Photosensitive resin composition for forming underlayer film of resist film

Abstract

To provide a photosensitive resin composition for forming an underlayer of a resist film.SOLUTION: A photosensitive resin composition for forming an underlayer of a resist film contains the following component (A), component (C), and component (D). The component (A) is an alkali-soluble resin with an amide group (where the amide group is derived from at least one monomer selected from acrylamide and methacrylamide), component (C) is a solvent, and component (D) is a photosensitizer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for forming a bank pattern of a cured film obtained from a photosensitive resin composition. The method for forming a bank pattern of a cured film using the photosensitive resin composition is particularly suitable as a method for forming an interlayer insulating film in a liquid crystal display or an EL display, or a light-shielding wall or partition wall compatible with an inkjet system. [Background technology]

[0002] In recent years, full-color display substrate fabrication technology using inkjet has been actively studied in the fabrication process of display elements such as thin-film transistor (TFT) type liquid crystal display elements and organic electroluminescent (EL) elements. For example, in relation to the fabrication of color filters in liquid crystal display elements, in contrast to the conventional printing method, electrodeposition method, dyeing method or pigment dispersion method, a color filter and its fabrication method (Patent Document 1) have been proposed in which a partition (hereinafter referred to as a bank) that defines a patterned pixel is formed in advance using a light-blocking photosensitive resin layer, and ink droplets are dropped into the area surrounded by this bank. Also, in the case of organic EL display elements, a method has been proposed in which a bank is formed in advance, and ink that will become a light-emitting layer is similarly dropped to fabricate the organic EL display element (Patent Document 2).

[0003] Also, in order to increase the contrast and improve visibility in an organic EL display device, attempts have been made to mix a pigment into the bank material to impart light blocking properties. Also, attempts have been made to mix fine particles into the bank material in order to improve the resolution of the bank material. Also, attempts have been made to mix fine particles into the photosensitive resin composition in order to improve the refractive index and transparency of the photosensitive resin composition. However, in all of these methods, there is a problem in that the residue of the added pigment or fine particles remains in the pattern openings, which can cause defects in the organic EL display device.

[0004] As a method for suppressing residues at the openings of the bank, a method has been proposed in which a layer containing a hydrophilic compound is provided under the liquid-repellent bank material, and this is developed and removed together with the upper layer of the bank material to prevent contamination of the bank openings, which should be liquid-philic, by the components of the bank material (Patent Documents 5 to 7). However, this method has problems such as the pattern peeling off due to the high hydrophilicity of the lower layer, which is prone to moisture absorption.

[0005] As a method for suppressing residues in the openings of the bank, a method has been proposed in which an organic layer is provided under a liquid-repellent bank material, and after forming a pattern with the upper layer of the bank material, the lower layer is removed by a dry etching process to improve the lyophilicity of the bank openings (Patent Document 8). However, this method has the problem of being complicated.

[0006] In addition, Patent Documents 9 and 10 have proposed a method for forming a pattern by performing one exposure step and one development step on two laminated organic layers. However, neither of these methods aims to suppress residues at the opening of the pattern. In addition, in the method of Patent Document 9, the lower organic layer does not have photosensitivity, so precise process control is required to control the dimensions of the pattern. In the method of Patent Document 10, a heat treatment is required after the exposure step, making the process complicated. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2000-187111 A [Patent Document 2] Japanese Patent Application Publication No. 11-54270 [Patent Document 3] JP 2000-353594 A [Patent Document 4] Japanese Patent Application Publication No. 10-197715 [Patent Document 5] JP 2010-33925 A [Patent Document 6] JP 2010-73340 A [Patent Document 7] JP 2010-129344 A [Patent Document 8] JP 2011-216250 A [Patent Document 9] Patent No. 4182358 [Patent Document 10] Patent No. 5083566 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention provides a method for forming a bank pattern in which residues of pigments, fine particles, components of liquid-repellent resist materials, etc. are unlikely to remain in areas other than the bank, even when using a bank containing pigments or fine particles that can improve the performance of a display element, or a liquid-repellent bank that is process-friendly and advantageous in terms of production costs. [Means for solving the problem]

[0009] The present inventors have found that a first photosensitive resin composition containing an alkali-soluble resin having an amide group is applied directly or through another layer onto a substrate to provide an underlayer film, a second photosensitive resin composition containing a polymer or fine particles as a liquid-repellent component is applied onto the underlayer film to provide a resist film, and the resist film is exposed and developed to form a bank. In this development process, the underlayer film in the non-bank portion is removed together with the resist film in the non-bank portion, thereby reducing the amount of resist film residue containing the liquid-repellent component, fine particles, etc. on the substrate and efficiently imparting water repellency and liquid repellency to the film surface while maintaining the lyophilicity of the openings, and have completed the present invention. Here, the area on the substrate where the banks are located is referred to as a bank portion, and the area other than the banks is referred to as a non-bank portion.

[0010] That is, the present invention relates to the following. 1. A method for forming a bank and an area defined by the bank on a substrate, the method comprising the steps of: forming a bank pattern for forming an organic thin film in the area defined by the bank, the method comprising the steps of: an underlayer film forming step of applying a first photosensitive resin composition containing the following components (A), (C) and (D) directly onto a substrate or via another layer to provide an underlayer film; a resist film forming step of coating a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the underlayer film to provide a resist film; a bank forming step of forming banks by exposing and developing the resist film, and removing the underlying film in the non-bank portions together with the resist film in the non-bank portions during the development process. Component (A): an alkali-soluble resin having an amide group, (C) component: solvent, (D) component: photosensitizer, (a) component: alkali-soluble resin, (b) Component: fine particles, (c) component: solvent, (d) Ingredient: Photosensitizer. 2. The method for forming a bank pattern according to the above item 1, wherein component (b) is inorganic fine particles. 3. The method for forming a bank pattern according to the above 1, wherein the component (b) is fine particles containing a colorant. 4. The method for forming a bank pattern according to any one of the above 1 to 3, wherein the average particle size of the component (b) is 5 nm to 1000 nm. 5. The method for forming a bank pattern according to any one of the above items 1 to 4, wherein the first photosensitive resin composition satisfies at least one of the following (Z1) to (Z4): (Z1): The first photosensitive resin composition further contains a crosslinking agent as a component (E); (Z2): The alkali-soluble resin having an amide group of the component (A) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group; (Z3): A photoradical generator in which the component (D) is (D-2) and further contains a compound having two or more ethylenic double bonds as the component (F); (Z4): A photoacid generator in which the component (D) is (D-3), and which further contains, as the component (G), a compound having two or more functional groups that form a covalent bond with the acid generated from the component (D). 6. The second photosensitive resin composition comprises at least one of the following (z1) to (z4): The method for forming a bank pattern according to any one of the above items 1 to 5, further comprising: (z1): a crosslinking agent as a component (e); (z2): The alkali-soluble resin of the component (a) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group; (z3): A photoradical generator in which the component (d) is (d-2) and further contains a compound having two or more ethylenic double bonds as the component (f); (z4): A photoacid generator in which the component (d) is (d-3) and which further contains, as the component (g), a compound having two or more functional groups that form a covalent bond with the acid generated from the component (d). 7. The method for forming a bank pattern according to any one of the above 1 to 4, wherein the component (D) and / or (d) is a quinone diazide compound. 8. The method for forming a bank pattern as described in 5 above, wherein the component (D) is a quinone diazide compound and further satisfies either (Z1) and / or (Z2) above. 9. The method for forming a bank pattern as described in 6 above, wherein the component (d) is a quinone diazide compound and further satisfies either (z1) and / or (z2). 10. The method for forming a bank pattern according to the above item 8, wherein the component (D) is diazonaphthoquinone. 11. The method for forming a bank pattern as described in 9 above, wherein the component (d) is diazonaphthoquinone. 12. The method for forming a bank pattern according to any one of the above items 1 to 11, wherein the second photosensitive resin composition further contains the following component (h): Component (h): a polymer having a liquid repellent group (h1), 13. The method for forming a bank pattern as described in the above item 12, wherein the component (h) is a polymer further having the following (h2): (h2): at least one group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group. 14. The method for forming a bank pattern as described in 12 or 13 above, wherein the component (h) is a polymer further having the following (h3): (h3): at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group. 15. A method for forming a bank pattern described in any one of claims 12 to 14 above, wherein the liquid-repellent group (h1) of component (h) is at least one group selected from the group consisting of a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group represented by formula 5. -(SiR 1 R 2 -O) n -SiR 1 R 2 R 3 ...Formula 5 (However, R 1 , R 2 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group; R 3 represents hydrogen or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200. 16. The method for forming a bank pattern according to any one of the above 12 to 15, wherein the polymer of component (h) is an acrylic polymer. 17. The method for forming a bank pattern as described in the above item 16, wherein the acrylic polymer of component (h) has a number average molecular weight of 2,000 to 100,000 in terms of polystyrene. 18. The method for forming a bank pattern according to any one of claims 12 to 17, characterized in that component (h) accounts for 0.1 to 20 parts by mass per 100 parts by mass of component (a). 19. The method for forming a bank pattern according to any one of 1 to 11 above, wherein the component (a) is a resin having a liquid repellent group (h1) and does not contain the component (h). 20. The method for forming a bank pattern as described in 19 above, characterized in that the polymerized unit having the liquid repellent group (h1) accounts for 5 to 30 parts by mass in 100 parts by mass of the component (a). 21. A method for forming a bank pattern described in any one of claims 1 to 20, wherein the number average molecular weight of the alkali-soluble resin having an amide group (A) and / or the alkali-soluble resin (a) is 2,000 to 50,000 in terms of polystyrene. 22. A method for forming a bank pattern described in any one of claims 1 to 21 above, characterized in that the composition contains 5 to 500 parts by weight of component (b) per 100 parts by weight of component (a). 23. The method for forming a bank pattern described in any one of claims 5 to 22, characterized in that the amount of component (E) is 1 part by mass to 50 parts by mass per 100 parts by mass of component (A). 24. The method for forming a bank pattern according to any one of the above items 1 to 23, wherein the other layer is an organic electroluminescent hole injection layer. 25. A cured film formed by the method for forming a bank pattern according to any one of 1 to 24 above. 26. A display device having the cured film according to 25 above. 27. A display device having the cured film according to 25 above as a partition for image formation. 28. A photosensitive resin composition for forming an underlayer film of a resist film, comprising the following components (A), (C) and (D): Component (A): an alkali-soluble resin having an amide group, (C) component: solvent, (D) Ingredient: Photosensitizer. 29. The method according to claim 28, wherein the component (D) is a quinone diazide compound. For forming the undercoat of resist filmPhotosensitive resin composition. 30. The method according to claim 29, wherein the component (D) is diazonaphthoquinone. For forming the undercoat of resist film Photosensitive resin composition. 31. The method according to claim 28, which satisfies at least one of the following (Z1) to (Z4): For forming the undercoat of resist film Photosensitive resin composition. (Z1): Further containing a crosslinking agent as the component (E); (Z2): The alkali-soluble resin having an amide group of the component (A) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group; (Z3): A photoradical generator in which the component (D) is (D-2) and further contains a compound having two or more ethylenic double bonds as the component (F); (Z4): A photoacid generator in which the component (D) is (D-3), and which further contains, as the component (G), a compound having two or more functional groups that form a covalent bond with the acid generated from the component (D). 32. The composition according to claim 31, wherein the component (D) is a quinone diazide compound and satisfies either (Z1) or (Z2). For forming the undercoat of resist film Photosensitive resin composition. 33. The method according to claim 32, wherein the component (D) is diazonaphthoquinone. For forming the undercoat of resist film Photosensitive resin composition. 34. The composition according to any one of claims 28 to 33, wherein the number average molecular weight of the alkali-soluble resin having an amide group of component (A) is 2,000 to 50,000 in terms of polystyrene. For forming the undercoat of resist film Photosensitive resin composition. 35. The composition according to any one of claims 31 to 34, characterized in that the amount of component (E) is 1 to 50 parts by mass per 100 parts by mass of component (A). For forming the undercoat of resist film Photosensitive resin composition. 36. The method according to any one of claims 28 to 35 above. For forming the undercoat of resist film A cured film formed from a photosensitive resin composition. 37. A display element having the cured film according to 36 above. 38. A display device having the cured film according to 36 above as a partition for forming an image. Effect of the Invention

[0011] According to the method for forming a bank pattern of the present invention, even if a bank containing a pigment or fine particles that can improve the performance of a display element or a liquid-repellent bank that is easy to process and advantageous in terms of production costs is used, it is possible to form a bank pattern that improves the lyophilicity of the substrate surface by suppressing the residue of resist materials such as liquid-repellent components and fine particles on the substrate surface in non-bank areas. In other words, a uniform organic thin film can be formed within the area partitioned by the bank. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic cross-sectional view showing a manufacturing method for forming banks and areas partitioned by the banks on a substrate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The method for forming a bank pattern according to the present invention will now be described in detail. The method for forming a bank pattern of the present invention is a method for forming a bank and an area defined by the bank on a substrate, the method comprising the steps of: an underlayer film forming step of applying a first photosensitive resin composition containing the following components (A), (C) and (D) directly onto a substrate or via another layer to provide an underlayer film; a resist film forming step of coating a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the underlayer film to provide a resist film; The resist film is exposed to light and developed to form banks, and during the development process the underlying film in the non-bank portions is removed together with the resist film in the non-bank portions to form a bank. Component (A): Alkali-soluble resin having an amide group (C) Component: Solvent (D) Ingredient: Photosensitizer (a) Component: Alkali-soluble resin (b) Component: Fine particles (c) Ingredient: Solvent (d) Ingredient: Photosensitizer

[0014] In the second photosensitive resin composition of the present invention, the component (b) is preferably inorganic fine particles. In the second photosensitive resin composition of the present invention, the component (b) is preferably fine particles containing a colorant. In the second photosensitive resin composition of the present invention, the average particle size of component (b) is preferably from 1 nm to 1000 nm.

[0015] It is preferable that the first photosensitive resin composition of the present invention further satisfies at least one of the following (Z1) to (Z4). (Z1): Further containing a crosslinking agent as the component (E); (Z2): The alkali-soluble resin having an amide group of the component (A) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group; (Z3): A photoradical generator in which the component (D) is (D-2), and further in which the component (F) and and containing a compound having two or more ethylenically polymerizable groups; (Z4): A photoacid generator in which the component (D) is (D-3), and which further contains, as the component (G), a compound having two or more functional groups that form a covalent bond with the acid generated from the component (D-3).

[0016] It is preferable that the second photosensitive resin composition of the present invention further satisfies at least one of the following (z1) to (z4). (z1): Further containing a crosslinking agent which is the component (e); (z2): The alkali-soluble resin of the component (a) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group; (z3): A photoradical generator in which the component (d) is (d-2) and further contains a compound having two or more ethylenically polymerizable groups as the component (f); (z4): A photoacid generator in which the component (d) is (d-3), and which further contains, as a component (g), a compound having two or more functional groups that form a covalent bond with the acid generated from the component (d-3).

[0017] The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition in which the component (D) and / or (d) is diazonaphthoquinone.

