Photosensitive resin composition

Abstract

[Problem] The present invention is to provide a photosensitive resin composition that makes it possible to form a cured film that can be used in a liquid crystal display element, an organic EL display element, an inorganic EL display element, or the like. The water and oil repellency of the surface of the cured film are to be maintained without loss through a development step, and a substrate is to be given high water and oil repellency such that an EL element formation ink achieves favorable spread without overflowing a bank to an adjacent pixel or causing cissing or unevenness. In other words, the present invention is to provide a photosensitive resin composition that makes it possible to form a cured film that has developer resistance, liquid repellency, and ink wettability. [Solution] A photosensitive resin composition according to the present invention contains components (A)–(D). (A) An alkali-soluble polymer. (B) A liquid-repellent polymer that includes a copolymer that comprises at least (B1) a monomer that includes a liquid-repellent group, (B2) a monomer that includes a trialkoxysilyl group, and (B3) a monomer of a cyclic compound. (C) A photosensitizer. (D) A solvent.

Description

Photosensitive resin composition

[0001] The present invention relates to a photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a photosensitive resin composition and a cured film obtained therefrom that have high water-repellency and oil-repellency on the surface thereof and that can form a cured film that allows an organic functional ink to wet and spread well within a surrounded pattern without overflowing, as well as to the cured film and various materials using the cured film. This photosensitive resin composition is particularly suitable for use as an interlayer insulating film in display elements such as liquid crystal displays, electroluminescent displays, and micro LED displays, as well as a light-shielding material and partition wall material compatible with inkjet printing.

[0002] In general, display elements such as thin film transistor (TFT) liquid crystal display elements and organic electroluminescent (EL) elements are provided with patterned electrode protection films, planarizing films, insulating films, etc. As materials for forming these films, photosensitive resin compositions have been widely used because they require fewer steps to obtain the required pattern shape and have sufficient planarity.

[0003] In recent years, full-color display substrate fabrication techniques using inkjet printing have also been actively investigated in the fabrication of display elements. For example, in the fabrication of color filters for liquid crystal display elements, in contrast to conventional printing, electrodeposition, dyeing, or pigment dispersion methods, a color filter and manufacturing method thereof (Patent Document 1) have been proposed in which pre-patterned pixel-defining sections (hereinafter referred to as banks) are formed using a light-blocking photosensitive resin layer, and ink droplets are dispensed into openings surrounded by these banks. For organic EL display elements, a method has also been proposed in which banks are prepared in advance and ink, which will become the light-emitting layer, is dispensed into the openings (Patent Document 2). However, when dispensing ink droplets into openings surrounded by banks using the inkjet method, the substrate must be ink-philic (hydrophilic), and the bank surface must be water- and oil-repellent to prevent the ink droplets from spilling over the bank and into adjacent pixels.

[0004] To achieve the above object, it has been proposed that successive plasma (ozone) treatments such as oxygen gas plasma treatment and fluorine gas plasma treatment can be used to make the substrate hydrophilic and the bank water-repellent (Patent Document 3), but the process is complicated. Also, it has been proposed to incorporate a fluorine-based surfactant or a fluorine-based polymer into a photosensitive organic thin film (Patent Document 4), but there are many points to consider, including not only photosensitivity but also film properties, such as compatibility and addition amount, and the UV ozone treatment during the hydrophilic treatment of the substrate reduces the water-repellent properties of the surface, making it impractical.

[0005] In the bank formation process, the openings are developed with a developer to form the banks. At this time, the developer also comes into contact with the surface of the bank, so developer resistance is required to give the bank surface water and oil repellency. If the bank surface has low developer resistance, the water and oil repellency will decrease, and ink droplets dropped into the openings will overflow the bank and overflow into adjacent pixels.

[0006] As bank materials, negative-type photosensitive resin compositions (Patent Document 5) and positive-type photosensitive resin compositions have been proposed, but it is difficult to improve resolution with negative-type photosensitive resin compositions. Meanwhile, as a positive-type, WO 2007-132890 (Patent Document 6) uses a polymer having a carboxyl group as an alkali-soluble polymer, but when the alkaline developer used contains a high concentration of tetraethylammonium hydroxide, residues tend to be generated between patterns, making it difficult to use on all production lines.

[0007] JP 2000-187111 A JP 11-54270 A JP 2000-353594 A JP 10-197715 A JP 2015-172742 A JP 2007-132890 A

[0008] The present invention has been made in view of the above circumstances, and the problem to be solved is to improve the performance of cured films used in liquid crystal display elements, organic EL display elements, inorganic EL display elements, etc. Specifically, the water repellency and oil repellency of the cured film surface are maintained without being impaired by the development process, and high hydrophilicity and high oil repellency are imparted to the substrate without the need for plasma treatment, UV ozone treatment, etc. This makes it possible to achieve the property that the ink for forming EL elements does not overflow over the bank and into adjacent pixels, but remains within the pattern after pattern formation, and wetting and spreading is good without the occurrence of repelling or unevenness. That is, an object of the present invention is to provide a photosensitive resin composition capable of forming a cured film that simultaneously achieves the three properties of developer resistance, liquid repellency, and ink wettability.

[0009] The present inventors have conducted extensive research to achieve the above-mentioned object, and have come up with the present invention. Specifically, the present invention relates to the following: 1. A photosensitive resin composition containing the following components (A) to (D): component (A): an alkali-soluble polymer; component (B): a liquid-repellent polymer, wherein all unit structures of the liquid-repellent polymer contain at least (B1) a unit structure of a monomer component containing a liquid-repellent group, (B2) a unit structure of a monomer component containing a trialkoxysilyl group, and (B3) a unit structure of a monomer component of a cyclic compound; component (C): a photosensitizer; and component (D): a solvent. The cyclic compound is an alicyclic compound or a heteroalicyclic compound. 2. The photosensitive resin composition according to item 1 above, wherein the alicyclic compound is a compound having a polycyclic aliphatic ring having 3 to 15 carbon atoms. 3. The photosensitive resin composition according to any one of items 1 to 6, wherein the compound having a polycyclic aliphatic ring is a polycyclic aliphatic compound selected from the group consisting of compounds having an adamantyl group and compounds having a norbornyl group. 4. The photosensitive resin composition according to item 3, wherein the adamantyl group and / or norbornyl group is substituted with a hydroxy group or an alkyl group having 1 to 10 carbon atoms. 5. The photosensitive resin composition according to item 3, wherein the adamantyl group is a 1-adamantyl group or a 3-hydroxy-1-adamantyl group. 6. The photosensitive resin composition according to item 3, wherein the norbornyl group is an isobornyl group. 7. The photosensitive resin composition according to any one of items 1 to 6, wherein the liquid-repellent group of the unit structure (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. 8. 8. The photosensitive resin composition according to any one of items 1 to 7, wherein the alkali-soluble polymer of component (A) is a copolymer of a monomer mixture containing a monomer that exhibits alkali solubility. 9. The photosensitive resin composition according to item 8, wherein the monomer that exhibits alkali solubility is a monomer having at least one group selected from the group consisting of a phenolic hydroxy group and a carboxyl group.10. The photosensitive resin composition according to any one of items 8 to 9, wherein the alkali-soluble polymer of component (A) is a copolymer of a monomer mixture further containing an N-substituted maleimide compound. 11. The photosensitive resin composition according to item 10, wherein the N-substituted maleimide compound is a compound selected from the group consisting of N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. 12. The photosensitive resin composition according to any one of items 1 to 11, wherein the photosensitizer of component (C) is a quinone diazide compound. 13. The photosensitive resin composition according to any one of items 1 to 11, wherein the photosensitizer of component (C) is a photoradical generator or a photoacid generator. 14. The photosensitive resin composition according to any one of items 1 to 13, further containing a crosslinking agent (E). 15. The present invention relates to the photosensitive resin composition according to any one of items 1 to 14 above, which contains 0.01 to 20 parts by mass of component (B) per 100 parts by mass of component (A). 16. The photosensitive resin composition according to any one of items 12, 14, or 15 above, which contains 5 to 100 parts by mass of component (C) per 100 parts by mass of component (A). 17. The photosensitive resin composition according to any one of items 13 to 15 above, which contains 0.01 to 20 parts by mass of component (C) per 100 parts by mass of component (A). 18. The present invention relates to a cured film obtained using the photosensitive resin composition according to any one of items 1 to 17 above. 19. The present invention relates to a display element having the cured film according to item 18 above. 20. The present invention relates to a display element having the cured film according to item 18 above as an image formation bank.

