Positive photosensitive resin composition

Abstract

A positive photosensitive resin composition containing: a hydrophobic resin (A) as an addition (co) polymer; an alkali-soluble resin (B) having a structural unit represented by formula (1); a quinonediazide compound (C); a fluorine-based surfactant (D); and a cresol novolac resin. (In formula (1), x represents an integer of 0-3, R1 each independently represents an alkyl group having 1-5 carbon atoms, and R2 represents an organic group having an alkali-soluble functional group. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a positive photosensitive resin composition. More specifically, the present invention relates to a positive photosensitive resin composition containing a quinonediazide compound as a radiation sensitive compound. Background Art

[0002] Positive photosensitive resin compositions are widely used as interlayer insulating films, planarizing films, or protective films of semiconductor devices, or as insulating films, planarizing films, or partition wall materials of display devices such as organic EL displays (OLEDs) and liquid crystal displays.

[0003] For example, in display devices such as organic EL displays, in order to improve display characteristics, a partition material is used at the edge of the spacer of the colored pattern in the display area or the peripheral part of the display area. In the manufacture of an organic EL display device, in order to prevent the pixels of the organic substance from contacting each other, a partition is first formed, and the pixels of the organic substance are formed between the partitions. The partition is generally formed by a photolithography method using a photosensitive resin composition and has insulating properties. In detail, a photosensitive resin composition is applied to a substrate using a coating device, and after removing volatile components by heating and other means, it is exposed via a mask, and then in the case of a negative type, an alkaline aqueous solution or other developer is used to remove the unexposed part, and in the case of a positive type, an alkaline aqueous solution or other developer is used to remove the exposed part, thereby developing, and the obtained pattern is heat-treated to form a partition (insulating film). Then, by an inkjet method, an organic substance that emits red, green, and blue light is formed into a film between the partitions to form the pixels of an organic EL display device.

[0004] In this field, due to the miniaturization of display devices and the diversification of displayed contents in recent years, pixels are required to have higher performance and higher definition. In order to increase the contrast in display devices and improve visibility, attempts have been made to use colorants to impart light-shielding properties to partition wall materials.

[0005] Patent Document 1 (Japanese Patent Application Laid-Open No. 2001-281440) describes a composition in which titanium black is added to a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition that exhibits high light-shielding properties by heat treatment after exposure.

[0006] Patent Document 2 (Japanese Patent Application Laid-Open No. 2002-116536) describes a method of blackening a barrier rib material using carbon black in a radiation-sensitive resin composition containing [A] an alkali-soluble resin, [B] a 1,2-quinonediazide compound, and [C] a colorant.

[0007] Patent Document 3 (Japanese Patent Application Laid-Open No. 2010-237310) describes a composition in which a thermosensitive dye is added to a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition that exhibits light-shielding properties by heat treatment after exposure.

[0008] Patent Document 4 (International Publication No. 2017 / 069172) describes a positive photosensitive resin composition containing (A) a binder resin, (B) a quinonediazide compound, and (C) at least one black dye selected from black dyes specified in the color index of Solvent Black 27 to 47.

[0009] On the other hand, as a method for improving the sensitivity of a positive photosensitive resin composition, it is well known that the photosensitive resin composition is a chemical amplification system. A chemical amplification system photosensitive resin composition generally contains a resin in which an alkali-soluble functional group is protected by an acid-degradable group and a photoacid generator. The acid generated by the photoacid generator during exposure promotes the decomposition (deprotection) of the acid-degradable group and regenerates the alkali-soluble functional group. As a result, the alkaline dissolution of the resin in the exposed part is promoted during development. The acid from the photoacid generator regenerates after decomposing a certain acid-degradable group and participates in the decomposition of another acid-degradable group. The quantum efficiency of the chemical amplification system based only on the above-mentioned reaction mechanism is expressed by the product of the quantum efficiency of acid generation and the reaction chain, so high sensitivity can be achieved by using the photosensitive resin composition as a chemical amplification system.

[0010] Patent Document 5 (International Publication No. 2015 / 087830) describes a photosensitive resin composition containing a polybenzoxazole precursor having a specific repeating unit, a photoacid generator, a solvent, a crosslinking agent, and a compound having a group in which an acid group is protected by an acid-decomposable group in the molecule.

[0011] In patent document 6 (International Publication No. 2020 / 246517), a positive photosensitive resin composition is described, which contains: a first resin (A) having multiple phenolic hydroxyl groups, at least a portion of which are protected by an acid-decomposable group; a second resin (B) having an epoxy group and a phenolic hydroxyl group; a colorant (C) selected from at least one of the group consisting of a black dye and a black pigment; and a photoacid generator (D).

[0012] Prior art literature

[0013] Patent Literature

[0014] Patent Document 1: Japanese Patent Application Publication No. 2001-281440

[0015] Patent Document 2: Japanese Patent Application Publication No. 2002-116536

[0016] Patent Document 3: Japanese Patent Application Publication No. 2010-237310

[0017] Patent Document 4: International Publication No. 2017 / 069172

[0018] Patent Document 5: International Publication No. 2015 / 087830

[0019] Patent Document 6: International Publication No. 2020 / 246517 Summary of the invention

[0020] However, when the partition material has light-shielding properties, the photosensitive resin composition tends to have low sensitivity, resulting in a longer exposure time and a decrease in productivity. Therefore, a photosensitive resin composition used in forming a partition material containing a colorant is required to have higher sensitivity.

[0021] In the photosensitive resin composition used to form the colored partition material, in order to fully improve the light-shielding property of the cured film, a considerable amount of colorant needs to be used. When a large amount of colorant is used in this way, the radiation irradiated on the coating of the photosensitive resin composition is absorbed by the colorant, so the effective intensity of the radiation in the coating is reduced, and the photosensitive resin composition is not fully exposed, resulting in reduced pattern formation. This is significant in the case of forming a thick coating, such as a coating with a thickness of 2 to 3 μm, by adding a black colorant to the photosensitive resin composition for the purpose of improving the image quality, flexibility or power saving of the display device.

[0022] The positive photosensitive resin composition of the chemical amplification system has a higher sensitivity than the positive photosensitive resin composition containing a quinonediazide compound as a radiation-sensitive compound. However, the photoacid generator used in the chemical amplification system is expensive, and the positive photosensitive resin composition of the chemical amplification system is prone to uneven coating on the coating, and requires a post-exposure bake (PEB) for promoting the decomposition of the acid-decomposable group. In addition, in the chemical amplification system, the acid generated by the photoacid generator during exposure diffuses in the coating during the PEB process, so the shape, size, sensitivity, etc. of the pattern sometimes change depending on the conditions of the PEB. Therefore, it is difficult to form a step pattern with high precision on a thick coating using a positive photosensitive resin composition of the chemical amplification system.

[0023] In order to form a step pattern with high precision, in addition to the large difference in solubility between the exposed part and the unexposed part, it is important to suppress the surface roughness and the generation of pores in the step part (intermediate exposure part). The present inventors have found that in a positive photosensitive resin composition containing a quinonediazide compound as a radiation-sensitive compound, by combining a hydrophobic resin of an addition (co)polymer as a resin component, an alkali-soluble resin having a novolac skeleton, and a fluorine-based surfactant, the alkali solubility of the coating surface can be relatively reduced, and as a result, the contrast between the exposed part and the unexposed part can be increased. However, there is room for improvement in the surface smoothness in the step part.

[0024] An object of the present invention is to provide a positive photosensitive resin composition capable of forming a thick film pattern with high precision.

[0025] The present inventors have found that by adding a cresol novolac resin to a positive photosensitive resin composition containing a quinonediazide compound as a radiation-sensitive compound, a hydrophobic resin as an addition (co)polymer as a resin component, an alkali-soluble resin having a novolac skeleton, and a fluorine-based surfactant, the surface roughness of the step portion and the generation of pores can be suppressed, resulting in the formation of a thick film pattern with high precision.

[0026] That is, the present invention includes the following aspects.

[0027] [1] A positive photosensitive resin composition comprising:

[0028] A hydrophobic resin (A) as an addition (co)polymer;

[0029] an alkali-soluble resin (B) having a structural unit represented by formula (1);

[0030] Quinonediazide compounds (C);

[0031] a fluorine-based surfactant (D); and

[0032] Cresol novolac resin.

[0033] [Chemical formula 1]

[0034]

[0035] (In formula (1), x is an integer from 0 to 3, R 1 are each independently an alkyl group having 1 to 5 carbon atoms, R 2 It is an organic group having an alkali-soluble functional group. )

[0036] [2] The positive photosensitive resin composition according to [1], wherein in the formula (1), the alkali-soluble functional group is a phenolic hydroxyl group.

[0037] [3] The positive photosensitive resin composition according to [1] or [2], wherein the alkali-soluble resin (B) further has a structural unit represented by formula (2).

[0038] [Chemical formula 2]

[0039]

[0040] (In formula (2), y is an integer from 0 to 3, R 3 are each independently an alkyl group having 1 to 5 carbon atoms, R 4 It is an organic group that does not have an alkali-soluble functional group. )

[0041] [4] The positive photosensitive resin composition according to [3], wherein in the formula (2), R 4 It is an organic group having an epoxy group.

[0042] [5] A positive photosensitive resin composition according to [3] or [4], wherein the alkali-soluble resin (B) contains a structural unit represented by the formula (1) and a structural unit represented by the formula (2) in an amount of 30 mol % to 100 mol % in total, based on all structural units of the alkali-soluble resin (B).

[0043] [6] The positive photosensitive resin composition according to any one of [1] to [5], wherein the weight average molecular weight (Mw) of the cresol novolac resin is 500 to 17,500.

[0044] [7] The positive photosensitive resin composition according to any one of [1] to [6], comprising 0.5% by mass to 35% by mass of the cresol novolac resin based on the total mass of the resin components.

[0045] [8] The positive photosensitive resin composition according to any one of [1] to [7], wherein the hydrophobic resin (A) is a resin having at least one selected from the group consisting of a silicon-containing group and a fluorine-containing group.

[0046] [9] The positive photosensitive resin composition according to [8], wherein the hydrophobic resin (A) has a structural unit represented by formula (3),

[0047] [Chemical formula 3]

[0048]

[0049] In formula (3), R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 6 By SiR 7 R8 R 9 Indicates that R 7 , R 8 and R 9 are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 5, s is an integer of 0 to 5, but r+s is an integer of 1 to 5,

[0050] There is at least one structural unit represented by the formula (3) wherein s is an integer of 1 or more.

[0051]

[10] The positive photosensitive resin composition according to [9], wherein the hydrophobic resin (A) further has a structural unit represented by formula (4):

[0052] [Chemical formula 4]

[0053]

[0054] In formula (4), R 10 and R 11 are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 12 It is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0055]

[11] The positive photosensitive resin composition according to any one of [1] to

[10] , wherein the fluorine-based surfactant (D) contains an acrylic copolymer having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group.

[0056]

[12] A positive photosensitive resin composition according to any one of [1] to

[11] , wherein the positive photosensitive resin composition further contains an alkali-soluble resin, which is a copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers, and does not have a structural unit represented by the formula (1).

[0057]

[13] The positive photosensitive resin composition according to any one of [1] to

[12] , further comprising at least one colorant (E) selected from the group consisting of a black dye and a black pigment.

[0058]

[14] The positive photosensitive resin composition according to

[13] , wherein the positive photosensitive resin composition contains 10 to 150 parts by mass of the colorant (E) based on 100 parts by mass of the total resin components.

[0059]

[15] The positive photosensitive resin composition according to

[13] or

[14] , wherein the optical density (OD value) of a cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness.

[0060]

[16] An organic EL element partition wall comprising a cured product of the positive photosensitive resin composition described in any one of [1] to

[15] .

[0061]

[17] An organic EL element insulating film comprising a cured product of the positive photosensitive resin composition described in any one of [1] to

[15] .

[0062]

[18] An organic EL device comprising a cured product of the positive photosensitive resin composition described in any one of [1] to

[15] .

[0063] According to the present invention, a positive photosensitive resin composition capable of forming a thick film pattern with high precision can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 (A) is a FE-SEM image of the sample surface of Comparative Example 1, and (B) is a FE-SEM image of the sample surface of Example 1. DETAILED DESCRIPTION

[0065] The present invention is described in detail below.

[0066] In the present specification, when “to” is used for a numerical range, the numerical values ​​at both ends are respectively an upper limit value and a lower limit value, and are included in the numerical range.

[0067] In the present disclosure, "alkali-soluble" means that a positive photosensitive resin composition or a component thereof, or a coating or cured coating of a positive photosensitive resin composition can be dissolved in a 2.38 mass % tetramethylammonium hydroxide aqueous solution. "Alkali-soluble resin" refers to a resin that can be dissolved in a 2.38 mass % tetramethylammonium hydroxide aqueous solution in a monomer state or in a state contained in an unexposed or exposed positive photosensitive resin composition. "Alkali-soluble functional group" refers to a group that has the ability to impart such alkali solubility to a positive photosensitive resin composition or a component thereof, or a coating or cured coating of a positive photosensitive resin composition. Examples of alkali-soluble functional groups include phenolic hydroxyl groups, carboxyl groups, sulfonic groups, phosphoric acid groups, acid anhydride groups, and mercapto groups.

[0068] In the present disclosure, a "radical polymerizable functional group" refers to an ethylenically unsaturated group, and a "radical polymerizable compound" refers to a compound having one or more ethylenically unsaturated groups.

[0069] In the present disclosure, "structural unit" refers to an atomic group that constitutes a part of the basic structure of a polymer, and the atomic group may have a side group atom or a side group atomic group. For example, in the case of a free radical (co)polymer, it refers to a unit from a free radical polymerizable compound used as a monomer, and in the case of a phenol novolac resin, it refers to the following unit formed by the condensation reaction of 1 molecule of phenol (C6H5OH) and 1 molecule of formaldehyde (HCHO). For structural units having side groups (side groups), structural units having side groups for forming crosslinking sites or groups derived from the side groups are considered to be different from structural units having free side groups that do not participate in forming crosslinking sites. With regard to polymers having branched molecular chains (branches), structural units (branch units) containing branching points are considered to be different from structural units contained in linear molecular chains.