[0018] The method for forming a bank pattern of the present invention will now be described with reference to FIG.

[0019] <Lower film formation process> In the manufacturing method of the present invention, first, a first photosensitive resin composition comprising a monomer having an amide group and a monomer having an alkali-soluble group, which will be described later, is applied directly or through another layer to a substrate 11, and then prebaked to provide an underlayer film 12 that is not liquid repellent.

[0020] Each component of the underlayer film will be described in detail below.

[0021] <Component (A)> The component (A) of the present invention is an alkali-soluble resin having an amide group. The amide group forms hydrogen bonds within or between molecules, and when the upper resist film described below is applied, the resin exhibits resistance to the solvent. The upper resist film does not come into contact with the substrate at the time of application. The resin of component (A) contains an alkali-soluble group to impart alkali solubility, and examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid group, a boronic acid group, an active methylene group, and an active methine group. The phenolic hydroxyl group and the carboxyl group are alkali-soluble groups, and are also heat-reactive sites (sites that can form a crosslinked structure with the crosslinking agent of component (E)) as described below. In addition, the component (A) is not particularly limited in terms of other structure or functional groups contained therein, so long as it is an alkali-soluble resin having the above-mentioned amide group. For example, when the component (A) contains a compound having two or more functional groups that form a covalent bond with an acid (G) described later, the component (A) may not have a reactive site with the component (G), and when the component (A) has a reactive site with the component (G), the reactive site is not particularly limited as long as it is a group that can form a covalent bond with the component (G) by the action of an acid, or a group that can form a covalent bond with the component (G) by heating.

[0022] Here, the active methylene group refers to a methylene group (-CH2-) that has a carbonyl group adjacent to it and is reactive to nucleophiles. In the present invention, the active methine group refers to an active methylene group having a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group and is reactive to nucleophiles.

[0023] Among active methylene groups and active methine groups, active methylene groups are preferred, and active methylene groups represented by the following formula (A1) are more preferred. [ka] (In formula (A1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the dashed line represents a bond.)

[0024] In the above formula (A1), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferred. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. Of these, a methyl group, an ethyl group, an n-propyl group, etc. are preferred.

[0025] In the above formula (A1), examples of the alkoxy group represented by R include alkoxy groups having 1 to 20 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are preferred. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy and t-butoxy groups. Among these, a methoxy group, an ethoxy group, an i-propoxy group, an n-propoxy group, and the like are preferable.

[0026] Examples of the group represented by the above formula (A1) include the following structures: In the structural formula, the dashed lines represent bonds. [ka]

[0027] Among the alkali-soluble resins of the component (A) above, an alkali-soluble resin having an amide group and at least one group selected from the group consisting of a phenolic hydroxy group and a carboxyl group as an alkali-soluble group, and having a number average molecular weight of 2,000 to 50,000 is preferred.

[0028] The alkali-soluble resin of the component (A) may be any alkali-soluble resin having such a structure, and there are no particular limitations on the type of main chain skeleton and side chains of the polymer constituting the resin.

[0029] However, the number average molecular weight of the alkali-soluble resin of component (A) is within the range of 2,000 to 50,000. If the number average molecular weight is too high, exceeding 50,000, development residues are likely to be generated and sensitivity is significantly reduced, while if the number average molecular weight is too low, less than 2,000, a considerable amount of film loss occurs in exposed areas during development, and curing may be insufficient.

[0030] Examples of the alkali-soluble resin of the component (A) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, polyimides, etc. Among these, preferred resins include acrylic resins (acrylic polymers).

[0031] In the present invention, an alkali-soluble resin made of a copolymer obtained by polymerizing a plurality of types of monomers (hereinafter referred to as a specific copolymer) can also be used as component (A). In this case, the alkali-soluble resin of component (A) may be a blend of a plurality of specific copolymers.

[0032] That is, the above-mentioned specific copolymer is a copolymer formed by using, as essential constituent units, a monomer having an amide group, a monomer exhibiting alkali solubility, i.e., a monomer having at least one group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group as a suitable alkali soluble group, and, if desired, at least one monomer selected from the group of monomers copolymerizable with these monomers, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is more than 50,000, residues may be generated. The monomer having an amide group may also have an alkali-soluble group.

[0033] Examples of the monomer having an amide group include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-phenylmethacrylamide, N-phenylacrylamide, 4-hydroxyphenylmethacrylamide, 4-hydroxyphenylacrylamide, etc., which may be used alone or in combination of two or more. Among them, methacrylamide is preferred.

[0034] The above "monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group" includes a monomer having a carboxyl group and a monomer having a phenolic hydroxyl group. These monomers are not limited to those having one carboxyl group or one phenolic hydroxyl group, and may have multiple carboxyl groups or one phenolic hydroxyl group.

[0035] Specific examples of the monomer are given below, but the monomer is not limited thereto. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

[0036] Examples of monomers having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and 4-hydroxyphenyl methacrylate.

[0037] In the production of the alkali-soluble resin (specific copolymer) of component (A), the ratio of monomers that exhibit alkali solubility, for example, a monomer consisting of a carboxyl group and a phenolic hydroxyl group, is determined. The ratio of the monomer having at least one group selected from the group is preferably 5% by mass or more, more preferably 10% by mass or more, of all the monomers used in the production of the alkali-soluble resin (specific copolymer) of component (A). If the monomer exhibiting alkali solubility (monomer having at least one group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group) is less than 5% by mass, the alkali-soluble resin (acrylic polymer) will have insufficient alkali solubility.

[0038] In the alkali-soluble resin of component (A), the amount of amide groups introduced is preferably 5 to 60% by mass, more preferably 5 to 40% by mass, based on all repeating units. For example, in the production of a specific copolymer, the ratio of monomers having amide groups to all monomers used in the production of the specific copolymer can be, for example, 5 to 40% by mass.

[0039] The alkali-soluble resin, which is the component (A) of the present invention, is preferably one which is further copolymerized with a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, in order to further stabilize the pattern shape after curing.

[0040] Examples of monomers having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

[0041] In the production of the alkali-soluble resin (specific copolymer) of component (A), the ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group to all monomers used in the production of the specific copolymer is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, and most preferably 20% to 40% by mass. If the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 5% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If it is 60% by mass or more, the ratio of the alkali-soluble group of component (A) may be insufficient, and characteristics such as developability may be deteriorated.

[0042] The alkali-soluble resin, which is the component (A) of the present invention, can also be copolymerized with an N-substituted maleimide compound in order to increase the Tg of the copolymer.

[0043] Examples of N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, compounds having no aromatic ring are preferred, and from the viewpoints of developability, transparency, and heat resistance, compounds having an alicyclic skeleton are more preferred, and among these, cyclohexylmaleimide is most preferred.

[0044] In the production of the alkali-soluble resin (specific copolymer) of the component (A), the ratio of N-substituted maleimide to all monomers used in the production of the specific copolymer is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. If the N-substituted maleimide is less than 5% by mass, the effect of improving the Tg of the copolymer may not be obtained. If it is more than 60% by mass, the solubility in the solvent may decrease.

[0045] When the first photosensitive resin composition of the present invention satisfies the requirement (Z2), the alkali-soluble resin (A) used in the present invention further has a self-crosslinking group or a hydroxyl group, a carboxy ... It is preferable that the copolymer further has a group (hereinafter also referred to as a crosslinkable group) that reacts with at least one group selected from the group consisting of a carboxyl group, an amide group, and an amino group. For example, the requirement (Z2) can be satisfied by introducing a repeating unit having at least one group selected from the group consisting of the self-crosslinkable group and the crosslinkable group into the alkali-soluble resin (A).

[0046] Examples of the self-crosslinking group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group, and a blocked isocyanate group.

[0047] Examples of the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group.

[0048] When such self-crosslinking groups or crosslinkable groups are contained in the alkali-soluble resin of component (A), the content of the self-crosslinking groups or units having crosslinkable groups is preferably 10% by mass to 70% by mass, and particularly preferably 20% by mass to 60% by mass, based on the total of all repeating units in the resin of component (A).

[0049] When the alkali-soluble resin of component (A) further has a repeating unit having at least one self-crosslinking group selected from an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group, a blocked isocyanate group, and the like, and a crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a blocked isocyanate group, and the like, for example, an unsaturated compound (monomer) having radical polymerizability and having at least one crosslinking group selected from an epoxy group, an oxetanyl group, a vinyl group, a blocked isocyanate group, and the like, and a self-crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, a alkoxysilyl group, and the like may be copolymerized.

[0050] Examples of the radically polymerizable monomer having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide.

[0051] Examples of the monomer having radical polymerizability and further having an N-hydroxymethyl group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

[0052] Examples of the monomer having radical polymerization properties and further having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.

[0053] Examples of monomers having radical polymerization properties and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate, α-n-propyl acrylate, α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. Among these, glycidyl methacrylate, methacrylate, and glycidyl methacrylate are particularly preferred. Preferred examples of the compounds that can be used include 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate. These can be used alone or in combination.

[0054] Examples of the monomer having radical polymerizability and further having an oxetanyl group include (meth)acrylic acid esters having an oxetanyl group. In this specification, the term "(meth)acrylic acid" refers to both acrylic acid and methacrylic acid. Among such monomers are 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxymethyl)-4-trifluoromethyloxetane are preferred, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, etc. are preferably used.

[0055] Examples of the monomer having radical polymerizability and further having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

[0056] Examples of the monomer having radical polymerizability and further having a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.

[0057] When the first photosensitive resin composition of the present invention satisfies (Z2), it contains a structural unit derived from a monomer (unsaturated compound) having radical polymerizability and having at least one group selected from self-crosslinking groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetanyl groups, vinyl groups, and blocked isocyanate groups, and crosslinking groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups, preferably 10% by mass to 70% by mass, particularly preferably 20% by mass to 60% by mass, based on the total of all repeating units contained in the alkali-soluble resin (A). If the amount of this structural unit is less than 10% by mass, the heat resistance and surface hardness of the obtained cured film tend to decrease, while if the amount of this structural unit exceeds 70% by mass, the storage stability of the photosensitive resin composition tends to decrease.

[0058] In the present invention, the alkali-soluble resin (specific copolymer, for example, acrylic polymer) of the component (A) may be a copolymer formed using monomers other than the above-mentioned monomers (hereinafter referred to as other monomers) as structural units. Specifically, the other monomers may be those that are copolymerizable with at least one selected from the group consisting of the above-mentioned monomers having a carboxyl group and monomers having a phenolic hydroxyl group, and are not particularly limited as long as they do not impair the properties of the component (A). Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, N-substituted acrylamide compounds, maleimides, acrylonitrile, styrene compounds, and vinyl compounds. Specific examples of the other monomers are given below, but the present invention is not limited thereto.

[0059] Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxy ...2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-eth acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloyloxy)ethyl ester, and poly(ethylene glycol) ethyl ether acrylate.

[0060] Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, and poly(ethylene glycol) ethyl ether methacrylate.

[0061] Examples of the N-substituted acrylamide compounds include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide.

[0062] Examples of the styrene compound include styrenes having no hydroxy group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

[0063] Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0064] In the production of the alkali-soluble resin (specific copolymer) which is the component (A), the ratio of the above other monomers to all monomers used in the production of the specific copolymer is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 20% by mass or less. If it exceeds 80% by mass, the essential components (essential monomers constituting the component (A)) are relatively reduced, making it difficult to fully obtain the effects of the present invention.

[0065] The method for obtaining the alkali-soluble resin (specific copolymer) which is the component (A) used in the present invention is not particularly limited, but for example, a monomer having a group selected from an amide group and a carboxyl group and at least one group selected from a carboxyl group, a phenolic hydroxyl group, etc., which is an alkali-soluble group, and a monomer having a hydroxyalkyl group, if desired, an N-substituted maleimide compound, and a monomer having at least one group selected from a self-crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group, and a blocked isocyanate group, etc., and a crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group, if desired, other copolymerizable monomers, and if desired, a polymerization initiator, etc., are coexisted in a solvent at a temperature of 50 to 110 ° C. to obtain the resin. In this case, the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble resin (specific copolymer) and the alkali-soluble resin (specific copolymer). Specific examples include the solvents described below in relation to component (C).

[0066] The alkali-soluble resin (specific copolymer) of component (A) thus obtained is usually in the form of a solution dissolved in a solvent. In the present invention, the solution of the alkali-soluble resin (specific copolymer) of component (A) obtained may be used as it is for the preparation of a photosensitive resin composition described later.

[0067] In addition, the solution of the alkali-soluble resin (specific copolymer) of component (A) obtained as described above can be reprecipitated by adding it to diethyl ether, water, or the like under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the specific copolymer. By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. If the specific copolymer cannot be sufficiently purified by a single operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated. In the present invention, the powder of the specific copolymer may be used as it is as the alkali-soluble resin of component (A), or the powder may be redissolved in, for example, component (C) described below and used in the form of a solution.

[0068] In addition, the alkali-soluble resin of component (A) may be a polyimide precursor such as polyamic acid, polyamic acid ester, or partially imidized polyamic acid, or a polyimide such as a carboxylic acid group-containing polyimide, and the like. There are no particular limitations on the type of these that may be used as long as they are alkali-soluble.

[0069] The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensation of (i) a tetracarboxylic dianhydride compound and (j) a diamine compound.

[0070] The (a) tetracarboxylic acid dianhydride compound is not particularly limited, and specific examples thereof include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, and 3,3',4,4'-diphenyl sulfone tetracarboxylic acid dianhydride; alicyclic tetracarboxylic acids such as 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-cyclohexane tetracarboxylic acid dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride. Acid dianhydrides: aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride can be mentioned. These may be used alone or in combination of two or more compounds.

[0071] The diamine compound (j) is not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3,5-dicarboxyphenyl)ether, bis(4-amino-3-carboxyphenyl)sulfone, bis(4-amino-3,5-dicarboxyphenyl)sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl ... diamine compounds having a carboxyl group, such as 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxyphenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, and 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane;2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl)ether, bis(4-amino-3-hydroxyphenyl)ether, bis(4-amino-3,5-dihydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl)methane, bis (3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(4-amino-3,5-dihydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-di Hydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]sulfone, bis[4-(3-amino-4-hydrox- yphenoxy)phenyl]sulfone, diamine compounds having a phenolic hydroxy group, such as 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, and 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane; diamine compounds having a thiophenol group, such as 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, and 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane;Examples of diamine compounds having a sulfonic acid group include 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis(4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, and 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. In addition, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6; -Tetramethyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3',5,5'-tetramethylbenzidine, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-anilino) Examples of diamine compounds include hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4-toluyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 2,2'-bis(trifluoromethyl)benzidine. These may be used alone or in combination of two or more compounds.

[0072] When the polyamic acid used in the present invention is produced from (i) a tetracarboxylic dianhydride compound and (j) a diamine compound, the compounding ratio of the two compounds, i.e., the total number of moles of (j) the diamine compound / the total number of moles of (i) the tetracarboxylic dianhydride compound, is preferably 0.7 to 1.2. As in a normal polycondensation reaction, the closer this molar ratio is to 1, the greater the polymerization degree of the polyamic acid produced, and the greater the molecular weight.