[0010] The photosensitive resin composition of the present invention contains component (B), particularly a liquid-repellent polymer having a monomer unit structure of a compound having a cyclic compound, preferably a polycyclic aliphatic ring, which can impart high water repellency and high oil repellency to the cured film surface without being impaired by the development process. Furthermore, after pattern formation, the ink for forming EL devices remains within the pattern, achieving good wetting and spreading properties without overflowing or repelling. This allows the formation of a cured film that simultaneously exhibits the three properties of developer resistance, liquid repellency, and ink wettability. It is speculated that the polycyclic aliphatic ring in particular contributes to improved hydrophobicity, etc.

[0011] The photosensitive resin composition of the present invention is a photosensitive resin composition containing at least the following components (A) to (D): Component (A): an alkali-soluble polymer Component (B): a liquid-repellent polymer, the entire unit structure of which contains at least (B1) a unit structure of a monomer component containing a liquid-repellent group, (B2) a unit structure of a monomer component containing a trialkoxysilyl group, and (B3) a unit structure of a monomer component of a cyclic compound Component (C): a photosensitizer Component (D): a solvent Each component will be described in detail below.

[0012] <Component (A): Alkali-Soluble Polymer> In the present invention, an alkali-soluble polymer formed by polymerizing one or more types of monomers can be used as the component (A).

[0013] In the present invention, examples of the polymer include acrylic polymers, polyamic acids, polyimides, polyamides, polyureas, polyurethanes, phenolic resins, epoxy resins, polysiloxanes, and polyesters, and preferred examples of the polymer include acrylic polymers.

[0014] Here, the acrylic polymer refers to a polymer obtained using a monomer having a polymerizable group containing a C═C double bond in the structure, such as an acrylic acid ester, a methacrylic acid ester, styrene, or maleimide.

[0015] 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 anhydride, and polyurea obtained by reacting diamine with diisocyanate. Polyimide precursors such as polyamic acid, polyamic acid ester, and partially imidized polyamic acid, and polyimides such as carboxylic acid group-containing polyimides can also be used, and these can be used without any particular limitation on the type as long as they are alkali-soluble.

[0016] The polyurethane may be obtained by reacting a polyol with a polyisocyanate.

[0017] The phenolic resin may be a novolac resin obtained by polymerizing phenol and formaldehyde.

[0018] The epoxy resin may be an epoxy resin obtained by reacting bisphenol A and / or bisphenol F with a diglycidyl ether of bisphenol A and / or bisphenol F.

[0019] The polysiloxane may be a copolymer obtained by copolymerizing a silane monomer mixture containing a trialkoxysilane or a dialkoxysilane.

[0020] The polyester may be a polyester obtained by reacting a dicarboxylic acid or tetracarboxylic dianhydride with a polyol.

[0021] The alkali-soluble polymer of component (A) is preferably a copolymer obtained by copolymerizing a plurality of monomers including a monomer that exhibits alkali solubility. The alkali-soluble polymer of component (A) is more preferably a copolymer obtained by copolymerizing at least a monomer that exhibits alkali solubility and a monomer containing an N-substituted maleimide compound. Alternatively, the alkali-soluble polymer of component (A) may be a copolymer obtained by copolymerizing a monomer that exhibits alkali solubility and a monomer containing an N-substituted maleimide compound with a monomer copolymerizable with the monomer that exhibits alkali solubility and the monomer containing an N-substituted maleimide compound (other monomer A). Here, monomers containing an N-substituted maleimide compound are not included in the monomers that exhibit alkali solubility.

[0022] (Alkali-Solubility-Exhibiting Monomer) The alkali-solubility-exhibiting monomer has an alkali-soluble group, such as a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid group, a boronic acid group, an active methylene group, or an active methine group.

[0023] An active methylene group refers to a methylene group (-CH-) that has a carbonyl group adjacent to it and is reactive to nucleophiles. In the present invention, the active methine group refers to an active methylene group in which one hydrogen atom of the methylene group is substituted with an alkyl group and is reactive to nucleophiles.

[0024] The active methylene group is more preferably a group represented by the following formula (a1). (In formula (a1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the dashed line represents a bond.)

[0025] In the above formula (a1), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and preferably alkyl groups having 1 to 5 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, and i-propyl groups. Of these, methyl, ethyl, and n-propyl groups are preferred.

[0026] In the above formula (a1), examples of the alkoxy group represented by R include alkoxy groups having 1 to 20 carbon atoms, and preferably alkoxy groups having 1 to 5 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, and t-butoxy groups. Of these, methoxy, ethoxy, and n-propoxy groups are preferred.

[0027] Examples of the group represented by the above formula (a1) include the following structures: In the structural formula, the dashed lines represent bonds.

[0028] The alkali-soluble monomer is preferably a monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group. The "monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group" includes a monomer having a carboxyl group and / or a monomer having a phenolic hydroxy group. These monomers are not limited to those having one carboxyl group or one phenolic hydroxy group, but may also have multiple carboxyl groups or phenolic hydroxy groups.

[0029] Specific examples of the above-mentioned monomers are listed below, but are not limited to these. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

[0030] Examples of monomers having a phenolic hydroxy group include p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, and 4-hydroxyphenyl methacrylate.

[0031] (Monomer Containing N-Substituted Maleimide Compound) Examples of N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-(hydroxyphenyl)maleimide, N-(carboxyphenyl)maleimide, and N-cyclohexylmaleimide. In terms of developability, transparency, and heat resistance, compounds having an alicyclic skeleton are preferred, and N-cyclohexylmaleimide is more preferred.

[0032] (Other Monomer A) Examples of monomers copolymerizable with the alkali-soluble monomer and the N-substituted maleimide compound-containing monomer include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate. , methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, styrene, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethyl methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α-Ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl glycidyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane dimethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2 -(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxymethyl)-4-trifluoromethyloxetane, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-methylolacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate, 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.

[0033] The alkali-soluble polymer of component (A) has a number-average molecular weight in the range of 2,000 to 60,000. If the number-average molecular weight is too high, exceeding 60,000, development residues are likely to be generated and sensitivity will be significantly reduced, while if the number-average molecular weight is too low, less than 2,000, a considerable amount of film loss will occur in exposed areas during development, which may result in insufficient curing.

[0034] The alkali-soluble polymer of the component (A) may be any alkali-soluble polymer having such a structure, and there are no particular limitations on the types of main chain skeleton and side chains of the polymer constituting the polymer.

[0035] (Production of Alkali-Soluble Polymer) The proportion of the monomer that exhibits alkali solubility in the production of the alkali-soluble polymer of component (A) is 5 to 100 mass % of all the monomers used in the production of the alkali-soluble polymer of component (A), preferably 5 to 90 mass %, more preferably 15 to 85 mass %, and most preferably 20 to 80 mass %. If the proportion of the monomer that exhibits alkali solubility is less than 5 mass %, the alkali solubility of the polymer will be insufficient.

[0036] The ratio of the N-substituted maleimide in the production of the alkali-soluble polymer of component (A) is 0 to 90% by mass, preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and most preferably 15 to 60% by mass.

[0037] In the production of the alkali-soluble polymer (A), the proportion of the other monomer A is 95% by mass or less, preferably 80% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 50% by mass or less. If the proportion exceeds 95% by mass, the amount of the essential components will be relatively reduced, making it difficult to fully obtain the effects of the present invention.