[0070] [Chemical formula 5]

[0071]

[0072] In the present disclosure, “(meth)acrylic acid” means acrylic acid or methacrylic acid, “(meth)acrylate” means acrylate or methacrylate, “(meth)acryloyl” means acryloyl or methacryloyl, and “(meth)allyl” means allyl or methallyl.

[0073] In the present disclosure, "(co)polymer" refers to a homopolymer or a copolymer.

[0074] In the present disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) of a resin, a polymer or a copolymer refer to standard polystyrene conversion values ​​measured by gel permeation chromatography (GPC).

[0075] In the present disclosure, the phenolic hydroxyl equivalent is a theoretical value calculated from the molecular weight and composition ratio of the structural units constituting the resin. Specifically, when the resin is a (co)polymer of n monomers i (i = a natural number of 1 to n), the phenolic hydroxyl equivalent is defined by the following formula:

[0076] [Mathematical formula 1]

[0077]

[0078] In the formula, the total of the copolymerization ratios (molar basis) of the monomers i (i=1 to n) is 1.

[0079] In the case of a resin having an epoxy group and a phenolic hydroxyl group described later, the phenolic hydroxyl group equivalent is represented by the following formula:

[0080] Phenolic hydroxyl equivalent =

[0081] (Epoxy equivalent of raw material + molecular weight of added carboxylic acid) / (number of phenolic hydroxyl groups of carboxylic acid)

[0082] The calculated value.

[0083] In the present disclosure, "resin component" refers to the hydrophobic resin (A), the alkali-soluble resin (B), the cresol novolac resin, and the copolymer having an alkali-soluble functional group optionally included. The component corresponding to the fluorine-based surfactant (D) is not included in the hydrophobic resin (A), the alkali-soluble resin (B), and the copolymer having an alkali-soluble functional group optionally included.

[0084] In the present disclosure, "solid content" refers to the total mass of components other than the liquid solvent (G), including any components such as the hydrophobic resin (A), the alkali-soluble resin (B), the quinonediazide compound (C), the fluorine-based surfactant (D), the cresol novolac resin and the copolymer having an alkali-soluble functional group, the colorant (E), and the dissolution accelerator (F), etc.

[0085] [Positive photosensitive resin composition]

[0086] A positive photosensitive resin composition according to one embodiment includes a hydrophobic resin (A) as an addition (co)polymer, an alkali-soluble resin (B) having a structural unit represented by formula (1), a quinonediazide compound (C), a fluorine-based surfactant (D), and a cresol novolac resin.

[0087] [Chemical formula 6]

[0088]

[0089] (In formula (1), x is an integer from 0 to 3, R 1 are each independently an alkyl group having 1 to 5 carbon atoms, R 2 It is an organic group having an alkali-soluble functional group. )

[0090] 〈Hydrophobic resin (A)〉

[0091] The hydrophobic resin (A) (also referred to as hydrophobic resin (A)) as an addition (co)polymer is a resin that promotes the unevenness of the coating surface by a fluorine-based surfactant (D), so that the coating surface of the positive photosensitive resin composition is insoluble in an alkaline aqueous solution. Although not limited by any theory, the hydrophobic resin (A) is easily moved to the coating surface accompanied by the fluorine-based surfactant (D) that moves to the coating surface during the formation of the coating of the positive photosensitive resin composition. Therefore, after the coating is formed, the hydrophobic resin (A) exists at a high concentration on the coating surface compared to the inside of the coating, so that the alkali solubility of the coating surface is reduced. During development, the hydrophobic resin (A) as a resin component with low alkali solubility suppresses the dissolution of the coating surface of the unexposed part, and at the same time, in the exposed part, it is accompanied by the dissolution of the carboxylic acid compound from the quinonediazide compound (C), other resin components with high alkali solubility, and any dissolution promoter, and is released from the coating into the developer. When the coating surface temporarily dissolves in the exposed part, the concentration of the hydrophobic resin (A) is relatively low, so the dissolution of the coating interior, which is more alkali-soluble than the coating surface, proceeds rapidly. This can increase the contrast between the exposed part and the unexposed part, and as a result, can improve the pattern forming property of the thick film of the positive photosensitive resin composition.

[0092] As long as the hydrophobic resin (A) is an addition (co)polymer, it is not particularly limited and can be a free radical (co)polymer, a cationic (co)polymer or an anionic (co)polymer. As the hydrophobic resin (A), for example, olefin (co)polymers, (meth)acrylic acid (co)polymers, styrene (co)polymers, acrylamide (co)polymers, acrylonitrile (co)polymers, N-substituted maleimide (co)polymers and derivatives of these resins can be cited. The derivatives of these resins preferably have a hydrophobic group. As the hydrophobic group, for example, silicon-containing groups and fluorine-containing groups can be cited. As the hydrophobic resin (A), it is also possible to use a homopolymer or copolymer of a polymerizable monomer with an alkali-soluble functional group as a base resin, and convert a part or all of the alkali-soluble functional group into a resin with a group having the above-mentioned hydrophobic group. The hydrophobic resin (A) can be used alone or in combination of two or more.

[0093] In one embodiment, the hydrophobic resin (A) is a resin having at least one selected from the group consisting of a silicon-containing group and a fluorine-containing group. The silicon-containing group and the fluorine-containing group may constitute the main chain of the hydrophobic resin (A) or may be a side group.

[0094] Examples of the silicon-containing group include a silyl group substituted with an aliphatic hydrocarbon group or an aryl group, a group having a cyclic siloxane structure, and a group having a silsesquioxane structure.

[0095] The silyl group substituted by an aliphatic hydrocarbon group or an aryl group is a 1-substituted, 2-substituted or 3-substituted group. The substituents of the silyl group substituted by an aliphatic hydrocarbon group or an aryl group may be the same or different from each other. The silyl group substituted by an aliphatic hydrocarbon group or an aryl group is preferably a 3-substituted group. The silyl group substituted by an aliphatic hydrocarbon group or an aryl group may further have a substituent other than an alkyl group or an aryl group, for example, a siloxy group substituted by an aliphatic hydrocarbon group or an aryl group.

[0096] The number of ring members of the cyclic siloxane moiety of the group having a cyclic siloxane structure is preferably 6 to 14. A part or all of the hydrogen atoms on the silicon atoms of the group having a cyclic siloxane structure may be substituted independently with an aliphatic hydrocarbon group or an aryl group.

[0097] A part or all of the hydrogen atoms on the silicon atoms of the group having a silsesquioxane structure may be substituted independently with an aliphatic hydrocarbon group or an aryl group.

[0098] The aliphatic hydrocarbon group of the silyl group substituted with an aliphatic hydrocarbon group or an aryl group, the aliphatic hydrocarbon group as a substituent of the group having a cyclic siloxane structure, the aliphatic hydrocarbon group as a substituent of the group having a silsesquioxane structure, and the aliphatic hydrocarbon group as a substituent of the siloxy group substituted with an aliphatic hydrocarbon group or an aryl group are preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include saturated hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; unsaturated hydrocarbon groups such as vinyl, propenyl, butenyl, ethynyl and propynyl; saturated monocyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl; unsaturated monocyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl and cyclodecenyl; saturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octanyl and adamantyl; and unsaturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptenyl and bicyclo[2.2.2]octenyl.

[0099] The aryl group of the silyl group substituted with an aliphatic hydrocarbon group or an aryl group, the aryl group as a substituent of the group having a cyclic siloxane structure, the aryl group as a substituent of the group having a silsesquioxane structure, and the aryl group as a substituent of the siloxy group substituted with an aliphatic hydrocarbon group or an aryl group are preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 14 carbon atoms. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, fluorenyl, anthracenyl, and phenanthryl.

[0100] Examples of the silyl group substituted with an aliphatic hydrocarbon group or an aryl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, and a trimethylsilyloxydimethylsilyl group.

[0101] Examples of the group having a cyclic siloxane structure include a pentamethylcyclotrimethylsilyloxy group, a heptamethylcyclotetramethylsilyloxy group, and a nonamethylcyclopentamethylsilyloxy group.

[0102] Examples of the group having a silsesquioxane structure include a silsesquioxane group, a heptamethylmethylsilsesquioxane group, a heptamethylethylsilsesquioxane group, a heptamethyl(n-propyl)silsesquioxane group, and a heptamethyl(n-butyl)silsesquioxane group.

[0103] Examples of the fluorine-containing group include a fluorine-substituted alkyl group, a fluorine-substituted aryl group and a fluorinated acryloyl group.

[0104] The fluorine-substituted alkyl group may be a perfluoroalkyl group or a partially fluorinated alkyl group. The substituents of the fluorine-substituted alkyl group may be the same or different from each other. The fluorine-substituted alkyl group may also have a substituent other than a fluorine atom, such as a hydroxyl group.

[0105] The fluorine-substituted alkyl group is preferably a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group having 1 to 20 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 8 carbon atoms or a partially fluorinated alkyl group having 1 to 8 carbon atoms. Examples of the perfluoroalkyl group having 1 to 20 carbon atoms and the partially fluorinated alkyl group having 1 to 20 carbon atoms include a straight-chain or branched fluorine-substituted alkyl group such as a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a pentafluoropropyl group, a hexafluoroisopropyl group, a hexafluoroisopropyl group, a hexafluoro(2-methyl)isopropyl group, a heptafluorobutyl group, a nonafluorobutyl group, an octafluoroisobutyl group, a nonafluoro-tert-butyl group, a perfluoroisopentyl group, a nonafluorohexyl group, a perfluoro(trimethyl)hexyl group, a perfluorooctyl group, and a 2-perfluorohexylethyl group; and a cyclic fluorine-substituted alkyl group such as a 2,2,3,3-tetrafluorocyclobutyl group and a perfluorocyclohexyl group. The fluorine-substituted alkyl group is preferably a 2,2,2-trifluoroethyl group or a 2-perfluorohexylethyl group.

[0106] Examples of the fluorine-substituted alkyl group having a hydroxyl group as a substituent include -CH(CF3)OH, -C(CF3)2OH, -C(CF3)(CH3)OH and -C(C2F5)2OH, and -C(CF3)2OH is preferred.

[0107] The fluorine-substituted aryl group may be a perfluorinated aryl group or a partially fluorinated aryl group. The substituents of the fluorine-substituted aryl group may be the same or different from each other. The fluorine-substituted aryl group may also have a substituent other than a fluorine atom, such as a hydroxyl group.

[0108] The fluorine-substituted aryl group is preferably a perfluorinated aryl group having 6 to 20 carbon atoms or a partially fluorinated aryl group having 6 to 20 carbon atoms. Examples of the perfluorinated aryl group having 6 to 20 carbon atoms and the partially fluorinated aryl group having 6 to 20 carbon atoms include p-fluorophenyl, pentafluorophenyl and 3,5-bis(trifluoromethyl)phenyl. The fluorine-substituted aryl group is preferably a pentafluorophenyl group.

[0109] The hydrophobic resin (A) can be manufactured, for example, by subjecting a polymerizable monomer having a hydrophobic group to free radical polymerization, or by subjecting a polymerizable monomer having a hydrophobic group to free radical copolymerization with other polymerizable monomers. In the case of manufacturing the hydrophobic resin (A) by free radical polymerization, a polymerization initiator and a RAFT (Reversible Addition Fragmentation Transfer) agent can be used as needed. As polymerizable monomers having a hydrophobic group and polymerizable functional groups possessed by other polymerizable monomers, for example, free radical polymerizable functional groups such as CH2=CH-, CH2=C(CH3)-, CH2=CHCO-, CH2=C(CH3)CO-, -OC-CH=CH-CO- can be cited. The hydrophobic resin (A) can also be manufactured by reacting a resin having functional groups such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group with a compound having a hydrophobic group, and converting the functional group into a group containing a hydrophobic group.

[0110] In one embodiment, the hydrophobic resin (A) is a copolymer of a polymerizable monomer having a hydrophobic group and other polymerizable monomers. Examples of the polymerizable monomer having a hydrophobic group include a polymerizable monomer having a silicon-containing group and a polymerizable monomer having a fluorine-containing group.

[0111] Examples of the polymerizable monomer having a silicon-containing group include trimethylvinylsilane, trimethylallylsilane, trimethyl(3-butenyl)silane, tert-butyldimethylvinylsilane, (trimethylsilyloxy)dimethylvinylsilane, (trimethylsilyloxy)dimethylallylsilane, triethylvinylsilane, triethylallylsilane, triethyl(3-butenyl)silane, methyl(trimethylsilyl)(meth)acrylate, ethyl 2-(trimethylsilyl)(meth)acrylate, 3-(trimethylsilyl)propyl(meth)acrylate, tert-butyldimethylsilyl(meth)acrylate, triisopropylsilyl(meth)acrylate, and the like. methyl ester, methyl bis(trimethylsilylmethyl)(meth)acrylate, cyclohexyl 4-(trimethylsilyl)(meth)acrylate, 3-[(trimethylsilyloxy)dimethylsilyl]propyl(meth)acrylate, 3-[tris(trimethylsiloxy)silyl]propyl(meth)acrylate, 4-trimethylsilyloxyphenyl(meth)acrylate, 4-triethylsiloxyphenyl(meth)acrylate, 4-triisopropylsiloxyphenyl(meth)acrylate, 4-tert-butyldimethylsiloxyphenyl(meth)acrylate, vinylheptamethylcyclotetrasiloxane, and 3-(heptamethylsesquioxalyl)propyl(meth)acrylate.