[0073] In addition, when polymerization is carried out using an excess of a diamine compound, the terminal amino groups of the remaining polyamic acid can be protected by reacting them with a carboxylic acid anhydride. Examples of such carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

[0074] In the production of polyamic acid, the reaction temperature for the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from the range of −20 to 150° C., preferably −5 to 100° C. To obtain a high molecular weight polyamic acid, the reaction temperature is appropriately selected from the range of 5° C. to 40° C. and the reaction time is appropriately selected from the range of 1 to 48 hours. To obtain a low molecular weight, partially imidized polyamic acid with high storage stability, it is more preferable to select the reaction temperature from 40° C. to 90° C. and the reaction time from 10 hours or more. When the terminal amino group is protected with an acid anhydride, the reaction temperature can be selected from the range of -20 to 150°C, preferably -5 to 100°C.

[0075] The reaction of the diamine compound with the tetracarboxylic dianhydride compound can be carried out in a solvent. Examples of the solvent that can be used at that time include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethylene glycol monomethyl ether. Examples of suitable solvents include ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These may be used alone or in combination. Furthermore, even if the solvent does not dissolve polyamic acid, it may be mixed with the above solvent as long as the polyamic acid produced by the polymerization reaction does not precipitate.

[0076] The thus obtained solution containing the polyamic acid can be used as it is for the preparation of a photosensitive resin composition, or the polyamic acid can be recovered and used by precipitating and isolating it in a poor solvent such as water, methanol, or ethanol.

[0077] Any polyimide can also be used as component (A). The polyimide used in the present invention is a polyimide precursor such as the polyamic acid described above that is chemically or thermally imidized to 50% or more.

[0078] The polyimide used in the first photosensitive resin composition of the present invention preferably has an amide group and, in order to impart alkali solubility, a group selected from a carboxyl group and a phenolic hydroxy group. Methods for introducing amide groups into polyimides include a method using a monomer having an amide group, and a method for blocking the amine end with an acid anhydride having an amide group. Methods for introducing a carboxyl group or a phenolic hydroxyl group into a polyimide include a method using a monomer having a carboxyl group or a phenolic hydroxyl group, a method of blocking the amine end with an acid anhydride having a carboxyl group or a phenolic hydroxyl group, or a method of imidizing a polyimide precursor such as polyamic acid to an imidization rate of 99% or less.

[0079] Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid, and then carrying out chemical imidization or thermal imidization. A typical method for chemical imidization is to add excess acetic anhydride and pyridine to a polyimide precursor solution and react them at room temperature to 100° C. A typical method for thermal imidization is to heat a polyimide precursor solution at a temperature of 180° C. to 250° C. while dehydrating it.

[0080] Furthermore, as the alkali-soluble resin of the component (A), a phenol novolak resin can also be used.

[0081] The alkali-soluble resin of component (A) may also be a polyester polycarboxylic acid, which can be obtained from an acid dianhydride and a diol by the method described in WO 2009 / 051186. The acid dianhydride includes the above (i) tetracarboxylic dianhydride. Examples of diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol; alicyclic diols such as hydrogenated bisphenol A, hydrogenated bisphenol F, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; and aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0082] In the present invention, the alkali-soluble resin of the component (A) is a mixture of a plurality of alkali-soluble The resin may be a mixture of various resins.

[0083] <(C) component> The component (C) used in the present invention serves as a solvent that dissolves the component (A) and, if necessary, the components (D), (E), (F), and (G) described below, and also dissolves other additives that are added as desired, as described below. As long as the solvent has such dissolving ability, there are no particular limitations on the type or structure of the solvent.

[0084] Examples of such component (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl 2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0085] These solvents may be used alone or in combination of two or more. Among these (C) components, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. are preferred from the viewpoint of good film-forming properties and high safety, and propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, butyl lactate, etc. are particularly preferred from the viewpoint of the solubility of the (A) component. These solvents are generally used as solvents for photoresist materials.

[0086] <(D) component> Examples of the photosensitizer, which is the component (D), include (D-1) a 1,2-quinonediazide compound, (D-2) a photoradical generator, and (D-3) a photoacid generator.

[0087] The (D-1) 1,2-quinonediazide compound is a compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group, in which preferably 10 mol % to 100 mol %, particularly preferably 20 mol % to 95 mol %, of these hydroxy groups or amino groups (in the case of having both hydroxy groups and amino groups, the total amount of these groups) is esterified or amidated with 1,2-quinonediazide sulfonic acid. Examples of the 1,2-quinone diazide sulfonic acid include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and 1,2-benzoquinone-2-diazide-4-sulfonic acid. In the reaction with the compound having either or both of a hydroxy group or an amino group, a chloride of the 1,2-quinone diazide sulfonic acid can be used. As the (D-1) 1,2-quinonediazide compound, diazonaphthoquinone can be used.

[0088] Examples of the compound having a hydroxy group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris(4-hydroxyphenyl)butane, 4,4-isopropylidenediphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4',4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene, [N] phenol compounds such as bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, and 2,5-bis(2-hydroxy-5-methylbenzyl)methyl; and aliphatic alcohols such as ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.

[0089] Examples of the compound containing an amino group include anilines such as aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, and 4,4'-diaminodiphenyl ether, and aminocyclohexane.

[0090] Furthermore, examples of compounds containing both a hydroxy group and an amino group include aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4'-diamino-4''-hydroxytriphenylmethane, 4-amino-4',4''-dihydroxytriphenylmethane, bis(4-amino-3-carboxy-5-hydroxyphenyl)ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)propane, and 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane; and alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

[0091] These 1,2-quinonediazide compounds can be used alone or in combination of two or more kinds.

[0092] When the first photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content of the compound having a quinone diazide group of the component (D-1) is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the component (A). If it is less than 5 parts by mass, the difference in dissolution rate between the exposed and unexposed parts of the positive photosensitive resin composition in the developer may become small, making patterning by development difficult. If it exceeds 100 parts by mass, the 1,2-quinone diazide compound may not be sufficiently decomposed by short-term exposure, resulting in a decrease in sensitivity, or the component (D-1) may absorb light, resulting in a decrease in transparency of the cured film.

[0093] (D-2) The photoradical generator is not particularly limited as long as it generates radicals upon exposure to light. Specific examples include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, Aromatic ketones such as 2-ethylanthraquinone and phenanthrene, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoins such as methylbenzoin and ethylbenzoin, 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-( o-Methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methylphenyl)imidazole dimer, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl- Halomethyloxadiazole compounds such as 5-(p-methoxystyryl)-1,3,4-oxadiazole, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-S-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-triazine, 2-(naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine halomethyl-S-triazine compounds such as 2-(4-ethoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,1-Hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoic acid isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 1-(4-phenylthiophenyl)-1,2-octanedione-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetone) oxime), 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, etc., The above-mentioned photoradical generators are readily available as commercial products. Specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250 (all manufactured by BASF), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE Examples of such compounds include 2-EAQ (all manufactured by Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-140, and TAZ-204 (all manufactured by Midori Kagaku Co., Ltd.). These photoradical generators can be used alone or in combination of two or more kinds.

[0094] The content of the (D-2) component in the first photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass, relative to 100 parts by mass of the (A) component. If this ratio is too small, the exposed part may not be cured sufficiently, and the pattern may not be formed, or even if it is formed, the film may be unreliable. If this ratio is too large, the transmittance of the coating film may decrease, or the unexposed part may be poorly developed.

[0095] The photoacid generator (D-3) is not particularly limited as long as it is a compound that generates an acid by photolysis when irradiated with ultraviolet light. Examples of the acid generated when the photoacid generator is photodecomposed include sulfonic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octane sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctane sulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid, or hydrates or salts thereof.

[0096] Examples of photoacid generators include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano-containing oxime sulfonate compounds. Any photoacid generator that has been known or used in the past can be applied to the present invention without any particular limitation. In the present invention, the photoacid generator of component (D) may be used alone or in combination of two or more. Specific examples include compounds represented by the following formulas [PAG-1] to [PAG-41].

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] The content of the (D-3) component in the first photosensitive resin composition of the present embodiment is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, based on 100 parts by mass of the (A) component. By making the content of the (D-3) component 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if it is more than 20 parts by mass, the unexposed area may be poorly developed, or the storage stability of the composition may decrease.

[0105] <(E) component> The component (E) is a crosslinking agent, which is introduced into the composition when the first photosensitive resin composition of the present invention satisfies the requirement (Z1). More specifically, it is a compound having a structure capable of forming a crosslinked structure by thermal reaction with the thermally reactive site (e.g., carboxyl group and / or phenolic hydroxyl group) of the component (A). Specific examples are given below, but are not limited to these. The thermal crosslinking agent is preferably selected from, for example, (E1) a crosslinking compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group, or (E2) a crosslinking compound represented by the following formula (1). These crosslinking agents can be used alone or in combination of two or more.

[0106] The crosslinkable compound (E1) having two or more substituents selected from alkoxymethyl and hydroxymethyl groups undergoes a crosslinking reaction by dehydration condensation reaction when exposed to high temperatures during thermal curing. Examples of such compounds include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine, and phenoplast compounds.

[0107] Specific examples of alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds (trade name: Cymel (registered trademark)) manufactured by Mitsui Cytec Co., Ltd. Examples of suitable urea resins include compounds such as UFR (registered trademark) 1170 and Powderlink (registered trademark) 1174, methylated urea resins (trade name: UFR (registered trademark) 65), butylated urea resins (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins manufactured by DIC Corporation (high condensation type, trade name: Beckamin (registered trademark) J-300S, P-955, and N).

[0108] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (product name: Cymel (registered trademark) 1123) and those manufactured by Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).

[0109] Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine, etc. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506, 508) manufactured by Sanwa Chemical Co., Ltd., methoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, MX-035) manufactured by Sanwa Chemical Co., Ltd., butoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, MX-302) manufactured by Sanwa Chemical Co., Ltd.

[0110] Also, it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound described in U.S. Patent No. 6,323,310 may be mentioned. An example of a commercially available product of the melamine compound is a product name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and an example of a commercially available product of the benzoguanamine compound is a product name: Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0111] Specific examples of phenoplast compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6-bis(hydroxmethyl)phenol], 2,6-bis(methoxymethyl)phenol], 2,6-bis(methoxymethyl)cresol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(methoxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-methoxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4'-methylenebis[2-methyl-6-methoxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol], 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol], and the like. These are also available as commercially available products, and specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Yukizai Kogyo Co., Ltd.).

[0112] Furthermore, as the component (E1), polymers produced using an acrylamide compound or methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, or N-butoxymethylmethacrylamide, can also be used.

[0113] Examples of such polymers include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate, etc. The weight-average molecular weight of such polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

[0114] The first photosensitive resin composition of the present invention may contain, as the component (E2), a crosslinkable compound represented by the following formula (1). [ka] (In the formula, k is an integer from 2 to 10, m is an integer from 0 to 4, and R 11 represents an organic group with a valence of k)

[0115] The component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by formula (1). Specific examples thereof include the following formulas E2-1 and E2-2, and the following commercially available products. [ka] [ka]

[0116] Commercially available products include Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 (trade names, manufactured by Daicel Corporation), and Denacol EX-252, an alicyclic epoxy resin (trade name, manufactured by Nagase ChemteX Corporation). Examples of suitable crosslinking compounds include CY175, CY177, CY179 (all trade names manufactured by Huntsman Corporation), Araldite CY-182, CY-192, CY-184 (all trade names manufactured by Huntsman Corporation), Epiclon 200, 400 (all trade names manufactured by DIC Corporation), Epicoat 871, 872 (all trade names manufactured by Mitsubishi Chemical Corporation), ED-5661, ED-5662 (all trade names manufactured by Celanese Coatings Co., Ltd.), etc. These crosslinking compounds may be used alone or in combination of two or more kinds.

[0117] Among these, from the viewpoints of process resistance such as heat resistance, solvent resistance, and long-term baking resistance, as well as transparency, compounds having a cyclohexene oxide structure and represented by formulas E2-1 and E2-2, Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 are preferred.

[0118] In addition, as component E, compounds other than those shown as components (E1) and (E2) that can form a crosslinked structure by thermal reaction with the thermally reactive sites of component (A) (for example, a carboxyl group and / or a phenolic hydroxy group) can also be used. Specifically, for example, epoxy compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, VESTANAT B1358 / 100, VESTAGON BF Examples of isocyanate compounds include Takenate (registered trademark) B-1540 (all isocyanurate-type modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, and Takenate (registered trademark) B-7075 (all isocyanurate-type modified polyisocyanates, manufactured by Mitsui Chemicals, Inc.).

[0119] Furthermore, as component E, a polymer having two or more structures capable of forming a crosslinked structure upon thermal reaction with the thermally reactive site (for example, a carboxyl group and / or a phenolic hydroxy group) of component (A) can be used. Specific examples of the polymer include polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate; polymers produced using compounds having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane; compounds having an isocyanate group such as 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko K.K.) and 2-isocyanatoethyl acrylate (Karenz AOI [registered trademark], manufactured by Showa Denko K.K.); and polymers produced using compounds having a blocked isocyanate group such as 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karenz MOI-BM [registered trademark], manufactured by Showa Denko K.K.) and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko K.K.). These compounds may be used alone or in combination to produce a polymer, or may be combined with other compounds to produce a polymer.

[0120] When component (A) has a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group, a compound having two or more groups represented by a hydroxyl group, a carboxyl group, an amide group, and an amino group is used as component (E). It can be used as such.

[0121] These crosslinkable compounds may be used alone or in combination of two or more kinds.

[0122] When the (E) component is selected as the crosslinking agent in the first photosensitive resin composition of the present invention, the content is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the (A) component. When the content of the crosslinkable compound is low, the density of the crosslink formed by the crosslinkable compound is insufficient, so that the effect of improving the heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation may not be obtained. On the other hand, when it exceeds 50 parts by mass, uncrosslinked crosslinkable compound exists, and the heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation are reduced, and the storage stability of the photosensitive resin composition may be deteriorated.

[0123] <(F) Component> The component (F) is a compound having two or more ethylenically polymerizable groups. The compound having two or more ethylenically polymerizable groups means a compound having two or more polymerizable groups in one molecule, and the polymerizable groups are located at the molecular terminals, and the polymerizable groups mean at least one type of polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group, and an allyl group. The compound having two or more ethylenic polymerizable groups as component (F) is preferably a compound having a molecular weight of 1,000 or less (when the compound is a polymer, the weight average molecular weight) from the viewpoints of having good compatibility with each component in the solution of the negative type photosensitive resin composition in the first photosensitive resin composition of the present invention and not affecting the developability.