[0038] The method for obtaining the alkali-soluble polymer, which is component (A) used in the present invention, is not particularly limited, but can be obtained, for example, by carrying out a polymerization reaction at a temperature of 50 to 110°C in a solvent containing a monomer having a phenolic hydroxy group, optionally a monomer containing an N-substituted maleimide compound, the other monomer A, other copolymerizable monomers, and optionally a polymerization initiator. The solvent used in this case is not particularly limited as long as it dissolves the monomers that constitute the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. Specific examples include the solvents described below in the section on solvent (D).

[0039] The acrylic polymer thus obtained is usually in the form of a solution dissolved in a solvent.

[0040] Furthermore, the solution of the specific polymer obtained as described above can be reprecipitated by adding diethyl ether, water, or the like under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the specific polymer. This procedure can remove the polymerization initiator and unreacted monomers coexisting with the specific polymer, resulting in a purified powder of the specific polymer. If the specific polymer cannot be sufficiently purified in a single procedure, the obtained powder can be redissolved in a solvent and the above procedure can be repeated. In the present invention, the powder of the specific polymer may be used as is, or the powder may be redissolved in, for example, the solvent (D) described below and used in the form of a solution.

[0041] In the present invention, the alkali-soluble polymer of the component (A) may be a mixture of a plurality of alkali-soluble polymers.

[0042] <Component (B): Liquid-Repellent Polymer> The component (B) is a liquid-repellent polymer, and the entire unit structure of the liquid-repellent polymer contains at least (B1) a unit structure of a monomer component containing a liquid-repellent group, (B2) a unit structure of a monomer component containing a trialkoxysilyl group, and (B3) a unit structure of a monomer component of a cyclic compound.

[0043] ((B1) Monomer Component Containing a Liquid-Repellent Group) Examples of the liquid-repellent group include at least one group selected from a fluoroalkyl group, a polyfluoroether group, a silyl ether group, and a polysiloxane group.

[0044] The fluoroalkyl group includes an Ra group having a fluoroalkyl structure represented by the following formula 1: ａ -Y ａ ...Formula 1 In Formula 1, X ａ represents a single bond or an optionally substituted divalent saturated hydrocarbon group, Y ａ represents a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, provided that the total number of fluorine atoms in formula 1 is 3 or more.

[0045] Above X ａ When is a divalent saturated hydrocarbon group, the number of carbon atoms is not particularly limited as long as it does not impair the liquid repellency.

[0046] The number of carbon atoms in the fluoroalkyl group is not particularly limited as long as it does not impair the liquid repellency. Examples of such fluoroalkyl groups include a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2-(perfluorobutyl)ethyl group, a 3-perfluorobutyl-2-hydroxypropyl group, a 2-(perfluorohexyl)ethyl group, a 3-perfluorohexyl-2-hydroxypropyl group, a 2-(perfluorooctyl)ethyl group, a 3-perfluorooctyl-2-hydroxypropyl group, a 2-(perfluorodecyl)ethyl group, a 2-(perfluoro-3-methylbutyl)ethyl group, a 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl group, a 2-(perfluoro-5-methylhexyl)ethyl group, a 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl group, a 2-(perfluoro-7-methyloctyl)ethyl group, and a 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl group.

[0047] To introduce a fluoroalkyl group into the copolymer (B) of the present invention, a monomer having a fluoroalkyl group may be copolymerized. Alternatively, a polymer having a reactive site may be reacted with a compound having a functional group reactive with the fluoroalkyl group and the reactive site of the polymer.

[0048] Specific examples of the monomer having a fluoroalkyl group when component (B) is an acrylic copolymer 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 ... perfluorooctyl-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 acrylate, 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.

[0049] The polyfluoroether group includes an Rf group (a) having a polyfluoroether structure represented by the following formula 2: -(X ｂ -O) n -Y ｂ ...Formula 2 In Formula 2, X ｂ represents a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and each unit enclosed by n may be the same or different; Y ｂ is a hydrogen atom (Y ｂ (provided that a fluorine atom is not bonded to the carbon atom adjacent to the oxygen atom adjacent ...

[0050] X in Formula 2 ｂ , Y ｂ As an embodiment of the present invention, preferably, X ｂ represents an alkylene group having 1 to 10 carbon atoms which has been fluorinated by removing one hydrogen atom or a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit enclosed by n represents the same group or different groups; Y ｂ represents an alkyl group having 1 to 20 carbon atoms which has been fluorinated by removing one hydrogen atom, or a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0051] X in Formula 2 ｂ , Y ｂ More preferably, X ｂ represents a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit bounded by n may be the same or different; Y ｂ represents a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0052] In formula 2, n represents an integer of 2 to 50. n is preferably 2 to 30, and more preferably 2 to 15. When n is 2 or more, good liquid repellency is achieved. When n is 50 or less, good compatibility of the monomers is achieved when the copolymer, which is component (A), is synthesized by copolymerizing a monomer having an Rf group (a) with a monomer having a hydroxy group, a carboxyl group, an amide group, an amino group, or a trialkoxysilyl group, or other monomer.

[0053] The total number of carbon atoms in the Rf group (a) having a polyfluoroether structure represented by formula 2 is preferably 2 to 50, more preferably 2 to 30. Within this range, the copolymer serving as component (A) exhibits good liquid repellency. Furthermore, when the copolymer serving as component (A) is synthesized by copolymerizing a monomer having the Rf group (a) with a monomer having a hydroxy group, a carboxyl group, an amide group, an amino group, or a trialkoxysilyl group, or other monomer, the compatibility of the monomers is good.

[0054] X ｂ Specific examples include -CH2CF(CF3)-, -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF(CF3)-, -CF2CF2CF2CF2-, -CF2CF2CF(CF3)-, and CF2CF(CF3)CF2-.

[0055] Y ｂ Specific examples of the alkyl group include -CF3, -CF2CF3, -CF2CHF2, -(CF2)2CF3, -(CF2)3CF3, -(CF2)4CF3, -(CF2)5CF3, -(CF2)6CF3, -(CF2)7CF3, -(CF2)8CF3, -(CF2)9CF3, and (CF2) 11 CF3, -(CF2) 15 CF3 is an example.

[0056] Preferred embodiments of the Rf group (a) having a polyfluoroether structure represented by formula 2 include the Rf group (a) represented by formula 3 or the Rf group (a) represented by formula 4.

[0057] -C p-1 F 2(p-1) -O-(C pF 2p -O) n-1 -C q F 2q+1 In Formula 3, p represents an integer of 2 or 3, and each unit grouped by n represents the same group, q represents an integer of 1 to 20, and n represents an integer of 2 to 50. —(CH2) ｍ -C p-1 F 2(p-1) -O-(C p F 2p -O) n-1 -C q F 2q+1 In Formula 4, p represents an integer of 2 or 3, and each unit enclosed by n represents the same group; m and q represent integers of 1 to 20; and n represents an integer of 2 to 50.

[0058] Specific examples of the Rf group (a) represented by formula 3 include: -CF2O(CF2CF2O) n-1 CF3 (n is 2 to 9), —CF(CF3)O(CF2CF(CF3)O) n-1 C6F 13 (n is 2 to 6), —CF(CF3)O(CF2CF(CF3)O) n-1 C3F7 (n is 2 to 6) is preferred from the viewpoint of ease of synthesis.

[0059] Specific examples of the Rf group (a) represented by formula 4 include: -CH2-CF(CF3)O(CF2CF(CF3)O) n-1 C6F 13 (n is 2 to 6), —CH—CF(CF)O(CFCF(CF)O) n-1 C3F7 (n is 2 to 6) is preferred from the viewpoint of ease of synthesis.

[0060] The Rf groups (a) in the copolymer that is the component (B) may all be the same or different.

[0061] In order to introduce the Rf group (a) into the copolymer which is the component (B) of the present invention, a monomer having the Rf group (a) may be copolymerized.

[0062] When the component (B) is an acrylic copolymer, examples of the monomer having the Rf group (a) include 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy]propyl methacrylate and 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy]propyl acrylate.

