Method of forming a bank pattern

Abstract

To provide a formation method of a bank pattern.SOLUTION: A formation method of a bank pattern includes: an underlay film formation step of coating a first photosensitive resin composition which contains following component (A), component (C) and component (D) and contains no component (E) directly onto a substrate or through other layer, and providing an underlayer film; a resist film formation step of coating a second photosensitive resin composition containing the following component (a), component (b), component (c) and component (d) onto the underlay film, and providing a resist film; and a bank formation step of exposing and developing the resist film, thereby forming a bank, and removing an underlay film of a non-bank part in the development step together with the resist film of the non-bank part. Component (A): an alkali-soluble resin having an amide group, component (C): a solvent, component (D): a photosensitizing agent, component (E): a crosslinking agent, component (a): an alkali-soluble resin, component (b): a polymer having a water-repellent group (b1), component (c): a solvent, and component (d): a photosensitizing agent.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 this photosensitive resin composition is particularly suitable as a method for forming an interlayer insulating film in a liquid crystal display or an EL display, a light-shielding wall or a partition corresponding to an inkjet method.

Background Art

[0002] In recent years, full-color display substrate manufacturing technology using inkjet has been actively studied in the manufacturing process of display elements such as thin-film transistor (TFT) type liquid crystal display elements and organic EL (electroluminescent) elements. For example, regarding the production of color filters in liquid crystal display elements, a color filter and its manufacturing method (Patent Document 1) in which a partition (hereinafter referred to as a bank) that defines a pixel pre-patterned with respect to a conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method is formed of a photosensitive resin layer that blocks light, and ink droplets are dropped into the region surrounded by this bank have been proposed. Also, a method (Patent Document 2) for producing an organic EL display element by producing a bank in advance and dropping ink that will similarly become a light-emitting layer has been proposed. However, when dropping ink droplets into the region surrounded by the bank by the inkjet method, it is necessary to make the substrate have ink affinity (hydrophilicity) and make the bank surface have water repellency in order to prevent the situation where the ink droplets overflow to adjacent pixels beyond the bank.

[0003] In order to achieve the above object, it has been proposed that hydrophilicity can be imparted to a substrate and water repellency can be imparted to a bank by continuous plasma (ozone) treatment such as oxygen gas plasma treatment and fluorine gas plasma treatment (Patent Document 3), but the process is complicated. In addition, a proposal has been made to incorporate a fluorine-based surfactant or a fluorine-based polymer into a photosensitive organic thin film (Patent Document 4). However, there are many points to be considered, including not only photosensitivity but also coatability, such as compatibility and addition amount. Moreover, since the water repellency of the surface decreases during UV ozone treatment for hydrophilic treatment of the substrate, it has not been practical.

[0004] In addition, in order to achieve the above object, a method has been proposed in which a layer containing a hydrophilic compound is provided under a bank material having liquid repellency, and the bank opening portion that should have lyophilicity due to the components of the bank material is prevented from being contaminated by developing and removing it together with the upper bank material (Patent Documents 5 to 7). However, this method has a problem that moisture absorption easily occurs because the hydrophilicity of the lower layer is high, and there is also a problem that pattern peeling easily occurs during the developing process.

[0005] In addition, in order to achieve the above object, a method has been proposed in which an organic layer is provided under a bank material having liquid repellency, and after forming a pattern with the upper bank material, the lower layer is removed by a dry etching process to improve the lyophilicity of the bank opening (Patent Document 8). However, this method has a problem that the process becomes complicated.

[0006] In addition, Patent Documents 9 and 10 have been proposed as a method of forming a pattern by performing one exposure process and one developing process on a laminated two-layer organic layer. However, none of these are aimed at forming a bank pattern having liquid repellency. In addition, in the method of Patent Document 9, since the lower organic layer does not have photosensitivity, precise process control is required to control the pattern dimensions. In the method of Patent Document 10, heat treatment is required after the exposure process, and the process is complicated.

Prior Art Documents

Patent Documents

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

[0008] The present invention provides a method for forming a bank pattern in which residues such as components of a liquid-repellent resist material are less likely to remain in areas other than the bank, even when using a liquid-repellent bank that is simple in process and advantageous in production cost. [Means for Solving the Problems]

[0009] The inventors applied a first photosensitive resin composition containing an alkali-soluble resin having an amide group directly on a substrate or via another layer to provide an underlying film, and then applied a second photosensitive resin composition containing a polymer as a liquid-repellent component on the underlying film to provide a resist film. A bank was formed by exposing and developing the resist film. In this developing process, the inventors found that the underlying film in the non-bank portion was removed together with the resist film in the non-bank portion, thereby reducing the resist film residue containing the liquid-repellent component on the substrate and efficiently imparting water repellency and liquid repellency to the film surface while maintaining the lyophilicity of the opening, and thus completed the present invention. Here, the region where the bank is located on the substrate is defined as the bank portion, and the region other than the bank is defined as the non-bank portion.

[0010] That is, the present invention relates to the following. 1. A method for forming a bank and a region defined by the bank on a substrate, which is a method for forming a bank pattern for forming an organic thin film in the region defined by the bank, an underlying film forming step of applying a first photosensitive resin composition containing the following components (A), (C), and (D) directly on the substrate or via another layer to provide an underlying film, a resist film forming step of applying a second photosensitive resin composition containing the following components (a), (b), (c), and (d) on the underlying film to provide a resist film, a bank pattern forming method including a bank forming step of forming a bank by exposing and developing the resist film, and in the developing process, the underlying film in the non-bank portion is removed together with the resist film in the non-bank portion. Component (A): An alkali-soluble resin having an amide group, Component (C): A solvent, Component (D): A photosensitizer, Component (a): An alkali-soluble resin, Component (b): A polymer having a liquid-repellent group (b1), Component (c): A solvent, Component (d): A photosensitizer. 2. The method for forming the bank pattern according to the above 1, wherein the first photosensitive resin composition satisfies at least one of the following (Z1) to (Z4). (Z1): Further containing a crosslinking agent which is the (E) component; (Z2): The alkali-soluble resin having an amide group as the (A) component further has a self-crosslinkable group, or further has a 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; (Z3): The (D) component is a photo radical generator which is (D-2), and further contains a compound having two or more ethylenic double bonds as the (F) component; (Z4): The (D) component is a photoacid generator which is (D-3), and further contains a compound having two or more functional groups that form a covalent bond by the acid generated from (D-3) as the (G) component. 3. The method for forming the bank pattern according to the above 1 or 2, wherein the second photosensitive resin composition satisfies at least one of the following (z1) to (z4). (z1): Further containing a crosslinking agent which is the (e) component; (z2): The alkali-soluble resin having an amide group as the (a) component further has a self-crosslinkable group, or further has a 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; (z3): The (d) component is a photo radical generator which is (d-2), and further contains a compound having two or more ethylenic double bonds as the (f) component; (z4): The (d) component is a photoacid generator which is (d-3), and further contains a compound having two or more functional groups that form a covalent bond by the acid generated from (d-3) as the (g) component. 4. The method for forming the bank pattern according to any one of the above 1 to 3, wherein the (D) and / or (d) component is a quinonediazide compound. 5. The method for forming the bank pattern according to the above 2, wherein the (D) component is a quinonediazide compound and further satisfies any one of the above (Z1) or (Z2). 6. (d) The component is a quinonediazide compound, and further, the method for forming the bank pattern according to the above 3, which satisfies any one of (z1) or (z2). 7. The method for forming the bank pattern according to the above 5, wherein the component (D) is diazonaphthoquinone. 8. The method for forming the bank pattern according to the above 6, wherein the component (d) is diazonaphthoquinone. 9. The method for forming the bank pattern according to any one of the above 1 to 8, wherein the liquid-repellent group (b1) is 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 represented by the following formula 4. -(SiR 1 R 2 -O) n -SiR 1 R 2 R 3 Formula 4 (However, R 1 , R 2 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R 3 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200.) 10. The method for forming the bank pattern according to any one of the above 1 to 9, wherein the number average molecular weight of the alkali-soluble resin having an amide group of the component (A) and / or the alkali-soluble resin of the component (a) is 2,000 to 50,000 in terms of polystyrene. 11. The method for forming the bank pattern according to any one of the above 2 to 10, characterized in that the component (E) is 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). 12. The method for forming the bank pattern according to any one of the above 1 to 11, characterized by containing 0.1 to 20 parts by mass of the component (b) with respect to 100 parts by mass of the component (a). 13. The method for forming the bank pattern according to any one of the above 1 to 12, wherein the polymer of the component (b) is an acrylic polymer. 14. The method for forming the bank pattern according to the above 13, wherein the number average molecular weight of the acrylic polymer of the component (b) is 2,000 to 100,000 in terms of polystyrene. 15. Based on a total of 100 parts by mass of component (a) and component (b), component (e) is from 1 part by mass to 50 parts by mass, and the method for forming a bank pattern according to any one of claims 3 to 14 above. 16. The method for forming a bank pattern according to any one of claims 1 to 15 above, wherein component (b) is further a polymer having the following (b2). (b2): At least one group selected from an N - alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group. 17. The method for forming a bank pattern according to any one of claims 1 to 16 above, wherein component (b) is further a polymer having the following (b3). (b3): At least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. 18. The method for forming a bank pattern according to any one of claims 1 to 11 above, wherein the (a) component is a resin having a liquid - repellent group (b1) and does not contain the (b) component. 19. The method for forming a bank pattern according to claim 18 above, wherein the polymer unit having a liquid - repellent group (b1) occupies 5 parts by mass to 30 parts by mass in 100 parts by mass of the (a) component. 20. The method for forming a bank pattern according to claim 18 or 19 above, wherein based on 100 parts by mass of component (a), component (e) is from 1 part by mass to 50 parts by mass. 21. The method for forming a bank pattern according to any one of claims 1 to 20 above, wherein the other layer is a hole injection layer of organic electroluminescence. 22. A cured film formed by the method for forming a bank pattern according to any one of claims 1 to 21 above. 23. A display element having the cured film according to claim 22 above. 24. A display element having the cured film according to claim 22 above as an image - forming partition wall. 25. A photosensitive resin composition for forming an underlayer film of a resist film, containing the following components (A), (C), and (D). (A) component: An alkali - soluble resin having an amide group, (C) Component: Solvent, (D) Component: Photosensitive agent.

Advantages of the Invention

[0011] According to the method for forming a bank pattern of the present invention, even when using a liquid repellent bank that is simple in process and advantageous in production cost, by suppressing residues such as components of the liquid repellent resist material on the substrate surface in the non-bank portion, a bank pattern can be formed in which the lyophilicity of the substrate surface is improved. That is, it is possible to achieve both the liquid repellency of the bank and the lyophilicity of the non-bank portion, and a uniform organic thin film can be formed within the region partitioned by the bank.

Brief Description of the Drawings

[0012]

Figure 1

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the details of the method for forming a bank pattern of the present invention will be described. The method for forming a bank pattern of the present invention is a method for forming a bank and a region partitioned by the bank on a substrate, and in the method for forming a bank pattern for forming an organic thin film in the region partitioned by the bank, A lower layer film forming step of applying a first photosensitive resin composition containing the following components (A), (C), and (D) directly on the substrate or via another layer to provide a lower layer film, A resist film forming step of applying a second photosensitive resin composition containing the following components (a), (b), (c), and (d) on the lower layer film to provide a resist film, A bank forming step of exposing and developing the resist film to form a bank, and in the developing process, the lower layer film in the non-bank portion is removed together with the resist film in the non-bank portion is a method for forming a bank pattern including. (A) Component: An alkali-soluble resin having an amide group (C) Component: Solvent (D) Component: Photosensitizer (a) Component: An alkali-soluble resin (b) Component: A polymer having a liquid-repellent group (b1) (c) Component: Solvent (d) Component: Photosensitizer

[0014] In the second photosensitive resin composition of the present invention, it is preferable that the (b) component is further a polymer having the following (b2). (b2): At least one group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group. In the second photosensitive resin composition of the present invention, it is preferable that the (b) component is further a polymer having the following (b3). (b3): At least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group.

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

[0016] The second photosensitive resin composition of the present invention preferably further satisfies at least any one of the following (z1) to (z4). (z1): Further containing a crosslinking agent which is a component (e); (z2): The alkali-soluble resin of component (a) further has a self-crosslinking group or further has a 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; (z3): Component (d) is a photo radical generator (d-2), and further contains, as component (f), a compound having two or more ethylenically polymerizable groups; (z4): Component (d) is a photoacid generator (d-3), and further contains, as component (g), a compound having two or more functional groups that form a covalent bond by the acid generated from component (d-3).

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

[0018] Hereinafter, the method for forming a bank pattern of the present invention will be described with reference to FIG. 1.