[0112] Examples of the polymerizable monomer having a fluorine-containing group include 2-perfluorohexyl ethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoropropyl) (meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylate, 3,3,4,4,5,5,6,6,6-nonafluorohexyl (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoro-2-methylpropyl) (meth)acrylate, and 2-(1,1,1,3,3,3-hexafluoro-2-phenylpropyl) (meth)acrylate. Acrylates, phenyl pentafluoro(meth)acrylate, phenyl 3,5-bis(trifluoromethyl)(meth)acrylate, cyclohexyl perfluoro(meth)acrylate, 2,2,2-trifluoroethyl vinyl ether, 2-(1,1,1,3,3,3-hexafluoropropyl)vinyl ether, 2,3,4,5,6-pentafluorostyrene, isopropyl 2-fluoroacrylate, tert-butyl 2-fluoroacrylate, cyclohexyl 2-fluoroacrylate, 4-tert-butylcyclohexyl 2-fluoroacrylate, isopropyl 2-(trifluoromethyl)acrylate, tert-butyl 2-(trifluoromethyl)acrylate, cyclohexyl 2-(trifluoromethyl)acrylate and 4-tert-butylcyclohexyl 2-(trifluoromethyl)acrylate.

[0113] As other polymerizable monomers, there may be mentioned, for example, styrene; styrene derivatives such as α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; ether compounds of vinyl alcohol such as vinyl n-butyl ether; (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; and N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide.

[0114] Other polymerizable monomers may also be polymerizable monomers having alkali-soluble functional groups. Examples of polymerizable monomers having alkali-soluble functional groups include maleic acid derivatives such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; and unsaturated carboxylic acids such as maleic acid, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propionic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidocaproic acid. Compounds; polymerizable monomers having phenolic hydroxyl groups, such as 4-hydroxystyrene, 4-hydroxyphenyl (meth) acrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl acrylamide, and 4-hydroxyphenylmaleimide; polymerizable monomers having sulfonic groups, such as (meth) allyl sulfonic acid, 2-(meth) acrylamide-2-methylpropane sulfonic acid, and styrene sulfonic acid; polymerizable monomers having phosphate groups, such as mono(2-(meth)acryloyloxyethyl) phosphate; and polymerizable monomers having anhydride groups, such as itaconic anhydride, citraconic anhydride, and maleic anhydride.

[0115] As a polymerizable monomer having a hydrophobic group, after polymerization, it is represented by the formula (3):

[0116] [Chemical formula 7]

[0117]

[0118] (In formula (3), R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 6 By SiR 7 R 8 R 9 Indicates that R 7, R 8 and R 9 Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r represents an integer of 0 to 5, s represents an integer of 0 to 5, wherein r+s represents an integer of 1 to 5. ) is preferably a structural unit in which s is an integer greater than 1. 5 It is preferably a hydrogen atom or a methyl group. 7 , R 8 and R 9 Each of them is independently preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or a phenyl group. r is preferably an integer of 0 to 3, and more preferably 0. s is preferably an integer of 1 to 3, and more preferably 1. As the polymerizable monomer having such a hydrophobic group, 4-triethylsilyloxyphenyl methacrylate and 4-tert-butyldimethylsilyloxyphenyl methacrylate are particularly preferred.

[0119] As other polymerizable monomers, it is preferred that after polymerization, a monomer having the formula (4) is formed:

[0120] [Chemical formula 8]

[0121]

[0122] (In formula (4), R 10 and R 11 are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 12 A structural unit represented by a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted by at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. 10 and R 11 Preferably it is a hydrogen atom. 12 Preferably, it is a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and more preferably, it is a cyclic alkyl group or a phenyl group having 3 to 12 carbon atoms. As such other polymerizable monomers, phenylmaleimide and N-cyclohexylmaleimide are particularly preferred.

[0123] As other polymerizable monomers having an alkali-soluble functional group, it is preferred that after polymerization, a monomer having the formula (5) is formed:

[0124] [Chemical formula 9]

[0125]

[0126] (In formula (5), R 13is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. 13 It is preferably a hydrogen atom or a methyl group. a is preferably an integer of 1 to 3, and more preferably 1. As another polymerizable monomer having such an alkali-soluble functional group, 4-hydroxyphenyl methacrylate is particularly preferred.

[0127] In one embodiment, the hydrophobic resin (A) has the formula (3):

[0128] [Chemical formula 10]

[0129]

[0130] (In formula (3), R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 6 By SiR 7 R 8 R 9 Indicates that R 7 , R 8 and R 9 Each of them is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 5, s is an integer of 0 to 5, wherein r+s is an integer of 1 to 5. ) is a structural unit represented by formula (3), and has at least one structural unit represented by formula (3) in which s is an integer greater than 1.

[0131] In this embodiment, the hydrophobic resin (A) preferably further has a

[0132] [Chemical formula 11]

[0133]

[0134] (In formula (4), R 10 and R 11 are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 12 A structural unit represented by a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted by at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0135] In this embodiment, the hydrophobic resin (A) preferably further has a

[0136] [Chemical formula 12]

[0137]

[0138] (In formula (5), R 13is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. ) is a structural unit represented by

[0139] In the above-mentioned hydrophobic resin (A), the molar ratio of the structural unit represented by formula (3), the structural unit represented by formula (4), and the structural unit represented by formula (5), wherein s is an integer greater than 1, is preferably formula (3): formula (4): formula (5) = 5 to 60: 3 to 10: 20 to 90, and more preferably formula (3): formula (4): formula (5): = 6 to 50: 4 to 9: 30 to 85.

[0140] As the polymerizable monomer having a hydrophobic group, 4-triethylsiloxyphenyl methacrylate or 4-tert-butyldimethylsiloxyphenyl methacrylate is used, and as other polymerizable monomers, phenylmaleimide or N-cyclohexylmaleimide and 4-hydroxyphenyl methacrylate are particularly preferably used. By using a resin obtained by free radical polymerization of these polymerizable monomers, the sensitivity and pattern forming properties of the positive photosensitive resin composition can be improved, and degassing can also be reduced.

[0141] When the hydrophobic resin (A) has a silicon-containing group, the content of silicon atoms is preferably 1.0% to 10% by mass, more preferably 3.0% to 8.0% by mass, based on the mass of the hydrophobic resin (A). The hydrophobic resin (A) having a silicon-containing group preferably contains a structural unit having a silicon-containing group in an amount of 3 mol% to 60 mol%, more preferably 5 mol% to 50 mol%, based on all structural units of the hydrophobic resin (A).

[0142] When the hydrophobic resin (A) has a fluorine-containing group, the content of fluorine atoms is preferably 1% to 35% by mass, more preferably 5% to 30% by mass, based on the mass of the hydrophobic resin (A). The hydrophobic resin (A) having a fluorine-containing group preferably contains a structural unit having a fluorine-containing group in an amount of 5mol% to 55mol%, more preferably 6mol% to 50mol%, based on the total structural units of the hydrophobic resin (A).

[0143] The hydrophobic resin (A) may or may not have an alkali-soluble functional group. The hydrophobic resin (A) preferably contains a structural unit having an alkali-soluble functional group in an amount of 20 mol% to 90 mol%, more preferably 30 mol% to 85 mol%, and further preferably 40 mol% to 80 mol%, based on all structural units of the hydrophobic resin (A). In one embodiment, the hydrophobic resin (A) does not have an alkali-soluble functional group.

[0144] The weight average molecular weight (Mw) of the hydrophobic resin (A) is preferably 3000 to 80000, more preferably 4000 to 70000, and further preferably 5000 to 60000. The number average molecular weight (Mn) of the hydrophobic resin (A) is preferably 1000 to 30000, more preferably 1500 to 25000, and further preferably 2000 to 20000. The polydispersity (Mw / Mn) of the hydrophobic resin (A) is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, and further preferably 1.2 to 2.8. By setting the weight average molecular weight, number average molecular weight and polydispersity to the above ranges, a positive photosensitive resin composition having excellent sensitivity and pattern forming properties can be obtained.

[0145] In one embodiment, the positive photosensitive resin composition contains 1% to 50% by mass, preferably 2% to 40% by mass, and more preferably 3% to 30% by mass of a hydrophobic resin (A) based on 100% by mass of solid content. If the content of the hydrophobic resin (A) is 1% to 50% by mass based on 100% by mass of solid content, the hydrophobic resin (A) is promoted to be uneven on the surface of the film by a fluorine-based surfactant (D), and the hydrophobic resin (A) becomes a high concentration on the surface of the film, and the surface of the film is insoluble in an alkaline aqueous solution, so that high sensitivity can be achieved. If the content of the hydrophobic resin (A) is 50% or less by mass based on 100% by mass of solid content, the dissolution of the surface of the film is rapidly carried out with the dissolution of the carboxylic acid compound from the quinone diazide compound in the exposure portion, other resin components with high alkali solubility, and any dissolution promoter, so that high sensitivity can be achieved.

[0146] The positive photosensitive resin composition preferably contains 1% to 50% by mass, more preferably 3% to 45% by mass, and further preferably 5% to 40% by mass of a hydrophobic resin (A) based on the total mass of the resin components. If the content of the hydrophobic resin (A) is 1% or more by mass based on the total mass of the resin components, the hydrophobic resin (A) is promoted to be uneven on the surface of the film by a fluorine-based surfactant (D), and the hydrophobic resin (A) becomes a high concentration on the surface of the film, and the surface of the film is poorly soluble in an alkaline aqueous solution, so that high sensitivity can be achieved. If the content of the hydrophobic resin (A) is 50% or less by mass based on the total mass of the resin components, the dissolution of the surface of the film is rapidly carried out with the dissolution of the carboxylic acid compound from the quinone diazide compound in the exposure portion, other resin components with high alkali solubility, and any dissolution promoter, so that high sensitivity can be achieved.

[0147] <Alkali-soluble resin (B)>

[0148] The alkali-soluble resin (B) has a structural unit represented by formula (1).

[0149] [Chemical formula 13]

[0150]

[0151] In formula (1), x is an integer from 0 to 3, R 1 are each independently an alkyl group having 1 to 5 carbon atoms, R 2 is an organic group having an alkali-soluble functional group. x is preferably 0 or 1. 1 Preferably it is methyl. 2 There is no particular limitation, but preferably it has an alkali-soluble functional group and contains an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylene group, an alkenylene group, an alkynylene group, an ester group, an ether group, a carbonyl group, an arylene group, an amino group, an imino group, an imine group, an amide group, a heterocyclic group, a sulfonyl group, or an organic group combining two or more of these groups. In one embodiment, R 2 It is an alkali-soluble functional group and an organic group composed of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylene group, an alkenylene group, an alkynylene group, an ester group, an ether group, a carbonyl group, an arylene group, an amino group, an imino group, an imine group, an amide group, a heterocyclic group, a sulfonyl group, or a combination of two or more of them. 2 The number of carbon atoms is, for example, 1 to 30, preferably 2 to 25. The alkali-soluble functional group is not particularly limited, and examples thereof include phenolic hydroxyl groups, carboxyl groups, sulfonyl groups, phosphoric acid groups, acid anhydride groups, and mercapto groups, preferably phenolic hydroxyl groups. 2 It is preferably an organic group having one or more phenolic hydroxyl groups, and more preferably an organic group represented by -CH2CH(OH)CH2-O-(C=O)-X (X represents a phenyl group substituted with one or more hydroxyl groups).

[0152] An alkali-soluble resin (B) having two or more alkali-soluble functional groups may also be used. The alkali-soluble resin (B) may be used alone or in combination of two or more.

[0153] The alkali-soluble resin (B) preferably contains the structural unit represented by formula (1) in an amount of 20 mol% to 95 mol%, more preferably 25 mol% to 90 mol%, and further preferably 30 mol% to 85 mol%, based on all structural units of the alkali-soluble resin (B). If it is 20 mol% or more, alkali solubility is fully manifested and the problem of residue at the bottom of the pattern will not occur. If it is 95 mol% or less, the solubility of the unexposed part will not be affected.

[0154] The alkali-soluble resin (B) may contain other structural units other than the structural unit represented by the formula (1). Examples of other structural units include a structural unit represented by the following formula (2).

[0155] [Chemical formula 14]

[0156]

[0157] (In formula (2), y is an integer from 0 to 3, R 3 are each independently an alkyl group having 1 to 5 carbon atoms, R 4 It is an organic group that does not have an alkali-soluble functional group. )

[0158] In formula (2), y is preferably 0 or 1. 3 Preferably it is methyl. 4 Preferably, it is an organic group containing an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylene group, an alkenylene group, an alkynylene group, an ester group, an ether group, a carbonyl group, an arylene group, an amino group, an imino group, an imine group, an amide group, a heterocyclic group, a sulfonyl group, or a combination of two or more of these groups. 4 The organic group may be a monovalent group or a polyvalent group. In the case of a polyvalent group, it means that it is bonded with other parts of the alkali-soluble resin (B) to form a crosslinked structure. 4 The number of carbon atoms is, for example, 1 to 30, preferably 1 to 20, and more preferably 2 to 10. In formula (2), R 4 It is preferably an organic group having a heterocyclic group, and more preferably an organic group having an epoxy group. More specifically, R 4 An organic group (glycidyl group) represented by -CH2-Y (Y represents an epoxy group) is preferred.

[0159] The alkali-soluble resin (B) contains the structural unit represented by the formula (1) and the structural unit represented by the formula (2) in an amount of preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and further preferably 50 mol% to 100 mol%, based on all the structural units of the alkali-soluble resin (B). If it is 30 mol% or more, the effect of improving the compatibility between the hydrophobic resin (A) and the alkali-soluble resin (B) can be sufficiently obtained by adding the cresol novolac resin to the resin component.