[0063] The silyl ether group refers to a group in which the hydroxy group of an alcohol is protected with a trialkylsilyl group, and is preferably a group represented by the following formula 5: 4 -Si(O-SiX 1 X 2 X 3 )3...Formula 5 (In formula 5, X 1 , X 2 , X 3 each independently represents an alkyl group having 1 to 3 carbon atoms; X 4 represents an alkylene group having 1 to 6 carbon atoms.

[0064] To introduce a silyl ether group into the copolymer which is the component (B) of the present invention, a monomer having a silyl ether group may be copolymerized.

[0065] When component (B) is an acrylic copolymer, examples of the monomer having a silyl ether group include methacryloxypropyltris(trimethylsiloxy)silane and acryloxypropyltris(trimethylsiloxy)silane.

[0066] The polysiloxane group may be a group (a) having a polysiloxane structure represented by formula 6. Hereinafter, the group (a) having a polysiloxane structure represented by formula 6 will be referred to as a pSi group (a). -(SiR 1 R 2 -O) n -SiR 1 R 2 R 3 ...Equation 6 (where R 1 , R 2 independently represent hydrogen, an alkyl group, a cycloalkyl group, or an aryl group; R3 represents hydrogen or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200.

[0067] R 1 , R 2 independently represent hydrogen, an alkyl group, a cycloalkyl group, or an aryl group, and may be the same or different for each siloxy unit. 1 , R 2 is preferably a hydrogen atom, a methyl group, or a phenyl group, and further, R of all the siloxy units 1 , R 2 is preferably a methyl group. 3 may contain a nitrogen atom, an oxygen atom, etc.

[0068] Examples of methods for introducing the pSi group (a) into the copolymer, which is component (B), include a method of copolymerizing a monomer having the pSi group (a), various modification methods in which a copolymer having a reactive site is reacted with a compound having the pSi group (a), and a method using a polymerization initiator having the pSi group (a).

[0069] Examples of the monomer having the pSi group (a) include CH2=CHCOO(pSi), CH2=C(CH3)COO(pSi), etc., where pSi represents the pSi group (a). The monomer having the pSi group (a) may be used alone or in combination of two or more.

[0070] Examples of various modification methods for reacting a copolymer having a reactive site with a compound having a pSi group (a) include the following methods.

[0071] A method in which a monomer having an epoxy group is copolymerized in advance, followed by reaction with a compound having a carboxyl group at one end and a pSi group (a) at the other end. A method in which a monomer having an epoxy group is copolymerized in advance, followed by reaction with a compound having an amino group at one end and a pSi group (a) at the other end. A method in which a monomer having an epoxy group is copolymerized in advance, followed by reaction with a compound having a mercapto group at one end and a pSi group (a) at the other end. A method in which a monomer having an amino group is copolymerized in advance, followed by reaction with a compound having a carboxyl group at one end and a pSi group (a) at the other end.

[0072] A method in which a monomer having an amino group is copolymerized in advance, followed by reaction with a compound having an epoxy group at one end and a pSi group (a) at the other end. A method in which a monomer having a carboxyl group is copolymerized in advance, followed by reaction with a compound having an epoxy group at one end and a pSi group (a) at the other end. A method in which a monomer having a carboxyl group is copolymerized in advance, followed by reaction with a compound having an amino group at one end and a pSi group (a) at the other end. A method in which a monomer having a carboxyl group is copolymerized in advance, followed by reaction with a compound having a silyl chloride group at one end and a pSi group (a) at the other end. A method in which a monomer having a hydroxyl group is copolymerized in advance, followed by reaction with a compound having a silyl chloride group at one end and a pSi group (a) at the other end.

[0073] The polymerization initiator having a pSi group (a) may contain a group having a divalent polysiloxane structure in the main chain of the initiator molecule, or may contain a group having a monovalent polysiloxane structure in the terminal portion or side chain of the initiator molecule. Examples of initiators containing a group having a divalent polysiloxane structure in the main chain of the initiator molecule include compounds having alternating groups having a divalent polysiloxane structure and azo groups. Commercially available products include VPS-1001 and VPS-0501 (both manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0074] ((B2) Monomer Component Containing Trialkoxysilyl Group) In order to introduce a trialkoxysilyl group (B2) into the copolymer which is the component (B) of the present invention, a monomer having a trialkoxysilyl group (B2) may be copolymerized.

[0075] When component (B) is an acrylic copolymer, examples of the monomer having a trialkoxysilyl group include 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, and 3-triethoxysilylpropyl methacrylate.

[0076] ((B3) Monomer Component of Cyclic Compound) The (B3) cyclic compound is an alicyclic compound or a heteroalicyclic compound.

[0077] The alicyclic compounds include monocyclic compounds and polycyclic compounds. The aliphatic ring of these alicyclic compounds is preferably a monocyclic or polycyclic aliphatic ring having 3 to 15 carbon atoms. In this specification, the term "alicyclic compound" refers to a compound having an aliphatic ring composed of carbon atoms and hydrogen atoms, and excludes compounds having a ring containing a heteroatom such as an oxygen atom or a nitrogen atom as an intracyclic atom (e.g., heteroalicyclic compounds).

[0078] Examples of the heteroalicyclic compound include compounds having thietane, tetrahydrothiophene, tetrahydrothiopyran, tetrahydropyran, tetrahydrofuran, γ-butyrolactone, succinimide, maleimide, etc. Examples of compounds having tetrahydrofuran include tetrahydrofurfuryl methacrylate and tetrahydrofurfuryl acrylate. Examples of compounds having γ-butyrolactone include γ-butyrolactone methacrylate and γ-butyrolactone acrylate. Examples of compounds having maleimide include N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc. Preferred heteroalicyclic compounds are N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide.

[0079] Examples of the above-mentioned "monocyclic or polycyclic aliphatic ring having 3 to 15 carbon atoms" include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohexene, cycloheptane, cyclooctane, cyclononane, cyclodecane, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, tricyclo[3.2.1.0] ２，７ ]octane, spiro[3,4]octane, norbornane, norbornene, tricyclo[5.2.1.0 ２，６ ] decane, tricyclo[3.3.1.1 ３，７ ] decane (adamantane), pentacyclo[7.3.1.1 ４，１２ .0 ２，７ .0 ６，１１ ] tetradecane (diamantane), and the like.

[0080] The polycyclic aliphatic ring is preferably a polycyclic aliphatic ring selected from the group consisting of an adamantane ring or a norbornane ring. Among these, polycyclic aliphatic compounds having an adamantane ring are compounds having an adamantyl group, such as 1-adamantyl methacrylate, 1-adamantyl acrylate, 2-propyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl methacrylate, and 3-hydroxy-1-adamantyl acrylate. Compounds in which the adamantyl group is a 1-adamantyl group or a 3-hydroxy-1-adamantyl group are preferred, with 1-adamantyl methacrylate, 1-adamantyl acrylate, 3-hydroxy-1-adamantyl methacrylate, and 3-hydroxy-1-adamantyl acrylate being more preferred. Among these, the polycyclic aliphatic compound having a norbornane ring is a compound having a norbornyl group, such as norbornyl methacrylate, norbornyl acrylate, isobornyl methacrylate, isobornyl acrylate, etc. Compounds in which the norbornyl group is an isobornyl group are preferred, and isobornyl methacrylate and isobornyl acrylate are more preferred.

[0081] Furthermore, the adamantyl group and / or norbornyl group may be substituted with a hydroxy group or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl ... a 1,1-dimethyl-n-pentyl group, a 2,2-dimethyl-n-pentyl group, a 1,1-dimethyl-n-propyl group, a 1,1-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1,1-dimethyl-n-propyl group, a 1,1-dimethyl-n-pentyl group, a 2,2-dimethyl-n-pentyl group, a 1,1-dimethyl-n-propyl group, a 2,2-dimethyl-n-pentyl group, a -pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group.