[0124] Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetra ... 1,3,5-Triacryloylhexahydro-S-triazine, 1,3,5-Trimethacryloylhexahydro-S-triazine, Tris(hydroxyethylacryloyl)isocyanurate, Tris(hydroxyethylmethacryloyl)isocyanurate, Triacryloylformal, Trimethacryloylformal, 1,6-Hexamethylpropanetetramethacrylate, ...6-Hexamethylpropanetetramethacrylate, 1,3,5-Triacryloylhexahydro-S-triazine, 1,3,5-Trimethacryloylhexahydro-S-triazine, Tris(hydroxyethylacryloyl)isocyanurate, Tris(hydroxyethylmethacryloyl)isocyanurate, Triacryloylformal, Trimethacryloylformal, Xanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N,N'-bis(acryloyl)cysteine, N,N'-bis(methacryloyl)cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, diallyl A Examples include terbisphenol A, o-diallyl bisphenol A, diallyl maleate, and triallyl trimellitate.

[0125] The above-mentioned polyfunctional acrylate compounds are readily available as commercial products. Specific examples thereof include, for example, KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX620, R-551, R-712, R-604, and R- 684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M -210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-131 0, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050 (manufactured by Toagosei Co., Ltd.), Viscoat 295, 300, 360, G PT, 3PA, 400, 260, 312, 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-T Examples of such copolymers include MM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, and 1G (all manufactured by Shin-Nakamura Chemical Co., Ltd.). These compounds having two or more ethylenically polymerizable groups can be used alone or in combination of two or more.

[0126] When the first photosensitive resin composition of the present invention contains the component (F), the content is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and particularly preferably 50 to 150 parts by mass, relative to 100 parts by mass of the component (A). If this ratio is too small, the exposed part may not be cured sufficiently, and the pattern may not be formed, or even if it is formed, the film may be unreliable. If this ratio is too large, tack may occur in the coating film after pre-baking, or the unexposed part may not dissolve well during development.

[0127] <(G) component> The component (G) used in the first photosensitive resin composition of the present invention is a compound having two or more functional groups that form a covalent bond with an acid, such as an epoxy group, an alkoxymethyl group, and a hydroxymethyl group.

[0128] Examples of compounds having two or more epoxy groups include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether.

[0129] In addition, as a compound having two or more epoxy groups, commercially available Compounds may be used. Specific examples (product names) are given below, but are not limited thereto: epoxy resins having an amino group such as YH-434 and YH434L (manufactured by Shin-Nikka Epoxy Manufacturing Co., Ltd.); epoxy resins having a cyclohexene oxide structure such as Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 (manufactured by Daicel Corporation); bisphenol A type epoxy resins such as Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (all manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)); bisphenol A type epoxy resins such as Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)). phenol novolac type epoxy resins such as Epicoat 152 and 154 (both manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)), EPPN201 and 202 (both manufactured by Nippon Kayaku Co., Ltd.); cresol novolac type epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (both manufactured by Nippon Kayaku Co., Ltd.), and Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)); Denacol EX-252 (manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, CY-192 and CY-184 (manufactured by Huntsman alicyclic epoxy resins such as Epiclon 200 and 400 (manufactured by Dainippon Ink and Chemicals Co., Ltd. (currently DIC Corporation)), Epicoat 871 and 872 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)), ED-5661 and ED-5662 (manufactured by Celanese Coatings Co., Ltd.); aliphatic polyglycidyl ethers such as Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314 and EX-321 (manufactured by Nagase ChemteX Corporation).

[0130] Furthermore, as the compound having two or more epoxy groups, a polymer having an epoxy group can also be used. The polymer having an epoxy group can be produced by addition polymerization using an addition-polymerizable monomer having an epoxy group, for example. Examples include addition polymerization polymers such as polyglycidyl acrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, a copolymer of glycidyl methacrylate, styrene, and 2-hydroxyethyl methacrylate, and condensation polymerization polymers such as epoxy novolac.

[0131] Alternatively, the polymer having an epoxy group can also be produced by reacting a polymer compound having a hydroxy group with a compound having an epoxy group, such as epichlorohydrin or glycidyl tosylate.

[0132] The weight average molecular weight of such a polymer is, for example, 300 to 20,000.

[0133] These compounds having two or more epoxy groups can be used alone or in combination of two or more kinds.

[0134] Examples of compounds having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, as well as phenoplast compounds.

[0135] Specific examples of alkoxymethylated glycoluril are as described in the above paragraph

[0108] .

[0136] Specific examples of alkoxymethylated benzoguanamines are as described in paragraph

[0109] above.

[0137] Specific examples of alkoxymethylated melamine are as described in paragraph

[0110] above.

[0138] Also, it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound described in U.S. Patent No. 6,323,310 may be mentioned. An example of a commercially available product of the melamine compound is a product name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and an example of a commercially available product of the benzoguanamine compound is a product name: Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0139] Specific examples of phenoplast compounds are as described in paragraph

[0112] above.

[0140] Furthermore, as the component (G), a polymer produced using an acrylamide compound or methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, or N-butoxymethylmethacrylamide, can also be used.

[0141] Examples of such polymers include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate, etc. The weight-average molecular weight of such polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

[0142] When the first photosensitive resin composition of the present invention contains a compound having two or more functional groups that form a covalent bond with an acid of component (G), the content is preferably 5 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of component (A). If this proportion is too small, the photocurability of the negative photosensitive resin composition may decrease, while if it is too large, the developability of the unexposed area may decrease, causing a residual film or residue.

[0143] <Other additives> Furthermore, the first photosensitive resin composition used in the present invention may contain, as necessary, a leveling agent, a surfactant, a rheology adjuster, a pigment, a dye, a storage stabilizer, an antifoaming agent, an adhesion promoter, or a dissolution promoter such as a polyhydric phenol or a polyvalent carboxylic acid, as long as the effects of the present invention are not impaired. As the surfactant, a fluorosurfactant of a fluorine-containing polymer is preferably used. Examples of such a fluorosurfactant include Megafac (registered trademark) F-251, F-281, F-430, F-444, R-30, R-40, F-553, F-554, F-555, F-556, F-557, and F-558 (all manufactured by DIC Corporation), Surflon (registered trademark) S-242, S-243, S-385, and S-386. , S-420, and S-611 (all manufactured by ACG Seimi Chemical Co., Ltd.) These fluorine-based surfactants may be used alone or in combination of two or more kinds.

[0144] <Resist film formation process> After the underlayer film 12 is formed as described above, a second photosensitive resin composition is applied onto the underlayer film 12 and prebaked to form a resist film 13 (FIG. 1). Usually, this second photosensitive resin composition is applied onto the entire surface of the underlayer film 12 to form the resist film 13. Each component of the resist film will be described in detail below.

[0145] <Component (a)> The component (a) of the present invention is a resin having an alkali-soluble group, such as a phenolic hydroxy group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid group, a boronic acid group, an active methylene group, and an active methine group.

[0146] An active methylene group refers to a methylene group (-CH2-) that has a carbonyl group adjacent to it and is reactive to nucleophiles. In the present invention, the active methine group refers to an active methylene group in which one hydrogen atom of the methylene group is substituted with an alkyl group and is reactive to nucleophiles.

[0147] Among active methylene groups and active methine groups, active methylene groups are preferred, and active methylene groups represented by the following formula (a1) are more preferred. [ka] (In formula (a1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the dashed line represents a bond.)

[0148] In the above formula (a1), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferred. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. Of these, a methyl group, an ethyl group, an n-propyl group, etc. are preferred.

[0149] In the above formula (a1), examples of the alkoxy group represented by R include alkoxy groups having 1 to 20 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are preferred. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy and t-butoxy groups. Among these, a methoxy group, an ethoxy group, an n-propoxy group, and the like are preferable.

[0150] Examples of the group represented by the above formula (a1) include the following structures: In the structural formula, the dashed lines represent bonds. [ka]

[0151] Among the above alkali-soluble groups, an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxyl group and having a number average molecular weight of 2,000 to 50,000 is preferred.

[0152] The alkali-soluble resin of the component (a) may be any alkali-soluble resin having such a structure, and there are no particular limitations on the type of main chain skeleton and side chains of the polymer constituting the resin.

[0153] However, the number average molecular weight of the alkali-soluble resin of component (a) is within the range of 2,000 to 50,000. If the number average molecular weight is too high, exceeding 50,000, development residues are likely to be generated and sensitivity is significantly reduced, while if the number average molecular weight is too low, less than 2,000, a considerable amount of film loss occurs in exposed areas during development, and curing may be insufficient.

[0154] Examples of the alkali-soluble resin of component (a) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.

[0155] In the present invention, an alkali-soluble resin made of a copolymer obtained by polymerizing a plurality of types of monomers (hereinafter referred to as a specific copolymer) can also be used as component (a). In this case, the alkali-soluble resin of component (a) may be a blend of a plurality of specific copolymers.

[0156] That is, the specific copolymer is a copolymer formed from, as essential constituent units, a monomer exhibiting alkali solubility, i.e., a monomer having at least one monomer selected from the group consisting of a phenolic hydroxyl group and a carboxyl group, and at least one monomer selected from the group of monomers copolymerizable with these monomers, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is more than 50,000, residues may be generated.

[0157] The above-mentioned "monomer having at least one selected from the group consisting of a phenolic hydroxyl group and a carboxyl group" includes a monomer having a phenolic hydroxyl group and a monomer having a carboxyl group. These monomers are not limited to those having one phenolic hydroxyl group or one carboxyl group, and may have multiple phenolic hydroxyl groups or carboxyl groups.

[0158] Specific examples of the monomer are given below, but the monomer is not limited thereto. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N- (carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and the like.

[0159] Examples of monomers having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and 4-hydroxyphenyl methacrylate.

[0160] The ratio of the unsaturated carboxylic acid derivative and / or the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group in the production of the alkali-soluble resin of component (a) is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 60 mol%, and most preferably 10 mol% to 30 mol% of all the monomers used in the production of the alkali-soluble resin of component (a). If the unsaturated carboxylic acid derivative is less than 5% by weight, the alkali solubility of the polymer is insufficient.

[0161] The alkali-soluble resin which is the component (a) of the present invention is preferably one which is further copolymerized with a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, from the viewpoint of further stabilizing the pattern shape after curing.

[0162] Examples of monomers having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

[0163] The ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the alkali-soluble resin component (a) is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and most preferably 20% by mass to 40% by mass. If the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 5% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If it is 60% by mass or more, the alkali-soluble group of component (a) may be insufficient, and characteristics such as developability may be deteriorated.

[0164] The alkali-soluble resin which is the component (a) of the present invention is preferably one which has been further copolymerized with an N-substituted maleimide compound in order to increase the Tg of the copolymer.

[0165] Examples of N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, those having no aromatic ring are preferred, and from the viewpoints of developability, transparency, and heat resistance, those having an alicyclic skeleton are more preferred, and among these, cyclohexylmaleimide is the most preferred.

[0166] The ratio of N-substituted maleimide in the production of the alkali-soluble resin of component (a) is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and most preferably 20% by mass to 40% by mass. If the N-substituted maleimide is less than 5% by mass, the Tg of the copolymer may be low and the heat resistance may be poor. If it is 60% by mass or more, the transparency may be reduced.

[0167] When the second photosensitive resin composition of the present invention satisfies the requirement (z2), The alkali-soluble resin of component (a) is preferably a copolymer further having a self-crosslinking group or further having a group (hereinafter also referred to as a crosslinking group) that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group.

[0168] Examples of the self-crosslinking group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a blocked isocyanate group.

[0169] Examples of the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group.

[0170] When such a self-crosslinking group or crosslinkable group is contained in the alkali-soluble resin of component (a), the content thereof is preferably from 0.1 to 0.9 per repeating unit in the resin of component (a), and from the viewpoints of developability and solvent resistance, is more preferably from 0.1 to 0.8.

[0171] When the alkali-soluble resin of component (a) further has a repeating unit having at least one self-crosslinking group selected from an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, a blocked isocyanate group, and the like, and a crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a blocked isocyanate group, and the like, for example, an unsaturated compound having radical polymerizability and having at least one crosslinking group selected from an epoxy group, an oxetane group, a vinyl group, a blocked isocyanate group, and the like, and a self-crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, a alkoxysilyl group, and the like may be copolymerized.

[0172] Examples of the unsaturated compound having a radical polymerizability and an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide.

[0173] Examples of the monomer having radical polymerizability and further having an N-hydroxymethyl group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

[0174] Examples of the monomer having radical polymerization properties and further having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.

[0175] Examples of the unsaturated compound having radical polymerization and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate, α-n-propyl acrylate, α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate are preferably used. These can be used alone. or in combination.

[0176] Examples of unsaturated compounds having radical polymerization properties and further having an oxetane group include (meth)acrylic acid esters having an oxetane group. Among such monomers, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, and 3-(methacryloyloxymethyl)-2-phenyl-oxetane are listed. , 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxymethyl)-4-trifluoromethyloxetane are preferred, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, etc. are preferably used.

[0177] Examples of the monomer having radical polymerizability and further having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

[0178] Examples of the monomer having radical polymerizability and further having a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.

[0179] When the second photosensitive resin composition of the present invention satisfies (z1), it contains a structural unit derived from an unsaturated compound having radical polymerizability and at least one group selected from self-crosslinking groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, vinyl groups, and blocked isocyanate groups, and crosslinking groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups, in an amount of preferably 10% to 70% by mass, particularly preferably 20% to 60% by mass, based on the total of all repeating units contained in the alkali-soluble resin of component (a). If the amount of this structural unit is less than 10% by mass, the heat resistance and surface hardness of the obtained cured film tend to decrease, while if the amount of this structural unit exceeds 70% by mass, the storage stability of the radiation-sensitive resin composition tends to decrease.

[0180] In the present invention, the acrylic polymer of the component (a) may be a copolymer formed by using a monomer other than the above-mentioned monomer (hereinafter referred to as other monomer) as a constituent unit. Specifically, the other monomer may be one that can be copolymerized with at least one selected from the group consisting of the monomer having a carboxyl group and the monomer having a phenolic hydroxyl group, and is not particularly limited as long as it does not impair the properties of the component (a). Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimides, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds. Specific examples of the other monomers are given below, but the present invention is not limited thereto.

[0181] Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, and the like. acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, and the like.

[0182] Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2- Examples of the methacrylates include ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, and poly(ethylene glycol) ethyl ether methacrylate.

[0183] Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide.

[0184] Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0185] Examples of the styrene compound include styrenes having no hydroxy group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

[0186] In the production of the alkali-soluble resin (a), the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 20% by mass or less. If the ratio exceeds 80% by mass, the amount of the essential components is relatively reduced, making it difficult to fully obtain the effects of the present invention.

[0187] The method for obtaining the alkali-soluble resin, which is the component (a) used in the present invention, is not particularly limited. For example, a monomer having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a group that generates a carboxylic acid or a phenolic hydroxyl group by the action of heat or acid, a monomer having a hydroxyalkyl group, and optionally a self-crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, or a blocked isocyanate group, and an N-alkoxymethyl group may be used. The resin is obtained by polymerization reaction at a temperature of 50°C to 110°C in a solvent containing a monomer having at least one crosslinking group selected from a crosslinkable group such as an alkyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a blocked isocyanate group, and optionally other copolymerizable monomers and optionally a polymerization initiator. The solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble resin and the acrylic polymer having the specific functional group. Specific examples include the solvents described in the component (c) below.