[0160] The alkali-soluble resin (B) preferably contains R 2 It is a structural unit of an organic group having a phenolic hydroxyl group. As such an alkali-soluble resin (B), for example, a resin in which an organic group having a phenolic hydroxyl group is introduced into a novolac-type epoxy resin such as a phenol novolac-type epoxy resin and a cresol novolac-type epoxy resin. The novolac-type epoxy resin is a resin in which a glycidyl group is introduced into the hydroxyl portion of a phenol novolac and a cresol novolac. The novolac-type epoxy resin in which an organic group having a phenolic hydroxyl group is introduced may also have an alkali-soluble functional group other than the phenolic hydroxyl group.

[0161] In the case where the alkali-soluble resin (B) contains the structural unit represented by the formula (1) and the structural unit represented by the formula (2), the alkali-soluble resin (B) preferably contains R in the formula (1): 2 is a structural unit of an organic group having a phenolic hydroxyl group and R in formula (2) 4 More preferably, the alkali-soluble resin (B) comprises R in formula (1): 2 A structural unit of an organic group represented by -CH2CH(OH)CH2-O-(C=O)-X (X represents a phenyl group substituted with one or more hydroxyl groups), and R in formula (2) 4 It is a structural unit of an organic group represented by -CH2-Y (Y represents an epoxy group).

[0162] Such an alkali-soluble resin (B) can be obtained by reacting a part of the epoxy group of the novolac epoxy resin with the carboxyl group of the hydroxybenzoic acid compound (hereinafter, the resin is sometimes referred to as "resin having epoxy group and phenolic hydroxyl group."). The resin has unreacted epoxy groups from the novolac epoxy resin and phenolic hydroxyl groups from the hydroxybenzoic acid compound. Since the resin is a thermosetting type, as common sense of those skilled in the art, its structure cannot be uniquely recorded according to the presence or absence of epoxy groups, the type of functional groups, the degree of polymerization, etc. The epoxy groups of the resin having epoxy groups and phenolic hydroxyl groups react with phenolic hydroxyl groups during the heat treatment (post-baking) after development to form crosslinks, thereby improving the chemical resistance and heat resistance of the coating. Since the phenolic hydroxyl group contributes to the solubility in the alkaline aqueous solution during development, the resin having epoxy groups and phenolic hydroxyl groups also functions as a dissolution promoter for other resins when exposed at a low exposure amount, thereby enabling the photosensitive resin composition to become highly sensitive.

[0163] An example of a reaction in which one of the epoxy groups of the novolac epoxy resin reacts with the carboxyl group of the hydroxybenzoic acid compound to produce a resin having an epoxy group and a phenolic hydroxyl group is shown in the following reaction formula 1.

[0164] [Chemical formula 15]

[0165]

[0166] An example of the structure of a novolac-type epoxy resin is shown in Formula (6). In Formula (6), R 14 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m is an integer of 1 to 50.

[0167] [Chemical formula 16]

[0168]

[0169] Examples of phenol novolac epoxy resins include EPICLON (trademark) N-770 (DIC Corporation) and jER (trademark)-152 (Mitsubishi Chemical Corporation). Examples of cresol novolac epoxy resins include EPICLON (trademark) N-695 (DIC Corporation) and EOCN (trademark)-102S (Nippon Kayaku Co., Ltd.).

[0170] The novolac epoxy resin is preferably at least one selected from the group consisting of a phenol novolac epoxy resin and a cresol novolac epoxy resin, and more preferably a cresol novolac epoxy resin. A positive photosensitive resin composition containing a resin having an epoxy group and a phenolic hydroxyl group derived from a novolac epoxy resin, particularly a cresol novolac epoxy resin, has excellent pattern forming properties, is easy to adjust alkali solubility, and has little degassing.

[0171] The hydroxybenzoic acid compound is a compound in which at least one of the 2-6 positions of benzoic acid is substituted with a hydroxyl group, and examples thereof include salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, and 4-hydroxy-3-nitrobenzoic acid. From the viewpoint of improving alkali developability, dihydroxybenzoic acid compounds are preferred. The hydroxybenzoic acid compounds may be used alone or in combination of two or more.

[0172] In one embodiment, the alkali-soluble resin (B) is a reaction product of a novolac-type epoxy resin and a hydroxybenzoic acid compound, having the formula (7):

[0173] [Chemical formula 17]

[0174]

[0175] (In formula (7), b is an integer of 1 to 5, and * represents a bonding portion of the novolac epoxy resin with the residue of the epoxy group involved in the removal reaction.)

[0176] In the method of obtaining an alkali-soluble resin (B) from a novolac epoxy resin and a hydroxybenzoic acid compound, 0.2 to 0.95 equivalents of the hydroxybenzoic acid compound can be used relative to 1 equivalent of epoxy groups of the novolac epoxy resin, preferably 0.3 to 0.9 equivalents, and more preferably 0.4 to 0.8 equivalents. If the hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkali solubility can be obtained, and if it is 0.95 equivalents or less, the increase in molecular weight due to side reactions can be suppressed.

[0177] In order to promote the reaction of the epoxy group of the novolac epoxy resin and the carboxyl group of the hydroxybenzoic acid compound, a catalyst can also be used. The amount of the catalyst used can be set to 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture consisting of the novolac epoxy resin and the hydroxybenzoic acid compound. The reaction temperature can be set to 60 to 150° C., and the reaction time can be set to 3 to 30 hours. As the catalyst used in the reaction, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, and zirconium octanoate can be cited.

[0178] The number average molecular weight (Mn) of the alkali-soluble resin (B) is preferably 500 to 8000, more preferably 800 to 6000, and further preferably 1000 to 5000. The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 500 to 30000, more preferably 2000 to 25000, and further preferably 3000 to 20000. If the number average molecular weight is 500 or more or the weight average molecular weight is 500 or more, the alkali development speed is appropriate and the difference in dissolution speed between the exposed part and the unexposed part is sufficient, so the resolution of the pattern is good. If the number average molecular weight is 8000 or less or the weight average molecular weight is 30000 or less, the coating property and alkali developability are good.

[0179] When the alkali-soluble resin (B) is a resin having an epoxy group and a phenolic hydroxyl group, the epoxy equivalent thereof is preferably 300 to 7000, more preferably 400 to 6000, and further preferably 500 to 5000. If the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300 or more, sufficient alkali solubility can be imparted to the resin having an epoxy group and a phenolic hydroxyl group. If the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 7000 or less, the strength and heat resistance of the cured film can be improved. The epoxy equivalent is determined by JIS K 7236:2009.

[0180] In one embodiment, the positive photosensitive resin composition contains 5% to 60% by mass, preferably 10% to 50% by mass, and more preferably 15% to 40% by mass of an alkali-soluble resin (B) based on 100% by mass of solid content. If the content of the alkali-soluble resin (B) is 5% or more by mass based on 100% by mass of solid content, the phase separation with the hydrophobic resin (A) can be maintained, and the inhomogenization of the hydrophobic resin (A) to the surface will not be hindered. If the content of the alkali-soluble resin (B) is 60% or less by mass based on 100% by mass of solid content, the phase separation with the hydrophobic resin (A) can be maintained, and the inhomogenization of the hydrophobic resin (A) to the surface will not be hindered, and the solubility of the unexposed portion will not be affected.

[0181] Based on the total mass of the resin components, the positive photosensitive resin composition preferably contains 15% to 80% by mass, more preferably 20% to 75% by mass, and further preferably 25% to 70% by mass of the alkali-soluble resin (B). If the content of the alkali-soluble resin (B) is 15% or more by mass based on the total mass of the resin components, the phase separation with the hydrophobic resin (A) can be maintained, and the non-uniformization of the hydrophobic resin (A) to the surface will not be hindered. If the content of the alkali-soluble resin (B) is 80% or less by mass based on the total mass of the resin components, the phase separation with the hydrophobic resin (A) is maintained, and the non-uniformization of the hydrophobic resin (A) to the surface will not be hindered, and the solubility of the unexposed portion will not be affected.

[0182] <Alkali-soluble resin which is a copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers and does not have a structural unit represented by formula (1)>

[0183] In one embodiment, the positive photosensitive resin composition is a copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers, and may further contain an alkali-soluble resin not having the structural unit represented by formula (1) (also referred to as a "copolymer having an alkali-soluble functional group").

[0184] As the alkali-soluble functional group possessed by the copolymer having an alkali-soluble functional group, for example, phenolic hydroxyl group, carboxyl group, sulfonic group, phosphoric acid group, acid anhydride group and mercapto group can be mentioned. The copolymer of the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers can have two or more alkali-soluble functional groups. As the polymerizable functional group possessed by the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers, for example, free radical polymerizable functional groups such as CH2=CH-, CH2=C(CH3)-, CH2=CHCO-, CH2=C(CH3)CO-, -OC-CH=CH-CO- can be mentioned.

[0185] From the viewpoint of heat resistance, the copolymer having an alkali-soluble functional group preferably has one or more cyclic structures selected from the group consisting of an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure.

[0186] The copolymer with alkali-soluble functional groups can be manufactured, for example, by subjecting a polymerizable monomer with alkali-soluble functional groups and other polymerizable monomers to free radical polymerization. In the case of manufacturing a copolymer with alkali-soluble functional groups by free radical polymerization, a polymerization initiator and a RAFT (Reversible Addition Fragmentation Transfer) agent can be used as required. Alkali-soluble functional groups can also be added to the copolymer after the copolymer is synthesized by free radical polymerization.

[0187] As the polymerizable monomer having an alkali-soluble functional group, for example, the polymerizable monomer having an alkali-soluble functional group described with respect to the hydrophobic resin (A) can be used.

[0188] From the viewpoint of sensitivity, the polymerizable monomer having an alkali-soluble functional group is preferably a polymerizable monomer having a carboxyl group or a phenolic hydroxyl group, and more preferably a polymerizable monomer having a phenolic hydroxyl group.

[0189] As other polymerizable monomers, for example, the other polymerizable monomers described with respect to the hydrophobic resin (A) can be used.

[0190] As the polymerizable monomer having an alkali-soluble functional group, it is preferred that after polymerization, a monomer having the formula (5) is formed:

[0191] [Chemical formula 18]

[0192]

[0193] (In formula (5), R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. 13 It is preferably a hydrogen atom or a methyl group. a is preferably an integer of 1 to 3, and more preferably 1. As the polymerizable monomer having such an alkali-soluble functional group, 4-hydroxyphenyl methacrylate is particularly preferred.

[0194] As other polymerizable monomers, it is preferred that after polymerization, a monomer having the formula (4) is formed:

[0195] [Chemical formula 19]

[0196]

[0197] (In formula (4), R 10 and R 11 are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 12A structural unit represented by a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted by at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. 10 and R 11 Preferably it is a hydrogen atom. 12 It is preferably a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and more preferably a cyclic alkyl group or a phenyl group having 3 to 12 carbon atoms. As such other polymerizable monomers, phenylmaleimide and N-cyclohexylmaleimide are particularly preferred.

[0198] In one embodiment, the copolymer having alkali-soluble functional groups has the formula (5):

[0199] [Chemical formula 20]

[0200]

[0201] (In formula (5), R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. ) and a structural unit represented by formula (4)

[0202] [Chemical formula 21]

[0203]

[0204] (In formula (4), R 10 and R 11 are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 12 A structural unit represented by a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted by at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0205] In the copolymer having an alkali-soluble functional group, the molar ratio of the structural unit represented by formula (5) to the structural unit represented by formula (4) is preferably formula (5): formula (4) = 70 to 95: 30 to 5, and more preferably formula (5): formula (4) = 75 to 90: 25 to 10.

[0206] As the polymerizable monomer having an alkali-soluble functional group, 4-hydroxyphenyl methacrylate is used, and as the other polymerizable monomer, phenylmaleimide or N-cyclohexylmaleimide is particularly preferably used. By using a resin obtained by free radical polymerization of these polymerizable monomers, the shape retention and developability of the coating of the positive photosensitive resin composition can be improved, and degassing can also be reduced.

[0207] The weight average molecular weight (Mw) of the copolymer having an alkali-soluble functional group is preferably 3,000 to 80,000, more preferably 4,000 to 70,000, and further preferably 5,000 to 60,000. The number average molecular weight (Mn) of the copolymer having an alkali-soluble functional group is preferably 1,000 to 30,000, more preferably 1,500 to 25,000, and further preferably 2,000 to 20,000. The polydispersity (Mw / Mn) of the copolymer having an alkali-soluble functional group is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, and further preferably 1.2 to 2.8. By setting the weight average molecular weight, number average molecular weight and polydispersity of the copolymer having an alkali-soluble functional group to the above ranges, a positive photosensitive resin composition having excellent coating properties, pattern forming properties and alkali developability can be obtained.

[0208] When the alkali-soluble functional group of the copolymer having an alkali-soluble functional group is a phenolic hydroxyl group, the phenolic hydroxyl equivalent of the copolymer having an alkali-soluble functional group is preferably 60 to 400, more preferably 80 to 350, and further preferably 100 to 300. If the phenolic hydroxyl equivalent of the copolymer having an alkali-soluble functional group is 60 or more, the film thickness of the unexposed portion can be sufficiently maintained during alkali development. If the phenolic hydroxyl equivalent of the copolymer having an alkali-soluble functional group is 400 or less, the desired alkali solubility can be obtained.

[0209] In one embodiment, the positive photosensitive resin composition contains 1% to 70% by mass, preferably 3% to 60% by mass, and more preferably 5% to 50% by mass of a copolymer having an alkali-soluble functional group, based on 100% by mass of solid content. If the content of the copolymer having an alkali-soluble functional group is 1% by mass or more based on 100% by mass of solid content, the dissolution of the exposed portion can be promoted, high sensitivity can be achieved, and the stability and durability of the coating after thermal curing can be ensured. If the content of the copolymer having an alkali-soluble functional group is 70% by mass or less based on 100% by mass of solid content, the problem of residue at the bottom of the exposed portion pattern will not be caused, and a beautiful pattern can be formed.