[0019] <Lower layer film forming step> In the production method of the present invention, first, a first photosensitive resin composition composed of a monomer having an amide group and a monomer having an alkali-soluble group described later is applied to the substrate 11 directly or via another layer and prebaked to provide a non-liquid-repellent lower layer film 12. The details of each component of the lower layer film will be described below.

[0020] Hereinafter, the details of each component of the lower layer film will be described.

[0021] <Component (A)> Component (A) of the present invention is an alkali-soluble resin having an amide group. By having an amide group, it can form hydrogen bonds intramolecularly or intermolecularly, and can exhibit solvent resistance to its solvent when applying the upper resist film described later, and the upper resist film does not contact 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 hydroxy group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphate group, a boronic acid group, and an active methylene group and an active methine group. Note that the phenolic hydroxy group and the carboxyl group are alkali-soluble groups and are also sites having thermal reactivity (sites capable of forming a cross-linked structure with the cross-linking agent of component (E)) as described later. Moreover, as long as component (A) is an alkali-soluble resin having the above amide group, other structures and functional groups contained therein are not particularly limited. For example, when it contains a compound having two or more functional groups that form a covalent bond with the (G) acid described later, component (A) may not have a reaction site with component (G), or when it has a reaction site with component (G), the reaction site is not particularly limited as long as it is a group capable of forming a covalent bond with component (G) by the action of an acid or a group capable of forming a covalent bond with component (G) by heating.

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

[0023] Among the active methylene group and the active methine group, the active methylene group is preferred, and the active methylene group represented by the following formula (A1) is more preferred.

Chemical formula

[0024] In the above formula (A1), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferred. Examples of such alkyl groups include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and the like. Among them, 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 an alkoxy group having 1 to 5 carbon atoms is preferred. Examples of such alkoxy groups include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, and the like. Among them, a methoxy group, an ethoxy group, an i-propoxy group, an n-propoxy group, etc. are preferred.

[0026] Examples of the group represented by the above formula (A1) include the following structures, etc. In the structural formula, a broken line represents a bond.

Chemical formula

[0027] Among the alkali-soluble resins of the above component (A), it is preferably an alkali-soluble resin having an amide group, having 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.

[0028] The alkali-soluble resin of the above component (A) may be an alkali-soluble resin having such a structure, and is not particularly limited with respect to the skeleton of the main chain of the polymer constituting the resin and the types of side chains.

[0029] However, the alkali-soluble resin of component (A) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight is excessively large exceeding 50,000, development residues are likely to occur and the sensitivity is greatly reduced. On the other hand, if the number average molecular weight is excessively small less than 2,000, a considerable amount of film loss occurs in the exposed area during development, and insufficient curing may occur.

[0030] Examples of the alkali-soluble resin of component (A) include acrylic resins, polyhydroxystyrene resins, or polyimide precursors or polyimides, etc. Among them, acrylic resins (acrylic polymers) can be mentioned as preferred resins.

[0031] In the present invention, an alkali-soluble resin composed 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 types of specific copolymers.

[0032] That is, the above-mentioned specific copolymer is a copolymer formed with a monomer having an amide group, a monomer that exhibits alkali solubility, that is, a monomer having at least one group selected from the group consisting of a carboxyl group and a phenolic hydroxy group as a suitable alkali-soluble group, and at least one monomer selected from the group of monomers copolymerizable with these monomers as essential structural units, and its number average molecular weight is in the range of 2,000 to 50,000. If the number average molecular weight is excessively large exceeding 50,000, residues may occur. Note that the monomer having an amide group may also have an alkali-soluble group at the same time.

[0033] The monomers having the above amide group include, for example, acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-phenylmethacrylamide, N-phenylacrylamide, 4-hydroxyphenylmethacrylamide, 4-hydroxyphenylacrylamide, etc., and these can 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 phenolic hydroxyl group, and may have a plurality of them.

[0035] Hereinafter, specific examples of the above monomers are given, but the present invention is not limited thereto. Examples of the monomer 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, etc.

[0036] Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N-(hydroxyphenyl) acrylamide, N-(hydroxyphenyl) methacrylamide, N-(hydroxyphenyl) maleimide, 4-hydroxyphenyl methacrylate, etc.

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

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

[0039] The alkali-soluble resin which is component (A) of the present invention is preferably a copolymer obtained by further copolymerizing a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, from the viewpoint of further stabilizing the pattern shape after curing.

[0040] Examples of the monomer 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, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and the like.

[0041] In the production of the alkali-soluble resin (specific copolymer) of component (A), when using a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, the ratio thereof 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% with respect to all the monomers used in the production of the specific copolymer. When the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 5% by mass, the stabilizing effect of the pattern shape of the copolymer may not be obtained. When it is 60% by mass or more, the proportion of the alkali-soluble group of component (A) may be insufficient, and properties such as developability may deteriorate.

[0042] The alkali-soluble resin which is component (A) of the present invention can further be copolymerized with an N-substituted maleimide compound in terms of raising the Tg of the copolymer.

[0043] Examples of the N-substituted maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. A compound having no aromatic ring is preferable from the viewpoint of transparency, and a compound having an alicyclic skeleton is more preferable from the viewpoints of developability, transparency, and heat resistance. Among them, cyclohexylmaleimide is most preferable.

[0044] In the production of the alkali-soluble resin (specific copolymer) of component (A), when using N-substituted maleimide, the ratio is preferably 5 to 60% by mass, more preferably 10% by mass to 50% by mass with respect to all the monomers used in the production of the specific copolymer. When the N-substituted maleimide is less than 5% by mass, the Tg improvement effect of the copolymer may not be obtained. When it is 60% by mass or more, 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 preferably has a self-crosslinkable group or is a copolymer further having a 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 (hereinafter also referred to as a crosslinkable group). For example, 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), the requirement (Z2) can be satisfied.

[0046] Examples of the self-crosslinkable 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, a blocked isocyanate group, and the like.

[0048] When the self-crosslinkable group or the crosslinkable group is contained in the alkali-soluble resin of the component (A), the content is 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 in the resin of the component (A), of the unit having the self-crosslinkable group or the crosslinkable group.

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

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

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

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

[0053] Examples of the monomer having radical polymerizability and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, glycidyl α-n-butylacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl-6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like are preferably used. These may be used alone or in combination.

[0054] Examples of the monomer having radical polymerizability and further having an oxetanyl group include (meth)acrylate having an oxetanyl group. In the present specification, the description "(meth)acrylic acid" represents both acrylic acid and methacrylic acid. 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, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 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, 2-(2-vinyloxyethoxy)ethyl methacrylate, etc.

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

[0057] When the first photosensitive resin composition of the present invention satisfies (Z2), a structural unit derived from a monomer (unsaturated compound) having radical polymerizability and having at least one group selected from self-crosslinkable groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetanyl group, vinyl group and blocked isocyanate group and crosslinkable groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, blocked isocyanate group, etc. is preferably contained in an amount of 10% by mass to 70% by mass, particularly preferably 20% by mass to 60% by mass, based on the total of all repeating units of the alkali-soluble resin (A). When the content of this structural unit is less than 10% by mass, the heat resistance and surface hardness of the resulting cured film tend to decrease. On the other hand, when 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) as the component (A) may be a copolymer formed with monomers other than the above-mentioned monomers (hereinafter referred to as other monomers) as structural units. The other monomers may be specifically any monomers copolymerizable with at least one selected from the group consisting of the monomers having the above carboxyl group and the monomers having phenolic hydroxyl group, and are not particularly limited as long as the properties of the component (A) are not impaired. Specific examples of such monomers include acrylate compounds, methacrylate compounds, N-substituted acrylamide compounds, maleimide, acrylonitrile, styrene compounds and vinyl compounds. Hereinafter, specific examples of the other monomers are given, but the present invention is not limited thereto.

[0059] Examples of the acrylic 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, methoxy triethylene glycol acrylate, 2-ethoxyethyl 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, etc.

[0060] Examples of the methacrylic 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, methoxy triethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrola Examples thereof include ketone 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, etc.

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

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

[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, etc.

[0064] In the production of the alkali-soluble resin (specific copolymer) as the component (A), the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 20% by mass or less, based on all the monomers used in the production of the specific copolymer. If it exceeds 80% by mass, the relative amount of the essential components (the essential monomers constituting the component (A)) decreases, 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. For example, a monomer having a group selected from an amide group and a carboxyl group and having at least one group selected from a carboxyl group, a phenolic hydroxy group, etc., which is an alkali-soluble group, and optionally a monomer having a hydroxyalkyl group, an N-substituted maleimide compound, and optionally an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group, a blocked isocyanate group, etc., self-crosslinkable groups and at least one group selected from crosslinkable groups such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a blocked isocyanate group, etc. In a solvent in which a monomer, and optionally other copolymerizable monomers and optionally a polymerization initiator, etc. coexist, a polymerization reaction is carried out at a temperature of 50 to 110 °C to obtain it. At that time, the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble resin (specific copolymer) and the alkali-soluble resin (specific copolymer). Specific examples include the solvents described in component (C) described later.

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

[0067] Also, the solution of the alkali-soluble resin (specific copolymer) of component (A) obtained as described above is poured into diethyl ether, water, etc. under stirring for reprecipitation, and the generated precipitate is filtered and washed, and then dried at normal pressure or reduced pressure at room temperature or by heating 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 purified powder of the specific copolymer can be obtained. If it cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may 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 later and used in a solution state.

[0068] As the alkali-soluble resin of component (A), polyimide precursors such as polyamic acid, polyamic acid ester, and partially imidized polyamic acid, and polyimides such as carboxylic acid group-containing polyimide can also be used. As long as they are alkali-soluble, their types are not particularly limited and can be used.

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

[0070] The above (a) tetracarboxylic dianhydride compound is not particularly limited. Specific examples include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3’,4,4’-biphenyltetracarboxylic dianhydride, 3,3’,4,4’-benzophenonetetracarboxylic dianhydride, 3,3’,4,4’-diphenylethertetracarboxylic dianhydride, 3,3’,4,4’-diphenylsulfonetetracarboxylic dianhydride; alicyclic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride; and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride. These may be used alone or in combination of two or more compounds.

[0071] Also, the above (j) diamine compound is not particularly limited. For example, 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 and other diamine compounds having a carboxyl group; 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) Diamine compounds having phenolic hydroxy groups such as 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'-dihydroxy-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-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane; diamine compounds having thiophenol groups such as 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane; diamine compounds having sulfonic acid groups 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, 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid are included.In addition, diamine compounds such as 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)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4-tolyl)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, 2,2'-bis(trifluoromethyl)benzidine can be mentioned. 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 blending ratio of both compounds, that is, the total number of moles of (j) diamine compound / the total number of moles of (i) tetracarboxylic dianhydride compound is desirably 0.7 to 1.2. Similar to ordinary polycondensation reactions, the closer this molar ratio is to 1, the higher the degree of polymerization of the polyamic acid produced and the higher the molecular weight.

[0073] In addition, when polymerizing using an excessive amount of a diamine compound, a carboxylic acid anhydride can be reacted with the terminal amino groups of the remaining polyamic acid to protect the terminal amino groups. 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, tetrahydrophthalic anhydride, and the like.

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

[0075] The reaction between the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Solvents that can be used in this case 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, 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, 2-heptanone, etc. These can be used alone or in combination. Furthermore, even a solvent that does not dissolve polyamic acid can be mixed with the above solvents and used as long as the polyamic acid generated by the polymerization reaction does not precipitate.

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

[0077] In addition, as the component (A), any polyimide can also be used. The polyimide used in the present invention is one obtained by chemically or thermally imidizing 50% or more of a polyimide precursor such as the polyamic acid.

[0078] The polyimide used in the first photosensitive resin composition of the present invention preferably has an amide group and a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility. As a method for introducing an amide group into the polyimide, a method using a monomer having an amide group, a method of sealing an amine terminal with an acid anhydride having an amide group, etc. are used. As a method for introducing a carboxyl group or a phenolic hydroxy group into the polyimide, a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of sealing an amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxy group, or a method of making the imidization rate 99% or less when imidizing a polyimide precursor such as a polyamic acid is used.

[0079] Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization. As a method for chemical imidization, generally, a method of adding excessive acetic anhydride and pyridine to a polyimide precursor solution and reacting it at room temperature to 100 °C is used. As a method for thermal imidization, generally, a method of heating a polyimide precursor solution while dehydrating it at a temperature of 180 °C to 250 °C is used.

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

[0081] In addition, as the alkali-soluble resin of the component (A), a polyester polycarboxylic acid can also be used. The polyester polycarboxylic acid can be obtained from an acid dianhydride and a diol by the method described in International Publication No. 2009 / 051186. Examples of the dianhydride include the above (i) tetracarboxylic dianhydrides. Examples of the diol 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 component (A) may be a mixture of a plurality of kinds of alkali-soluble resins.