[0082] (Method for Producing Polymer of Component (B)) When the component (B) is an acrylic copolymer, the copolymer of component (B) can be produced by polymerizing a monomer having a liquid-repellent group, such as at least one of a monomer having a fluoroalkyl group, a monomer having a polyfluoroether group (or an Rf group (a)), a monomer having a silyl ether group, and a monomer having a polysiloxane group (or a pSi group (a)), a monomer having a trialkoxysilyl group, a monomer of a cyclic compound, and, if desired, a monomer other than the above (hereinafter also referred to as other monomer B) or a chain transfer agent, in a solvent in the presence of a polymerization initiator at a temperature of 50°C to 110°C. The solvent used in this case is not particularly limited as long as it dissolves the monomer that constitutes the alkali-soluble polymer and the polymer having a specific functional group. Specific examples include the solvents described below in the section on (D) solvent.

[0083] Specific examples of other monomers B include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, 3-methoxybutyl methacrylate methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, 3-methoxybutyl acrylate styrene, vinyl naphthalene, vinyl anthracene, and vinyl biphenyl.

[0084] The polymer having a specific functional group thus obtained is usually in the form of a solution dissolved in a solvent.

[0085] In addition, the solution of the specific copolymer obtained as described above can be reprecipitated by adding diethyl ether, water, or the like under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the specific copolymer. This procedure can remove polymerization initiators and unreacted monomers coexisting with the specific copolymer, resulting in a purified powder of the specific copolymer. If the specific copolymer cannot be sufficiently purified in a single procedure, the obtained powder can be redissolved in a solvent and the above procedure can be repeated. In the present invention, the powder of the specific copolymer can be used as is, or the powder can be redissolved in, for example, the solvent (D) described below and used in the form of a solution.

[0086] In the copolymer of component (B), the amount of the liquid-repellent group (B1) introduced is preferably 5 mol % to 60 mol % based on the total 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.

[0087] In the copolymer of component (B), the amount of trialkoxysilyl group (B2) introduced is preferably 5 mol% to 70 mol%, more preferably 5 mol% to 50 mol%, based on the total repeating units. If it is less than 5 mol%, the heat resistance and solvent resistance of the resulting film may be impaired. If it is more than 70 mol%, the developability may be affected.

[0088] In the copolymer of component (B), the amount of (B3) aliphatic ring or heteroalicyclic ring introduced is preferably 3 to 60 mol %, more preferably 5 to 40 mol %, based on the total repeating units. If it is less than 3 mol %, problems may arise in the heat resistance and solvent resistance of the resulting film. If it is more than 60 mol %, the number of liquid-repellent repeating units will be too small.

[0089] The number average molecular weight of the copolymer of component (B) is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 2,000 to 30,000. If the number average molecular weight is greater than 100,000, residues may be generated.

[0090] In the present invention, the copolymer of component (B) may be a mixture of a plurality of specific copolymers.

[0091] The ratio of component (A) to component (B) is preferably 0.01 to 20 parts by mass of component (B) per 100 parts by mass of component (A).

[0092] <Component (C): Photosensitizer> Examples of the photosensitizer of the component (C) include (C-1) a quinone diazide compound, (C-2) a photoradical generator, and (C-3) a photoacid generator.

[0093] ((C-1) Quinonediazide Compound) The quinonediazide compound is preferably a 1,2-quinonediazide compound. The 1,2-quinonediazide compound is a compound having either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group, in which preferably 10 mol % to 100 mol %, particularly preferably 20 mol % to 95 mol %, of these hydroxyl groups or amino groups (when both hydroxyl groups and amino groups are present, the total amount of these groups) 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, and 1,2-benzoquinone-2-diazide-4-sulfonic acid. In the reaction with the compound having either a hydroxyl group or an amino group, or both, a chloride of the 1,2-quinonediazide sulfonic acid can be used.

[0094] Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris(4-hydroxyphenyl)butane, 4,4-isopropylidenediphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4',4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene phenolic compounds such as bisphenol [phenol], 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, and 2,5-bis(2-hydroxy-5-methylbenzyl)methyl; and aliphatic alcohols such as ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.

[0095] Examples of the compound containing an amino group include anilines such as aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, and 4,4'-diaminodiphenyl ether, and aminocyclohexane.

[0096] Furthermore, examples of the compound containing both a hydroxyl group and an amino group include aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4'-diamino-4''-hydroxytriphenylmethane, 4-amino-4',4''-dihydroxytriphenylmethane, bis(4-amino-3-carboxy-5-hydroxyphenyl)ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)propane, and 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane; and alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

[0097] These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

[0098] The content of the quinone diazide compound as component (C) in the photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of component (A). If the content is less than 5 parts by mass, the difference in dissolution rate between exposed and unexposed portions of the photosensitive resin composition in a developer may become small, making patterning by development difficult. If the content exceeds 100 parts by mass, the quinone diazide compound may not be sufficiently decomposed by short-term exposure, resulting in reduced sensitivity or the generation of residues between patterns.

[0099] ((C-2) Photoradical Generator) The photoradical generator is not particularly limited as long as it generates radicals upon exposure to light. 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 methylbenzoin and ethylbenzoin; 2-(o-chlorophenyl)-4,5-phenylimidazole dimer; 2-(o-chlorophenyl)-4,5-di(m 2-(o-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methylphenyl)imidazole dimer, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- halomethyloxadiazole compounds such as (p-cyanostyryl)-1,3,4-oxadiazole and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4-bis(trichloromethyl)-6-p-methoxystyryl-S-triazine; 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-S-triazine; 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-triazine; 2-(naphth-1-yl)-4,6- Halomethyl-S-triazine compounds such as bis-trichloromethyl-S-triazine, 2-(4-ethoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, and 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine; 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,1-Hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, 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-carbazol-3-yl]-1-(O-acetyloxime), 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, and the like. The above-mentioned photoradical generators are readily available as commercial products, and specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, and IRGACURE 1870. 250 (all manufactured by BASF), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ (all manufactured by Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-140, TAZ-204 (all manufactured by Midori Chemical Co., Ltd.). These photoradical generators can be used alone or in combination of two or more.

[0100] When the photosensitive resin composition of the present invention contains the component (C-2), the content thereof is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the component (A). If this proportion is too small, the exposed area may not be sufficiently cured, making it impossible to form a pattern. Even if a pattern can be formed, the resulting film may have low reliability. If this proportion is too large, the transmittance of the coating film may decrease, or poor development of the unexposed areas may occur.

[0101] ((C-3) Photoacid Generator) The photoacid generator (C-3) is not particularly limited as long as it is a compound that is photodecomposed upon irradiation with ultraviolet light to generate an acid. Examples of the acid generated upon photolysis of the photoacid generator include sulfonic acids such as 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, and dodecylbenzenesulfonic acid, as well as hydrates and salts of such acids.

[0102] Examples of photoacid generators include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano-containing oxime sulfonate compounds. Any conventionally known or conventionally used photoacid generator can be used in the present invention without any particular limitation. In the present invention, the photoacid generator of component (C) may be used alone or in combination of two or more. Specific examples include compounds represented by the following formulae [PAG-1] to [PAG-41].

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] When the photosensitive resin composition of the present embodiment contains the component (C-3), the content thereof is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the component (A). By ensuring that the content of the component (C-3) is 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if the content is more than 20 parts by mass, unexposed areas may undergo poor development, or the storage stability of the composition may be reduced.

[0111] <Component (D): Solvent> The solvent (D) used in the present invention dissolves the components (A), (B), and (C), and also dissolves other additives, which are added as desired, as described below. There are no particular limitations on the type or structure of the solvent, as long as it is a solvent that has such dissolving ability.

[0112] Examples of such solvents (D) 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, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 4 ... pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxyisobutyrate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0113] These solvents can be used alone or in combination of two or more. Among these (D) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. are preferred from the viewpoints of good film-forming properties and high safety. These solvents are generally used as solvents for photoresist materials.