[0210] The positive photosensitive resin composition preferably contains 1% to 80% by mass, more preferably 3% to 70% by mass, and further preferably 5% to 60% by mass of a copolymer having an alkali-soluble functional group, based on the total mass of the resin components. If the content of the copolymer having an alkali-soluble functional group is 1% by mass or more based on the total mass of the resin components, the dissolution of the exposed portion can be promoted, high sensitivity can be achieved, and the stability and durability of the coating after thermal curing can be ensured. If the content of the copolymer having an alkali-soluble functional group is 80% by mass or less based on the total mass of the resin components, the problem of residue at the bottom of the exposed portion pattern will not be caused, and a beautiful pattern can be formed.

[0211] 〈Quinonediazide compounds (C)〉

[0212] When the quinonediazide compound (C) is irradiated with radiation such as visible light, ultraviolet light, gamma rays, electron beams, etc., it undergoes the reaction shown in the following reaction formula 2 to generate an alkali-soluble carboxylic acid compound. The quinonediazide compound (C) interacts with the alkali-soluble functional groups such as phenolic hydroxyl groups of the alkali-soluble resin (B) and the cresol novolac resin and the copolymer having alkali-soluble functional groups optionally contained before exposure (for example, forming hydrogen bonds), making these resins insoluble in alkaline aqueous solution. On the other hand, by the presence of an alkali-soluble carboxylic acid compound in the portion irradiated with radiation, the resin located in the portion is easily dissolved in the alkaline aqueous solution together with the carboxylic acid compound. In addition, the carboxylic acid compound has a relatively large molecular structure compared to the acid generated by the photoacid generator commonly used in chemically amplified resists, such as p-toluenesulfonic acid, 1-propanesulfonic acid, etc., and is difficult to diffuse in the coating. As a result of their synergistic effect, the difference in alkali solubility between the unexposed portion and the exposed portion can be increased, thereby forming a high-resolution pattern with high sensitivity even at a low exposure amount. The quinonediazide compound (C) can be used alone or in combination of two or more. The positive photosensitive resin composition preferably does not substantially contain a photoacid generator commonly used in a chemically amplified resist, and more preferably does not contain the photoacid generator and contains only a quinonediazide compound (C) as a photosensitizer. "Substantially containing no photoacid generator" means that the amount of the photoacid generator contained in the positive photosensitive resin composition is 0.2 parts by mass or less, 0.1 parts by mass or less, or 0.05 parts by mass or less, based on 100 parts by mass of the total resin component.

[0213] [Chemical formula 22]

[0214]

[0215] In one embodiment, a high-resolution pattern can be formed without performing a post-exposure heat treatment (PEB) required for a general chemically amplified resist. The quantum yield of the quinonediazide compound (C) is high, and a carboxylic acid compound can be efficiently generated in the exposed portion. By omitting PEB, it is possible to avoid a decrease in pattern formation caused by excessive diffusion of the acid generated by the quinonediazide compound (C) to the unexposed portion under the high temperature environment of the PEB process. In addition, in the case where the alkali-soluble resin (B) contains a resin having an epoxy group and a phenolic hydroxyl group, if PEB is omitted, the ring-opening polymerization of the epoxy group of the resin having an epoxy group and a phenolic hydroxyl group is not performed, so that the alkali solubility of the resin having an epoxy group and a phenolic hydroxyl group can be maintained during development.

[0216] Examples of the quinonediazide compound (C) include products formed by bonding sulfonic acid of quinonediazide to a polyhydroxy compound via an ester bond, products formed by bonding sulfonic acid of quinonediazide to a polyamino compound via a sulfonamide bond, products formed by bonding sulfonic acid of quinonediazide to a polyhydroxypolyamino compound via an ester bond or a sulfonamide bond, etc. From the viewpoint of the contrast between the exposed portion and the unexposed portion, it is preferred that 20 mol% or more of the functional groups of the polyhydroxy compound, polyamino compound or polyhydroxypolyamino compound as a whole are substituted with quinonediazide.

[0217] Examples of the polyhydroxy compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML -MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade names, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are trade names, Asahi Organic Materials Co., Ltd.), tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.), etc., but are not limited to these.

[0218] The quinonediazide compound (C) is preferably a 1,2-naphthoquinonediazide-4-sulfonate or a 1,2-naphthoquinonediazide-5-sulfonate of a polyhydroxy compound.

[0219] In one embodiment, the positive photosensitive resin composition contains 5 to 70 parts by mass, preferably 7 to 65 parts by mass, and more preferably 10 to 60 parts by mass of a quinonediazide compound (C) based on 100 parts by mass of the total resin component. If the content of the quinonediazide compound (C) is 5 parts by mass or more based on the above total 100 parts by mass, high sensitivity can be achieved. If the content of the quinonediazide compound (C) is 70 parts by mass or less based on the above total 100 parts by mass, alkali developability is good.

[0220] 〈Fluorine-based surfactant (D)〉

[0221] Fluorine-based surfactant (D) is not particularly limited, and a surfactant having at least one fluorinated hydrocarbon group and a hydrophilic group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group can be used. As such a fluorine-based surfactant (D), for example, perfluoroalkyl sulfonic acid, partially fluorinated alkyl sulfonic acid, perfluoroalkyl carboxylic acid, partially fluorinated alkyl carboxylic acid, perfluoroalkyl phosphate, partially fluorinated alkyl phosphate, perfluoroalkyl trimethyl ammonium salt, partially fluorinated alkyl trimethyl ammonium salt, perfluoroalkyl betaine, partially fluorinated alkyl betaine, perfluoroalkyl EO addition and fluorotelomer alcohol can be cited. As a fluorine-based surfactant (D), a homopolymer or copolymer having a perfluoroalkyl group, a partially fluorinated alkyl group, a perfluoroalkyl group or a partially fluorinated alkylene group, and a hydrophilic group such as a sulfonic group, a carboxyl group, a phosphoric group, an ammonium group, an oxyalkyl group, a polyoxyalkylene group in the molecule can also be used. Fluorine-based surfactant (D) can be used alone or in combination of two or more.

[0222] The fluorinated surfactant (D) preferably contains an acrylic copolymer having at least one fluorinated hydrocarbon group selected from the group consisting of fluorinated alkyl groups and fluorinated alkylene groups. The acrylic copolymer can promote the migration of the hydrophobic resin (A) to the surface of the film of the positive photosensitive resin composition, making the film surface less soluble in alkali.

[0223] In one embodiment, the acrylic copolymer is represented by formula (8):

[0224] [Chemical formula 23]

[0225]

[0226] (In formula (8), R 15 is a hydrogen atom or a methyl group, L 1 is a divalent group having 1 to 30 carbon atoms, Rf 1 It is a perfluoroalkyl or partially fluorinated alkyl group having 4 to 6 carbon atoms and may contain one or more ether bonds in the chain.

[0227] The fluorine-containing polymerizable monomer represented by formula (9)

[0228] [Chemical formula 24]

[0229]

[0230] (In formula (9), R 16 is a hydrogen atom or a methyl group, R 17 are each independently a linear or branched alkylene group having 2 to 4 carbon atoms, R 18 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and c is an integer of 2 to 50.

[0231] A copolymer (D1) of a polymerizable monomer having a polyoxyalkylene group.

[0232] In formula (8), L 1 The divalent group having 1 to 30 carbon atoms represented by L may contain at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, and may contain a perfluoroalkyl group or a partially fluorinated alkyl group having 4 to 6 carbon atoms. 1 Preferred are -OCH2CH2-, -OCH2CH2NH(C=O)OCH(CH2OCH2CH2C4F9)CH2OCH2CH2-, -OCH2CH2NH(C=O)OCH(CH2OCH2CH2C6F9) 13 )CH2OCH2CH2-, -OCH2CH2N(C3H7)SO2-, -OCH2CH2NH(C=O)OCH2CH2-, -OCH2CH(OH)CH2O- or -N(C4H9)CH2CH2-.

[0233] In formula (8), Rf 1 Preferably -C4F9 or -C6F 13 .

[0234] The fluorine-containing polymerizable monomer represented by the formula (8) can be used alone or in combination of two or more.

[0235] In formula (9), as R 17 The linear or branched alkylene group having 2 to 4 carbon atoms represented by R includes ethylene, propylene, tetramethylene and isobutenyl. 17 They may be the same or different from each other. From the perspective of leveling, R 17 It is preferably a propylene group, a tetramethylene group or an isobutylene group, and more preferably a plurality of the same groups are linked via adjacent oxygen atoms to form a polyoxypropylene chain, a polyoxytetramethylene chain or a polyoxyisobutylene chain.

[0236] In formula (9), as R 18 Examples of the alkyl group having 1 to 6 carbon atoms represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl.

[0237] The polymerizable monomer having a polyoxyalkylene group represented by formula (9) can be used alone or in combination of two or more.

[0238] The copolymer (D1) may be a copolymer with other polymerizable monomers besides the fluorine-containing polymerizable monomer represented by the formula (8) and the polymerizable monomer having a polyoxyalkylene group represented by the formula (9).

[0239] As other polymerizable monomers, for example, those represented by formula (10)

[0240] [Chemical formula 25]

[0241]

[0242] (In formula (10), R 19 is a hydrogen atom or a methyl group, R 20 It is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms.

[0243] Represents a polymerizable monomer.

[0244] In formula (10), as R 20 The linear, branched or cyclic alkyl group having 1 to 18 carbon atoms represented by alkyl includes, for example, methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, stearyl, isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, isobornyl, adamantyl and dicyclopentyl.

[0245] As other polymerizable monomers, there can be mentioned aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene; and maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, n-propylmaleimide, isopropylmaleimide, n-butylmaleimide, n-hexylmaleimide, n-octylmaleimide, n-dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide.

[0246] Other polymerizable monomers can be used alone or in combination of two or more.

[0247] From the viewpoint of leveling properties, the mass ratio of the fluorine-containing polymerizable monomer represented by formula (8) to the polymerizable monomer having a polyoxyalkylene group represented by formula (9) in the copolymer (D1) (mass of the fluorine-containing polymerizable monomer represented by formula (8) / mass of the polymerizable monomer having a polyoxyalkylene group represented by formula (9)) is preferably 10 / 90 to 70 / 30, more preferably 15 / 85 to 60 / 40, and further preferably 25 / 75 to 50 / 50. When other polymerizable monomers are used, they are preferably used in an amount of 50% by mass or less based on the mass of the copolymer (D1).

[0248] Copolymer (D1) can be obtained, for example, by free radical polymerization of a fluorine-containing polymerizable monomer represented by formula (8), a polymerizable monomer having a polyoxyalkylene group represented by formula (9), and other polymerizable monomers used as needed using a polymerization initiator in an organic solvent. As organic solvents, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfoxides such as dimethyl sulfoxide; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; and aromatic hydrocarbons such as toluene and xylene. As polymerization initiators, peroxide polymerization initiators such as benzoyl peroxide and azo polymerization initiators such as 2,2'-azobisisobutyronitrile can be mentioned. Chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethyl mercaptoacetic acid, and octyl mercaptoacetic acid can also be used as needed.

[0249] The number average molecular weight (mn) of the copolymer (d1) is preferably 2,000 to 100,000, more preferably 2,500 to 50,000, because the compatibility or miscibility with the resin component is good and excellent leveling properties can be obtained.

[0250] From the viewpoint of compatibility or miscibility with the resin component and leveling properties, the fluorine atom content of the copolymer (D1) is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass. The fluorine atom content of the copolymer (D1) is a value calculated from the mass ratio of fluorine atoms based on the total mass of the polymerizable monomers used.

[0251] In another embodiment, the acrylic copolymer is represented by formula (11):

[0252] [Chemical formula 26]

[0253]

[0254] (In formula (11), R 21 is a free radical polymerizable functional group, L 2 is a divalent group having 1 to 8 carbon atoms, L 3 is a divalent group having 1 to 8 carbon atoms, Rf 2 are each independently a fluorinated alkylene group having 1 to 3 carbon atoms, and d is an integer of 1 to 100.

[0255] The fluorine-containing polymerizable monomer represented by formula (12)

[0256] [Chemical formula 27]

[0257]

[0258] (In formula (12), R 22 is a hydrogen atom or a methyl group, R 23 are each independently a linear or branched alkylene group having 2 to 4 carbon atoms, R 24 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and e is an integer of 1 to 80.

[0259] A copolymer (D2) of a polymerizable monomer having an oxyalkylene group.

[0260] In formula (11), as R 21 Examples of the radical polymerizable functional group represented by include CH2=CHCO-, CH2=C(CH3)CO-, and CH2=CH-C6H4-. 21 From the viewpoint of availability and free radical polymerizability, R 21 CH2=CHCO- or CH2=C(CH3)CO- is preferred, and CH2=CHCO- is more preferred from the viewpoint of excellent leveling properties.

[0261] In formula (11), L 2 The divalent group having 1 to 8 carbon atoms represented by may contain at least one hetero atom selected from the group consisting of an oxygen atom and a nitrogen atom. 2 Preferred are -OCH2-, -OC H2CH2-, -OCH2CH2NH(C=O)OCH2-, -OCH2CH2NH(C=O)OCH2CH2-, -OC H2CH2CH2CH2OCH2CH(OH)CH2O(C=O)-, -OCH2CH(OH)CH2O(C=O)-, -OCH2CH(OH)CH2OCH2- or -CH2OCH2-, more preferably -OCH2- or -OCH2CH2NH(C=O)OCH2-, and further preferably -OCH2-.

[0262] In formula (11), L 3 The divalent group having 1 to 8 carbon atoms represented by may contain at least one hetero atom selected from the group consisting of an oxygen atom and a nitrogen atom. 3 Preferred are -CH2O-, -CH2CH2O-, -CH2O(C=O)NHCH2CH2O-, -CH2CH2O(C=O)NHCH2CH2O-, -(C=O)OCH2CH(OH)CH2OCH2CH2CH2CH2O-, -(C=O)OCH2CH(OH)CH2O-, -CH2OCH2CH(OH)CH2O- or -CH2OCH2-, more preferably -CH2O- or -CH2O(C=O)NHCH2CH2O-, further preferably -CH2O-.