[0083] <(Component (C))> The component (C) used in the present invention is a solvent that dissolves the component (A) and, if necessary, the following components (D), (E), (F), and (G), and also dissolves other additives, etc. to be added as desired. As long as it is a solvent having such solubility, its type, structure, etc. are not particularly limited.

[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-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, etc.

[0085] These solvents can be used singly or in combination of two or more. Among these component (C), 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 viewpoints of good coating film 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 component (A). These solvents are generally used as solvents for photoresist materials.

[0086] <Component (D)> Examples of the photosensitive agent as the component (D) include a (D-1) 1,2-quinonediazide compound, a (D-2) photo radical generator, and a (D-3) photoacid generator.

[0087] As the (D-1) 1,2-quinonediazide compound, a compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group can be used. Among these hydroxy groups or amino groups (when having both a hydroxy group and an amino group, the total amount thereof), preferably 10 mol% to 100 mol%, particularly preferably 20 mol% to 95 mol% is esterified or amidated with 1,2-quinonediazide sulfonic acid. Examples of the 1,2-quinonediazide sulfonic acid include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-benzoquinone-2-diazide-4-sulfonic acid, etc. In the reaction with the compound having either one or both of the aforementioned hydroxy group or amino group, the chloride of the 1,2-quinonediazide 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 phenolic compounds such as 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'-dihydroxyphenyl sulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4',4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 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, 4,4'-diaminodiphenyl ether, and aminocyclohexane.

[0090] Furthermore, examples of the compound 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, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane, and alkanolamines such as 2-aminoethanol, 3-aminopropanol, 4-aminocyclohexanol.

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

[0092] When the first photosensitive resin composition of the present invention is a positive photosensitive resin composition and contains a compound having a quinonediazide group as the component (D-1), the content is preferably 5 parts by mass to 100 parts by mass, more preferably 8 parts by mass to 50 parts by mass, still more preferably 10 parts by mass to 40 parts by mass with respect to 100 parts by mass of the component (A). If it is less than 5 parts by mass, the difference in the dissolution rate of the exposed part and the unexposed part of the positive photosensitive resin composition in the developer becomes small, and patterning by development may be difficult. On the other hand, if it exceeds 100 parts by mass, the sensitivity may decrease because the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time, or the component (D-1) may absorb light and reduce the transparency of the cured film.

[0093] (D-2) The photo radical generator is not particularly limited as long as it generates radicals upon exposure. Specific examples include aromatic ketones such as benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, and phenanthrene; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoins such as methyl benzoin and ethyl benzoin; 2-(o-chlorophenyl)-4,5-diphenylimidazole 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-triaryl imidazole 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-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyl oxadiazole compounds, 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, 2-(4-ethoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine and other halomethyl-S-triazine compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,1-Hydroxy-cyclohexyl-phenylketone, benzyl, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethyl a, minobenzoate, isoamyl p-dimethylaminobenzoate, 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-carbazole-3-yl]-1-(O-acetoxime), 4-benzoyl-methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenylketone, 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 and the like. The above-mentioned photo radical generator is easily available as a commercial product. Specific examples thereof include, for example, IRGACURE173, 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 (manufactured by BASF), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ (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, TAZ-204 (manufactured by Midori Chemical Co., Ltd.), and the like. These photo radical generators can be used alone or in combination of two or more kinds.

[0094] When the (D-2) component is contained in the first photosensitive resin composition of the present invention, the content is preferably 0.1 part by mass to 30 parts by mass, more preferably 0.5 part by mass to 20 parts by mass, and particularly preferably 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the (A) component. When this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, the film may have low reliability. Also, when this ratio is too large, the transmittance of the coating film may decrease, or development failure of the unexposed portion may occur.

[0095] (D-3) The photoacid generator is not particularly limited as long as it is a compound that decomposes upon ultraviolet irradiation to generate an acid. Examples of the acid generated when the photoacid generator decomposes by light include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic 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-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, and other sulfonic acids or their hydrates, salts, etc.

[0096] Examples of the photoacid generator include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone-based compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, halogen-containing triazine compounds, acetophen non-derivative compounds, and cyanide group-containing oxime sulfonate compounds, etc. Any of the conventionally known or conventionally used photoacid generators can be applied in the present invention without 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]

Chemical formula

[0098]

Chemical formula

[0099] [Chemistry]

[0100] [Chemistry]

[0101] [Chemistry]

[0102] [Chemistry]

[0103] [Chemistry]

[0104] When the component (D-3) is contained in the first photosensitive resin composition of this embodiment, the content is preferably 0.01 part by mass to 20 parts by mass, more preferably 0.1 part by mass to 10 parts by mass, still more preferably 0.5 part by mass to 8 parts by mass with respect to 100 parts by mass of the component (A). By setting the content of the component (D-3) to 0.01 part by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, when it is more than 20 parts by mass, the unexposed part may have poor development, or the storage stability of the composition may decrease.

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

[0106] (E1) When the crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group of the component is exposed to a high temperature during thermosetting, the crosslinking reaction proceeds by a dehydration condensation reaction. Examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.

[0107] Specific examples of alkoxymethylated glycoluril include, for example, 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. As commercially available products, compounds such as glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel® 1170, Powderlink® 1174), methylated urea resins (trade name: UFR® 65), butylated urea resins (trade name: UFR® 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resins manufactured by DIC Corporation (highly condensed type, trade name: Beckamine® J-300S, P-955, N) can be mentioned.

[0108] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. As commercially available products, those manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel® 1123), those manufactured by Sanwa Chemical Co., Ltd. (trade name: Nikalac® BX-4000, BX-37, BL-60, BX-55H) can be mentioned.

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

[0110] Moreover, it may also be a compound obtained by condensing such a melamine compound, urea compound, glycoluril compound, and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds produced from the melamine compound and benzoguanamine compound described in U.S. Patent No. 6323310 can be mentioned. Commercially available products of the melamine compound include, for example, the trade name: Cymel® 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the benzoguanamine compound include, for example, the trade name: Cymel® 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0111] Specific examples of phenoplast compounds include, for example, 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-hyd Loxymethylphenol, 4,4'-(1-methylethylidene)bis[2,6-bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6-bis(hydroxymethyl)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], etc. are included. They are also available as commercial products, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (all of the above are manufactured by Asahi Organic Chemical Industry Co., Ltd.), etc.

[0112] Furthermore, as the component (E1), polymers produced using acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, 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. The weight average molecular weight of such polymers is from 1,000 to 50,000, preferably from 1,500 to 20,000, and more preferably from 2,000 to 10,000.

[0114] Further, the first photosensitive resin composition of the present invention can contain, as the component (E2), a crosslinkable compound represented by the following formula (1).

Chemical formula

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

Chemical formula

Chemical formula

[0116] Examples of commercially available products include Epolead GT-401, GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (trade names, manufactured by Daicel Corporation), Denacol EX-252 (trade name, manufactured by Nagase ChemteX Corporation), which is an alicyclic epoxy resin, CY175, CY177, CY179 (above, trade names, manufactured by Huntsman Corporation), Araldite CY-182, CY-192, CY-184 (above, trade names, manufactured by Huntsman Corporation), Epiklon 200, 400 (above, trade names, manufactured by DIC Corporation), Epicoat 871, 872 (above, trade names, manufactured by Mitsubishi Chemical Corporation), ED-5661, ED-5662 (above, trade names, manufactured by Celanese Coating Corporation), and the like. These crosslinkable compounds can be used alone or in combination of two or more kinds.

[0117] Among these, compounds represented by Formula E2-1 and Formula E2-2, which have a cyclohexene oxide structure, Epolead GT-401, GT-403, GT-301, GT-302, Celoxide 2021, and Celoxide 3000 are preferable from the viewpoints of heat resistance, solvent resistance, process resistance such as long-time firing resistance, and transparency.

[0118] In addition, as the component (E), compounds that can form a crosslinked structure by a thermal reaction with the thermally reactive sites of the component (A) (for example, carboxyl group and / or phenolic hydroxyl group) other than those shown as the component (E1) and the component (E2) can also be used. Specifically, for example, 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 epoxy compounds such as N,N,N’,N’,-tetraglycidyl - 4,4’ - diaminodiphenylmethane, VESTANAT B1358 / 100, VESTAGON BF 1540 (the above are isocyanurate - type modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B - 882N, the same Takenate B - 7075 (the above are isocyanurate - type modified polyisocyanates, manufactured by Mitsui Chemicals, Inc.), etc. Examples thereof include isocyanate compounds such as .

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

[0120] (A) When the component 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 can be used as the component (E).

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

[0122] When component (E) is selected as the crosslinking agent in the first photosensitive resin composition of the present invention, its content is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of component (A). When the content of the crosslinkable compound is low, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so the effects of improving the heat resistance, solvent resistance, and resistance to long-term baking after pattern formation may not be obtained. On the other hand, when it exceeds 50 parts by mass, uncrosslinked crosslinkable compounds are present, and the heat resistance, solvent resistance, and resistance to long-term baking after pattern formation decrease, and the storage stability of the photosensitive resin composition may deteriorate.

[0123] <(Component (F))> (Component (F)) is a compound having two or more ethylenically polymerizable groups. The compound having two or more ethylenically polymerizable groups referred to here means a compound having two or more polymerizable groups in one molecule and having those polymerizable groups at the molecular terminals, and those polymerizable groups mean at least one kind of polymerizable group selected from the group consisting of acrylate groups, methacrylate groups, vinyl groups, and allyl groups. The compound having two or more ethylenically polymerizable groups, which is this 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 good compatibility with each component and no influence on developability in the solution of the negative photosensitive resin composition in the first photosensitive resin composition of the present invention.

[0124] Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacry Rate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-triacryloylhexahydro-S-triazine, 1,3,5-trimethacryloylhexahydro-S-triazine, tris(hydroxyethylacryloyl)isocyanurate, tris(hydroxyethylmethacryloyl)isocyanurate, triacryloyl formal, trimethacryloyl formal, 1,6-hexanediol 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 ether bisphenol A, o-diallyl bisphenol A, diallyl maleate, triallyl trimellitate, etc. can be mentioned.

[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, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (manufactured by Nippon Kayaku Co., Ltd. as above), Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050 (manufactured by Toagosei Co., Ltd. as above), Biscoat 295, 300, 360, GPT, 3PA, 400, 260, 312, 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd. as above), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-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, 1G (manufactured by Shin-Nakamura Chemical Co., Ltd. as above), and the like. These compounds having two or more ethylenically polymerizable groups can be used alone or in combination of two or more.

[0126] When the component (F) is contained in the first photosensitive resin composition of the present invention, 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 with respect to 100 parts by mass of the component (A). If this ratio is too small, the exposed portion may be insufficiently cured, resulting in the inability to form a pattern or, even if a pattern is formed, a film with low reliability. On the other hand, if this ratio is too large, tack may occur on the coating film after pre-baking, or the unexposed portion may have poor solubility during development.

[0127] <(G) component> The (G) component 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. Examples of such functional groups that form a covalent bond with an acid include 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-diglycidyl phenyl 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 the compound having two or more epoxy groups, a commercially available compound may be used from the viewpoint of easy availability. Specific examples (trade names) are given below, but are not limited thereto: epoxy resins having an amino group such as YH-434, YH434L (manufactured by Shin-Nichi Kasei Epoxy Co., Ltd.); epoxy resins having a cyclohexene oxide structure such as Epolead GT-401, GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Corporation); bisphenol A type epoxy resins such as Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)); bisphenol F 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, 154 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)), EPPN201, 202 (manufactured by Nippon Kayaku Co., Ltd.); cresol novolac type epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)); alicyclic epoxy resins such as Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, CY-192, CY-184 (manufactured by Huntsman Corporation), Epiklon 200, 400 (manufactured by Dainippon Ink and Chemicals, Inc. (currently DIC Corporation)), Epicoat 871, 872 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Mitsubishi Chemical Corporation)), ED-5661, ED-5662 (manufactured by Celanese Coating 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, EX-321 (manufactured by Nagase ChemteX Corporation), etc.

[0130] In addition, 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, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. As an example, polyglycidyl acrylate , addition polymerized polymers such as a copolymer of glycidyl methacrylate and ethyl methacrylate, a copolymer of glycidyl methacrylate, styrene and 2-hydroxyethyl methacrylate, and condensation polymerized polymers such as epoxy novolac can be mentioned.

[0131] Alternatively, the polymer having an epoxy group can also be produced by reacting a high molecular 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, from 300 to 20,000.

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

[0134] Examples of the compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.

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

[0108] .