[0114] <Component (E)> Furthermore, the photosensitive resin composition of the present invention may contain a crosslinking agent (component (E)) as necessary, as long as the effects of the present invention are not impaired. Specific examples are given below, but the present invention is not limited to these. Preferred examples of the thermal crosslinking agent include (E1) a crosslinkable compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups, (E2) a compound selected from crosslinkable compounds represented by the following formula (7), and (E3) a crosslinking agent having two or more isocyanate groups. These crosslinking agents can be used alone or in combination of two or more.

[0115] The crosslinkable compound (E1) having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups undergoes a dehydration condensation reaction when exposed to high temperatures during thermal curing. Examples of such compounds include alkoxymethylated glycolurils, alkoxymethylated benzoguanamines, alkoxymethylated melamines, and phenoplast compounds.

[0116] Specific examples of alkoxymethylated glycolurils include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (high condensation type, trade names: Beckamin (registered trademark) J-300S, P-955, N) manufactured by DIC Corporation.

[0117] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123) and Sanwa Chemical Co., Ltd. (trade names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).

[0118] Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine, etc. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) and butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506, 508) manufactured by Mitsui Cytec Co., Ltd., and methoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, MX-035) and butoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, MX-302) manufactured by Sanwa Chemical Co., Ltd.

[0119] The compound may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, or a benzoguanamine compound in which the hydrogen atom of the amino group has been substituted with a methylol group or an alkoxymethyl group. For example, the compound may be a high molecular weight compound produced from a melamine compound or a benzoguanamine compound as described in U.S. Patent No. 6,323,310. Commercially available melamine compounds include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available benzoguanamine compounds include Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0120] Specific examples of the phenoplast-based compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6-bis(hydroxmethyl)phenol], 2,6-bis(methoxymethyl)phenol], 2,6-bis(methoxymethyl)cresol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(methoxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-methoxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4'-methylenebis[2-methyl-6-methoxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol], 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol], and the like. These are also commercially available, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Organic Chemicals Co., Ltd.).

[0121] Furthermore, as the component (E1), polymers produced using an acrylamide compound or methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, or N-butoxymethylmethacrylamide, can also be used.

[0122] 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 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

[0123] These crosslinkable compounds may be used alone or in combination of two or more.

[0124] When component (E1) is selected as the crosslinking agent in the photosensitive resin composition of the present invention, the content thereof is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of component (A). If the content is less than 5 parts by mass, outgassing may increase during the display element production process, components of the photosensitive resin composition may leach into other layers, and the element characteristics and reliability may deteriorate. Furthermore, if the content exceeds 50 parts by mass, storage stability may decrease, adhesion during development may decrease, and sensitivity may decrease.

[0125] The photosensitive resin composition of the present invention may also contain, as component (E2), a crosslinkable compound having an epoxy group represented by formula (7). (wherein k is an integer of 2 to 10, m is an integer of 0 to 4, R １１ represents a k-valent organic group)

[0126] Commercially available products include Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 (trade names manufactured by Daicel Chemical Industries, Ltd.), alicyclic epoxy resins such as Denacol EX-252 (trade name manufactured by Nagase Chemtex Corporation), CY175, CY177, and CY179 (trade names manufactured by CIBA-GEIGY A.G.), Araldite CY-182, CY-192, and CY-184 (trade names manufactured by CIBA-GEIGY A.G.), Epiclon 200 and 400 (trade names manufactured by DIC Corporation), and Epicoat 871 and 872 (trade names manufactured by Yuka Shell Epoxy Co., Ltd.). ED-5661, ED-5662 (all trade names, manufactured by Celanese Coatings Co., Ltd.) and the like. These crosslinkable compounds may be used alone or in combination of two or more.

[0127] Of these, compounds having a cyclohexene oxide structure, Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 are preferred from the viewpoint of process resistance such as heat resistance, solvent resistance, and long-term baking resistance.

[0128] When component (E2) is selected as the crosslinking agent, the content thereof is 3 to 50 parts by mass, preferably 7 to 40 parts by mass, and more preferably 10 to 30 parts by mass, per 100 parts by mass of component (A). If the content of the crosslinkable compound is less than 3 parts by mass, the density of the crosslinks formed by the crosslinkable compound is insufficient, which may result in increased outgassing during the display element production process, elution of components of the photosensitive resin composition into other layers, and deterioration of element characteristics and reliability. On the other hand, if the content exceeds 50 parts by mass, uncrosslinked crosslinkable compound may remain, reducing the heat resistance, solvent resistance, and resistance to long-term baking after pattern formation, and may also deteriorate the storage stability of the photosensitive resin composition.

[0129] <Other Additives> Furthermore, the photosensitive resin composition of the present invention may contain, as necessary, a rheology adjuster, a pigment, a dye, a coloring matter, a storage stabilizer, an antifoaming agent, an adhesion promoter, or a dissolution promoter such as a polyhydric phenol or a polycarboxylic acid, as long as the effects of the present invention are not impaired.

[0130] <Photosensitive Resin Composition> The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following components (A), (B), (C), and (D), and may further contain one or more other additives as desired: (A) an alkali-soluble polymer; (B) a liquid-repellent polymer containing a copolymer of at least (B1) a monomer containing a liquid-repellent group, (B2) a monomer containing a trialkoxysilyl group, and (B3) a monomer of a cyclic compound; (C) a photosensitizer; and (D) a solvent.

[0131] Among these, preferred examples of the photosensitive resin composition of the present invention are as follows: A photosensitive resin composition containing, per 100 parts by mass of component (A), 0.01 to 20 parts by mass of component (B), and as component (C), 5 to 100 parts by mass of component (C-1), or 0.01 to 20 parts by mass of component (C-2) or component (C-3), and these components dissolved in solvent (D).

[0132] The proportion of solids in the photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80 mass %, or 5 to 60 mass %, or 10 to 50 mass %. Here, the solids refer to all components of the photosensitive resin composition excluding the solvent (D).

[0133] The method for preparing the photosensitive resin composition of the present invention is not particularly limited, but examples of the preparation method include a method in which the liquid-repellent polymer of component (B) is dissolved in the solvent (D), and the alkali-soluble polymer of component (A) and the photosensitizer of component (C) are mixed with this solution in a predetermined ratio to prepare a homogeneous solution, or a method in which other additives are further added and mixed as necessary at an appropriate stage of this preparation method.

[0134] In preparing the photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the (D) solvent can be used as is, and in this case, when the (A) component, the (C) component, etc. are added to the (B) component solution as described above to prepare a uniform solution, additional (D) solvent may be added for the purpose of adjusting the concentration. In this case, the (D) solvent used in the process of forming the specific copolymer and the (D) solvent used to adjust the concentration in preparing the photosensitive resin composition may be the same or different.

[0135] The prepared solution of the photosensitive resin composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

[0136] <Coated Film and Cured Film> The photosensitive resin composition of the present invention can be applied onto a semiconductor substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, inkjet coating, or the like, and then pre-dried on a hot plate or in an oven, etc., to form a coated film. The coated film is then heat-treated to form a photosensitive resin film.

[0137] The conditions for this heat treatment are, for example, a heating temperature of 70° C. to 160° C. and a heating time of 0.3 to 60 minutes, and the heating temperature and heating time are preferably 80° C. to 140° C. and 0.5 to 10 minutes.

[0138] The thickness of the photosensitive resin film formed from the photosensitive resin composition is, for example, 0.1 to 30 μm, or, for example, 0.2 to 10 μm, or, further, for example, 0.3 to 5 μm.

[0139] A mask having a predetermined pattern is attached to the coating film obtained above, and the film is irradiated with light such as ultraviolet light, and then developed with an alkaline developer, whereby the exposed areas are washed out and a sharp relief pattern with sharp edge surfaces is obtained.

[0140] Examples of alkaline developers that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers.

[0141] Among the above, a 0.1 to 3 mass % aqueous solution of tetraethylammonium hydroxide is generally used as a developer for photoresists, and the photosensitive resin composition of the present invention can also be developed satisfactorily using this alkaline developer without causing problems such as swelling. Preferably, a 1.0 to 2.5 mass % aqueous solution is used, which allows a relief pattern to be obtained more effectively.