[0188] The acrylic polymer having a specific functional group thus obtained is usually in the state of a solution dissolved in a solvent.

[0189] The solution of the specific copolymer obtained as described above can be reprecipitated by adding diethyl ether or water under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the specific copolymer. By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. If the specific copolymer cannot be sufficiently purified by a single operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated. In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the component (c) described below and used in the form of a solution.

[0190] In addition, as the alkali-soluble resin of component (a), polyimide precursors such as polyamic acids, polyamic acid esters, and partially imidized polyamic acids, and polyimides such as carboxylic acid group-containing polyimides can also be used, and there are no particular limitations on the type of these that can be used as long as they are alkali-soluble.

[0191] The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensation of (i) a tetracarboxylic dianhydride compound and (j) a diamine compound.

[0192] The (i) tetracarboxylic acid dianhydride compound is not particularly limited, and specific examples thereof include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 1,2-dimethyl-1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include alicyclic tetracarboxylic acid dianhydrides such as cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-cyclohexane tetracarboxylic acid dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butane tetracarboxylic acid dianhydride. These may be used alone or in combination of two or more compounds.

[0193] The (j) diamine compound is not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3,5-dicarboxyphenyl)ether, bis(4-amino-3-carboxyphenyl)sulfone, bis(4-amino-3,5-dicarboxyphenyl)sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy- 5,5'-Dimethylbiphenyl, 4,4'-Diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-Bis(4-amino-3-carboxyphenoxy)benzene, 1,3-Bis(4-amino-3-carboxyphenoxy)benzene, Bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, Bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, 2,2-Bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane, 2,4-Diamino Phenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl)ether, bis(4-amino-3-hydroxyphenyl)ether, bis(4-amino-3,5-dihydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)methane 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethyl Biphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]sulfone, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane, 2,Examples of the diamine compound include a diamine compound having a phenolic hydroxy group such as 2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane; a diamine compound having a thiophenol group such as 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, and 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane; and a diamine compound having a sulfonic acid group such as 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis(4-aminobenzene-3-sulfonic acid)ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, and 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. In addition, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3',5,5'-tetramethylbenzidine, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl] 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane,Examples of diamine compounds include 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 2,2'-bis(trifluoromethyl)benzidine. It is possible to do this. These may be used alone or in combination of two or more compounds.

[0194] When the polyamic acid used in the present invention is produced from (i) a tetracarboxylic dianhydride compound and (j) a diamine compound, the compounding ratio of the two compounds, i.e., the total number of moles of (j) the diamine compound / the total number of moles of (i) the tetracarboxylic dianhydride compound, is preferably 0.7 to 1.2. As in a normal polycondensation reaction, the closer this molar ratio is to 1, the greater the polymerization degree of the polyamic acid produced, and the greater the molecular weight.

[0195] In addition, when polymerization is carried out using an excess of a diamine compound, the terminal amino groups of the remaining polyamic acid can be protected by reacting them with a carboxylic acid anhydride. Examples of such carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

[0196] In the production of polyamic acid, the reaction temperature for the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from any temperature range of -20°C to 150°C, preferably -5°C to 100°C. To obtain a high molecular weight polyamic acid, the reaction temperature is appropriately selected from the range of 5°C to 40°C and the reaction time is appropriately selected from the range of 1 hour to 48 hours. To obtain a low molecular weight, partially imidized polyamic acid with high storage stability, it is more preferable to select the reaction temperature from 40°C to 90°C and the reaction time from 10 hours or more. When the terminal amino group is protected with an acid anhydride, the reaction temperature can be selected from the range of -20°C to 150°C, preferably -5°C to 100°C.

[0197] The reaction of the diamine compound with the tetracarboxylic dianhydride compound can be carried out in a solvent. Examples of the solvent that can be used at that time include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ... Examples of the solvent include ethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These may be used alone or in combination. Furthermore, even if the solvent does not dissolve polyamic acid, it may be mixed with the above solvent and used within the range in which the polyamic acid produced by the polymerization reaction does not precipitate.

[0198] The thus obtained solution containing the polyamic acid can be used as it is for the preparation of a photosensitive resin composition, or the polyamic acid can be recovered and used by precipitating and isolating it in a poor solvent such as water, methanol, or ethanol.

[0199] Any polyimide can also be used as component (a). The polyimide used in the present invention is a polyimide precursor such as the polyamic acid described above that is chemically or thermally imidized to 50% or more.

[0200] The polyimide used in the second photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility. Methods for introducing a carboxyl group or a phenolic hydroxyl group into a polyimide include a method using a monomer having a carboxyl group or a phenolic hydroxyl group, a method of blocking the amine end with an acid anhydride having a carboxyl group or a phenolic hydroxyl group, or a method of imidizing a polyimide precursor such as polyamic acid to an imidization rate of 99% or less.

[0201] Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid, and then carrying out chemical imidization or thermal imidization. A typical method for chemical imidization is to add excess acetic anhydride and pyridine to a polyimide precursor solution and react at room temperature to 100° C. A typical method for thermal imidization is to heat a polyimide precursor solution at a temperature of 180° C. to 250° C. while dehydrating it.

[0202] Furthermore, as the alkali-soluble resin of component (a), a phenol novolak resin can also be used.

[0203] The alkali-soluble resin of component (a) may also be a polyester polycarboxylic acid, which can be obtained from an acid dianhydride and a diol by the method described in WO2009 / 051186. The acid dianhydride includes the above (i) tetracarboxylic dianhydride. Examples of diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol; alicyclic diols such as hydrogenated bisphenol A, hydrogenated bisphenol F, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; and aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0204] In the present invention, the alkali-soluble resin of the component (a) may be a mixture of a plurality of types of alkali-soluble resins.

[0205] <(b) Component> The fine particles of the component (b) used in the present invention are fine particles of a colorant such as a pigment or a dye, or organic or inorganic fine particles.

[0206] Examples of the dye include benzene azo dyes and anthraquinone dyes.

[0207] Examples of the pigment include black organic pigments such as carbon black, benzofuranone-based black pigments, and perylene-based black pigments; black inorganic pigments such as fine particles of metals such as titanium, copper, iron, and silver, or oxides and nitrides thereof; and CI Pigment Yellow 20, 86, 93, 109, 110, 117, 125, 138, 148, 154, and 166, CI Pigment Orange 36, 43, 51, and 61, CI Pigment Red 9, 97, 122, 149, 168, 177, 180, 192, 217, 220, 228, and 240, CI Pigment Red 10, 117, 120, 138, 148, 154, and 166. Examples of pigments include CI Pigment Violet 19, 23, 30, 40, 50, CI Pigment Blue 15, 15:1, 15:4, 22, 60, 64, CI Pigment Green 7, and CI Pigment Brown 23, 25, and 26.

[0208] The colorant includes pigments, dyes, etc., and when component (b) is a colorant, it is preferably fine particles containing a pigment.

[0209] Depending on the structure, the fine particles of component (b) may be able to impart stability such as solvent resistance and heat resistance to the resist film, as well as optical properties such as transparency, light diffusibility, and refractive index control.

[0210] There are no particular limitations on the fine particles of component (b) so long as they fulfill the above-mentioned role, and examples of such particles include organic fine particles and inorganic fine particles.

[0211] The shape of the organic and inorganic fine particles is not particularly limited, and may be, for example, approximately spherical like beads, a chain of linked beads, or amorphous like powder.

[0212] The organic fine particles used in the present invention preferably have an average particle size of 5 nm to 1000 nm. Here, the average particle size (μm) is the 50% volume diameter (median diameter) obtained by measurement using a laser diffraction / scattering method based on the Mie theory.

[0213] Examples of the organic fine particles include polymethyl methacrylate particles (PMMA particles), silicone particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, polyamide particles, polyimide particles, and polyethylene fluoride particles.

[0214] The organic fine particles may suitably be commercially available products, such as Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, ARX series, AFX series, MB series, MBP series, MB-C series, ACX series, and ACP series (all manufactured by Sekisui Chemical Co., Ltd.); Tospearl (registered trademark) series (manufactured by Momentive Performance Materials Japan, Inc.); Eposter (registered trademark) series, MA series, ST series, and MX series (all manufactured by Nippon Shokubai Co., Ltd.); Optobeads (registered trademark) series (manufactured by Nissan Chemical Co., Ltd.); Flowbeads series (manufactured by Sumitomo Seikagaku Co., Ltd.); Trepearl (registered trademark) PPS, PAI, PES, and EP (all manufactured by Nippon Shokubai Co., Ltd.). , Toray Industries, Inc.]; 3M (registered trademark) Dyneon TF Micropowder series [manufactured by 3M]; Chemisnow (registered trademark) MX series, MZ series, MR series, KMR series, KSR series, MP series, SX series, and SGP series [all manufactured by Soken Chemical & Engineering Co., Ltd.]; Tuftic (registered trademark) AR650 series, AR-750 series, FH-S series, A-20, YK series, ASF series, HU series, F series, C series, and WS series [all manufactured by Toyobo Co., Ltd.]; Art Pearl (registered trademark) GR series, SE series, G series, GS series, J series, MF series, and BE series [all manufactured by Negami Chemical Industries, Ltd.]; Shin-Etsu Silicone (registered trademark) KMP series [manufactured by Shin-Etsu Chemical Co., Ltd.], etc. can be used.

[0215] Examples of the inorganic fine particles include silica, aluminum oxide, aluminum hydroxide, talc, calcium carbonate, mica, magnesium hydroxide, tin oxide, zirconium oxide, titanium oxide, and composite oxides containing these.

[0216] Among these inorganic fine particles, silica, zirconium oxide, and titanium oxide are preferred. In particular, particles having an average primary particle diameter of 5 nm to 100 nm are preferred. The average primary particle diameter here is the average value of primary particle diameters measured by transmission electron microscopy.

[0217] Among the above-mentioned particles, the colloidal silica particles may be silica sol. The silica sol may be an aqueous silica sol produced by a known method using an aqueous sodium silicate solution as a raw material, or an organic solvent-dispersed silica sol obtained by replacing water, which is the dispersion medium of the aqueous silica sol, with an organic solvent.

[0218] Also usable is a silica sol obtained by hydrolyzing and condensing an alkoxysilane such as methyl silicate or ethyl silicate in an organic solvent such as alcohol in the presence of a catalyst (e.g., an alkali catalyst such as ammonia, an organic amine compound, or sodium hydroxide), or an organosilica sol obtained by replacing the dispersion medium of the silica sol with another organic solvent. Examples of commercially available organosilica sols include MA-ST-S (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), MT-ST (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), MA-ST-UP (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), MA-ST-M (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), MA-ST-L (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), and IPA-ST- S (silica sol dispersed in isopropanol, manufactured by Nissan Chemical Industries, Ltd.), trade name IPA-ST (silica sol dispersed in isopropanol, manufactured by Nissan Chemical Industries, Ltd.), trade name IPA-ST-UP (silica sol dispersed in isopropanol, manufactured by Nissan Chemical Industries, Ltd.), trade name IPA-ST-L (silica sol dispersed in isopropanol, manufactured by Nissan Chemical Industries, Ltd.), trade name IPA-ST-ZL (silica sol dispersed in isopropanol, manufactured by Nissan Chemical Industries, Ltd.), trade name NPC-ST-30 (n-propyl cellosolve Product name: PGM-ST (1-methoxy-2-propanol dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), Product name: DMAC-ST (Dimethylacetamide dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), Product name: XBA-ST (Xylene / n-butanol mixed solvent dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), Product name: EAC-ST (Ethyl acetate dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), Product name: PMA-ST (Propylene glycol monomethyl ether dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), Examples of silica sol dispersed in methyl ethyl ketone (manufactured by Nissan Chemical Industries, Ltd.), trade name MEK-ST (silica sol dispersed in methyl ethyl ketone, manufactured by Nissan Chemical Industries, Ltd.), trade name MEK-ST-UP (silica sol dispersed in methyl ethyl ketone, manufactured by Nissan Chemical Industries, Ltd.), trade name MEK-ST-L (silica sol dispersed in methyl ethyl ketone, manufactured by Nissan Chemical Industries, Ltd.), and trade name MIBK-ST (silica sol dispersed in methyl isobutyl ketone, manufactured by Nissan Chemical Industries, Ltd.), but are not limited to these.

[0219] Among the above-mentioned particles, examples of zirconium oxide and composite oxide particles containing zirconium oxide include, but are not limited to, Nanouse ZR-40BL (water-dispersed zirconia sol), Nanouse OZ-S30M (methanol-dispersed zirconia sol), Nanouse OZ-S30K (methyl ethyl ketone-dispersed zirconia sol), Nanouse OZ-S40K-AC (methyl ethyl ketone-dispersed zirconia sol), Suncolloid HZ-400M7 (methanol-dispersed zirconia sol) (all of the above are trade names, manufactured by Nissan Chemical Industries, Ltd.).

[0220] Among the above-mentioned particles, examples of titanium oxide and composite oxide particles containing titanium oxide include, but are not limited to, the product name Suncolloid HT-R305M7-20 (titania sol dispersed in methanol, manufactured by Nissan Chemical Industries, Ltd.).

[0221] These organic and inorganic fine particles may be used alone or in combination of two or more kinds.

[0222] The content of the component (b) in the second photosensitive resin composition of the present invention is preferably 5 parts by mass to 1,000 parts by mass, and more preferably 10 parts by mass, relative to 100 parts by mass of the total mass of the component (a) and the components (d), (e), (f), (h) and (q) described below. The content of component (b) is preferably from 10 to 500 parts by mass, and more preferably from 10 to 200 parts by mass. If the content of component (b) is less than 5 parts by mass, the intended properties such as coloring, improved stability, and control of optical properties may not be obtained. If the content of component (b) is more than 1000 parts by mass, the film formability of the resist film may decrease.

[0223] <(c) component> The component (c) used in the present invention serves as a solvent that dissolves the components (a), (b), and, if necessary, the components (d), (e), (f), (g), (h), and (q) described below, and also dissolves other additives that are added as desired, as described below. As long as the solvent has such dissolving ability, there are no particular limitations on the type or structure of the solvent.

[0224] Examples of such component (c) include the same as the component (C) used in the above-mentioned composition for forming the upper layer film.

[0225] These solvents may be used alone or in combination of two or more. Among these components (c), solvents not having a hydroxyl group are preferred in terms of not dissolving the underlayer film, namely, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, etc. These solvents are generally used as solvents for photoresist materials. When using a solvent having a hydroxyl group, it is preferable to use it in combination with a solvent having no hydroxyl group, so as not to dissolve the underlayer film as described above. The solvent to be combined is not particularly limited, and may be one or more kinds, as long as it has good coating properties and does not dissolve the underlayer film. In this case, the amount of the solvent having a hydroxyl group is preferably 70% by weight or less, more preferably 60% by weight or less, even more preferably 50% by weight or less, and most preferably 30% by weight or less, based on the total amount of the (c) component, so as not to dissolve the underlayer film.