[0136] Specific examples of alkoxymethylated benzoguanamine are as described in the above paragraph

[0109] .

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

[0110] .

[0138] Alternatively, 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 such an amino group is substituted with a hydroxymethyl group or an alkoxymethyl group. For example, a high molecular weight compound produced from the melamine compound and the benzoguanamine compound described in US Patent No. 6323310 can be mentioned. Examples of commercially available products of the melamine compound include those with the trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), etc., and examples of commercially available products of the benzoguanamine compound include those with the trade name: Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.), etc.

[0139] Specific examples of the phenoplast-based compound are as described in the above paragraph

[0112] .

[0140] Furthermore, as the component (G), polymers produced using acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, etc. 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 and ben zyl methacrylate and 2-hydroxypropyl methacrylate, etc. The weight average molecular weight of such polymers is from 1,000 to 50,000, preferably from 1,500 to 20,000, and more preferably from 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 the acid of component (G), the content is preferably 5 parts by mass to 200 parts by mass, more preferably 50 parts by mass to 150 parts by mass, based on 100 parts by mass of component (A). If this ratio is too small, the photocurability of the negative photosensitive resin composition may decrease. On the other hand, if it is too large, the developability of the unexposed portion may decrease, causing 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 rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, an adhesion promoter, or a dissolution accelerator such as a polyhydric phenol or a polycarboxylic acid, as long as the effects of the present invention are not impaired.

[0144] <Resist Film Formation Step> After forming the lower layer film 12 as described above, a second photosensitive resin composition containing a liquid repellent component is applied onto the lower layer film 12 and pre-baked to form a resist film 13 for a liquid repellent bank (Fig. 1). Usually, this second photosensitive resin composition is applied over the entire surface of the lower layer film 12 to form a resist film 13 for a liquid repellent bank. Hereinafter, the details of each component of the resist film for a liquid repellent bank will be described.

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

[0146] The active methylene group refers to a methylene group (-CH2-) having a carbonyl group adjacent thereto and having reactivity with a nucleophilic reagent. In the present invention, the active methine group has a structure in which one hydrogen atom of the methylene group in the active methylene group is substituted with an alkyl group and has reactivity with a nucleophilic reagent.

[0147] Among the active methylene group and the active methine group, the active methylene group is preferred, and the active methylene group represented by the following formula (a1) is more preferred.

Chemical formula

[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 alkyl groups include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, etc. Among them, 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 a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, etc. Among them, a methoxy group, an ethoxy group, an n-propoxy group, etc. are preferred.

[0150] Examples of the group represented by the above formula (a1) include the following structures, etc. In the structural formula, the dashed line represents a bond.

Chemical formula

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

[0152] The alkali-soluble resin of the component (a) may be any alkali-soluble resin having such a structure, and is not particularly limited with respect to the skeleton of the main chain of the polymer constituting the resin and the types of side chains.

[0153] However, the alkali-soluble resin of the component (a) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight is excessive, exceeding 50,000, development residues are likely to occur and the sensitivity is greatly reduced. On the other hand, if the number average molecular weight is too small, less than 2,000, a considerable amount of film loss occurs in the exposed area during development, and insufficient curing may occur.

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

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

[0156] That is, the above-mentioned specific copolymer is a copolymer formed from a monomer that exhibits alkali solubility, that is, at least one monomer selected from the group consisting of phenolic hydroxy groups and carboxyl groups, and at least one monomer selected from the group of monomers copolymerizable with these monomers as essential structural units, and its number average molecular weight is in the range of 2,000 to 50,000. If the number average molecular weight is greater than 50,000, residues may occur.

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

[0158] Hereinafter, specific examples of the above monomer are given, but the present invention is not limited thereto. Examples of the monomer 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 the monomer having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl) acrylamide, N-(hydroxyphenyl) methacrylamide, N-(hydroxyphenyl) maleimide, 4-hydroxyphenyl methacrylate and the like.

[0160] The ratio of the unsaturated carboxylic acid derivative and / or the monomer having a phenolic hydroxy 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% among all the monomers used in the production of the alkali-soluble resin of component (a). When the unsaturated carboxylic acid derivative is less than 5% by weight, the alkali solubility of the polymer is insufficient.

[0161] The alkali-soluble resin as component (a) of the present invention is preferably a copolymer obtained by further copolymerizing 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 the monomer 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, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and the like.

[0163] The ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group 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. When the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 5% by mass, the stabilizing effect of the pattern shape of the copolymer may not be obtained. When it is 60% by mass or more, the alkali-soluble group of component (a) may be insufficient, and properties such as developability may deteriorate.

[0164] The alkali-soluble resin as component (a) of the present invention is preferably a copolymer further copolymerized with an N-substituted maleimide compound in terms of raising the Tg of the copolymer. Examples of the N-substituted maleimide compound include N-methyl maleimide, N-ethyl maleimide, N-phenyl maleimide, and N-cyclohexyl maleimide. Those having no aromatic ring are preferable from the viewpoint of transparency, and those having an alicyclic skeleton are more preferable from the viewpoints of developability, transparency, and heat resistance. Among them, cyclohexyl maleimide is most preferable.

[0165]

[0166] ​(a) The ratio of N-substituted maleimide in the production of the alkali-soluble resin of the component 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. When 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. When it is 60% by mass or more, the transparency may decrease.

[0167] When the second photosensitive resin composition of the present invention satisfies the requirement (z2), the alkali-soluble resin of the component (a) used in the present invention preferably further has a self-crosslinkable group or is a copolymer further having a 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 (hereinafter also referred to as a crosslinkable group).

[0168] Examples of the self-crosslinkable 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, a blocked isocyanate group, and the like.

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

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

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

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

[0174] Examples of the monomer having radical polymerizability and further having an alkoxysilyl group include 3-a cryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, 3-methacryloyloxytriethoxysilane, and the like.

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

[0176] Examples of the unsaturated compound having radical polymerizability 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, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxymethyl)-4-trifluoromethyloxetane are preferable, 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, 2-(2-vinyloxyethoxy)ethyl methacrylate, etc.

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

[0179] When the second photosensitive resin composition of the present invention satisfies (z1), a structural unit derived from an unsaturated compound having radical polymerizability and having at least one group selected from self-crosslinkable groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group and blocked isocyanate group and crosslinkable groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, blocked isocyanate group, etc. is preferably contained in an amount of 10% by mass to 70% by mass, particularly preferably 20% by mass to 60% by mass, based on the total of all repeating units of the alkali-soluble resin of the component (a). When the content of this structural unit is less than 10% by mass, the heat resistance and surface hardness of the obtained cured film tend to decrease. On the other hand, when 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 with monomers other than the above-mentioned monomers (hereinafter referred to as other monomers) as structural units. The other monomers may be specifically any monomers copolymerizable with at least one selected from the group consisting of the monomers having a carboxyl group and the monomers having a phenolic hydroxyl group, and are not particularly limited as long as the properties of the component (a) are not impaired. Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide, acrylamide compounds, acrylonitrile, styrene compounds, vinyl compounds and the like. Hereinafter, specific examples of the other monomers will be given, but the present invention is not limited thereto.

[0181] Examples of the acrylic 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, methoxy triethylene 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, 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, methoxy triethylene glycol methacrylate, 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, poly(ethylene glycol) ethyl ether methacrylate, and the like.

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

[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, 1,7-octadiene monoepoxide, and the like.

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

[0186] In the production of the alkali-soluble resin as the component (a), the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 20% by mass or less. When it exceeds 80% by mass, the essential components relatively decrease, making it difficult to sufficiently obtain the effects of the present invention.

[0187] The method for obtaining the alkali-soluble resin as 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 hydroxy group, and a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or an acid, a monomer having a hydroxyalkyl group, optionally an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, a block isocyanate group, and other self-crosslinkable groups, and an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a block isocyanate group, and other crosslinkable groups. At least one selected from the group consisting of monomers having a group, optionally other copolymerizable monomers, and optionally a polymerization initiator and the like are coexisted in a solvent, and a polymerization reaction is carried out at a temperature of 50°C to 110°C to obtain it. At this time, the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble resin and the acrylic polymer having a specific functional group. Specific examples include the solvents described in the component (c) described later.

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

[0189] Also, the solution of the specific copolymer obtained as described above is poured into diethyl ether, water, etc. under stirring for reprecipitation. After the formed precipitate is filtered and washed, it can be dried at normal temperature or under reduced pressure, either at normal pressure or under 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 purified powder of the specific copolymer can be obtained. If it cannot be sufficiently purified in one 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 later and used in a solution state.

[0190] Also, as the alkali-soluble resin of the component (a), polyimide precursors such as polyamic acid, polyamic acid ester, and partially imidized polyamic acid, and polyimides such as carboxylic acid group-containing polyimide can be used, and as long as they are alkali-soluble, their types are not particularly limited and can be used.

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

[0192] The above (i) tetracarboxylic dianhydride compound is not particularly limited. Specific examples include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Examples thereof include alicyclic tetracarboxylic dianhydrides such as carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride. These may be used alone or in combination of two or more compounds.

[0193] Also, the above (j) diamine compound is not particularly limited. For example, 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-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminhydroquinone, 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'-dihydroxy-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-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane and other diamine compounds having phenolic hydroxy groups, 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane and other diamine compounds having thiophenol groups, 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, 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid and other diamine compounds having sulfonic acid groups. Also, 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-anilinophenyl)hexafluoropropane, 2,2-bis(3-anilinophenyl)hexafluoropropane, 2,2-bis(3-amino-4-tolyl)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, 2,2'-bis(trifluoromethyl)benzidine and other diamine compounds can be mentioned. 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 mixing ratio of both compounds, that is, the total number of moles of the (j) diamine compound / the total number of moles of the (i) tetracarboxylic dianhydride compound is preferably 0.7 to 1.2. Similar to the usual polycondensation reaction, the closer this molar ratio is to 1, the higher the degree of polymerization of the resulting polyamic acid and the higher the molecular weight.

[0195] Also, when polymerizing using an excess of the diamine compound, a carboxylic anhydride can be reacted with the terminal amino group of the remaining polyamic acid to protect the terminal amino group. 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, tetrahydrophthalic anhydride, and the like.

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

[0197] The reaction between the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Solvents that can be used 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 ether, di Examples 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, 2-heptanone, etc. These can be used alone or in combination. Furthermore, even if it is a solvent that does not dissolve polyamic acid, it may be mixed with the above solvent and used as long as the polyamic acid generated by the polymerization reaction does not precipitate.

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

[0199] Also, as the component (a), any polyimide can be used. The polyimide used in the present invention is one in which a polyimide precursor such as the above polyamic acid is imidized by 50% or more chemically or thermally.

[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 hydroxy group into the polyimide include a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of terminating an amine end with an acid anhydride having a carboxyl group or a phenolic hydroxy group, or a method of making the imidization rate 99% or less when imidizing a polyimide precursor such as polyamic acid.

[0201] Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization. As a method of chemical imidization, generally, a method of adding an excess of acetic anhydride and pyridine to a polyimide precursor solution and reacting it at room temperature to 100 ° C is used. As a method of thermal imidization, generally, a method of heating a polyimide precursor solution while dehydrating it at a temperature of 180 ° C to 250 ° C is used.

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

[0203] In addition, as the alkali-soluble resin of the component (a), a polyester polycarboxylic acid can also be used. The polyester polycarboxylic acid can be obtained from an acid dianhydride and a diol by the method described in WO2009 / 051186. Examples of the acid dianhydride include the above-mentioned (i) tetracarboxylic acid dianhydride. Examples of the diol 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 component (b) is a polymer having a liquid-repellent group (b1).

[0206] In the present invention, examples of the polymer include polyimide, polyamic acid, polyamide, polyurea, polyurethane, phenol resin, epoxy resin, polysiloxane, polyester, and acrylic polymer. A preferred polymer is an acrylic polymer.

[0207] Here, the acrylic polymer refers to a polymer obtained by using a polymerizable unsaturated group such as an acrylate ester, methacrylate ester, styrene, maleimide, etc., that is, a monomer having a polymerizable group containing a C=C double bond in the structure.

[0208] 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. In addition, polymers obtained from a monomer mixture containing at least one monomer having a fluoroalkyl group or fluoroalkoxy group and at least one monomer having a hydroxy group are included.

[0209] Examples of the polyurethane include polyurethanes obtained by reacting a diol having a fluoroalkyl group or fluoroalkoxy group and a diol having an amino group with a diisocyanate.

[0210] Examples of the phenol resin include novolac resins obtained by polymerizing a phenol having a fluoroalkyl group or fluoroalkoxy group and formaldehyde.

[0211] Examples of the epoxy resin include epoxy resins obtained by reacting bisphenol A and / or bisphenol F having a fluoroalkyl group or fluoroalkoxy group with glycidyl ether of the bisphenol A and / or bisphenol F.