[0142] The developing method may be any of the puddle method, dipping method, and swing immersion method, etc. The developing time is usually 15 to 180 seconds.

[0143] 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, thereby removing water from the substrate and obtaining a patterned film.

[0144] Subsequently, the pattern-forming film is post-baked for thermal curing, specifically by heating using a hot plate, oven, or the like, to obtain a film having excellent heat resistance, transparency, flattening properties, low water absorption, chemical resistance, and the like, and having a good relief pattern.

[0145] Post-baking is generally performed at a heating temperature selected from the range of 140°C to 270°C for 5 to 30 minutes on a hot plate or for 15 to 90 minutes in an oven.

[0146] Thus, by such post-baking, it is possible to obtain a cured film having the desired good pattern shape.

[0147] As described above, the photosensitive resin composition of the present invention can form a coating film having a fine pattern, which has high storage stability, sufficiently high sensitivity, very little film loss in unexposed areas during development, excellent inkjet wettability and liquid repellency, and can be suitably used as an image-forming bank for a display device.

[0148] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows:

[0149] (1) Ultraviolet irradiation device Device: PLA-600FA manufactured by Canon Inc. (2) Developing device Device: AD-1200 manufactured by Takizawa Sangyo Co., Ltd. (3) Gel permeation chromatography (GPC) Device: Shimadzu Corporation Column: Shodex (registered trademark) GPC KF-803L, GPC KF-804L manufactured by Resonaq Co., Ltd. Column temperature: 40°C Eluent: Tetrahydrofuran The number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) are expressed in polystyrene equivalent values. (4) Contact angle evaluation Device: Drop Master manufactured by Kyowa Interface Science Co., Ltd. (5) Wettability evaluation Device: Inkjet Designer manufactured by Cluster Technology Co., Ltd.

[0150] 1 H-NMR spectra were measured using a nuclear magnetic resonance spectrometer Ascend 500 (manufactured by Bruker). Chemical shift values ​​are expressed in ppm, and deuterated chloroform was used as the solvent. 1 In the H-NMR spectrum, a signal derived from residual protons of the solvent was used, and chloroform was used as the internal standard at δ 7.26 ppm. Silica gel chromatography was performed using silica gel 60N spherical neutral (Kanto Chemical Co., Ltd.) as the packing material.

[0151] The abbreviations have the following meanings: HEMA: 2-hydroxyethyl methacrylate, NHPMA: N-(4-hydroxyphenyl)methacrylamide, CHMI: N-cyclohexylmaleimide, PO3OH: 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]-1-propanol [manufactured by Unimatec Co., Ltd., Cheminox PO-3-OH], NFHMA: 1H,1H,2H,2H-nonafluorohexyl methacrylate, KBM-503: 3-methacryloxypropyltriethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503], ADMA: 1-adamantyl methacrylate [manufactured by Osaka Organic Chemical Industry Ltd., ADMA]. OHADMA: 3-hydroxy-1-adamantyl methacrylate [Adamantate HM, manufactured by Osaka Organic Chemical Industry Co., Ltd.] IBMA: Isobornyl methacrylate AIBN: α,α'-azobisisobutyronitrile MAIB: 2,2'-azobis(2-methylpropionate) dimethyl QD: Compound synthesized by condensation reaction of 1 mol of α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride GT-401: Butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone [Epolead GT-401, manufactured by Daicel Corporation] PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate TMAH: tetramethylammonium hydroxide

[0152] Synthesis Example 1 3.00 g of NHPMA, 0.98 g of HEMA, 2.34 g of CHMI, and 0.12 g of AIBN were dissolved in 24.20 g of PGME and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 21% by mass) (A1). The resulting acrylic polymer had an Mn of 6,200 and an Mw of 9,900.

[0153] Synthesis Example 2: 3.00 g of NHPMA, 1.11 g of HEMA, 3.04 g of CHMI, and 0.14 g of AIBN were dissolved in 27.30 g of PGME and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 21% by mass) (A2). The resulting acrylic polymer had an Mn of 5,600 and an Mw of 9,300.

[0154] [Synthesis Example 3]

[0155] PO3OH (25.00 g, 51.9 mmol) and triethylamine (7.35 g, 72.6 mmol) were dissolved in acetonitrile (39.70 g). ２ While the reaction vessel was immersed in an ice bath under a gas atmosphere, a solution of methacrylic acid chloride (7.59 g, 72.6 mmol) in acetonitrile (17.71 g) was added dropwise over approximately 1 hour. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for approximately 16 hours. Water was added to the reaction solution, which was then extracted with ethyl acetate. The resulting organic layer was washed with saturated saline. Anhydrous sodium sulfate was added to the resulting organic layer for dehydration, and the filtrate was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (hexane) to obtain Monomer F1 as a colorless, transparent liquid (22.14 g, 40.24 mmol, yield 78%). １ H-NMR (500MHz, CDCl ３ ): δ 6.19 (s, 1H), 5.70 (s, 1H), 4.74-4.65 (q, J=10.0Hz, 2H), 1.96 (s, 3H).

[0156] Synthesis Example 4 1.50 g of F1, 1.15 g of KBM-503, 0.45 g of ADMA, 0.08 g of AIBN, and 0.10 g of 1-dodecanethiol were dissolved in 9.81 g of PGMEA, and the mixture was reacted at 70° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 25% by mass) (B1). The resulting acrylic polymer had an Mn of 2,700 and an Mw of 5,600.

[0157] Synthesis Example 5: 2.00 g of F1, 1.54 g of KBM-503, 0.61 g of ADMA, and 0.21 g of MAIB were dissolved in 10.18 g of PGMEA, and the mixture was allowed to react at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 30% by mass) (B2). The resulting acrylic polymer had an Mn of 9,200 and an Mw of 18,600.

[0158] Synthesis Example 6: 1.60 g of F1, 0.98 g of KBM-503, 0.15 g of HEMA, 0.58 g of ADMA, and 0.17 g of MAIB were dissolved in 8.12 g of PGMEA, and the mixture was allowed to react at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 30% by mass) (B3). The resulting acrylic polymer had an Mn of 9,500 and an Mw of 19,300.

[0159] Synthesis Example 7 0.77 g of F1, 0.54 g of KBM-503, 0.14 g of IBMA, 0.04 g of AIBN, and 0.06 g of 1-dodecanethiol were dissolved in 8.78 g of PGMEA, and the mixture was reacted at 70° C. for 20 hours to obtain an acrylic polymer solution (solids concentration: 15% by mass) (B4). The resulting acrylic polymer had an Mn of 2,800 and an Mw of 4,200.

[0160] Synthesis Example 8: 6.00 g of NFHMA, 4.60 g of KBM-503, 1.81 g of OHADMA, and 0.62 g of MAIB were dissolved in 30.39 g of PGMEA, and the mixture was allowed to react at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 30% by mass) (B5). The resulting acrylic polymer had an Mn of 10,000 and an Mw of 15,900.

[0161] Synthesis Example 9: 1.00 g of F1, 0.76 g of KBM-503, 0.30 g of CHMI, 0.05 g of AIBN, and 0.07 g of 1-dodecanethiol were dissolved in 6.56 g of PGMEA, and the mixture was allowed to react at 70° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 25% by mass) (B6). The resulting acrylic polymer had an Mn of 2,700 and an Mw of 5,600.

[0162] Synthesis Example 10: 0.71 g of F1, 0.55 g of KBM-503, 0.22 g of HEMA, 0.04 g of AIBN, and 0.05 g of 1-dodecanethiol were dissolved in 8.90 g of PGMEA, and the mixture was allowed to react at 70° C. for 20 hours to obtain an acrylic polymer solution (solids concentration: 15% by mass) (B7). The resulting acrylic polymer had an Mn of 3,500 and an Mw of 5,600.

[0163] Synthesis Example 11: 6.00 g of NFHMA, 4.60 g of KBM-503, 1.81 g of HEMA, and 0.62 g of MAIB were dissolved in 30.39 g of PGMEA, and the mixture was allowed to react at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 30% by mass) (B8). The resulting acrylic polymer had an Mn of 11,300 and an Mw of 19,200.