[0226] <(d) component> Examples of the photosensitizer that is the component (d) include (d-1) a 1,2-quinonediazide compound, (d-2) a photoradical generator, and (d-3) a photoacid generator.

[0227] Examples of the (d-1) 1,2-quinonediazide compound include the same compounds as (D-1) listed in the component (D) used in the composition for forming the upper layer film described above.

[0228] These 1,2-quinonediazide compounds can be used alone or in combination of two or more kinds.

[0229] When the second photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content of the compound having a quinone diazide group as component (d-1) is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the total of components (a) and (h). If the content is less than 5 parts by mass, the difference in dissolution rate in the developer between the exposed and unexposed parts of the positive photosensitive resin composition becomes small, making patterning by development difficult. If the content exceeds 100 parts by mass, the 1,2-quinone diazide compound may not be sufficiently decomposed by short-term exposure, resulting in a decrease in sensitivity, or component (d-1) may absorb light, resulting in a decrease in transparency of the cured film. There are cases.

[0230] The photoradical generator (d-2) is not particularly limited as long as it generates radicals upon exposure to light. Specific examples include the same ones as (D-2) listed in the component (D) used in the composition for forming the upper layer film described above.

[0231] The content of the (d-2) component in the second photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass, relative to 100 parts by mass of the total of the (a) and (h) components. If this ratio is too small, the exposed part may not be cured sufficiently, and the pattern may not be formed, or even if it is formed, the film may be unreliable. If this ratio is too large, the transmittance of the coating film may decrease, or the unexposed part may be poorly developed.

[0232] The photoacid generator (d-3) is not particularly limited as long as it is a compound that generates an acid by photodecomposition upon irradiation with ultraviolet light. The acid generated when the photoacid generator is photodecomposed may be the same as the acid generated when the photoacid generator listed in (D-3) of the component (D) used in the composition for forming the upper layer film is photodecomposed.

[0233] Examples of the photoacid generator include the same photoacid generators as those listed in (D-3) of the component (D) used in the composition for forming the upper layer film described above.

[0234] The content of the (d-3) component in the second photosensitive resin composition of the present embodiment is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, based on 100 parts by mass of the total of the (a) and (h) components. By making the content of the (d-3) component 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if it is more than 20 parts by mass, the unexposed part may be poorly developed, or the storage stability of the composition may decrease.

[0235] <(e) component> The component (e) is a crosslinking agent, which is introduced into the composition when the second photosensitive resin composition of the present invention satisfies the requirement (z1). More specifically, it is a compound having a structure capable of forming a crosslinked structure by thermal reaction with the thermally reactive site (e.g., carboxyl group and / or phenolic hydroxyl group) of the component (a). Specific examples are given below, but are not limited thereto. The thermal crosslinking agent is preferably selected from, for example, (e1) a crosslinking compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group, or (e2) a crosslinking compound represented by the following formula (2). These crosslinking agents can be used alone or in combination of two or more kinds.

[0236] The crosslinkable compound (e1) having two or more substituents selected from alkoxymethyl and hydroxymethyl groups undergoes a crosslinking reaction by dehydration condensation reaction when exposed to high temperatures during thermal curing. Examples of such compounds include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine, and phenoplast compounds.

[0237] Specific examples of the alkoxymethylated glycoluril that can be used are the same as those exemplified as the component (E) used in the composition for forming the upper layer film described above.

[0238] Specific examples of the alkoxymethylated benzoguanamine that can be used are the same as those exemplified as the component (E) used in the composition for forming the upper layer film described above.

[0239] Specific examples of the phenoplast-based compound that can be used are the same as those listed in the component (E) used in the composition for forming the upper layer film described above.

[0240] Furthermore, as the component (e1), a polymer produced using an acrylamide compound or methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, or N-butoxymethylmethacrylamide, can also be used.

[0241] As such a polymer, the same polymers as (E1) exemplified in the component (E) used in the composition for forming the upper layer film described above can be used.

[0242] In addition, in the second photosensitive resin composition of the present invention, as the component (e2), the same (E2) as that exemplified in the component (E) used in the composition for forming the upper layer film described above can be used.

[0243] In addition, as component e, compounds capable of forming a crosslinked structure by thermal reaction with the thermally reactive sites of component (a) (e.g., carboxyl groups and / or phenolic hydroxyl groups) other than those shown as components (e1) and (e2) can also be used. Specifically, for example, epoxy compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, VESTANAT B1358 / 100, VESTAGON BF Examples of the isocyanate compounds include Takenate (registered trademark) B-882N and Takenate (registered trademark) B-7075 (all of which are isocyanurate-type modified polyisocyanates, manufactured by Mitsui Chemicals, Inc.).

[0244] Furthermore, as component (e), a polymer having two or more structures capable of forming a crosslinked structure upon thermal reaction with the thermally reactive sites (for example, carboxyl groups and / or phenolic hydroxyl groups) of component (a) can be used. Specific examples of the polymer include polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate; polymers produced using compounds having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane; compounds having an isocyanate group such as 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko K.K.) and 2-isocyanatoethyl acrylate (Karenz AOI [registered trademark], manufactured by Showa Denko K.K.); and polymers produced using compounds having a blocked isocyanate group such as 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karenz MOI-BM [registered trademark], manufactured by Showa Denko K.K.) and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko K.K.). These compounds may be used alone or in combination to produce a polymer, or may be combined with other compounds to produce a polymer.

[0245] When component (a) has a group that reacts with at least one group selected from the group consisting of groups represented by hydroxyl groups, carboxyl groups, amide groups, and amino groups, a compound having two or more groups represented by hydroxyl groups, carboxyl groups, amide groups, and amino groups can be used as component (e).

[0246] These crosslinkable compounds may be used alone or in combination of two or more kinds.

[0247] When the (e) component is selected as the crosslinking agent in the second photosensitive resin composition of the present invention, the content is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the total of the (a) and (h) components. When the content of the crosslinkable compound is low, the density of the crosslink formed by the crosslinkable compound is insufficient, so that the effect of improving the heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation may not be obtained. On the other hand, when it exceeds 50 parts by mass, uncrosslinked crosslinkable compound exists, and the heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation are reduced, and the storage stability of the photosensitive resin composition may be deteriorated.

[0248] <Component (f)> The component (f) is a compound having two or more ethylenically polymerizable groups. The compound having two or more ethylenically polymerizable groups means a compound having two or more polymerizable groups in one molecule, and the polymerizable groups are located at the molecular terminals, and the polymerizable groups mean at least one type of polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group, and an allyl group. The compound having two or more ethylenic polymerizable groups as component (f) is preferably a compound having a molecular weight (weight average molecular weight when the compound is a polymer) of 1,000 or less, from the viewpoints of having good compatibility with each component in the solution of the negative type photosensitive resin composition in the second photosensitive resin composition of the present invention and not affecting the developability.

[0249] Specific examples of such compounds that can be used are the same as those exemplified in the component (F) used in the composition for forming the upper layer film described above.

[0250] When the second photosensitive resin composition of the present invention contains the component (f), the content is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and particularly preferably 50 to 150 parts by mass, relative to 100 parts by mass of the total of the components (a) and (h). If this ratio is too small, the exposed part may not be cured sufficiently, and the pattern may not be formed, or even if it is formed, the film may be unreliable. If this ratio is too large, tack may occur in the coating film after pre-baking, or the unexposed part may not dissolve well during development.

[0251] <(g) component> The component (g) used in the second photosensitive resin composition used in the present invention is a compound having two or more functional groups that form a covalent bond with an acid. As such functional groups that form a covalent bond with an acid, the same ones as those listed in the component (G) used in the composition for forming the upper layer film described above can be used.

[0252] When the second photosensitive resin composition used in the present invention contains the compound having two or more functional groups that form a covalent bond with an acid (component (g)), the content is preferably 5 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of the total of components (a) and (h). If this proportion is too small, the composition may not be a negative photosensitive composition. The photocurability of the resin composition may decrease, while an excessively large value may decrease the developability of the unexposed areas, resulting in a residual film or residue.

[0253] <(h) component> The component (h) is a polymer having a liquid repellent group (h1).

[0254] In the present invention, examples of the polymer include polyimide, polyamic acid, polyamide, polyurea, polyurethane, phenol resin, epoxy resin, polysiloxane, polyester, and acrylic polymer, and preferred examples of the polymer include acrylic polymer.

[0255] Here, the acrylic polymer refers to a polymer obtained by using a monomer having a polymerizable unsaturated group such as an acrylic acid ester, a methacrylic acid ester, styrene, or maleimide, that is, a polymerizable group containing a C=C double bond in the structure.

[0256] Examples of polyamic acid, polyimide, polyamide, and polyurea include polyamic acid obtained by reacting diamine with acid dianhydride, polyimide obtained by imidizing the polyamic acid, polyamide obtained by reacting diamine with dicarboxylic acid anhydride, or polyurea obtained by reacting diamine with diisocyanate, and further include polymers obtained from a monomer mixture containing at least one monomer having a fluoroalkyl group or a fluoroalkoxy group, and at least one monomer having a hydroxyl group.

[0257] Examples of the polyurethane include polyurethanes obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group and a diol having an amino group with a diisocyanate.

[0258] The phenol resin may be a novolak resin obtained by polymerizing a phenol having a fluoroalkyl group or a fluoroalkoxy group with formaldehyde.

[0259] Examples of the epoxy resin include those obtained by reacting bisphenol A and / or bisphenol F having a fluoroalkyl group or a fluoroalkoxy group with a diglycidyl ether of the bisphenol A and / or bisphenol F.

[0260] Examples of polysiloxanes include polymers obtained by polymerizing a silane monomer mixture containing a trialkoxysilane having a fluoroalkyl group or a dialkoxysilane having a fluoroalkyl group and a trialkoxysilane having an amino group or a dialkoxysilane having an amino group.

[0261] The polyester may be a polyester obtained by reacting a dicarboxylic acid or a tetracarboxylic dianhydride with a diol having a fluoroalkyl group or a fluoroalkoxy group.

[0262] <(h1) Introduction of Liquid-Repellent Group> The liquid repellent group may be, for example, at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group.

[0263] The fluoroalkyl group has 3 to 10 carbon atoms, and preferably has 4 to 10 carbon atoms. Examples of such fluoroalkyl groups include 2,2,2-trifluoroethyl groups, 2,2 , 3,3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 3-perfluorobutyl-2-hydroxypropyl group, 2-(perfluorohexyl)ethyl group, 3-perfluorohexyl-2-hydroxypropyl group, 2-(perfluorooctyl)ethyl group, 3-perfluorooctyl-2-hydroxypropyl group, 2-(perfluorodecyl)ethyl group, 2-(perfluoro-3-methylbutyl)ethyl group, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl group, 2-(perfluoro-5-methylhexyl)ethyl group, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl group, 2-(perfluoro-7-methyloctyl)ethyl group, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl group.

[0264] In order to introduce a fluoroalkyl group having 3 to 10 carbon atoms into the polymer which is the component (h) of the present invention, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms may be copolymerized.

[0265] Specific examples of the monomer having a fluoroalkyl group having 3 to 10 carbon atoms when component (h) is an acrylic polymer include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl acrylate, 2-(perfluorobutyl)ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 3 -Perfluorobutyl-2-hydroxypropyl methacrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2-(perfluorooctyl)ethyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxy Propyl methacrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-3-methylbutyl)ethyl acrylate, 2-(perfluoro-3-methylbutyl)ethyl methacrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-5-methylhexyl)ethyl acrylate, 2-(perfluoro-5-methylhexyl)ethyl perfluoro-5-methylhexyl)ethyl methacrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-7-methyloctyl)ethyl acrylate, 2-(perfluoro-7-methyloctyl)ethyl methacrylate, 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl acrylate, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl methacrylate.

[0266] The polyfluoroether group includes an Rf group having a polyfluoroether structure represented by the following formula 3. -(XO) n -Y···Equation 3 In formula 3, X represents a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and each unit grouped by n represents the same or different groups, Y represents a hydrogen atom (only when a fluorine atom is not bonded to the carbon atom adjacent to the oxygen atom adjacent to Y), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer from 2 to 50, with the proviso that the total number of fluorine atoms in formula 3 is 2 or more.

[0267] As a preferred embodiment of X and Y in formula 3, X is an alkylene group having 1 to 10 carbon atoms which has been fluorinated by removing one hydrogen atom or a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit grouped by n represents the same group or a different group, and Y is an alkyl group having 1 to 20 carbon atoms which has been fluorinated by removing one hydrogen atom or a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0268] As a more preferred embodiment of X and Y in formula 3, X is a perfluorinated alkylene group having 1 to 10 carbon atoms, each unit grouped by n being the same or different, and Y is a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0269] In formula 3, n represents an integer of 2 to 50. n is preferably 2 to 30, and more preferably 2 to 15. When n is 2 or more, the liquid repellency is good. When n is 50 or less, when the polymer, which is component (A), is synthesized by copolymerizing a monomer having an Rf group with a monomer having a hydroxyl group, a carboxyl group, an amide group, an amino group, an N-alkoxymethylamide group, a blocked isocyanate group, or a trialkoxysilyl group, or with another monomer, the compatibility of the monomers is good.

[0270] The total number of carbon atoms in the Rf group consisting of the polyfluoroether structure represented by formula 3 is preferably 2 to 50, more preferably 2 to 30. Within this range, the polymer (h) exhibits good liquid repellency. When the polymer (h) is synthesized by copolymerizing a monomer having an Rf group with a monomer having a hydroxyl group, a carboxyl group, an amide group, an amino group, an N-alkoxymethylamide group, a blocked isocyanate group, or a trialkoxysilyl group, or with another monomer, the compatibility of the monomers is good.

[0271] Specific examples of X include -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF(CF3)-, -CF2CF2CF2CF2-, -CF2CF2CF(CF3)-, and CF2CF(CF3)CF2-.

[0272] Specific examples of Y include -CF3, -CF2CF3, -CF2CHF2, -(CF2)2CF3, -(CF2)3CF3, -(CF2)4CF3, -(CF2)5CF3, -(CF2)6CF3, -(CF2)7CF3, -(CF2)8CF3, -(CF2)9CF3, and (CF2) 11 CF3, -(CF2) 15 CF3 is an example.

[0273] A preferred embodiment of the Rf group having a polyfluoroether structure represented by formula 3 is an Rf group represented by formula 4. -C p-1 F 2(p-1) -O-(Cp F 2p -O) n-1 -C q F 2q+1 ...Formula 4 In formula 4, p represents an integer of 2 or 3 and is the same group for each unit grouped by n; q represents an integer of 1 to 20; and n represents an integer of 2 to 50.

[0274] Specific examples of the Rf group represented by formula 4 include: -CF2O(CF2CF2O) n-1 CF3 (n is 2 to 9), -CF(CF3)O(CF2CF(CF3)O) n-1 C6F 13 (n is 2 to 6), -CF(CF3)O(CF2CF(CF3)O) n-1 C3F7(n is 2 to 6) are preferred from the viewpoint of ease of synthesis.