[0212] Examples of the polysiloxane 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.

[0213] Examples of the polyester include polyesters obtained by reacting a dicarboxylic acid or tetracarboxylic dianhydride with a diol having a fluoroalkyl group or a fluoroalkoxy group.

[0214] <(b1) Introduction of a liquid-repellent group> Examples of the liquid-repellent group include at least one group selected from fluoroalkyl groups having 3 to 10 carbon atoms, polyfluoroether groups, silyl ether groups, and polysiloxane groups.

[0215] The fluoroalkyl group has 3 to 10 carbon atoms, and preferably 4 to 10 carbon atoms. Examples of such fluoroalkyl groups include 2,2,2-trifluoroethyl group, 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, etc.

[0216] In order to introduce a fluoroalkyl group having 3 to 10 carbon atoms into the polymer which is the component (b) of the present invention, it is sufficient to copolymerize a monomer having a fluoroalkyl group having 3 to 10 carbon atoms.

[0217] Specific examples of the monomer having a fluoroalkyl group having 3 to 10 carbon atoms in the case where the component (b) 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-hydroxypropyl 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 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 and the like.

[0218] Examples of the polyfluoroether group include an Rf group having a polyfluoroether structure represented by the following formula (2). -(X-O) n -Y···Formula (2) In formula (2), X is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and represents the same group or different groups for each unit enclosed by n. 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. n represents an integer of 2 to 50. However, the total number of fluorine atoms in formula (2) is 2 or more.

[0219] As aspects of X and Y in formula (2), preferably, X is an alkylene group fluorinated by removing one hydrogen atom having 1 to 10 carbon atoms or a perfluorinated alkylene group having 1 to 10 carbon atoms, and represents the same group or different groups for each unit enclosed by n. Y represents an alkyl group fluorinated by removing one hydrogen atom having 1 to 20 carbon atoms or a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0220] As more preferable aspects of X and Y in formula (2), X is a perfluorinated alkylene group having 1 to 10 carbon atoms, and represents the same group or different groups for each unit enclosed by n. Y represents a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0221] In Formula 2, n represents an integer of 2 to 50. n is preferably 2 to 30, 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 as component (b) is synthesized by copolymerization with a monomer having an Rf group and a monomer having a hydroxy group, a carboxyl group, an amide group, an amino group, an N-alkoxymethylamide group, a blocked isocyanate group or a trialkoxysilyl group or other monomers, the compatibility of the monomers becomes good.

[0222] Further, the total number of carbon atoms in the Rf group having a polyfluoroether structure represented by Formula 2 is preferably 2 to 50, more preferably 2 to 30. In this range, the polymer as component (b) exhibits good liquid repellency. Also, when the polymer as component (b) is synthesized by copolymerization with a monomer having an Rf group and a monomer having a hydroxy group, a carboxyl group, an amide group, an amino group, an N-alkoxymethylamide group, a blocked isocyanate group or a trialkoxysilyl group or other monomers, the compatibility of the monomers becomes good.

[0223] Specific examples of X include -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF(CF3)-, -CF2CF2CF2CF2-, -CF2CF2CF(CF3)-, and CF2CF(CF3)CF2-.

[0224] 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.

[0225] Preferred embodiments of the Rf group having a polyfluoroether structure represented by Formula 2 include the Rf group represented by Formula 3. -C p-1 F 2(p-1) -O-(Cp F 2p -O) n-1 -C q F 2q+1 ···Formula 3 In Formula 3, p represents an integer of 2 or 3, is the same group for each unit enclosed by n, q represents an integer from 1 to 20, and n represents an integer from 2 to 50.

[0226] As the Rf group represented by Formula 3, specifically, -CF2O(CF2CF2O) n-1 CF3 (n is from 2 to 9), -CF(CF3)O(CF2CF(CF3)O) n-1 C6F 13 (n is from 2 to 6), -CF(CF3)O(CF2CF(CF3)O) n-1 C3F7 (n is from 2 to 6) are preferably exemplified from the viewpoint of ease of synthesis.

[0227] (b) The Rf groups in the polymer as the component may all be the same or different.

[0228] The above silyl ether group means a group in which the hydroxy group of an alcohol is protected by a trialkylsilyl group, and is preferably a group represented by the following formula. is preferably 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, and X 4 represents an alkylene group having 1 to 6 carbon atoms.)

[0229] To introduce a silyl ether group into the polymer as the (b) component of the present invention, a monomer having a silyl ether group may be copolymerized.

[0230] When the (b) component is an acrylic polymer, examples of the monomer having a silyl ether group include methacryloxypropyltris(trimethylsiloxy)silane and acryloxypropyltris(trimethylsiloxy)silane.

[0231] Examples of the polysiloxane group include a group having a polysiloxane structure represented by Formula 4. Hereinafter, the group having a polysiloxane structure represented by Formula 4 is referred to as a pSi group. -(SiR 1 R 2 -O) n -SiR 1 R 2 R 3 ···Formula 4 (However, R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R 3 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200.).

[0232] R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and may be the same or different for each siloxy unit. Since the polymer as the (b) component exhibits good liquid repellency, R 1 and R 2 are preferably a hydrogen atom, a methyl group or a phenyl group, and more preferably, R 1 and R 2 of all siloxy units are methyl groups. Further, R 3 may contain a nitrogen atom, an oxygen atom or the like.

[0233] Examples of the method for introducing a pSi group into the polymer as the (b) component include a method of copolymerizing a monomer having a pSi group, various modification methods of reacting a compound having a pSi group with a polymer having a reactive site, and a method of using a polymerization initiator having a pSi group.

[0234] Examples of monomers having a pSi group include CH2=CHCOO(pSi) and CH2=C(CH3)COO(pSi). Here, pSi represents a pSi group. Monomers having a pSi group may be used alone or in combination of two or more.

[0235] Examples of various modification methods for reacting a compound having a pSi group with a polymer having a reactive site include, for example, the following methods.

[0236] A method of copolymerizing in advance a monomer having an epoxy group and then reacting a compound having a carboxyl group at one end and a pSi group at the other end. A method of copolymerizing in advance a monomer having an epoxy group and then reacting a compound having an amino group at one end and a pSi group at the other end. A method of copolymerizing in advance a monomer having an epoxy group and then reacting a compound having a mercapto group at one end and a pSi group at the other end. A method of copolymerizing in advance a monomer having an amino group and then reacting a compound having a carboxyl group at one end and a pSi group at the other end.

[0237] A method of copolymerizing in advance a monomer having an amino group and then reacting a compound having an epoxy group at one end and a pSi group at the other end. A method of copolymerizing in advance a monomer having a carboxyl group and then reacting a compound having an epoxy group at one end and a pSi group at the other end. A method of copolymerizing in advance a monomer having a carboxyl group and then reacting a compound having an amino group at one end and a pSi group at the other end. A method of copolymerizing in advance a monomer having a carboxyl group and then reacting a compound having a silyl chloride group at one end and a pS i group at the other end. A method of copolymerizing in advance a monomer having a hydroxy group and then reacting a compound having a silyl chloride group at one end and a pSi group at the other end.

[0238] As the polymerization initiator having a pSi group, a group having a divalent polysiloxane structure may be included in the main chain of the initiator molecule, or a group having a monovalent polysiloxane structure may be included in the terminal portion or side chain of the initiator molecule. Examples of the initiator 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. Commercially available products include VPS-1001 and VPS-0501 (both manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0239] Component (b) is preferably a polymer having a group selected from (b2): an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group.

[0240] <Introduction of a group selected from (b2): 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 as component (b), a monomer having a group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group may be copolymerized.

[0241] Examples of the monomer having an N-alkoxymethylamide group in the case where component (b) is an acrylic polymer 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.

[0242] Examples of the monomer having a blocked isocyanate group in the case where component (b) is an acrylic polymer include 2-(0-(1'-methylpropylideneamino)carboxamido)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.

[0243] (b) When the component is an acrylic polymer, examples of the monomer having a trialkoxysilyl group include 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, 3-triethoxysilylpropyl methacrylate, and the like.

[0244] (b) The component is preferably a polymer having at least one group selected from the group consisting of a (b3) hydroxy group, a carboxyl group, an amide group, and an amino group.

[0245] <Introduction of at least one group selected from the group consisting of a (b3) hydroxy group, a carboxyl group, an amide group, and an amino group> To introduce at least one group selected from the group consisting of a (b3) hydroxy group, a carboxyl group, an amide group, and an amino group into the polymer which is the component (b) of the present invention, it is only necessary to copolymerize a monomer having at least one group selected from the group consisting of a (b3) hydroxy group, a carboxyl group, an amide group, and an amino group.

[0246] (b) When the component is an acrylic polymer, examples of the monomer 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.

[0247] (b) When the component is an acrylic polymer, examples of the monomer having a hydroxy group include, for example, 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) acrylate, poly(propylene glycol) acrylate, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenyl maleimide, N-hydroxyphenyl acrylamide, N-hydroxyphenyl methacrylamide, p-hydroxyphenyl acrylate, p-hydroxyphenyl methacrylate, etc. Among them, monomers selected from 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

[0248] (b) When the component is an acrylic polymer, examples of the monomer having an amide group include, for example, acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, etc. Among them, methacrylamide is preferred.

[0249] (b) When the component is an acrylic polymer, examples of the monomer having an amino group include, for example, aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate, etc.

[0250] (b) When the component is an acrylic polymer, the method for producing the polymer of the component (b) is as follows: 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, optionally a monomer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group, and optionally a further monomer other than the above (hereinafter also referred to as other monomer A) are polymerized in a solvent in the presence of a polymerization initiator at a temperature of 50°C to 110°C. At this time, the solvent used is not particularly limited as long as it can dissolve the monomer constituting the alkali-soluble polymer and the polymer having a specific functional group. Specific examples include the solvents described in component (c) below.

[0251] Specific examples of other monomer b include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxy triethylene 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-e Chil-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, methoxy triethylene 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-methyl maleimide, N-ethyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, styrene, vinyl naphthalene, vinyl anthracene, and vinyl biphenyl, etc. can be mentioned.

[0252] The polymer having a specific functional group obtained in this way is usually in a state of a solution dissolved in a solvent.

[0253] Also, the solution of the specific copolymer obtained as described above is poured into diethyl ether, water, etc. under stirring for reprecipitation, and after the generated precipitate is filtered and washed, it can be made into a powder of the specific copolymer by drying at normal pressure or reduced pressure at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If it cannot be sufficiently purified by one 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 later and used in a state of a solution.

[0254] In the polymer of the component (b), the introduction amount of the liquid-repellent group (b1) is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, based on all repeating units. If it is less than 5 mol%, the liquid-repellent effect may not be achieved. If it is more than 60 mol%, problems such as aggregation may occur.

[0255] In the polymer of the component (b), the introduction amount of the group (b2) selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group is preferably 5 mol% to 70 mol%, more preferably 5 mol% to 50 mol%, based on all repeating units. If it is less than 5 mol%, problems may occur in the heat resistance and solvent resistance of the resulting film. If it is more than 60 mol%, the developability may be affected.

[0256] When introducing at least one group (b3) selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group in the polymer of the component (b), the introduction amount is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, based on all repeating units. If it is less than 5 mol%, the effect of improving the heat resistance and solvent resistance of the resulting film may not be obtained. If it is more than 60 mol%, the repeating units of the liquid-repellent property will be too small.

[0257] Also, the number average molecular weight of the polymer of the component (b) is preferably 2,000 to 100,000. More preferably, it is 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 occur.

[0258] Also, in the present invention, the polymer of the component (b) may be a mixture of a plurality of specific copolymers.

[0259] The ratio of the component (b) to the component (a) is 0.1 part by mass to 20 parts by mass of the component (b) with respect to 100 parts by mass of the component (a).

[0260] When the component (a) has a liquid-repellent group (b1) in the component (b), the component (a) can also serve as the component (b), and in this case, it is not always necessary to use the component (b). In this case, it is preferable that the polymer unit (monomer) having the liquid-repellent group (b1) occupies 5 to 30 parts by mass in 100 parts by mass of the component (a).

[0261] <Component (c)> The component (c) used in the present invention is a solvent that dissolves the component (a), the component (b), and, if necessary, the components (d), (e), (f), and (g) described later, and also dissolves other additives and the like that are added as desired. As long as it is a solvent having such a dissolving ability, its type, structure, etc. are not particularly limited.

[0262] Examples of such a component (c) include the same ones as the component (C) used in the above-described upper-layer film-forming composition.