[0164] Synthesis Example 12 An ink for forming an EL device was obtained in the same manner as in Comparative Example 1-2 of WO 2019 / 124413, except that the solid content concentration was 1.7% by mass.

[0165] [Examples 1 to 6, Comparative Examples 1 to 4] Photosensitive resin compositions were prepared by mixing the following components according to the description in Table 1. In the table, [parts] represents [parts by mass], and the solid content ratio was adjusted to the numerical value in the table.

[0166] [Contact Angle Evaluation] The photosensitive resin composition was applied to a silicon wafer using a spin coater and then prebaked on a hot plate at 100°C for 120 seconds to form a coating film with a thickness of 1.20 μm. The coating film was developed by immersing it in a 2.38% TMAH aqueous solution for 50 seconds, and then washed with running ultrapure water for 30 seconds. It was then postbaked and cured by heating at 230°C for 30 minutes. 1 μL of PGMEA was applied to the cured coating film, and the contact angle was measured at five points after 7 seconds. The average value was taken as the contact angle value θI and evaluated according to the following criteria. Considering actual specifications, at least B is required, and A is desirable. A: θI≧45° B: 40°≦θI<45° C: θI<40°

[0167] [Evaluation of developer resistance] The photosensitive resin composition was applied to a silicon wafer using a spin coater, and then pre-baked on a hot plate at 100°C for 120 seconds to form a coating film with a thickness of 1.20 μm. The coating was then post-baked by heating at 230°C for 30 minutes to harden it. 1 μL of PGMEA was applied to the cured coating film, and the contact angle was measured at five points after 7 seconds, and the average value was taken as the contact angle value θII. The value Δ of the contact angle value θII - θI was evaluated according to the following criteria. Note that, assuming actual specifications, at least B is required, and A is desirable. A: Δ≦2° B: 5°≧Δ>2° C: Δ>5°

[0168] [Evaluation of Inkjet Wettability] The photosensitive resin composition was applied to ITO glass using a spin coater and then prebaked on a hot plate at 100°C for 120 seconds to form a coating film with a thickness of 1.20 μm. This coating film was then irradiated with ultraviolet light at 365 nm with a light intensity of 5.5 mW / cm2 for a certain period of time through a mask with a pattern of numerous rectangles with long sides of 160 μm and short sides of 80 μm. The coating film was then developed by immersion in a 2.38% TMAH aqueous solution for 50 seconds, followed by rinsing with running ultrapure water for 30 seconds. The coating film with the rectangular pattern then was postbaked and cured by heating at 230°C for 30 minutes. A certain number of shots (approximately 3 pL per shot) of the ink for forming EL devices prepared in Synthesis Example 12 were ejected into the openings of the cured rectangular pattern and allowed to dry naturally to form an organic functional film. The appearance of the organic functional film was observed using an optical microscope and evaluated according to the following criteria. In addition, assuming actual specifications, at least B is required, and A is desirable. A: Good with no crater or overflow after 2 shots B: Good with no crater or overflow after 6 shots C: Crater or overflow occurs even after 6 shots

[0169]

[0170]

[0171] As shown in Tables 1 and 2, the cured films prepared using the positive photosensitive compositions of Examples 1 to 6, which respectively contained an alkali-soluble polymer and liquid-repellent polymers B1 to B6 having a unit structure of a cyclic compound monomer component, were shown to have excellent contact angles, developer resistance, and inkjet wettability. Here, liquid-repellent polymers B1 to B5 are liquid-repellent polymers having a unit structure of a monomer of a compound having a polycyclic aliphatic ring, and liquid-repellent polymer B6 is a liquid-repellent polymer having a unit structure of a monomer of a compound having a heteroalicyclic compound.

[0172] On the other hand, it was shown that the cured films made from the positive photosensitive compositions of Comparative Examples 1 and 3, which used liquid-repellent polymers B7 and B8 that do not have a unit structure of a cyclic compound monomer component, were excellent in inkjet wettability but poor in contact angle and developer resistance. Also, it was shown that the cured films made from the positive photosensitive compositions of Comparative Examples 2 and 4, in which the added amounts of liquid-repellent polymers B7 and B8 were increased, were excellent in contact angle and developer resistance but poor in inkjet wettability. In other words, the cured films made from the positive photosensitive compositions of Comparative Examples 1 to 4 were unable to improve the contact angle, developer resistance, and inkjet wettability in a balanced manner, and it was impossible to form a cured film that achieved all three properties simultaneously.

[0173] As shown by the results of the Examples above, a cured film that satisfies the contact angle, developer resistance, and inkjet wettability can be obtained using a positive photosensitive composition that combines an alkali-soluble polymer, liquid-repellent polymers B1 to B6, a crosslinking agent, and a photosensitizer.

Claims

1. A photosensitive resin composition comprising the following components (A) to (D): component (A): an alkali-soluble polymer; component (B): a liquid-repellent polymer, wherein the entire unit structure of the liquid-repellent polymer contains at least (B1) a unit structure of a monomer component containing a liquid-repellent group, (B2) a unit structure of a monomer component containing a trialkoxysilyl group, and (B3) a unit structure of a monomer component of a cyclic compound; component (C): a photosensitizer; and component (D): a solvent. The photosensitive resin composition wherein the cyclic compound is an alicyclic compound or a heteroalicyclic compound.

2. The photosensitive resin composition according to claim 1, wherein the alicyclic compound is a compound having a polycyclic aliphatic ring having 3 to 15 carbon atoms.

3. The photosensitive resin composition according to claim 2, wherein the compound having a polycyclic aliphatic ring is a polycyclic aliphatic compound selected from the group consisting of compounds having an adamantyl group and compounds having a norbornyl group.

4. The photosensitive resin composition according to claim 3, wherein the adamantyl group and / or norbornyl group is substituted with a hydroxy group or an alkyl group having 1 to 10 carbon atoms.

5. The photosensitive resin composition according to claim 3, wherein the adamantyl group is a 1-adamantyl group or a 3-hydroxy-1-adamantyl group.

6. The photosensitive resin composition according to claim 3, wherein the norbornyl group is an isobornyl group.

7. The photosensitive resin composition according to claim 1, wherein the liquid-repellent group of the unit structure (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.

8. The photosensitive resin composition according to claim 1, wherein the alkali-soluble polymer of component (A) is a copolymer of a monomer mixture containing a monomer that exhibits alkali solubility.

9. The photosensitive resin composition according to claim 8, wherein the alkali-soluble monomer is a monomer having at least one group selected from the group consisting of a phenolic hydroxy group and a carboxyl group.

10. The photosensitive resin composition according to claim 8, wherein the alkali-soluble polymer of component (A) is a copolymer of a monomer mixture further containing an N-substituted maleimide compound.

11. The photosensitive resin composition according to claim 10, wherein the N-substituted maleimide compound is a compound selected from the group consisting of N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

12. The photosensitive resin composition according to claim 1, wherein the photosensitizer of component (C) is a quinone diazide compound.

13. The photosensitive resin composition according to claim 1, wherein the photosensitizer of component (C) is a photoradical generator or a photoacid generator.

14. The photosensitive resin composition according to claim 1, further comprising (E) a crosslinking agent.

15. The photosensitive resin composition according to claim 1, wherein the component (B) is contained in an amount of 0.01 to 20 parts by mass per 100 parts by mass of the component (A).

16. The photosensitive resin composition according to claim 12, wherein component (C) is contained in an amount of 5 to 100 parts by mass per 100 parts by mass of component (A).

17. The photosensitive resin composition according to claim 13, wherein component (C) is contained in an amount of 0.01 to 20 parts by mass per 100 parts by mass of component (A).

18. A cured film obtained using the photosensitive resin composition according to any one of claims 1 to 17.

19. A display device having the cured film according to claim 18.

20. A display device having the cured film according to claim 18 as an image forming bank.

Images