[0275] The Rf groups in the polymer that is the component (h) may all be the same or different.

[0276] The silyl ether group is a group in which the hydroxyl group of an alcohol is protected with a trialkylsilyl group. The preferred group is a group represented by the following formula: -X 4 -Si(O-SiX 1 X 2 X 3 )3 (In the formula, X 1 , X 2 , X 3 each independently represents an alkyl group having 1 to 3 carbon atoms; 4 represents an alkylene group having 1 to 6 carbon atoms.

[0277] In order to introduce a silyl ether group into the polymer which is the component (h) of the present invention, a monomer having a silyl ether group may be copolymerized.

[0278] When component (h) is an acrylic polymer, examples of the monomer having a silyl ether group include methacryloxypropyltris(trimethylsiloxy)silane and acryloxypropyltris(trimethylsiloxy)silane.

[0279] The polysiloxane group includes a group having a polysiloxane structure represented by formula 5. Hereinafter, the group having a polysiloxane structure represented by formula 5 will be referred to as a pSi group. -(SiR 1 R 2 -O) n -SiR 1 R 2 R 3 ...Formula 5 (However, R 1 , R 2 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group; R 3 represents hydrogen or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200.

[0280] R 1 , R 2 independently represent hydrogen, an alkyl group, a cycloalkyl group, or an aryl group, and may be the same or different for each siloxy unit. Since the polymer of component (h) exhibits good liquid repellency, R 1 , R 2 is preferably a hydrogen atom, a methyl group or a phenyl group, and further, R of all the siloxy units 1 , R 2 It is preferable that R is a methyl group. 3 may contain a nitrogen atom, an oxygen atom, etc.

[0281] Methods for introducing a pSi group into the polymer, component (h), include a method of copolymerizing a monomer having a pSi group, various modification methods in which a polymer having a reactive site is reacted with a compound having a pSi group, and a method using a polymerization initiator having a pSi group.

[0282] Examples of monomers having a pSi group include CH2=CHCOO(pSi), CH2=C(CH3)COO(pSi), etc. Here, pSi represents a pSi group. The monomers having a pSi group may be used alone or in combination of two or more kinds.

[0283] Examples of various modification methods for reacting a polymer having a reactive site with a compound having a pSi group include the following methods.

[0284] A method in which a monomer having an epoxy group is copolymerized in advance, and then reacted with a compound having a carboxyl group at one end and a pSi group at the other end.A method in which a monomer having an epoxy group is copolymerized in advance, and then reacted with a compound having an amino group at one end and a pSi group at the other end.A method in which a monomer having an epoxy group is copolymerized in advance, and then reacted with a compound having a mercapto group at one end and a pSi group at the other end.A method in which a monomer having an amino group is copolymerized in advance, and then reacted with a compound having a carboxyl group at one end and a pSi group at the other end.

[0285] A method in which a monomer having an amino group is copolymerized in advance, and then a compound having an epoxy group at one end and a pSi group at the other end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an epoxy group at one end and a pSi group at the other end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an amino group at one end and a pSi group at the other end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having a silyl chloride group at one end and a pS A method of reacting a compound having an i group with a monomer having a hydroxyl group, and then reacting it with a compound having a silyl chloride group at one end and a pSi group at the other end.

[0286] The polymerization initiator having a pSi group may contain a group having a divalent polysiloxane structure in the main chain of the initiator molecule, or may contain a group having a monovalent polysiloxane structure in the terminal portion or side chain of the initiator molecule. Examples of initiators having a group having a divalent polysiloxane structure in the main chain of the initiator molecule include compounds having a group having a divalent polysiloxane structure and an azo group alternately. Examples of commercially available products include VPS-1001 and VPS-0501 (both manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0287] The component (h) is preferably a polymer further having (h2): a group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group.

[0288] <(h2): Introduction of a group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group> To introduce a group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group into the polymer, which is component (h), a monomer having a group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group may be copolymerized.

[0289] When component (h) is an acrylic polymer, examples of the monomer having an N-alkoxymethylamide group include (meth)acrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide.

[0290] When component (h) is an acrylic polymer, examples of the monomer having a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.

[0291] When the component (h) is an acrylic polymer, examples of the monomer having a trialkoxysilyl group include 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, and 3-triethoxysilylpropyl methacrylate.

[0292] The component (h) is preferably a polymer further having (h3) at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group.

[0293] <(h3) Introduction of at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group> In order to introduce (h3) at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group into the polymer, which is the component (h) of the present invention, a monomer having (h3) at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group may be copolymerized.

[0294] When the component (h) is an acrylic polymer, examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, and mono-(2-(methacryloyloxy)ethyl)phthalate. , N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and the like.

[0295] Examples of monomers having a hydroxy group when component (h) is an acrylic polymer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy)ethyl ester, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol), Examples of the monomer include 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-hydroxyphenylacrylamide, N-hydroxyphenylmethacrylamide, p-hydroxyphenylacrylate, and p-hydroxyphenylmethacrylate. Among these, monomers selected from 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

[0296] When the component (h) is an acrylic polymer, examples of the monomer having an amide group include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, etc. Among these, methacrylamide is preferred.

[0297] When component (h) is an acrylic polymer, examples of monomers having an amino group include aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.

[0298] In the case where the component (h) is an acrylic polymer, the method for producing the polymer of the component (h) can be obtained by polymerizing a monomer having a liquid repellent group, for example, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms, a monomer having a polyfluoroether group, a monomer having at least one group selected from the group consisting of an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group, and optionally a monomer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group, at a temperature of 50°C to 110°C in a solvent in the presence of a polymerization initiator. The solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble polymer and the polymer having a specific functional group. Specific examples include the solvents described in the component (c) described above.

[0299] Specific examples of other monomers h include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-1,1-dimethylethyl methacrylate, 1,2 ... ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, vinyl naphthalene, vinyl anthracene, and vinyl biphenyl.

[0300] The polymer having a specific functional group thus obtained is usually in the state of a solution dissolved in a solvent.

[0301] The solution of the specific copolymer obtained as described above can be reprecipitated by adding diethyl ether or water under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the specific copolymer. By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. If the specific copolymer cannot be sufficiently purified by a single operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated. In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the above-mentioned component (c) and used in the form of a solution.

[0302] In the polymer of component (h), the amount of the liquid repellent group (h1) introduced is preferably 5 mol% to 60 mol% based on the total repeating units, and more preferably 5 mol% to 40 mol%. If it is less than 5 mol%, the liquid repellency effect may not be achieved. If it is more than 60 mol%, problems such as aggregation may occur.

[0303] In the polymer of component (h) above, the amount of group (h2) selected from N-alkoxymethylamide group, blocked isocyanate group, and trialkoxysilyl group introduced is preferably 5 mol% to 70 mol%, more preferably 5 mol% to 50 mol% based on the total repeating units. If it is less than 5 mol%, the heat resistance and solvent resistance of the resulting film may be problematic. If it is more than 60 mol%, the developability may be affected.

[0304] In the case where at least one group (h3) selected from the group consisting of hydroxyl group, carboxyl group, amide group and amino group is introduced into the polymer of the component (h), the amount introduced is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 40 mol% based on the total repeating units. If it is less than 5 mol%, the effect of improving the heat resistance and solvent resistance of the obtained film may not be obtained. If it is more than 60 mol%, the repeating units having liquid repellency become too small.

[0305] The number average molecular weight of the polymer of component (h) is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 4,000 to 10,000. If the number average molecular weight is more than 100,000, residues may be generated.

[0306] In the present invention, the polymer of component (h) may be a mixture of multiple types of specific copolymers.

[0307] The ratio of component (h) to component (a) is 0.1 to 20 parts by mass of component (h) per 100 parts by mass of component (a).

[0308] When the component (a) has the liquid repellent group (h1) in the component (h), the component (a) can also serve as the component (h), and in this case it is not always necessary to use the component (h). In this case, it is preferable that the polymerized unit (monomer) having the liquid repellent group (h1) accounts for 5 to 30 parts by mass in 100 parts by mass of the component (a).

[0309] <Other additives> Furthermore, the second photosensitive resin composition used in the present invention may contain, as necessary, a leveling agent, a surfactant, a rheology modifier, a storage stabilizer, an antifoaming agent, an adhesion promoter, or a dissolution promoter such as a polyhydric phenol or a polyvalent carboxylic acid, as long as the effects of the present invention are not impaired. As the surfactant, the same ones as those listed in <Other additives> used in the composition for forming the upper layer film described above can be used. In order to fulfill the role of liquid repellency, the surfactant may be used simultaneously with component (h), or only one type may be used.

[0310] <Bank formation process> After forming the resist film 13, the underlayer film 12 and the resist film 13 are collectively patterned by exposure and development to form a bank. A region partitioned by the bank (non-bank portion) is formed in the opening 14 (see FIG. 1).

[0311] 1, when the first and second photosensitive resin compositions are positive photosensitive resin compositions, the exposed portions are non-bank portions, which are removed together with the underlayer film of the non-bank portions and the resist film of the non-bank portions in the development process, forming openings 14. Alternatively, when the first and second photosensitive resin compositions of the present invention are negative photosensitive resin compositions, the exposed portions are bank portions, which are removed together with the underlayer film of the non-bank portions and the resist film of the non-bank portions in the development process.

[0312] In the conventional second photosensitive resin composition, residues are left behind during the development process, making it difficult to remove the composition cleanly. The residues left behind cause defects such as unevenness in the organic thin film during the process of forming an organic thin film in the region partitioned by the bank. If the bank is formed by the method for forming a bank pattern of the present invention, residues are unlikely to remain on the substrate or on other layers on the substrate, making it possible to produce a clean organic thin film.

[0313] Here, in the case of an organic electroluminescent device, examples of other layers that can be formed on the substrate 11 include an anode, a cathode, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a blocking layer, and a light emitting layer. When the bank pattern forming method of the present invention is used for an organic electroluminescent device, the other layer is particularly preferably a hole injection layer of an organic electroluminescent device. The other layer is composed of at least one layer.

[0314] <Photosensitive resin composition> The first photosensitive resin composition used in the present invention is a photosensitive resin composition containing the following components (A), (C), and (D), and may further contain, if desired, one or more of a crosslinking agent (component (E)), a compound having two or more ethylenic polymerizable groups (component (F)), a compound having two or more functional groups that form a covalent bond with an acid (component (G)), and other additives. Component (A): an alkali-soluble resin having an amide group, (C) component: solvent, (D) Ingredient: Photosensitizer.

[0315] Among them, preferred examples of the first photosensitive resin composition used in the present invention are as follows. [1]: A first photosensitive resin composition comprising 5 to 100 parts by mass of a component (D) per 100 parts by mass of a component (A), the components being dissolved in a component (C), the component (D) being a component (D-1). [2]: A first photosensitive resin composition comprising 5 to 100 parts by mass of a component (D) per 100 parts by mass of the component (A), the components being dissolved in a component (C), and further comprising 1 to 50 parts by mass of a crosslinking agent, which is a component (E), per 100 parts by mass of the component (A), wherein the component (D) is a component (D-1). [3]: A first photosensitive resin composition comprising 5 to 200 parts by mass of a component (F) per 100 parts by mass of the component (A), and 0.1 to 30 parts by mass of a component (D) per 100 parts by mass of the combined total of the components (A) and (F), dissolved in a component (C), wherein the component (D) is a component (D-2).

[0316] The solid content in the first photosensitive resin composition used in the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1% by mass to 80% by mass, or, for example, 5% by mass to 60% by mass, or 10% by mass to 50% by mass. Here, the solid content refers to the total components of the photosensitive resin composition excluding component (C).

[0317] The method for preparing the first photosensitive resin composition used in the present invention is not particularly limited, but examples of the preparation method include a method in which an alkali-soluble resin having an amide group (A) is dissolved in a component (C), and this solution is mixed with a photosensitizer (D), if necessary a crosslinking agent (E), a compound having two or more ethylenic polymerizable groups (F), and a compound having two or more functional groups that form a covalent bond with an acid (G) in a predetermined ratio to prepare a homogeneous solution, or a method in which other additives are further added and mixed at an appropriate stage of this preparation method, if necessary.

[0318] In preparing the first photosensitive resin composition used in the present invention, the solution of the copolymer obtained by the polymerization reaction in the component (C) can be used as is, and in this case, when the components (A), (D), and if necessary the components (E), (F), and (G) are added to prepare a uniform solution, the component (C) may be added for the purpose of adjusting the concentration. In this case, the component (C) used in the process of forming the specific copolymer and the component (C) used for adjusting the concentration in preparing the first photosensitive resin composition may be the same or different.

[0319] The solution of the first photosensitive resin composition thus prepared is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

[0320] The second photosensitive resin composition used in the present invention is a photosensitive resin composition containing the following components (a), (b), (c), and (d), and may further contain, if desired, one or more of a crosslinking agent (e), a compound having two or more ethylenic polymerizable groups (f), a compound having two or more functional groups that form a covalent bond with an acid (g), a component (h) and / or a component (q), and other additives. (a) component: alkali-soluble resin, (b) Component: fine particles, (c) component: solvent, (d) Ingredient: Photosensitizer.

[0321] Preferred examples of the second photosensitive resin composition used in the present invention are as follows. [1]: A second photosensitive resin composition comprising 0.1 to 20 parts by mass of component (h) per 100 parts by mass of component (a), the components being dissolved in component (c). [2]: A second photosensitive resin composition comprising, per 100 parts by mass of the component (a), 0.1 to 20 parts by mass of the component (h) and 5 to 100 parts by mass of the component (d), which are dissolved in the component (c), and further comprising the component (d-1) as the second photosensitive resin composition. [3]: A second photosensitive resin composition comprising 0.1 to 20 parts by mass of a component (h) and 5 to 100 parts by mass of a component (d) per 100 parts by mass of the component (a), wherein these components are dissolved in a component (c), and further comprising 1 to 50 parts by mass of a crosslinking agent as a component (e) per 100 parts by mass of the total of the components (a) and (h), wherein the component (d) is a component (d-1). [4]: A second photosensitive resin composition comprising: 0.1 to 20 parts by mass of a component (h) per 100 parts by mass of the component (a); 5 to 200 parts by mass of a component (f) per 100 parts by mass of the total of the components (a) and (b); and 0.1 to 30 parts by mass of a component (d) per 100 parts by mass of the total of the components (a), (b), and (f), dissolved in a component (c); and wherein the component (d) is a component (d-2). [5]: A second photosensitive resin composition comprising a component (a) containing a liquid repellent group (h1), wherein 5 to 30 parts by mass of polymerization units having a liquid repellent group (h1) are contained in 100 parts by mass of component (a) not including component (h).

[0322] The proportion of solids in the second photosensitive resin composition used in the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1% by mass to 80% by mass, or, for example, 5% by mass to 60% by mass, or 10% by mass to 50% by mass. Here, the solids refers to all the components of the second photosensitive resin composition excluding component (c).