[0263] These solvents can be used alone or in combination of two or more. Among these components (c), solvents having no hydroxy group are preferred from the viewpoint of not dissolving the lower-layer film, that is, 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. These solvents are generally used as solvents for photoresist materials. When using a solvent having a hydroxy group, it is preferably used in combination with a solvent having no hydroxy group from the viewpoint of not dissolving the lower layer film as described above. The solvent to be combined is not particularly limited as long as it has good coatability and does not dissolve the lower layer film, and it may be one kind or two or more kinds. In this case, from the viewpoint of not dissolving the lower layer film, the amount of the solvent having a hydroxy group is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, and most preferably 30% by weight or less based on the total amount of the component (c).

[0264] <(d) component> Examples of the photosensitizer as the component (d) include (d-1) 1,2-quinonediazide compounds, (d-2) photo radical generators, and (d-3) photoacid generators.

[0265] Examples of the (d-1) 1,2-quinonediazide compound include the same ones as (D-1) listed in the component (D) used in the above-described composition for forming the upper layer film.

[0266] When the second photosensitive resin composition of the present invention is a positive photosensitive resin composition and contains a compound having a quinonediazide group as the component (d-1), the content is preferably 5 parts by mass to 100 parts by mass, more preferably 8 parts by mass to 50 parts by mass, still more preferably 10 parts by mass to 40 parts by mass with respect to 100 parts by mass in total of the components (a) and (b). Or, when the component (a) has a liquid repellent group in the component (b1) and does not contain the component (b), the content of the component (d-1) is preferably 5 parts by mass to 100 parts by mass, more preferably 8 parts by mass to 50 parts by mass, still more preferably 10 parts by mass to 4 0 parts by mass. When it is less than 5 parts by mass, the difference in the dissolution rate of the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developer becomes small, and patterning by development may be difficult. Further, when it exceeds 100 parts by mass, the 1,2-quinonediazide compound may not be sufficiently decomposed by exposure in a short time, resulting in a decrease in sensitivity, or the component (d-1) may absorb light and reduce the transparency of the cured film.

[0267] (d-2) The photo radical generator is not particularly limited as long as it generates radicals upon exposure. Specific examples include the same ones as (D-2) listed in component (D) used in the above-described composition for forming the upper layer film.

[0268] When the second photosensitive resin composition of the present invention contains component (d-2), the content is preferably 0.1 part by mass to 30 parts by mass, more preferably 0.5 part by mass to 20 parts by mass, and particularly preferably 1 part by mass to 15 parts by mass, based on 100 parts by mass in total of components (a) and (b). Or, when component (a) has a liquid repellent group (b1) in component (b) and does not contain component (b), the content of component (d-2) is preferably 0.1 part by mass to 30 parts by mass, more preferably 0.5 part by mass to 20 parts by mass, and particularly preferably 1 part by mass to 15 parts by mass, based on 100 parts by mass of component (a). If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is formed, the film may have low reliability. Also, if this ratio is too large, the transmittance of the coating film may decrease, or development failure of the unexposed portion may occur.

[0269] (d-3) The photoacid generator is not particularly limited as long as it is a compound that generates an acid upon photolysis upon ultraviolet irradiation. Examples of the acid generated when the photoacid generator undergoes photolysis include the same ones as the acid generated when the photoacid generator listed in (D-3) of component (D) used in the above-described composition for forming the upper layer film undergoes photolysis.

[0270] Examples of the photoacid generator include the same ones as the photoacid generator listed in (D-3) of component (D) used in the above-described composition for forming the upper layer film.

[0271] When the second photosensitive resin composition of the present embodiment contains the component (d-3), the content is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, still more preferably 0.5 parts by mass to 8 parts by mass, based on 100 parts by mass in total of the components (a) and (b). Or, when the component (a) has a liquid-repellent group (b1) in the component (b) and does not contain the component (b), the content of the component (d-3) is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, still more preferably 0.5 parts by mass to 8 parts by mass, based on 100 parts by mass of the component (a). By setting the content of the component (d-3) to 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, when it is more than 20 parts by mass, the unexposed part may have poor developability or the storage stability of the composition may decrease.

[0272] <(e) component> (e) The component is a crosslinking agent and 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 a thermal reaction with a thermally reactive site (for example, a carboxyl group and / or a phenolic hydroxyl group) of the component (a). Hereinafter, specific examples are given, but the present invention is not limited thereto. The thermal crosslinking agent is preferably, for example, a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group in the component (e1) or a crosslinkable compound represented by the following formula (5) in the component (e2). These crosslinking agents can be used alone or in combination of two or more.

[0273] The crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group in the component (e1) undergoes a crosslinking reaction by a dehydration condensation reaction when exposed to a high temperature during thermosetting. Examples of such a compound include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.

[0274] As specific examples of the alkoxymethylated glycoluril, the same ones as those listed in the component (E) used in the above-described composition for forming the upper layer film can be used.

[0275] As specific examples of the alkoxymethylated benzoguanamine, the same ones as those listed in the component (E) used in the above-described composition for forming the upper layer film can be used.

[0276] As specific examples of the phenoplast-based compound, the same ones as those listed in the component (E) used in the above-described composition for forming the upper layer film can be used.

[0277] Furthermore, as the component (e1), polymers produced using acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide can also be used.

[0278] As such polymers, the same ones as (E1) listed in the component (E) used in the above-described composition for forming the upper layer film can be used.

[0279] In addition, in the second photosensitive resin composition of the present invention, as the component (e2), the same ones as (E2) listed in the component (E) used in the above-described composition for forming the upper layer film can be used.

[0280] In addition, as the e component, a compound capable of forming a crosslinked structure by a thermal reaction with a thermally reactive site of the (a) component (for example, a carboxyl group and / or a phenolic hydroxyl group) other than those shown as the (e1) component and the (e2) component can also be used. Specifically, for example, 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-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and epoxy compounds such as N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, VESTANAT B1358 / 100, VESTAGON BF 1540 (the above are isocyanurate-modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, the same Takenate B-7075 (the above are isocyanurate-modified polyisocyanates, manufactured by Mitsui Chemicals, Inc.), and isocyanate compounds such as these can be mentioned.

[0281] In addition, as the e component, a polymer having two or more structures capable of forming a crosslinked structure by a thermal reaction with a thermally reactive site of the (a) component (for example, a carboxyl group and / or a phenolic hydroxyl group) can also be used. Specifically, for example, a polymer produced using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, etc., 3 - Polymers produced using compounds having an alkoxysilyl group such as methacryloxypropyltrimethoxysilane, compounds having an isocyanate group such as 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko K.K.), 2-isocyanatoethyl acrylate (Karenz AOI [registered trademark], manufactured by Showa Denko K.K.), or polymers produced using compounds having a blocked isocyanate group such as 2-(0-[1'-methylpropylideneamino]carboxamido)ethyl methacrylate (Karenz MOI-BM [registered trademark], manufactured by Showa Denko K.K.), 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 polymers, or may be combined with other compounds to produce polymers.

[0282] (a) When the component has a 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, a compound having two or more groups represented by a hydroxy group, a carboxyl group, an amide group, and an amino group can be used as the (e) component.

[0283] These crosslinkable compounds can be used alone or in combination of two or more.

[0284] When component (e) 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, based on 100 parts by mass in total of component (a) and component (b). Or, when component (a) has a liquid repellent group (b1) in component (b) and component (b) is not included, the content of component (e) is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of component (a). When the content of the crosslinkable compound is small, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so the effects 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 compounds are present, and the heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation decrease, and the storage stability of the photosensitive resin composition may deteriorate.

[0285] <Component (f)> Component (f) is a compound having two or more ethylenically polymerizable groups. The compound having two or more ethylenically polymerizable groups referred to here means a compound having two or more polymerizable groups in one molecule and having those polymerizable groups at the molecular terminals, and those polymerizable groups mean at least one kind of polymerizable group selected from the group consisting of acrylate groups, methacrylate groups, vinyl groups, and allyl groups. This compound (f) having two or more ethylenically polymerizable groups 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 good compatibility with each component and no influence on developability in the solution of the negative photosensitive resin composition in the second photosensitive resin composition of the present invention.

[0286] As specific examples of such compounds, the same ones as those listed in component (F) used in the above-described composition for forming the upper layer film can be used.

[0287] 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 with respect to 100 parts by mass in total of the components (a) and (b). Or, when the component (a) has the liquid-repellent group (b1) in the component (b) and does not contain the component (b), the content of the component (f) 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 with respect to 100 parts by mass of the component (a). When the component (b) is not included, the content of the component (f) 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 with respect to 100 parts by mass of the component (a). If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, the film may have low reliability. On the other hand, if this ratio is too large, tack may occur in the coating film after pre-baking, or the unexposed portion may have poor solubility during development.

[0288] <(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 above-mentioned composition for forming the upper layer film can be used.

[0289] When the second photosensitive resin composition used in the present invention contains a compound having two or more functional groups that form a covalent bond with an acid of the 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 in total of the components (a) and (b). Or, when the component (a) has the liquid-repellent group (b1) in the component (b) and does not contain the component (b), the content of the component (g) is preferably 5 to 200 parts by mass, more preferably 50 to 150 parts by mass based on 100 parts by mass of the component (a). If this ratio is too small, the photocurability of the negative photosensitive resin composition may decrease. On the other hand, if it is too large, the developability of the unexposed portion may decrease, which may cause residual film or residue.

[0290] <Other additives> Furthermore, as long as the effects of the present invention are not impaired, the second photosensitive resin composition used in the present invention may contain, as necessary, a leveling agent, a rheology modifier, a pigment, a dye, organic / inorganic fine particles, a storage stabilizer, an antifoaming agent, an adhesion promoter, or a dissolution accelerator such as a polyhydric phenol or a polyvalent carboxylic acid.

[0291] <Bank formation process> After forming the resist film 13, it is exposed and developed to pattern the lower layer film 12 and the resist film 13 together to form a bank. The region (non-bank portion) partitioned by the bank is formed in the opening 14 (FIG. 1).

[0292] As shown in FIG. 1, when the first and second photosensitive resin compositions are positive photosensitive resin compositions, the exposed portion is the non-bank portion, and in the development process, the lower layer film of the non-bank portion and the resist film of the non-bank portion are removed together to form the opening 14. Alternatively, when the first and second photosensitive resin compositions of the present invention are negative photosensitive resin compositions, the exposed portion becomes the bank portion, and in the development process, the lower layer film of the non-bank portion and the resist film of the non-bank portion are removed together.

[0293] In the second photosensitive resin composition containing a conventional liquid-repellent component, residues are left in the development process and it is difficult to remove them cleanly. When residues are left, unevenness or other defects occur in the organic thin film in the process of further forming an organic thin film in the region partitioned by the bank. If a bank is formed by the method for forming a bank pattern of the present invention, the liquid-repellent effect of the bank is good, and it is difficult to leave residues on the substrate or other layers provided on the substrate, so a clean organic thin film can be formed.

[0294] Here, as the other layer that can be formed on the substrate 11, for example, in the case of an organic electroluminescent element, an anode, a cathode, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a blocking layer, a light-emitting Examples include layers such as layers. When the bank pattern forming method of the present invention is used for an organic electroluminescent element, as other layers, a hole injection layer of organic electroluminescence is particularly suitable. Other layers are composed of at least one layer.

[0295] <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 optionally, can further contain one or more of the crosslinking agent of component (E), the compound having two or more ethylenically polymerizable groups of component (F), the compound having two or more functional groups that form a covalent bond by an acid of component (G), and other additives. (A) component: An alkali-soluble resin having an amide group (C) component: Solvent (D) component: Photosensitizer

[0296] Among them, preferred examples of the first photosensitive resin composition used in the present invention are as follows. [1]: A photosensitive resin composition containing 5 to 100 parts by mass of component (D) with respect to 100 parts by mass of component (A), and these components are dissolved in component (C), and further, the first photosensitive resin composition in which the component (D) is component (D-1). [2]: A photosensitive resin composition containing 5 to 100 parts by mass of component (D) with respect to 100 parts by mass of component (A), and these components are dissolved in component (C), and further, a crosslinking agent which is component (E) is contained in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of component (A), and further, the first photosensitive resin composition in which the component (D) is component (D-1). [3]: A photosensitive resin composition containing 5 to 200 parts by mass of component (F) with respect to 100 parts by mass of component (A), and 0.1 to 30 parts by mass of component (D) with respect to 100 parts by mass of the total of component (A) and component (F), and these are dissolved in component (C), and further, the first photosensitive resin composition in which the component (D) is component (D-2).

[0297] The proportion of 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, from 1% by mass to 80% by mass, or, for example, from 5% by mass to 60% by mass, or from 10% by mass to 50% by mass. Here, the solid content means the components of the photosensitive resin composition excluding the component (C).