[0263] In formula (11), Rf 2 Specifically, the fluorinated alkylene group having 1 to 3 carbon atoms represented by is preferably selected from the group consisting of -CF2-(perfluoromethylene), -CF2CF2-(perfluoroethylene), -CF2CF2CF2-, -CF2CF(CF3)- and -CF(CF3)CF2-.

[0264] From the viewpoint of leveling, in formula (11), -(Rf 2 O) d R 2 The site represented by - preferably contains a combination of a perfluoromethylene group and a perfluoroethylene group. In this embodiment, the molar ratio of the perfluoromethylene group to the perfluoroethylene group (the number of moles of perfluoromethylene groups / the number of moles of perfluoroethylene groups) is preferably 1 / 10 to 10 / 1.

[0265] In formula (11), d is preferably 3-100, more preferably 6-70.

[0266] The fluorine-containing polymerizable monomer represented by the formula (11) preferably contains 18 to 200, more preferably 25 to 150 fluorine atoms from the viewpoint of compatibility or miscibility with the resin component and leveling properties.

[0267] The fluorine-containing polymerizable monomer represented by the formula (11) may be used alone or in combination of two or more.

[0268] In formula (12), as R 23 The linear or branched alkylene group having 2 to 4 carbon atoms represented by R includes ethylene, propylene, tetramethylene and isobutenyl. 23 They may be the same or different from each other. From the perspective of leveling, R 23 An ethylene group or a propylene group is preferred, and a plurality of the same groups are linked via adjacent oxygen atoms to form a polyoxyethylene chain, a polyoxypropylene chain, or a chain of a polyoxyethylene chain and a polyoxypropylene chain.

[0269] In formula (12), as R 24 Examples of the alkyl group having 1 to 6 carbon atoms represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl.

[0270] In formula (12), e is preferably 3-50.

[0271] The polymerizable monomer having an oxyalkylene group represented by formula (12) can be used alone or in combination of two or more.

[0272] The copolymer (D2) may be a copolymer with other polymerizable monomers besides the fluorine-containing polymerizable monomer represented by the formula (11) and the polymerizable monomer having an oxyalkylene group represented by the formula (12). Examples of other polymerizable monomers include the monomers described for the copolymer (D1).

[0273] The copolymer (D2) can be obtained by the radical polymerization described for the copolymer (D1).

[0274] From the viewpoint of good compatibility or miscibility with the resin component and excellent leveling properties, the number average molecular weight (Mn) of the copolymer (D2) is preferably 500 to 20,000, more preferably 1,500 to 10,000, and the weight average molecular weight (Mw) of the copolymer (D2) is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.

[0275] From the viewpoint of compatibility or miscibility with the resin component and leveling properties, the fluorine atom content of the copolymer (D2) is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass. The fluorine atom content of the copolymer (D2) is a value calculated from the mass ratio of fluorine atoms based on the total mass of the polymerizable monomers used.

[0276] Specific examples of the fluorine-based surfactant (D) include Megafac (trademark) F-251, F-281, F-430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-562, and F-563 (trade names, DIC Corporation) and Surflon (trademark) S-242, S-243, S-386, S-420, and S-611 (trade names, AGC Seimi Chemical Co., Ltd.). The fluorine-based surfactant (D) is preferably Megafac (trademark) F-563, F-559, F-554, R-40, or F-562, and more preferably Megafac (trademark) F-563, F-554, or R-40.

[0277] The content of the fluorinated surfactant (D) in the positive photosensitive resin composition is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and further preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the total resin component. If the content of the fluorinated surfactant (D) is 0.01 parts by mass or more based on the above-mentioned total 100 parts by mass, the leveling property of the positive photosensitive resin composition is improved, so that the positive photosensitive resin composition can be evenly coated on the substrate, thereby promoting the inhomogenization of the hydrophobic resin (A). If the content of the fluorinated surfactant (D) is 5 parts by mass or less based on the above-mentioned total 100 parts by mass, it will not adversely affect the cured film after post-baking, can improve the leveling property of the positive photosensitive resin composition, and can promote the inhomogenization of the hydrophobic resin (A).

[0278] 〈Cresol novolac resin〉

[0279] The positive photosensitive resin composition contains a cresol novolac resin. By adding the cresol novolac resin, the surface roughness and the generation of pores in the step portion can be suppressed. In the positive photosensitive resin composition, when a hydrophobic resin (A) as an addition (co)polymer and an alkali-soluble resin (B) having a novolac skeleton represented by formula (1) are used as resin components, phase separation occurs between the hydrophobic resin (A) and the alkali-soluble resin (B) inside the film, and surface roughness and pores are generated in the step portion, but it is not limited to any theory. By adding the cresol novolac resin to the resin component, the compatibility between the hydrophobic resin (A) and the alkali-soluble resin (B) is improved, and the phase separation inside the film is suppressed. As a result, the surface roughness and the generation of pores in the step portion can be suppressed.

[0280] The weight average molecular weight (Mw) of the cresol novolac resin is preferably 500 or more, more preferably 1000 or more, and further preferably 1500 or more. The weight average molecular weight (Mw) of the cresol novolac resin is preferably 17500 or less, more preferably 15000 or less, and further preferably 12500 or less. The combination of these lower limits and upper limits may be any combination. The weight average molecular weight (Mw) of the cresol novolac resin is preferably 500 to 17500, more preferably 1000 to 15000, and further preferably 1500 to 12500. By setting the weight average molecular weight to the above range, the smoothness of the step portion can be improved without generating residue at the bottom of the pattern.

[0281] Examples of the cresol novolac resin include TR4020G, TR4080G, and TR4000B (these are trade names, manufactured by Asahi Organic Materials Co., Ltd.).

[0282] In one embodiment, the positive photosensitive resin composition contains 0.1% to 40% by mass, preferably 0.2% to 30% by mass, and more preferably 0.3% to 20% by mass of a cresol novolac resin based on 100% by mass of solid content. If the content of the cresol novolac resin is 0.1% by mass or more based on 100% by mass of solid content, the surface smoothness of the step portion can be sufficiently improved. If the content of the cresol novolac resin is 40% by mass or less based on 100% by mass of solid content, it will not affect the reduction in sensitivity and the solubility of the unexposed portion.

[0283] The positive photosensitive resin composition preferably contains 0.5% by mass or more, more preferably 0.6% by mass or more, and further preferably 0.7% by mass or more of a cresol novolac resin, based on the total mass of the resin components. The positive photosensitive resin composition preferably contains 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less of a cresol novolac resin, based on the total mass of the resin components. Any combination of these lower limits and upper limits may be used. The positive photosensitive resin composition preferably contains 0.5% to 35% by mass, more preferably 0.6% to 30% by mass, and further preferably 0.7% to 25% by mass of a cresol novolac resin, based on the total mass of the resin components. If the content of the cresol novolac resin is 0.5% by mass or more based on the total mass of the resin components, the surface smoothness of the step portion can be sufficiently improved. When the content of the cresol novolac resin is 35% by mass or less based on the total mass of the resin components, there is no influence on the decrease in sensitivity and the solubility of the unexposed portion.

[0284] 〈Colorant (E)〉

[0285] The positive photosensitive resin composition may also contain at least one colorant (E) selected from the group consisting of black dye and black pigment. By using a photosensitive resin composition containing a colorant (E) to form a black partition wall on an organic EL element, the visual recognition of a display device such as an organic EL display can be improved. In this embodiment, due to the presence of a colorant (E), the transmittance of radiation during exposure is sharply reduced from the surface of the coating to the inside. Therefore, the carboxylic acid compound from the quinone diazide compound (C) is produced more near the coating surface, but is difficult to produce inside the coating. The carboxylic acid compound from the quinone diazide compound (C) has low diffusivity in the coating, so it stays near the coating surface, which helps to promote the dissolution of the coating surface of the exposure portion. Since the concentration of the hydrophobic resin (A) is relatively low inside the coating, the alkali solubility is relatively high. Therefore, even when the radiation is not fully transmitted to the inside of the coating, by using the positive photosensitive resin composition of this embodiment, a high-sensitivity and high-precision thick film pattern can be formed.

[0286] As the black dye, for example, there can be mentioned dyes specified by the color index (CI) of solvent black 27 to 47. The black dye is preferably specified by the CI of solvent black 27, 29 or 34. When at least one of the dyes specified by the CI of solvent black 27 to 47 is used as the black dye, the light shielding property of the coating of the positive photosensitive resin composition after curing can be maintained. Compared with the positive photosensitive resin composition containing a black pigment, the positive photosensitive resin composition containing a black dye has less colorant residue during development and can form a high-definition pattern.

[0287] As black pigment, for example, carbon black, carbon nanotube, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigment and lactam pigment can be cited. Pigments to which these black pigments have been surface treated can also be used. As examples of commercially available perylene pigments, K0084, K0086, Pigment Black 21, 30, 31, 32, 33 and 34 of BASF can be cited. As an example of commercially available lactam pigment, Irgaphor (trademark) black S0100CF of BASF can be cited. From the viewpoint of having high light-shielding properties, the black pigment is preferably selected from at least one of the group consisting of carbon black, titanium black, perylene pigment and lactam pigment.

[0288] The content of the colorant (E) in the positive photosensitive resin composition is preferably 10 to 150 parts by mass, more preferably 15 to 100 parts by mass, and further preferably 20 to 80 parts by mass, based on 100 parts by mass of the total resin component. If the content of the colorant (E) is 10 parts by mass or more based on the above-mentioned total 100 parts by mass, sufficient light-shielding properties can be obtained, and in particular, when the colorant (E) contains a black dye, the light-shielding properties of the cured film can be maintained. If the content of the colorant (E) is 150 parts by mass or less based on the above-mentioned total 100 parts by mass, the residual film rate and sensitivity are appropriate, and in particular, when the colorant (E) contains a black dye, high heat resistance can be imparted to the film.

[0289] 〈Optional Ingredients〉

[0290] The positive photosensitive resin composition may contain a dissolution accelerator (F), a thermosetting agent, a second surfactant other than the fluorine-based surfactant (D), a second colorant other than the colorant (E), etc. as optional components. In the present disclosure, the optional component is defined as any one that does not conform to (A) to (E), a cresol novolac resin, and a copolymer having an alkali-soluble functional group.

[0291] <Dissolution accelerator (F)>

[0292] The positive photosensitive resin composition may further contain a dissolution promoter (F) for improving the solubility of the alkali-soluble portion in the developer during development. Examples of the dissolution promoter (F) include organic low molecular weight compounds selected from the group consisting of compounds having a carboxyl group and compounds having a phenolic hydroxyl group. The dissolution promoter (F) may be used alone or in combination of two or more.

[0293] In the present disclosure, "low molecular weight compound" refers to a compound having a molecular weight of 1000 or less. The above-mentioned organic low molecular weight compound has one or more carboxyl groups or a plurality of phenolic hydroxyl groups and is alkali-soluble.

[0294] Examples of such organic low molecular weight compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, heptanoic acid, and octanoic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphortric acid; aromatic tricarboxylic acids such as benzoic acid, methylbenzoic acid, cuminic acid, and 3,5-dimethylbenzoic acid. Monocarboxylic acids; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, tetraphthalic acid, pyromellitic acid, and trimellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, and gallic acid; other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamyl acetic acid, coumaric acid, and umbelliferous acid; aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, and bisphenol, etc.

[0295] The content of the dissolution promoter (F) in the positive photosensitive resin composition can be set to 0.1 to 50 parts by mass, preferably 1 to 35 parts by mass, and more preferably 2 to 20 parts by mass, based on 100 parts by mass of the total resin component. If the content of the dissolution promoter (F) is 0.1 parts by mass or more based on 100 parts by mass, the dissolution of the resin component can be effectively promoted, and if it is 50 parts by mass or less, the excessive dissolution of the resin component can be suppressed, thereby improving the pattern forming properties and surface quality of the coating.

[0296] [Coating composition]

[0297] 〈Solvent (G)〉

[0298] The positive photosensitive resin composition can be dissolved or dispersed in a solvent (G) and used as a coating composition in a solution state or a dispersion state. For example, by dissolving a hydrophobic resin (A), an alkali-soluble resin (B), a cresol novolac resin, and a copolymer having an alkali-soluble functional group as required in a solvent (G), a quinonediazide compound (C), a fluorine-based surfactant (D), and a dissolution promoter (E), a thermosetting agent, other surfactants and other arbitrary components in a predetermined ratio in a solution obtained, a coating composition containing a positive photosensitive resin composition can be prepared. By changing the amount of the solvent (G), the coating composition can be adjusted to a viscosity suitable for the coating method used.

[0299] Examples of the solvent (G) include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol compounds such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol monoalkyl ether acetate compounds such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4- Ketones such as hydroxy-4-methyl-2-pentanone and cyclohexanone; esters such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; and amide compounds such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. The solvent (G) can be used alone or in combination of two or more.

[0300] The solid content concentration of the coating composition can be appropriately determined according to the intended use. For example, the solid content concentration of the coating composition may be 1 to 60% by mass, 3 to 50% by mass, or 5 to 40% by mass.

[0301] The dispersion and mixing method when using the pigment can use a known method. For example, a ball mill, a sand mill, a bead mill, a paint shaker, a swing mill, a ball type, a kneader, a paddle mixer, a planetary mixer, a Henschel mixer, a roller type, a three-roll mixer, etc. can be used. In addition, a crusher, a colloid mill, an ultrasonic wave, a homogenizer, a rotation / revolution mixer, etc. can also be used. From the viewpoint of dispersion efficiency and microdispersion, a bead mill is preferably used.

[0302] The prepared coating composition is usually filtered before use. Examples of the filtering method include a microporous filter having a pore size of 0.05 to 1.0 μm.