[0323] The method for preparing the second photosensitive resin composition used in the present invention is not particularly limited, but examples of the preparation method include a method in which component (h) (specific polymer) is dissolved in component (c), and this solution is mixed with component (a) alkali-soluble resin, component (b) fine particles, component (d) photosensitizer, and optionally component (e) crosslinking agent, component (f) compound having two or more ethylenic polymerizable groups, and component (g) compound having two or more functional groups that form covalent bonds with an acid in a predetermined ratio to obtain a homogeneous solution, or a method in which other additives are further added and mixed at an appropriate stage of this preparation method as necessary.

[0324] In preparing the second photosensitive resin composition used in the present invention, the solution of the copolymer obtained by the polymerization reaction in the (c) component can be used as it is, and in this case, when the (a), (d) component, and if necessary the (e), (f) and (g) components are added to the solution of this (h) component to prepare a uniform solution as in the preparation of the first photosensitive resin composition, the (c) component may be added for the purpose of adjusting the concentration. In this case, the (c) component used in the process of forming the specific copolymer and the (c) component used for adjusting the concentration in the preparation of the second photosensitive resin composition may be the same or different.

[0325] The solution of the second photosensitive resin composition thus prepared is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

[0326] <Coating film and cured film as undercoat film> The first photosensitive resin composition used in the present invention can be applied onto a semiconductor substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal (e.g., aluminum, molybdenum, chromium), a glass substrate, a quartz substrate, an ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, inkjet coating, or the like, and then pre-dried on a hot plate or in an oven, etc., to form a coating film. The coating film is then heat-treated to form a photosensitive resin film as an underlayer film.

[0327] The conditions for this heat treatment are, for example, a heating temperature of 70° C. to 160° C. and a heating time of 0.3 to 60 minutes, and are preferably 80° C. to 140° C. and 0.5 to 10 minutes.

[0328] The thickness of the photosensitive resin film formed from the first photosensitive resin composition is, for example, 0.1 μm to 30 μm, or, for example, 0.2 μm to 10 μm, or, for example, 0.3 μm to 8 μm.

[0329] <Coated film and cured film as resist film> The second photosensitive resin composition used in the present invention can be applied onto the underlayer film obtained above by spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, inkjet coating, or the like, and then pre-dried on a hot plate or in an oven, etc., to form a coating film. Then, the coating film is heat-treated to form a photosensitive resin film as a resist film.

[0330] The conditions for this heat treatment are, for example, a heating temperature of 70° C. to 160° C. and a heating time of 0.3 to 60 minutes, and are preferably 80° C. to 140° C. and 0.5 to 10 minutes.

[0331] The thickness of the photosensitive resin film formed from the second photosensitive resin composition is, for example, 0.1 μm to 30 μm, or, for example, 0.2 μm to 10 μm, or, for example, 0.3 μm to 8 μm.

[0332] A mask having a predetermined pattern is attached to the coating of the underlayer film and the resist film on the underlayer film obtained above, and light such as ultraviolet light is irradiated and developed with an alkaline developer, whereby either the exposed or unexposed areas are washed out depending on the material composition, and the remaining patterned film is heated at 80°C to 140°C for 0.5 to 10 minutes as necessary to obtain a sharp relief pattern on the end faces.

[0333] Examples of the alkaline developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can be added to these developers.

[0334] Among the above, an aqueous solution of 0.1 to 2.58 mass % tetraethylammonium hydroxide is generally used as a developer for photoresists, and the first and second photosensitive resin compositions of the present invention can also be developed satisfactorily using this alkaline developer without causing problems such as film swelling.

[0335] In addition, the development method can be any of the following: liquid puddle method, dipping method, and rocking immersion method. The development time is usually from 15 to 180 seconds.

[0336] After development, the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove water from the substrate and obtain a patterned film.

[0337] Subsequently, the pattern-forming film is post-baked for thermal curing, specifically by heating using a hot plate, oven, or the like, to obtain a film having excellent heat resistance, transparency, flattening properties, low water absorption, chemical resistance, and the like, and having a good relief pattern.

[0338] The post-bake step generally involves treating the substrate at a heating temperature selected from the range of 140° C. to 270° C. for 5 to 30 minutes on a hot plate or for 30 to 90 minutes in an oven.

[0339] Thus, by such post-baking, a cured film having a desired good pattern shape can be obtained.

[0340] As described above, the method for patterning a cured film makes it possible to form a liquid-repellent bank pattern in which residues such as components of a liquid-repellent resist material are unlikely to remain in areas other than the banks, and a uniform organic thin film can be formed within the areas partitioned by the banks. EXAMPLES

[0341] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The molecular weight of the polymer was measured as follows. [Measurement of molecular weight of polymer] The molecular weight of the polymer was measured using a GPC system manufactured by JASCO Corporation as an apparatus and Shodex (registered trademark) KF-804L and 803L as columns under the following conditions. Column oven: 40℃ Flow rate: 1mL / min Eluent: Tetrahydrofuran

[0342] The abbreviations used in the following examples have the following meanings. QDC: 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 4-hydroxyphenyl methacrylate CHMI: N-cyclohexylmaleimide PFHMA: 2-(perfluorohexyl)ethyl methacrylate TMSSMA: Methacryloxypropyltris(trimethylsiloxy)silane KBM-503: 3-Methacryloxypropyltriethoxysilane MAA: Methacrylic acid MAAm: methacrylamide HPMA-QD: A compound synthesized by the condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate with 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. AIBN: α,α'-azobisisobutyronitrile QD1: 1 mol of α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride Compounds synthesized by condensation reaction with 2 moles of aldehyde QD2: A compound synthesized by the condensation reaction of 1 mol of 4,4',4"-(3-methyl-1-propanyl-3-ylidene)trisphenol with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. CST: A styrene polymer made by mixing a polymer of 85% hydroxystyrene and 15% styrene with a polymer of 70% hydroxystyrene and 30% styrene in a ratio of 3:7 (manufactured by Maruzen Petrochemical Co., Ltd.) 8KQ: 8KQ-2001 (Taisei Fine Chemical Co., Ltd., alkali-soluble UV-curable acrylic resin) Poly-AA: Polyacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) I907: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907, manufactured by BASF) DEAB: 4,4'-bis(diethylamino)benzophenone DPHA: Dipentaerythritol hexaacrylate OXE-02: IRGACURE OXE-02 (manufactured by BASF) GT-401: butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone YH-434L: YH-434L manufactured by Nippon Chemical Epoxy Manufacturing Co., Ltd. (now Nippon Steel & Sumikin Chemical Co., Ltd.) CEL-2021P: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate R-30: Megafac R-30 (DIC Corporation) CB1: Propylene glycol monomethyl ether acetate dispersed carbon black (manufactured by Mikuni Color Co., Ltd.) CB2: Propylene glycol monomethyl ether dispersed carbon black (manufactured by Mikuni Color Co., Ltd.) TB1: Propylene glycol monomethyl ether acetate dispersion titanium black (Mitsubishi Materials Corporation) PMA-ST: Propylene glycol monomethyl ether acetate dispersed silica sol (Nissan Chemical Co., Ltd.) OZ-S30K: Nanouse OZ-S30K (MEK dispersed zirconia sol, manufactured by Nissan Chemical Industries, Ltd.) PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate CH: Cyclohexanone

[0343] <Synthesis Example 1> 3.00g of MAAm, 3.00g of HPMA, 4.00g of CHMI, and 0.8g of AIBN were dissolved in 43.2g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid concentration 30% by mass) (P1). The Mn and Mw of the obtained acrylic polymer were 3000 and 6200, respectively.

[0344] <Synthesis Example 2> 3.00g of MAAm, 3.00g of HPMA, 4.00g of CHMI, and 0.8g of AIBN were dissolved in 43.2g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid concentration 30% by mass) (P2). The Mn and Mw of the obtained acrylic polymer were 3000 and 6400, respectively.

[0345] <Synthesis Example 3> 3.00g of MAAm, 3.00g of HPMA, 4.00g of CHMI, and 0.8g of AIBN were dissolved in 43.2g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid concentration 30% by mass) (P3). The Mn and Mw of the obtained acrylic polymer were 3500 and 7500, respectively.

[0346] <Synthesis Example 4> 14.6g of MAA, 25.5g of HEMA, 24.6g of MMA, 35.3g of CHMI, and 6.0g of AIBN were dissolved in 159.6g of PGMEA and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid concentration 40% by mass) (P4). The Mn and Mw of the obtained acrylic polymer were 2400 and 4700, respectively.

[0347] <Synthesis Example 5> MAA 90.00g, HEMA 225.00g, HPMA 45.00g, MMA 180.00g of toluene, 360.00g of CHMI, and 57.60g of AIBN were dissolved in 1436.40g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid concentration 40% by mass) (P5). The obtained acrylic polymer had an Mn of 3100 and an Mw of 6100.

[0348] <Synthesis Example 6> 2.50 g of HPMA-QD, 2.58 g of TMSSMA, 5.26 g of PFHMA, 0.70 g of MAA, 1.46 g of CHMI, and 0.33 g of AIBN were dissolved in 51.3 g of CH, and the mixture was stirred at 110° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: The resulting acrylic polymer had an Mn of 7,200 and an Mw of 11,000.

[0349] The components (A), (D) and (E) and a solvent were mixed according to the compositions shown in Table 1 to prepare first photosensitive resin compositions of underlayer film materials 1 to 7. [Table 1]

[0350] Similarly, second photosensitive resin compositions of upper resist layer materials 1 to 7 were prepared according to the compositions shown in Table 2. The composition ratios in Tables 1 and 2 represent the ratios in terms of solid content.

[0351] [Table 2]

[0352] [Evaluation 1: Evaluation of pattern shape] The resin compositions of the lower layer materials 1 to 7 were applied onto an ITO-glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film of the lower layer material with a thickness of 0.2 μm. Next, the photosensitive resin compositions of the upper layer materials 1 to 7 were applied onto the coating film of the lower layer material using a spin coater, and then prebaked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film of the upper layer material with a thickness of 1.1 μm. This coating film was irradiated with ultraviolet light having a light intensity of 2.6 mW / cm2 at 365 nm for a certain period of time using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. through a photomask on which a 50 μm line & space pattern was drawn. Thereafter, the coating film was immersed in a 2.38 mass % or 0.4 mass % tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for a certain period of time, and then washed with running ultrapure water for 30 seconds. The coating film was then post-baked by heating at a temperature of 230° C. for 30 minutes. 5, Reference examples 6, 7Substrates of Comparative Examples 1 to 11 were also prepared. In Comparative Examples 1 to 7, substrates were prepared in the same manner as above, without carrying out the coating and pre-baking steps of Underlayer Materials 1 to 7. The state of the line and space patterns thus prepared was observed under an optical microscope. Patterns which had peeled off from the substrate were rated as "peeled", patterns where particulate residues were found on the substrate in the space areas were rated as "residue", and patterns which had been formed without peeling were rated as "good". The results are shown in Table 3.

[0353] [Evaluation 2: Evaluation of bank contact angle] The photosensitive resin composition of the lower layer material 2 was applied onto an ITO-glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film of the lower layer material with a thickness of 0.2 μm. Next, the photosensitive resin composition of the upper layer material 4 was applied onto the coating film of the lower layer material using a spin coater, and then prebaked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film of the upper layer material with a thickness of 1.1 μm. Thereafter, the coating film was immersed in a 2.38 mass % or 0.4 mass % TMAH aqueous solution for a predetermined time, and then washed with running ultrapure water for 30 seconds. Next, this coating film was postbaked by heating at a temperature of 230° C. for 30 minutes to form a cured film on the ITO-glass substrate of Example 4. In Examples 1 to 3, a cured film consisting of the upper layer material and the lower layer material was formed on the ITO-glass substrate in the same manner as above without exposure to ultraviolet light. In Comparative Example 4, a cured film consisting of only upper layer material 4 was formed on an ITO-glass substrate in the same manner as above, without carrying out the coating and pre-baking process of lower layer material 2. The contact angle of anisole on this cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 3. Evaluation 2 was carried out only for Example 4 and Comparative Example 4, in which the upper layer material contained component (h).

[0354] [Evaluation 3: Evaluation of contact angle of exposed area on ITO substrate] The photosensitive resin composition of the lower layer material 2 was applied onto an ITO-glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film of the lower layer material with a thickness of 0.2 μm. Next, the photosensitive resin composition of the upper layer material 4 was applied onto the coating film of the lower layer material using a spin coater, and then prebaked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film of the upper layer material with a thickness of 1.1 μm. This coating film was irradiated with ultraviolet light having a light intensity of 2.6 mW / cm2 at 365 nm for a certain period of time using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, the coating film was immersed in a 2.38 mass % or 0.4 mass % TMAH aqueous solution for a predetermined period of time, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230° C. for 30 minutes to form a cured film on the ITO-glass substrate of Example 4. In Examples 1 to 3, a cured film consisting of upper and lower layer materials was formed on an ITO-glass substrate in the same manner as above, without exposure to ultraviolet light. In Comparative Example 4, a cured film consisting of only upper layer material 4 was formed on an ITO-glass substrate in the same manner as above, without performing the coating and pre-baking process of lower layer material 2. The contact angle of anisole on this cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 3. Evaluation 3 was carried out only for Example 4 and Comparative Example 4, in which the upper layer material contained component (h).

[0355] [Table 3]

[0356] As shown in Table 3, in Evaluation 1, residues were observed in all of Comparative Examples 1 to 7 in which no underlayer material was used, whereas in Examples 1 to 5, Reference examples 6, 7 In all the cases, no residue was observed and a good pattern shape was obtained. In addition, in the cases of Comparative Examples 8 to 11 in which a hydrophilic resin not containing an amide group was used as the underlayer material, the pattern peeled off during development in Evaluation 1 and did not remain on the substrate.

Claims

1. A photosensitive resin composition for forming an underlayer film of a resist film, comprising the following components (A), (C), (D) and (E): Component (A): an alkali-soluble resin having an amide group (the amide group is derived from at least one monomer selected from acrylamide and methacrylamide), (C) component: solvent, Component (D): a photosensitizer which is a diazonaphthoquinone, or a compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group, in which 10 mol % to 100 mol % of the hydroxy groups or amino groups of the compound (in the case of having both a hydroxy group and an amino group, the total amount of the hydroxy groups or the amino groups) are esterified or amidated with 1,2-quinonediazidesulfonic acid, Component (E): Crosslinking agent

2. The photosensitive resin composition for forming an underlayer film of a resist film according to claim 1 , further satisfying the following (Z2): (Z2): The alkali-soluble resin having an amide group of the component (A) further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group.

3. 3. The photosensitive resin composition for forming an underlayer film of a resist film according to claim 1, wherein the alkali-soluble resin having an amide group as component (A) has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.

4. 4. The photosensitive resin composition for forming an underlayer film of a resist film according to claim 1, wherein the component (E) is 1 part by mass to 50 parts by mass per 100 parts by mass of the component (A).

5. A cured film formed from the photosensitive resin composition for forming an underlayer film of a resist film according to any one of claims 1 to 4.

6. A display device comprising the cured film according to claim 5 .

7. A display device having the cured film according to claim 5 as a partition wall for image formation.

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