[0298] The method for preparing the first photosensitive resin composition used in the present invention is not particularly limited. As the preparation method, for example, the component (A) (specific polymer) is dissolved in the component (C), and a photosensitizer of the component (D), a crosslinking agent of the component (E) as required, a compound having two or more ethylenically polymerizable groups of the component (F), and a compound having two or more functional groups that form a covalent bond with an acid of the component (G) are mixed at a predetermined ratio to form a uniform solution, or at an appropriate stage of this preparation method, other additives may be further added and mixed as required.

[0299] In the preparation of 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 it is. In this case, when the components (A), (D), the component (E) as required, the component (F), the component (G), etc. are added to form a uniform solution, the component (C) may be further added for the purpose of concentration adjustment. At this time, the component (C) used in the formation process of the specific copolymer and the component (C) used for concentration adjustment during the preparation of the first photosensitive resin composition may be the same or different.

[0300] Thus, the solution of the prepared first photosensitive resin composition is preferably filtered using a filter having a pore size of about 0.2 μm and then used.

[0301] 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, if desired, may further contain one or more of the crosslinking agent as component (e), the compound having two or more ethylenically polymerizable groups as component (f), the compound having two or more functional groups that form a covalent bond with an acid as component (g), and other additives. Component (a): An alkali-soluble resin Component (b): A polymer having a liquid-repellent group (b1) Component (c): A solvent Component (d): A photosensitizer

[0302] Preferred examples of the second photosensitive resin composition used in the present invention are as follows. [1]: A second photosensitive resin composition containing 0.1 to 20 parts by mass of component (b) with respect to 100 parts by mass of component (a), and these components being dissolved in component (c). [2]: A photosensitive resin composition containing 0.1 to 20 parts by mass of component (b) and 5 to 100 parts by mass of component (d) with respect to 100 parts by mass of component (a), and these components being dissolved in component (c), and further, a second photosensitive resin composition in which the component (d) is component (d-1). [3]: A photosensitive resin composition containing 0.1 to 20 parts by mass of component (b) and 5 to 100 parts by mass of component (d) with respect to 100 parts by mass of component (a), and these components being dissolved in component (c), and further containing 1 to 50 parts by mass of a crosslinking agent as component (e) with respect to 100 parts by mass of the total of component (a) and component (b), and further, a second photosensitive resin composition in which the component (d) is component (d-1). [4]: A photosensitive resin composition containing 0.1 to 20 parts by mass of component (b) with respect to 100 parts by mass of component (a), 5 to 200 parts by mass of component (f) with respect to 100 parts by mass of the total of component (a) and component (b), and 0.1 to 30 parts by mass of component (d) with respect to 100 parts by mass of the total of component (a), component (b), and component (f), and these being dissolved in component (c), and further, a second photosensitive resin composition in which the component (d) is component (d-2). [5]: A second photosensitive resin composition composed of component (a) which contains a liquid-repellent group (b1) in component (a) and in which the polymerized unit having the liquid-repellent group (b1) occupies 5 to 30 parts by mass in 100 parts by mass of component (a) and does not contain component (b).

[0303] The proportion of the solid content 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. For example, it is 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 means the one obtained by removing component (c) from all components of the second photosensitive resin composition.

[0304] The method for preparing the second photosensitive resin composition used in the present invention is not particularly limited. As the preparation method, for example, component (b) is dissolved in component (c), and the alkali-soluble resin of component (a), the photosensitizer of component (d), the crosslinking agent of component (e) if necessary, the compound having two or more ethylenically polymerizable groups of component (f), and the compound having two or more functional groups that form a covalent bond with an acid of component (g) are mixed in a predetermined ratio to form a uniform solution, or at an appropriate stage of this preparation method, other additives are further added and mixed as necessary.

[0305] In the preparation of the second photosensitive resin composition used in the present invention, the solution of the copolymer obtained by the polymerization reaction in component (c) can be used as it is. In this case, when making a uniform solution by putting component (a), component (d), component (e) if necessary, component (f), component (g), etc. into the solution of component (b) as in the preparation of the first photosensitive resin composition, component (c) may be additionally added for the purpose of concentration adjustment. At this time, the component (c) used in the formation process of the specific copolymer and the component (c) used for concentration adjustment during the preparation of the second photosensitive resin composition may be the same or different. When making a uniform solution by putting component (a), component (d), component (e) if necessary, component (f), component (g), etc. into the solution of component (b) as in the preparation of the first photosensitive resin composition, component (c) may be additionally added for the purpose of concentration adjustment. At this time, the component (c) used in the formation process of the specific copolymer and the component (c) used for concentration adjustment during the preparation of the second photosensitive resin composition may be the same or different.

[0306] Subsequently, the solution of the prepared second photosensitive resin composition is preferably filtered using a filter with a pore size of about 0.2 μm and then used.

[0307] <Coating film and cured film as the lower layer film> The first photosensitive resin composition used in the present invention is applied onto a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal (such as aluminum, molybdenum, chromium), a glass substrate, a quartz substrate, an ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit coating, inkjet coating, etc., and then pre-dried using a hot plate or an oven, etc., to form a coating film. Thereafter, by heat-treating this coating film, a photosensitive resin film as the lower layer film is formed.

[0308] As the conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70°C to 160°C and a time of 0.3 to 60 minutes are adopted. The heating temperature and the heating time are preferably 80°C to 140°C and 0.5 to 10 minutes.

[0309] Also, the film thickness of the photosensitive resin film formed from the first photosensitive resin composition is, for example, 0.1 μm to 30 μm, and for example, 0.2 μm to 10 μm, and further for example, 0.3 μm to 8 μm.

[0310] <Coating film and cured film as the resist film> The second photosensitive resin composition used in the present invention is applied onto the lower layer film obtained above by spin coating, flow coating, roll coating, slit coating, spin coating following slit coating, inkjet coating, etc., and then pre-dried using a hot plate or an oven, etc., to form a coating film. Thereafter, by heat-treating this coating film, a photosensitive resin film as the resist film is formed.

[0311] As the conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70°C to 160°C and a time of 0.3 to 60 minutes are adopted. The heating temperature and the heating time are preferably 80°C to 140°C and 0.5 to 10 minutes.

[0312] In addition, the film thickness of the photosensitive resin film formed from the second photosensitive resin composition is, for example, 0.1 μm to 30 μm, for example, 0.2 μm to 10 μm, and further for example, 0.3 μm to 8 μm.

[0313] On the coating films of the lower layer film and the resist film on the lower layer film obtained above, a mask having a predetermined pattern is mounted, irradiated with light such as ultraviolet rays, and developed with an alkaline developer. Depending on the material composition, either the exposed portion or the unexposed portion is washed out, 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 at the end face.

[0314] 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 alkaline aqueous solutions such as aqueous amine solutions of ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers. Examples include aqueous solutions of quaternary ammonium hydroxides such as tetraethylammonium hydroxide, and alkaline aqueous solutions such as aqueous amine solutions of ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers.

[0315] Among the above, a 0.1 to 2.58 mass% aqueous solution of tetraethylammonium hydroxide is generally used as a developer for photoresists. Also in the first and second photosensitive resin compositions of the present invention, this alkaline developer can be used for good development without causing problems such as swelling of the film.

[0316] In addition, as the developing method, any of a puddle method, a dipping method, a rocking immersion method, etc. can be used. The developing time at that time is usually 15 to 180 seconds.

[0317] After development, the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried using compressed air or compressed nitrogen or by spinning, whereby the moisture on the substrate is removed and a patterned film is obtained.

[0318] Subsequently, the patterned film is post-baked for thermosetting, specifically by heating using a hot plate, an oven, etc., whereby a film excellent in heat resistance, transparency, planarization property, low water absorption, chemical resistance, etc. and having a good relief pattern is obtained.

[0319] As the post-bake, generally, a method is adopted in which treatment is performed for 5 to 30 minutes on a hot plate or for 30 to 90 minutes in an oven at a heating temperature selected from the range of 140°C to 270°C.

[0320] Thus, by such post-baking, a cured film having a desired good pattern shape can be obtained.

[0321] As described above, by the method for patterning a cured film, a liquid-repellent bank pattern in which residues such as components of a liquid-repellent resist material hardly remain in regions other than the bank can be formed, and a uniform organic thin film can be formed within the region partitioned by the bank.

Example

[0322] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The measurement of the molecular weight of the polymer is 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 the apparatus and Shodex (registered trademark) KF-804L and 803L as the columns under the following conditions. Column oven: 40°C Flow rate: 1 ml / min Eluent: Tetrahydrofuran

[0323] The meanings of the abbreviations used in the following examples are as follows. 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 and 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride AIBN: α,α’-Azobisisobutyronitrile QD1: A compound synthesized by the condensation reaction of 1 mol of α,α,α’-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride QD2: A compound synthesized by the condensation reaction of 1 mol of 4,4’,4”-(3-methyl-1-propanil-3-ylidene)trisphenol and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride CST: A styrene polymer (manufactured by Maruzen Petrochemical Co., Ltd.) obtained by mixing a polymer of 85% hydroxystyrene and 15% styrene and a polymer of 70% hydroxystyrene and 30% styrene at a ratio of 3:7 8KQ: 8KQ-2001 (an alkali-soluble UV-curable acrylic resin manufactured by Taisei Fine Chemical Co., Ltd.) Poly-AA: Polyacrylic acid (manufactured by Fujifilm Wako Pure Chemical Corporation) 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: Tetra(3,4-epoxycyclohexylmethyl) butanetetracarboxylate modified ε-caprolactone YH-434L: YH-434L manufactured by Shin-Nichi Kasei Co., Ltd. (currently: Nippon Steel & Sumikin Chemical Co., Ltd.) CEL-2021P: 3,4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate CH: Cyclohexanone PMA-ST: Propylene glycol monomethyl ether acetate dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd.)

[0324] <Synthesis Example 1> 3.00 g of MAAm, 2.00 g of HPMA, 5.00 g of MMA, and 0.8 g of AIBN were dissolved in 43.2 g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 30% by mass) (P1). The Mn of the obtained acrylic polymer was 2300 and the Mw was 5500.

[0325] <Synthesis Example 2> 3.00 g of MAAm, 3.00 g of HPMA, 4.00 g of CHMI, and 0.8 g of AIBN were dissolved in 43.2 g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 30% by mass) (P2). The Mn of the obtained acrylic polymer was 3000 and the Mw was 6200.

[0326] <Synthesis Example 3> 3.00 g of MAAm, 3.00 g of HPMA, 4.00 g of CHMI, and 0.8 g of AIBN were dissolved in 43.2 g of PGME, and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 30% by mass) (P3). The Mn of the obtained acrylic polymer was 3000, and the Mw was 6400.

[0327] <Synthesis Example 4> 3.00 g of MAAm, 3.00 g of HPMA, 4.00 g of CHMI, and 0.8 g of AIBN were dissolved in 43.2 g of PGME, and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 30% by mass) (P4). The Mn of the obtained acrylic polymer was 3500, and the Mw was 7500.

[0328] <Synthesis Example 5> 10.9 g of MAA, 25.5 g of HEMA, 28.7 g of MMA, 35.3 g of CHMI, and 6.0 g of AIBN were dissolved in 159.6 g of PGME, and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 40% by mass) (P5). The Mn of the obtained acrylic polymer was 3800, and the Mw was 6700.

[0329] <Synthesis Example 6> 90.00 g of MAA, 225.00 g of HEMA, 45.00 g of HPMA, 180.00 g of MMA, 360.00 g of CHMI, and 57.60 g of AIBN were dissolved in 1436.40 g of PGME, and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 40% by mass) (P6). The Mn of the obtained acrylic polymer was 3100, and the Mw was 6100.

[0330] <Synthesis Example 7> 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 of CH It was dissolved in g and stirred at 110 °C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 20% by mass) (P7). The Mn of the obtained acrylic polymer was 7,200 and the Mw was 11,000.

[0331] <Synthesis Example 8> 5.00 g of PFHMA, 3.83 g of KBM-503, 1.51 g of HEMA, and 0.52 g of AIBN were dissolved in 25.32 g of PGME and reacted at 80 °C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 30% by mass) (P8). The Mn of the obtained acrylic polymer was 4,800 and the Mw was 6,700.

[0332] <Synthesis Example 9> 2.0 g of PFHMA, 5.0 g of HPMA, 3.0 g of CHMI, and 0.5 g of AIBN were dissolved in 24.5 g of PGME and reacted at 80 °C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 30% by mass) (P9). The Mn of the obtained acrylic polymer was 3,000 and the Mw was 6,500.

[0333] Each component of (A), (D), and (E) and the solvent (C) were mixed with the composition shown in Table 1 to prepare the first photosensitive resin compositions of the lower layer film materials 1 to 8.