[0303] The coating composition thus prepared is also excellent in long-term storage stability.

[0304] [Method of using the positive photosensitive resin composition]

[0305] When a positive photosensitive resin composition is used for radiation lithography, first, the positive photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition. Then, the coating composition is applied to the surface of a substrate, and the solvent is removed by heating or other means to form a coating film. The coating method for applying the coating composition to the surface of the substrate is not particularly limited, and for example, a spray coating method, a roll coating method, a slit coating method, or a spin coating method can be used.

[0306] After the coating composition is applied to the surface of the substrate, the solvent is usually removed by heating to form a coating (pre-baking). The heating conditions vary depending on the type and proportion of each component, and are usually heated at 70 to 130° C., for example, on a hot plate for 30 seconds to 20 minutes, or in an oven for 1 to 60 minutes, thereby obtaining a coating. In one embodiment, the thickness of the formed coating is 2 to 3 μm.

[0307] Next, the pre-baked film is irradiated with radiation (e.g., visible light, ultraviolet light, extreme ultraviolet light, X-rays, electron beams, gamma rays, or synchrotron radiation) via a photomask having a predetermined pattern (exposure step). Preferably, the radiation is ultraviolet light or visible light having a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-ray. In another embodiment, the radiation is ghi-ray.

[0308] After the exposure process, the coating is brought into contact with a developer to perform development, and unnecessary portions are removed to form a pattern on the coating (development process). As a developer, for example, inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of alkaline compounds such as cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane can be used. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, etc., is added to an alkaline aqueous solution can also be used as a developer. The development time is usually 30 to 180 seconds. The developing method may be any of a liquid method, a spray method, an immersion method, etc. After the development, the film is washed with running water for 30 to 90 seconds to remove unnecessary parts, and then dried with compressed air or compressed nitrogen, thereby forming a pattern on the film.

[0309] Then, the patterned film is heat-treated at 100 to 350° C. for 20 to 200 minutes by a heating device such as a hot plate or an oven, thereby obtaining a cured film (post-baking, heat treatment step). During the heat treatment, the temperature may be maintained constant, or the temperature may be raised continuously or in stages. The heat treatment is preferably performed under a nitrogen atmosphere.

[0310] 〈Residual film rate〉

[0311] In one embodiment, a positive photosensitive resin composition is coated to a film thickness of 3.0±0.3 μm after prebaking, and after prebaking at 125° C. for 120 seconds to form a coating, an alkaline development is performed at 23° C. with a 2.38 mass % tetramethylammonium hydroxide aqueous solution for 60 seconds, and the following formula is used:

[0312] Residual film rate (%) = film thickness after development (μm) / film thickness before development (μm)

[0313] The residual film rate is defined as 90% or more, preferably 95% or more, and more preferably 99% or more. The residual film rate is an indicator of the solubility of the unexposed portion. The higher the residual film rate, the greater the difference in solubility between the exposed portion and the unexposed portion, and a thick film pattern with a large height difference can be formed with high precision.

[0314] 〈Optical Density〉

[0315] In the embodiment where the positive photosensitive resin composition contains a colorant (E), the optical density (OD value) of the cured film of the positive photosensitive resin composition is preferably 0.5 or more per 1 μm of film thickness, more preferably 0.7 or more, and further preferably 1.0 or more. If the OD value of the cured film is 0.5 or more per 1 μm of film thickness, sufficient light-shielding properties can be obtained.

[0316] A method for manufacturing an organic EL element partition wall or an organic EL element insulating film according to one embodiment includes: preparing a coating composition by dissolving or dispersing a positive photosensitive resin composition in a solvent; applying the coating composition on a substrate to form a coating film; removing the solvent contained in the coating film and drying the coating film; irradiating the dried coating film with radiation through a photomask to expose the coating film; developing the exposed coating film by contacting the exposed coating film with a developer to form a pattern on the coating film; and heating the coating film with the pattern formed at a temperature of 100° C. to 350° C. to form an organic EL element partition wall or an organic EL element insulating film. The positive photosensitive resin composition disclosed herein can form a high-precision thick film pattern with high sensitivity even in an embodiment in which the positive photosensitive resin composition contains a colorant (E).

[0317] [Organic EL element partition wall]

[0318] One embodiment is an organic EL element partition wall containing a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a colorant (E).

[0319] [Organic EL element insulating film]

[0320] One embodiment is an organic EL element insulating film containing a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a colorant (E).

[0321] [Organic EL element]

[0322] One embodiment is an organic EL element containing a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a colorant (E).

[0323] Example

[0324] Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0325] (1) Raw materials

[0326] The raw materials used in Examples and Comparative Examples were produced or obtained as follows.

[0327] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were calculated using a calibration curve prepared using a polystyrene standard substance under the following measurement conditions.

[0328] Device name: Shodex (trademark) GPC-101

[0329] Column: Shodex (trademark) LF-804

[0330] Mobile phase: tetrahydrofuran

[0331] Flow rate: 1.0mL / min

[0332] Detector: Shodex (trademark) RI-71

[0333] Temperature: 40℃

[0334] [Production Example 1]

[0335] Copolymer with alkali-soluble functional groups (PCX-01): Production of copolymers of polymerizable monomers having phenolic hydroxyl groups and other polymerizable monomers

[0336] 28.0 g of 4-hydroxyphenyl methacrylate (Showa Denko KK "PQMA") and 7.89 g of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were completely dissolved in 77.1 g of 1-methoxy-2-propyl acetate (Daicel Co., Ltd.) as a solvent, and 3.66 g of V-601 (dimethyl 2,2'-azobis(2-methylpropionate), Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (Daicel Co., Ltd.). The obtained two solutions were simultaneously added dropwise to 61.2 g of 1-methoxy-2-propyl acetate (Daicel Co., Ltd.) heated to 85° C. in a 300 mL three-necked flask under a nitrogen atmosphere over 2 hours, and then reacted at 85° C. for 3 hours. The reaction solution cooled to room temperature was added dropwise to 815 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 90°C for 4 hours to recover 33.4 g of white powder. The number average molecular weight of the obtained PCX-01 was 6600 and the weight average molecular weight was 11600.

[0337] [Production Example 2]

[0338] Copolymer with alkali-soluble functional groups (PCX-02e): Production of copolymers of polymerizable monomers having phenolic hydroxyl groups and other polymerizable monomers

[0339] 25.5 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA") and 4.50 g of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were completely dissolved in 77.1 g of 1-methoxy-2-propyl acetate (Daicel Corporation) as a solvent, and 3.66 g of V-601 (dimethyl 2,2'-azobis(2-methylpropionate), Fuji Film Co., Ltd. Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (Daicel Corporation). The two solutions were added dropwise to 61.2 g of 1-methoxy-2-propyl acetate (Daicel Co., Ltd.) heated to 85°C in a 300 mL three-necked flask under a nitrogen atmosphere over 2 hours, and then reacted at 85°C for 3 hours. The reaction solution cooled to room temperature was added dropwise to 815 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 90°C for 4 hours to recover 32.4 g of white powder. The number average molecular weight of the obtained PCX-02e was 3100, the weight average molecular weight was 6700, and the phenolic hydroxyl equivalent was 210.

[0340] [Production Example 3]

[0341] Hydrophobic resin (A): Preparation of resin with silicon-containing groups (PCX-02e-TBDMS34)

[0342] 15.9 g of 4-hydroxyphenyl methacrylate (Showa Denko KK "PQMA"), 16.6 g of 4-tert-butyldimethylsiloxyphenyl methacrylate (PQMA-TBDMS) and 4.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 55.8 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent. 2.86 g of V-601 (dimethyl 2,2'-azobis(2-methylpropionate), Fuji Film Co., Ltd. Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two solutions were added dropwise to 90.5 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated to 89°C in a 300 mL three-necked flask with a reflux tube under a nitrogen atmosphere for 2 hours, and then reacted at 89°C for 4 hours. 50 g of the reaction solution cooled to room temperature was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 80°C for 5 hours to recover 9.73 g of white powder (PCX-02e-TBD MS34). The number average molecular weight of the obtained PCX-02e-TBDMS34 was 3753, and the weight average molecular weight was 7581. In PCX-02e-TBDMS34, the molar ratio of the structural unit represented by formula (3) wherein s is an integer greater than or equal to 1, the structural unit represented by formula (4), and the structural unit represented by formula (5) is formula (3): formula (4): formula (5) = 32:7:61, and the structural unit having an alkali-soluble functional group accounts for 61 mol% based on the total structural units. The content of silicon atoms is 4.0 mass% based on the mass of PCX-02e-TBDMS34.

[0343] [Production Example 4]

[0344] Hydrophobic resin (A): Preparation of resin with silicon-containing groups (PCX-02e-TES34)

[0345] 15.9 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA"), 16.6 g of 4-triethylsiloxyphenyl methacrylate (PQMA-TES), and 4.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 55.8 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent. 2.86 g of V-601 (dimethyl 2,2'-azobis(2-methylpropionate), Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two solutions were added dropwise to 90.4 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated to 89°C in a 300 mL three-necked flask with a reflux tube under a nitrogen atmosphere for 2 hours, and then reacted at 89°C for 4 hours. 50 g of the reaction solution cooled to room temperature was added dropwise to a mixed solvent of 200 g of hexane and 50 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 80°C for 5 hours to recover 9.49 g of white powder (PCX-02e-TES34). The number average molecular weight of the obtained PCX-02e-TES34 was 3847, and the weight average molecular weight was 7534. In PCX-02e-TES34, the molar ratio of the structural unit represented by formula (3) wherein s is an integer greater than or equal to 1, the structural unit represented by formula (4), and the structural unit represented by formula (5) is formula (3):formula (4):formula (5)=32:7:61, and the structural unit having an alkali-soluble functional group accounts for 61 mol% based on the total structural units. The content of silicon atoms is 4.0 mass% based on the mass of PCX-02e-TES 34.

[0346] [Production Example 5]

[0347] Hydrophobic resin (A): Preparation of resin having fluorine groups (PCX-02e-C6SFMA36)

[0348] 12.1 g of 4-hydroxyphenyl methacrylate (Showa Denko KK "PQMA"), 20.5 g of 2-perfluorohexylethyl methacrylate (Tokyo Chemical Industry Co., Ltd.), and 3.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 84.5 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent. 3.74 g of V-601 (dimethyl 2,2'-azobis(2-methylpropionate), Fuji Film Co., Ltd. Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 14.9 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two solutions were added dropwise to 51.0 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated to 89°C in a 300 mL three-necked flask with a reflux tube over 2 hours under a nitrogen atmosphere, and then reacted at 89°C for 4 hours. 50 g of the reaction solution cooled to room temperature was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 80°C for 5 hours to recover 5.58 g of white powder (PCX-02e-C6SFMA36). The number average molecular weight of the obtained PCX-02e-C6SFMA36 was 2869, and the weight average molecular weight was 5743. In PCX-02e-C6SFMA36, the molar ratio of the structural unit derived from 2-perfluorohexylethyl methacrylate, the structural unit represented by formula (4), and the structural unit represented by formula (5) is 36:6:58, and the structural unit having an alkali-soluble functional group is 58 mol% based on the total structural units. The content of fluorine atoms is 24 mass% based on the mass of PCX-02e-C6SFMA36.

[0349] [Production Example 6]

[0350] Alkali-soluble resin (B): Production of resin (N695OH70) having epoxy groups and phenolic hydroxyl groups

[0351] 75.2 g of γ-butyrolactone (Mitsubishi Chemical Corporation) as a solvent and 37.8 g of EPICLON (trademark) N-695 (DIC Corporation, cresol novolac type epoxy resin, epoxy equivalent 214) were added to a 300 mL three-necked flask and dissolved at 60° C. under a nitrogen atmosphere. 20.1 g of 3,5-dihydroxybenzoic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound (0.65 equivalents per 1 equivalent of epoxy group) and 0.166 g of triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) (0.660 mmol) as a reaction catalyst were added thereto and reacted at 110° C. for 21 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to obtain 274.2 g of a solution of a resin (N695OH70) having epoxy groups and phenolic hydroxyl groups. The obtained reactant had a number average molecular weight of 3,000, a weight average molecular weight of 5,100, an epoxy equivalent of 2,200, and a phenolic hydroxyl equivalent of 161.

[0352] [Hydrophobic resin (A)]

[0353] As the hydrophobic resin (A), PCX-02e-TBDMS34 of Production Example 3, PCX-02e-TES34 of Production Example 4 (resins having silicon groups), and PCX-02e-C6SFMA36 of Production Example 5 (resins having fluorine groups) were used.

[0354] [Alkali-soluble resin (B)]

[0355] As the alkali-soluble resin (B), N695OH70 of Production Example 6 was used.

[0356] [Quinonediazide compound (C)]

[0357] As the quinonediazide compound (C), TS-150A and TS-200A (ester of 4,4'-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylene)bisphenol (TrisP-PA) and 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid (1,2-naphthoquinonediazide-5-sulfonic acid, Toyo Gosei Kogyo Co., Ltd.) were used; TPPA(4)-150D F (1,2-naphthoquinonediazide-4-sulfonate of 4,4'-[1-4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylene]bisphenol (TrisP-PA), Toyo Gosei Kogyo Co., Ltd.); and THDPP-280 (1,2-naphthoquinonediazide-5-sulfonate of 2-(4-hydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, Toyo Gosei Kogyo Co., Ltd.).

[0358] The structures of TS-150A and TS-200A are shown below. In TS-150A, an average of 1.5 out of 3 Rs per molecule have a quinonediazide structure. In TS-200A, an average of 2.0 out of 3 Rs per molecule have a quinonediazide structure.

[0359] [Chemical formula 28]

[0360]

[0361] [Fluorine-based surfactant (D)]

[0362] As the fluorine-based surfactant (D), Megafac (trademark) F-554, Megafac (trademark) R-40, and Megafac (trademark) F-563 (all manufactured by DIC Corporation) were used.

