mw 8,600 (solid content concentration: 40% by mass). (A1)

[0294] [Synthesis example 2]

[0295] 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 and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration 21% by mass) (A2). The obtained acrylic polymer had an Mn of 6,200 and an Mw of 9,900.

[0296] [Synthesis example 3]

[0297] 4.10 g of PFBTMOS, 2.46 g of KBM-303, 0.17 g of 35 wt% TEAH, and 0.54 g of water were dissolved in 21.83 g of PGMEA, and stirred at 40°C for 4 hours. Next, 0.66 g of 15JWET washed with PGMEA was added, and stirred at 25°C for 1 hour. Next, the waste 15JWET was filtered with a membrane filter equipped with KCFLOCK to obtain a siloxane polymer solution (B1). The Mn of the obtained siloxane polymer was 2,300 and the Mw was 2,600.

[0298] [Synthesis Example 4]

[0299] PFHTMOS 2.34 g, KBM-303 2.29 g, 35 wt% TEAH 0.24 g, water 0.49 g, and MeOH 0.54 g were dissolved in PGMEA 15.54 g and stirred at 40°C for 4 hours. Next, 15JWET 0.93 g washed with a mixed solvent of PGMEA and MeOH was added and stirred at 25°C for 1 hour. Next, the waste 15JWET was filtered with a membrane filter equipped with KCFLOCK to obtain a siloxane polymer solution (B2). The Mn of the obtained siloxane polymer was 2,300 and the Mw was 2,700.

[0300] [Synthesis Example 5]

[0301] 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 content concentration was set to 1.7% by mass.

[0302] [Examples 1 to 9, Comparative Examples 1 to 5]

[0303] The following components were mixed to prepare a positive photosensitive resin composition as described in Table 1. In the table, [parts] represent [parts by mass], and the composition was adjusted so as to have the numerical values ​​in the table in terms of solid content ratio.

[0304] [Evaluation of inkjet wettability]

[0305] After applying the positive photosensitive resin composition on the ITO-glass using a spin coater, the composition 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 having a pattern of multiple ovals with a long side of 210 μm and a short side of 90 μm. 2 Ultraviolet rays. After development by immersion in a 0.20% TMAH aqueous solution for 60 seconds (only Example 9 and Comparative Example 5 were immersed in a 2.38% TMAH aqueous solution for 50 seconds), rinse with ultrapure water for 30 seconds. The coating film formed with this oval pie shape is then post-baked and cured by heating it at a temperature of 230°C for 30 minutes. The organic functional ink adjusted in Synthesis Example 5 is ejected into the opening of the cured oval pie shape at a fixed ejection volume (about 3pL each time), and the organic functional film is formed by natural drying. The state of the organic functional film is observed using an optical microscope and evaluated according to the following criteria. In addition, when set as an actual specification, at least B is required, and A is preferably.

[0306] A: No collapse or overflow within 14 sprays, good

[0307] B: No collapse or overflow within 20 sprays, good

[0308] C: Collapse or overflow occurs even after 20 sprays

[0309] [Evaluation of contact angle]

[0310] After applying the positive photosensitive resin composition on a silicon wafer using a spin coater, pre-bake it on a hot plate at 100°C for 120 seconds to form a coating with a film thickness of 1.15μm. After developing the coating by immersing it in a 0.20% TMAH aqueous solution for 60 seconds (only Example 9 and Comparative Example 5 were immersed in a 2.38% TMAH aqueous solution for 50 seconds), rinse it with ultrapure water for 30 seconds. Thereafter, post-bake it by heating it at 230°C for 30 minutes to cure it. 1μL of anisole is attached to the cured coating, and the contact angle θ at 5 points after 7 seconds is measured. The average value is set as the contact angle value and evaluated according to the following criteria. In addition, assuming the actual specifications, at least B is required, and A is preferred.

[0311] A: θ≥55°

[0312] B: 53°≤θ<55°

[0313] C: θ<53°

[0314] Table 1

[0315]

[0316] Table 2

[0317] Inkjet wettability Contact angle Example 1 A A Example 2 A A Example 3 B A Example 4 B A Example 5 A A Example 6 B B Example 7 B A Example 8 A A Example 9 A A Comparative Example 1 C A Comparative Example 2 A C Comparative Example 3 C A Comparative Example 4 C C Comparative Example 5 C A

[0318] As shown in Table 2, the cured films (Examples 1 to 9) produced using the positive photosensitive composition containing an acrylic polymer, a surfactant, and a vinyl ether were excellent in inkjet wettability and contact angle.