[0334]

Table 1

[0335] Similarly, the second photosensitive resin compositions of the upper layer resist film materials 1 to 5 were prepared with the composition shown in Table 2. In addition, in Table 1 and Table 2, the composition ratios represent the ratios in terms of solid content.

[0336]

Table 2

[0337] [Evaluation 1 Evaluation of Pattern Shape] After applying the first photosensitive resin composition of the lower layer materials 1 to 8 onto an ITO-glass substrate using a spin coater, pre-baking was performed 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 film thickness of 0.2 μm. Next, after applying the second photosensitive resin composition of the upper layer materials 1 to 5 onto the lower layer material coating film using a spin coater, pre-baking was performed 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 film thickness of 1.1 μm. This coating film was irradiated with ultraviolet light at 365 nm with a light intensity of 2.6 mW / cm2 for a certain period of time using a UV irradiation device PLA-600FA manufactured by Canon Inc. through a photomask on which a 50-μm line & space pattern was drawn. Then, the coating film was immersed in an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) at 2.38 mass% or 0.4 mass% for a predetermined period of time, and then washed with ultrapure water by running water for 30 seconds. Subsequently, this coating film was post-baked by heating at a temperature of 230 °C for 30 minutes to fabricate the substrates of Examples 1 to 5 and Comparative Examples 6 to 9. In Comparative Examples 1 to 5, the substrates were fabricated in the same manner as above without performing the coating and pre-baking steps of the lower layer materials 1 to 5. The state of the fabricated line & space pattern was observed with an optical microscope. Those with the pattern peeled off from the substrate were marked as "×", and those with the pattern formed without peeling were marked as "〇". The obtained results are shown in Table 3.

[0338] [Evaluation 2 Evaluation of Bank Contact Angle] After applying the first photosensitive resin composition of the lower layer material 5 onto an ITO-glass substrate using a spin coater, pre-baking was performed 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 film thickness of 0.2 μm. Next, after applying the second photosensitive resin composition of the upper layer material 5 onto the lower layer material coating film using a spin coater, pre-baking was performed 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 film thickness of 1.1 μm. This coating film was irradiated with ultraviolet light at 365 nm with a light intensity of 2.6 mW / cm2 for a certain period of time using a UV irradiation device PLA-600FA manufactured by Canon Inc. Then, 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 ultrapure water by running water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230°C for 30 minutes to create a cured film on the ITO-glass substrate of Example 5. In Examples 1 to 4, a cured film on an ITO-glass substrate composed of the upper layer material and the lower layer material was formed in the same manner as above without performing ultraviolet light exposure. In Comparative Example 5, a cured film on an ITO-glass substrate composed only of the upper layer material was formed in the same manner as above without performing the coating and pre-baking steps of the lower layer material 5. In Comparative Examples 1 to 4, a cured film on an ITO-glass substrate composed only of the upper layer material was formed in the same manner as above without performing the coating and pre-baking steps of the lower layer materials 1 to 4 and ultraviolet light exposure. The contact angle of anisole on this cured film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 3. Note that Evaluation 2 was not performed for Comparative Examples 6 to 9 in which pattern peeling occurred in Evaluation 1.

[0339] [Evaluation 3: Evaluation of the Contact Angle of the Exposed Portion on the ITO Substrate] After applying the first photosensitive resin compositions of the lower layer materials 1 to 4 onto an ITO-glass substrate using a spin coater, pre-baking was performed 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 film thickness of 0.2 μm. Next, after applying the second photosensitive resin compositions of the upper layer materials 1 to 4 onto the lower layer material coating film using a spin coater, pre-baking was performed 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 film thickness of 1.1 μm. This coating film was irradiated with ultraviolet light at 365 nm with a light intensity of 2.6 mW / cm2 for a certain period of time using a UV irradiation device PLA-600FA manufactured by Canon Inc. Then, 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 ultrapure water by running water for 30 seconds. Next, this coating film was post-baked by heating at a temperature of 230 °C for 30 minutes to prepare ITO-glass substrates on which the coating films of Examples 1 to 4 were developed and removed. In Example 5, an ITO-glass substrate on which the coating film was developed and removed in the same manner as above without ultraviolet exposure was prepared. In Comparative Examples 1 to 4, ITO-glass substrates on which the coating films were developed and removed in the same manner as above were prepared without performing the coating and pre-baking steps of the lower layer materials 1 to 4. In Comparative Example 5, a cured film on an ITO-glass substrate consisting only of the upper layer material was formed in the same manner as above without performing the coating and pre-baking steps of the lower layer material 5 and ultraviolet light exposure. The contact angle of anisole on this cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 3. Note that Evaluation 3 was not performed for Comparative Examples 6 to 9 in which pattern peeling occurred in Evaluation 1.

[0340]

Table 3

[0341] As shown in Table 3, in Examples 1 to 5 using the lower layer material, the contact angle of the opening was smaller and the lyophilicity was better than in Comparative Examples 1 to 5 that did not use the lower layer material. Further, in Example 3 using the lower layer material, no residue was observed in the space portion of the line & space pattern in Evaluation 1 and a good pattern was obtained, whereas in Comparative Example 3 that did not use the lower layer material, particulate residues were observed in the space portion. Further, in Comparative Examples 6 to 9 using a hydrophilic resin not containing an amide group in the lower layer material, the pattern peeled off during development in Evaluation 1 and did not remain on the substrate.

Claims

1. A method of forming a bank and regions defined by the bank on a substrate, the method of forming a bank pattern for forming an organic thin film in the regions defined by the bank, comprising: a lower layer film forming step of applying a first photosensitive resin composition containing the following components (A), (C) and (D) directly on the substrate or via another layer to provide a lower layer film; a resist film forming step of applying a second photosensitive resin composition containing the following components (a), (b), (c) and (d) on the lower layer film to provide a resist film; a bank forming step of exposing and developing the resist film to form a bank, and in the developing process, removing the lower layer film of the non-bank portion together with the resist film of the non-bank portion; Component (A): An alkali-soluble resin having an amide group Component (C): A solvent Component (D): A photosensitizer Component (a): An alkali-soluble resin Component (b): A polymer having a liquid-repellent group (b1) Component (c): A solvent Component (d): A photosensitizer The method of forming a bank pattern according to claim 1, wherein the first photosensitive resin composition satisfies the following (Z2) and (Z3). (Z2): The alkali-soluble resin having an amide group of component (A) is a copolymer of methacrylamide, 4-hydroxyphenyl methacrylate and N-cyclohexyl maleimide; (Z3): Component (D) is a photo radical generator which is (D-2), and further contains, as component (F), a compound having two or more ethylenic double bonds

2. The method of forming a bank pattern according to claim 1, wherein the second photosensitive resin composition satisfies at least one of the following (z1) to (z4). (z1): Further contains a crosslinking agent which is component (e); (z2): The alkali-soluble resin of component (a) further has a self-crosslinking group or further has a group which 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; (z3): Component (d) is a photo radical generator which is (d-2), and further contains, as component (f), a compound having two or more ethylenic double bonds; (z4): Component (d) is a photoacid generator which is (d-3), and further contains, as component (g), a compound having two or more functional groups which form a covalent bond by the acid generated from (d-3)

3. The method for forming a bank pattern according to claim 1 or claim 2, wherein the component (D) and / or the component (d) is a quinonediazide compound.

4. The method for forming a bank pattern according to claim 1, wherein the component (D) is a quinonediazide compound and further satisfies the above (Z2).

5. The method for forming a bank pattern according to claim 2, wherein the component (d) is a quinonediazide compound and further satisfies either the above (z1) or (z2).

6. The method for forming a bank pattern according to claim 4, wherein the component (D) is diazonaphthoquinone.

7. The method for forming a bank pattern according to claim 5, wherein the component (d) is diazonaphthoquinone.

8. The method for forming a bank pattern according to any one of claims 1 to 7, wherein the liquid repellent group (b1) is 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 represented by the following formula 4. -(SiR １ R ２ -O) ｎ -SiR １ R ２ R ３ Formula 4 (However, R １ , R ２ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R ３ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200.)

9. The method for forming a bank pattern according to any one of claims 1 to 8, wherein the number average molecular weight of the alkali-soluble resin having an amide group in the component (A) and / or the alkali-soluble resin in the component (a) is 2,000 to 50,000 in terms of polystyrene.

10. The method for forming a bank pattern according to any one of claims 1 to 9, characterized in that it contains 0.1 to 20 parts by mass of the component (b) with respect to 100 parts by mass of the component (a).

11. The method for forming a bank pattern according to any one of claims 1 to 10, wherein the polymer of the component (b) is an acrylic polymer.

12. The method for forming a bank pattern according to claim 11, wherein the number average molecular weight of the acrylic polymer of the component (b) is 2,000 to 100,000 in terms of polystyrene.

13. The method for forming a bank pattern according to any one of claims 2 to 12, characterized in that the component (e) is 1 to 50 parts by mass with respect to a total of 100 parts by mass of the components (a) and (b).

14. The method for forming a bank pattern according to any one of claims 1 to claim 13, wherein the component (b) is further a polymer having the following (b2). (b2): At least one group selected from an N-alkoxymethylamide group, a blocked isocyanate group, and a trialkoxysilyl group

15. The method for forming a bank pattern according to any one of claims 1 to 14, characterized in that the component (b) is further a polymer having the following (b3). (b3): At least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group

16. A method for forming a bank and a region partitioned by the bank on a substrate, in a method for forming a bank pattern for forming an organic thin film in the region partitioned by the bank, A lower layer film forming step of applying a first photosensitive resin composition containing the following components (A), (C), and (D) directly on the substrate or via another layer to provide a lower layer film; A resist film forming step of applying a second photosensitive resin composition containing the following components (a), (c), and (d) on the lower layer film to provide a resist film; A bank forming step of forming a bank by exposing and developing the resist film, and in the developing process, the lower layer film of the non-bank portion is removed together with the resist film of the non-bank portion; Component (A): An alkali-soluble resin having an amide group Component (C): A solvent Component (D): A photosensitizer Component (a): An alkali-soluble resin having a liquid repellent group (b1) Component (c): A solvent Component (d): A photosensitizer The method for forming a bank pattern, wherein the first photosensitive resin composition satisfies the following (Z2) and (Z3). (Z2): The alkali-soluble resin having an amide group of component (A) is a copolymer of methacrylamide, 4-hydroxyphenyl methacrylate, and N-cyclohexyl maleimide; (Z3): Component (D) is a photo radical generator which is (D-2), and further contains a compound having two or more ethylenic double bonds as component (F)

17. The method for forming a bank pattern according to claim 16, characterized in that the polymer unit having a liquid repellent group (b1) occupies 5 to 30 parts by mass in 100 parts by mass of component (a).

18. The method for forming a bank pattern according to claim 16 or claim 17, characterized in that component (e) is 1 to 50 parts by mass with respect to 100 parts by mass of component (a).

19. The method for forming a bank pattern according to any one of claims 1 to 18, wherein the other layer is a hole injection layer of organic electroluminescence

20. A bank pattern having a bank and a region partitioned by the bank on a substrate The bank has, at least from the substrate side, a substrate, a lower layer film made of a first photosensitive resin composition containing at least the following component (A) and component (D), and a resist film made of a second photosensitive resin composition containing at least the following components (a), (b), and (d). The region partitioned by the bank does not have the lower layer film and the resist film. The first photosensitive resin composition satisfies the following (Z2) and (Z3), and is a bank pattern. Component (A): An alkali-soluble resin having an amide group Component (D): A photosensitizer Component (a): An alkali-soluble resin Component (b): A polymer having a liquid-repellent group (b1) Component (d): A photosensitizer (Z2): The alkali-soluble resin having an amide group of component (A) is a copolymer of methacrylamide, 4-hydroxyphenyl methacrylate, and N-cyclohexyl maleimide; (Z3): Component (D) is a photo radical generator which is (D-2), and further contains, as component (F), a compound having two or more ethylenic double bonds

21. A display element having the bank pattern according to claim 20.

22. A display element having the bank pattern according to claim 20 as a partition wall for image formation.

23. In a bank pattern having a bank and a region partitioned by the bank on a substrate, a photosensitive resin composition for forming a lower layer film for forming a lower layer film under a resist film for the bank, containing the following components (A), (C), and (D), Component (A): An alkali-soluble resin having an amide group Component (C): A solvent Component (D): A photosensitizer A photosensitive resin composition for forming a lower layer film under a resist film, which satisfies the following (Z2) and (Z3). (Z2): The alkali-soluble resin having an amide group of component (A) is a copolymer of methacrylamide, 4-hydroxyphenyl methacrylate, and N-cyclohexyl maleimide; (Z3): Component (D) is a photo radical generator which is (D-2), and further contains, as component (F), a compound having two or more ethylenic double bonds

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