[0363] [Cresol novolac resin]

[0364] As the cresol novolac resin, TR4080G (weight average molecular weight (Mw): 4785), TR4020G (weight average molecular weight (Mw): 9920), and TR4000B (weight average molecular weight (Mw): 3021) (all from Asahi Organic Materials Co., Ltd.) were used.

[0365] [Copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers]

[0366] As the copolymer of the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers, PCX-01 of Production Example 1 and PCX-02e of Production Example 2 were used.

[0367] As phenol novolac resins, Shonol (trademark) BRG-556 (weight average molecular weight (Mw): 558 or less, manufactured by Showa Denko K.K.), Shonol (commercial product) BRG-558 (weight average molecular weight (Mw): 3000, manufactured by Showa Denko K.K.) and BRN-5834Y (weight average molecular weight (Mw): 7400, manufactured by Showa Denko K.K.) were used.

[0368] [Colorant (E)]

[0369] As colorants, VALIFAST (trademark) BLACK 3820 (black dye specified by CI of Solvent Black 27, manufactured by Orient Chemical Industry Co., Ltd.) and VALIFAST (trademark) BLACK 3804 (black dye specified by CI of Solvent Black 34, manufactured by Orient Chemical Industry Co., Ltd.) which are black dyes were used.

[0370] [Dissolution accelerator (F)]

[0371] Phloroglucinol was used as a dissolution promoter (F).

[0372] [Solvent (G)]

[0373] As the solvent (G), a mixed solvent of γ-butyrolactone (GBL) and propylene glycol monomethyl ether acetate (PGMEA) (GBL:PGMEA=40:60 (mass ratio)) was used.

[0374] (2) Evaluation method

[0375] The evaluation methods used in Examples and Comparative Examples are as follows.

[0376] [Sensitivity]

[0377] The positive photosensitive resin composition was bar-coated on a glass substrate (size: 100 mm × 100 mm × 1 mm) in such a manner that the dry film thickness was 3.0 ± 0.3 μm, and after vacuum drying at room temperature for 60 seconds, it was pre-baked by heating at 125° C. for 120 seconds on a covered hot plate. An exposure device (trade name: Multi-Light ML-251A / B, USHIO Electric Co., Ltd.) equipped with an ultra-high pressure mercury lamp was used to expose the film through a quartz photomask (with The coating was exposed using a photomask with an opening pattern. The exposure amount was measured using an ultraviolet integrated light meter (trade name UIT-150 light receiving unit UVD-S365, USHI O Electric Co., Ltd.). After exposure, alkali development was performed for 60 seconds at 23°C using a rotary developing device (AD-1200, Takizawa Industry Co., Ltd.) using a 2.38% by mass tetramethylammonium hydroxide aqueous solution. The above steps were repeated while changing the exposure amount to achieve the minimum exposure amount (mJ / cm 2 ) as the sensitivity.

[0378] [Evaluation method of intermediate exposure portion Ra]

[0379] The positive photosensitive resin composition was bar-coated on a glass substrate (size 100 mm×100 mm×1 mm) so that the dry film thickness was 3.0±0.3 μm, and after vacuum drying at room temperature for 60 seconds, it was pre-baked by heating at 125°C for 120 seconds on a covered hot plate. The dried film was exposed through a mercury exposure bandpass filter (trade name HB0365, Asahi Spectroscopy Co., Ltd.) using an exposure device equipped with an ultra-high pressure mercury lamp (trade name Multi-Light ML-251A / B, Ushio (USHIO) Electric Co., Ltd.). The exposure amount was measured using an ultraviolet integrated light meter (trade name UIT-150 light receiving unit UVD-S365, Ushio (USHIO) Electric Co., Ltd.), and the exposure amount was adjusted to 25% of the sensitivity of each formulation. After exposure, a rotary developing device (AD-1200, Takizawa Industry Co., Ltd.) was used to develop at 23°C for 80 seconds with a 2.38% by mass tetramethylammonium hydroxide aqueous solution. Then, in an inert oven, post-baking was performed at 250°C for 60 minutes under a nitrogen atmosphere to obtain a measurement sample. The surface of the obtained sample was measured for arithmetic mean roughness Ra at a magnification of 50 times and a measurement interval of 0.02 μm using a laser microscope (VK-X200, KEYENCE Co., Ltd.) as the intermediate exposure portion Ra. Regarding the evaluation of the roughness of the intermediate exposure portion, Ra less than 0.06 was qualified, and 0.06 or more was unqualified.

[0380] [Presence or absence of fine holes in the middle exposure area]

[0381] The positive photosensitive resin composition was bar-coated on a glass substrate (size 100 mm×100 mm×1 mm) so that the dry film thickness was 3.0±0.3 μm, and after vacuum drying at room temperature for 60 seconds, it was pre-baked by heating at 125°C for 120 seconds on a covered hot plate. The dried film was exposed through a mercury exposure bandpass filter (trade name HB0365, Asahi Spectroscopy Co., Ltd.) using an exposure device equipped with an ultra-high pressure mercury lamp (trade name Multi-Light ML-251A / B, Ushio (USHIO) Electric Co., Ltd.). The exposure amount was measured using an ultraviolet integrated light meter (trade name UIT-150 light receiving unit UVD-S365, Ushio (USHIO) Electric Co., Ltd.), and the exposure amount was adjusted to 25% of the sensitivity of each formulation. After exposure, a rotary developing device (AD-1200, Takizawa Industry Co., Ltd.) was used to develop with a 2.38 mass % tetramethylammonium hydroxide aqueous solution at a temperature of 23°C for 80 seconds. Then, in an inert oven, the sample was baked at 250°C for 60 minutes under a nitrogen atmosphere to obtain a measurement sample. The obtained sample was cut into 10 mm squares, and the surface of the sample was platinum-deposited under the conditions of 25s×2 groups using a fully automatic ion coater (JFC1500, JEOL Ltd.). The sample was introduced into a FE-SEM (JSM-7600F, JEOL Ltd.) and observed at an acceleration voltage of 2.0 kV and LEI (Lower Secondary Electron Image) mode at a magnification of 15,000 times. Regarding the evaluation of the presence or absence of pores, such as Figure 1 As shown in (A) (Comparative Example 1), the case where fine holes (pores) are observed on the surface of the sample is regarded as having pores, such as Figure 1 As shown in (B) (Example 1), the case where no fine pores (fine pores) were found on the surface of the sample was regarded as having no fine pores.

[0382] [Solubility of unexposed part]

[0383] The positive photosensitive resin composition was rod-coated on a glass substrate (size 100mm×100mm×1mm) in such a way that the dry film thickness became 3.0±0.3μm, and after vacuum drying at room temperature for 60 seconds, it was pre-baked by heating at 125°C for 120 seconds on a covered hot plate. After measuring the dry film thickness using an optical film thickness measuring device (F20-NIR, Filmetrics Co., Ltd.), alkaline development was performed for 60 seconds at a temperature of 23°C using a rotary developing device (AD-1200, Takizawa Sangyo Co., Ltd.) with a 2.38 mass % tetramethylammonium hydroxide aqueous solution. The film thickness after alkaline development was measured again using an optical film thickness measuring device (F20-NIR, Filmetrics Co., Ltd.), and the film thickness (μm) dissolved before and after development was used as an indicator of the solubility of the unexposed part. The solubility of the unexposed part is 0μm, which is related to the following formula:

[0384] Residual film rate (%) = film thickness after development (μm) / film thickness before development (μm)

[0385] The residual film rate defined as 100% is equivalent.

[0386] [OD value of cured film]

[0387] The positive photosensitive resin composition was spin-coated on a glass substrate (size 100mm×100mm×1mm) in a manner that the dry film thickness was about 1.5μm, and pre-baked by heating at 125°C for 120 seconds on a hot plate. Then, it was cured at 250°C for 60 minutes under a nitrogen atmosphere to obtain a coating. The OD value of the cured coating was measured using a transmission density meter (BMT-1, SAKATA INX ENG Co., Ltd.), and only the OD value of the glass was used for correction, and converted into the OD value of the coating per 1μm thickness. The thickness of the coating was measured using an optical film thickness measuring device (F20-NIR, Filmetrics Co., Ltd.).

[0388] (3) Preparation and evaluation of positive photosensitive resin composition

[0389] [Examples 1 to 14, Comparative Examples 1 to 4]

[0390] In a solution obtained by mixing and dissolving the resin component and the phenol novolac resin in a solvent (G) according to the composition described in Table 1, the quinonediazide compound (C), fluorine-based surfactant (D), colorant (E) and dissolution accelerator (F) described in Table 1 are added and further mixed. After visually confirming that the components have dissolved, filter with a microporous filter with a pore size of 0.22μm to prepare a positive photosensitive resin composition with a solid content concentration of 12% by mass. The mass parts of the composition in Table 1 are solid content conversion values. The evaluation results of the positive photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4 are shown in Table 1.

[0391] According to the evaluation results in Table 1, since the solubility of the unexposed part of the positive photosensitive resin composition of Examples 1 to 14 is 0 μm, the contrast between the exposed part and the unexposed part can be increased, and the surface roughness of the intermediate exposed part is small, and no pores are observed, so it is judged that a thick film pattern with a step structure can be formed with high precision. Furthermore, the exposure amount that can form a pattern with a pore diameter of 10 μm after development is 300 mJ / cm 2 The following also confirmed high sensitivity. In contrast, the positive photosensitive resin compositions of Comparative Examples 1 to 3 in which phenol novolac resin was added instead of cresol novolac resin, and the positive photosensitive resin composition of Comparative Example 4 in which cresol novolac resin was not added, had unqualified Ra (above 0.06) in the intermediate exposure portion, and pores were observed on the sample surface. In the case of phenol novolac resin, since there is no alkyl group on the benzene ring, it is soluble in the alkali-soluble resin (B) but not in the hydrophobic resin (A), and as a result, it is presumed that there is no effect of alleviating the phase separation of the two. It can be confirmed that by adding cresol novolac resin, the surface roughness of the step portion and the generation of pores can be suppressed.

[0392] [Table 1-1]

[0393] Table 1 (composition in parts by mass)

[0394]

[0395]

[0396]

[0397] [Table 1-2] (Continued from Table 1)

[0398]

[0399]

[0400] Industrial Applicability

[0401] The positive photosensitive resin composition of the present disclosure can be suitably used for radiation lithography for forming partition walls or insulating films of organic EL elements. In particular, an organic EL element having a partition wall or insulating film formed from a positive photosensitive resin composition of an embodiment containing a colorant (E) is suitable for use as an electronic component of a display device showing good contrast.

Claims

1. A positive photosensitive resin composition comprising: A hydrophobic resin (A) as an addition (co)polymer; an alkali-soluble resin (B) having a structural unit represented by formula (1); Quinonediazide compounds (C); a fluorine-based surfactant (D); and Cresol novolac resin, [Chemical formula 1] In formula (1), x is an integer from 0 to 3, R 1 are each independently an alkyl group having 1 to 5 carbon atoms, R 2 It is an organic group having an alkali-soluble functional group.

2. The positive photosensitive resin composition according to claim 1, wherein In the formula (1), the alkali-soluble functional group is a phenolic hydroxyl group.

3. The positive photosensitive resin composition according to claim 1, wherein The alkali-soluble resin (B) further has a structural unit represented by formula (2), [Chemical formula 2] In formula (2), y is an integer from 0 to 3, R 3 are each independently an alkyl group having 1 to 5 carbon atoms, R 4 It is an organic group having no alkali-soluble functional group.

4. The positive photosensitive resin composition according to claim 3, wherein In the formula (2), R 4 It is an organic group having an epoxy group.

5. The positive photosensitive resin composition according to claim 3 or 4, wherein The alkali-soluble resin (B) contains the structural unit represented by the formula (1) and the structural unit represented by the formula (2) in an amount of 30 mol% to 100 mol% in total based on all structural units of the alkali-soluble resin (B).

6. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein The weight average molecular weight (Mw) of the cresol novolac resin is 500 to 17,500.

7. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein The cresol novolac resin is contained in an amount of 0.5% by mass to 35% by mass based on the total mass of the resin components.

8. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein The hydrophobic resin (A) is a resin having at least one selected from the group consisting of a silicon-containing group and a fluorine-containing group.

9. The positive photosensitive resin composition according to claim 8, wherein The hydrophobic resin (A) has a structural unit represented by formula (3), [Chemical formula 3] In formula (3), R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 6 By SiR 7 R 8 R 9 Indicates that R 7 , R 8 and R 9 are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 5, s is an integer of 0 to 5, but r+s is an integer of 1 to 5, There is at least one structural unit represented by the formula (3) wherein s is an integer of 1 or more.

10. The positive photosensitive resin composition according to claim 9, wherein The hydrophobic resin (A) further has a structural unit represented by formula (4), [Chemical formula 4] In formula (4), R 10 and R 11 are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 12 It is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

11. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein The fluorine-based surfactant (D) contains an acrylic copolymer having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group.

12. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein The positive photosensitive resin composition further contains an alkali-soluble resin which is a copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers and does not have a structural unit represented by the formula (1).

13. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein The positive photosensitive resin composition further contains at least one colorant (E) selected from the group consisting of a black dye and a black pigment.

14. The positive photosensitive resin composition according to claim 13, wherein The positive photosensitive resin composition contains 10 to 150 parts by mass of the colorant (E) based on 100 parts by mass of the total resin components.

15. The positive photosensitive resin composition according to claim 13, wherein The optical density (OD value) of the cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness. 16 . An organic EL element partition wall comprising a cured product of the positive photosensitive resin composition according to claim 1 . 17 . An organic EL element insulating film comprising a cured product of the positive photosensitive resin composition according to claim 1 . 18 . An organic EL device comprising a cured product of the positive photosensitive resin composition according to claim 1 .

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