[0319] On the other hand, the cured films formed from the positive photosensitive compositions of Comparative Examples 1, 3, and 5, which used an acrylic polymer and a surfactant but did not add vinyl ether, were excellent in contact angle, but poor in inkjet wettability. In addition, the cured film formed from the positive photosensitive composition of Comparative Example 2, in which the amount of surfactant added was reduced, was excellent in inkjet wettability, but poor in contact angle. Comparative Example 4, which used an acrylic polymer and a vinyl ether but did not add a surfactant, showed poor inkjet wettability or contact angle.

[0320] As shown in the above examples, a cured film having both inkjet wettability and contact angle can be obtained by forming a positive photosensitive composition composed of an acrylic polymer, a surfactant, a vinyl ether, a crosslinking agent, and a photosensitizer.

Claims

1. A positive photosensitive resin composition capable of forming a cured film, comprising the following components (A), (B), (C), (D), (E) and (F) a solvent, but does not contain a photoacid generator, (A) component: at least one alkali-soluble polymer obtained by polymerizing a monomer mixture containing the following (AI), (AI): N-substituted maleimide compound, (B) ingredient: surfactant, Component (C): a compound having a vinyl ether group, (D) Ingredients: photosensitizer, (E) component: cross-linking agent, (F) Solvent. 2 . The positive photosensitive resin composition according to claim 1 , wherein the (AI) is N-methylmaleimide, N-phenylmaleimide or N-cyclohexylmaleimide.

3. The positive photosensitive resin composition according to claim 1, wherein the monomer mixture comprises the following (A-II): (A-II): A monomer having a hydroxyalkyl group and a polymerizable unsaturated group.

4. The positive photosensitive resin composition according to claim 1, wherein the monomer mixture comprises the following (A-III), (A-III): A monomer having a phenolic hydroxyl group and a polymerizable unsaturated group. 5 . The positive photosensitive resin composition according to claim 4 , wherein the (A-III) is a monomer having an N-hydroxyphenyl group. 6 . The positive photosensitive resin composition according to claim 1 , wherein the component (A) is an alkali-soluble polymer having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene. 7 . The positive photosensitive resin composition according to claim 1 , wherein the component (B) is a surfactant composed of a polymer having a lyophobic group. 8 . The positive photosensitive resin composition according to claim 7 , 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. 9 . The positive photosensitive resin composition according to claim 7 , wherein the monomer unit constituting the polymer having the lyophobic group is a monomer unit derived from an unsaturated hydrocarbon having the lyophobic group. 10 . The positive photosensitive resin composition according to claim 7 , wherein the monomer unit constituting the polymer having the lyophobic group is a monomer unit derived from an alkoxysilane compound having the lyophobic group. 11 . The positive photosensitive resin composition according to claim 7 , wherein the component (B) is a surfactant composed of a polymer having the lyophobic group and a thermosetting group.

12. The positive photosensitive resin composition according to claim 1, wherein the component (C) is at least one compound selected from cyclohexyl vinyl ether, octadecyl vinyl ether, tris[4-(vinyloxy)butyl]-1,2,4-benzenetricarboxylate, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,4-butanediol divinyl ether and triethylene glycol divinyl ether. 13 . The positive photosensitive resin composition according to claim 1 , wherein the component (D) is a 1,2-quinonediazide compound. 14 . The positive photosensitive resin composition according to claim 1 , wherein the component (E) is a crosslinking agent composed of a compound containing an epoxy group or a methoxymethyl group.

15. The positive photosensitive resin composition according to claim 1, comprising 0.05 to 20 parts by mass of component (B), 0.1 to 80 parts by mass of component (C), 5 to 100 parts by mass of component (D), and 5 to 50 parts by mass of component (E), based on 100 parts by mass of component (A). 16 . A cured film formed from the positive photosensitive resin composition according to claim 1 . 17 . A display element comprising the cured film according to claim 16 . 18 . A display element comprising the cured film according to claim 16 as an image-forming bank.

Images