Resist composition, resist film, and optical element

Abstract

Provided is a resist composition comprising: (A) a polymer having a repeating unit of a monomer represented by formula (1) and having a melting point of at least 20 °C; (B) an alkali-soluble resin; (C) a solvent; and (D) a photosensitive agent. (1): R-L-X-P [In formula (1), R is (i) a hydrogen atom or (ii) an organic group having 0-3 carbon atoms and having a hetero atom, a bonding part with L is a monovalent organic group that is a hetero atom or a carbon atom to which a hetero atom is directly bonded, L is a divalent organic group having 14-40 carbon atoms, X is a single bond or a divalent organic group having 0-4 carbon atoms and having a hetero atom, and P is a monovalent polymerizable group.]

Description

Resist composition, resist film, and optical element

[0001] The present invention relates to a resist composition, a resist film, and an optical element.

[0002] In recent years, resist compositions have attracted attention as materials for forming permanent films such as partition walls between pixels of color filters, partition walls between pixels of organic electroluminescence (EL) display elements, partition walls separating each TFT of an organic thin film transistor (TFT) array, partition walls between ITO electrodes of liquid crystal display elements, and partition walls of circuit wiring boards. For example, when manufacturing a color filter, a partition wall pattern (which may also serve as a black matrix) is formed using photolithography, and then R (red), G (green), and B (blue) inks are applied to the openings between the partition walls using an inkjet method to form pixels. Also, when manufacturing an organic EL element, a partition wall pattern is formed using photolithography, and then solutions of a hole transport material, a light-emitting material, etc. are applied to the openings between the partition walls using an inkjet method to form pixels having a hole transport layer, a light-emitting layer, etc.

[0003] To prevent color mixing between adjacent pixels in such color filters or organic EL elements, the upper surfaces of the partition walls must have ink-repellent properties, i.e., liquid repellency (particularly oil repellency). A suitable additive that can impart oil repellency is a fluoropolymer. Fluoropolymers have surface migration properties, and adding a small amount to a resist composition can impart oil repellency to the partition walls. Meanwhile, in recent years, from the perspective of reducing environmental impact, there has been an increasing need to replace currently fluorinated materials with materials that contain little or no fluorine. Among these, for liquid-repellent applications, active development has been underway for polymers having side chains that exhibit crystallinity near room temperature. For example, Patent Document 1 discloses the production of highly water-repellent polymers having long-chain alkyl side chains.

[0004] JP 2006-328624 A (Patent No. 4996875)

[0005] However, the polymer having a side chain that exhibits crystallinity at around room temperature, as disclosed in Patent Document 1, has not been added to a resist to make it function, and even if it is actually added, it does not fully exhibit oil repellency.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resist composition and the like that is capable of forming a cured film with excellent oil repellency.

[0007] The present invention is based on the discovery that a cured film with good oil repellency can be formed by using a resist composition containing a polymer (A) having a repeating unit of a specific monomer and having a melting point of 20°C or higher, an alkali-soluble resin (B), a solvent (C), and a photosensitizer (D).

[0008] The present invention provides the following means. [1] A resist composition comprising: a polymer (A) having a repeating unit of a monomer represented by the following formula (1) and having a melting point of 20°C or higher; an alkali-soluble resin (B); a solvent (C); and a photosensitizer (D): R-L-X-P... (1) [In the formula (1), R is (i) a hydrogen atom, or (ii) a monovalent organic group having 0 to 3 carbon atoms and containing a heteroatom, wherein the linkage to L is a heteroatom or a carbon atom directly bonded to a heteroatom; L is a divalent organic group having 14 to 40 carbon atoms; X is a single bond or a divalent organic group having 0 to 4 carbon atoms and containing a heteroatom; and P is a monovalent polymerizable group.] [2] The resist composition according to the above [1], wherein L is a divalent linear saturated hydrocarbon group. [3] The resist composition according to the above [1] or [2], wherein L is a divalent organic group having 16 to 24 carbon atoms. [4] The resist composition according to any one of the above [1] to [3], wherein P is a (meth)acryloyl group or a group represented by the following formula (A): ...(A) [In the formula (A), S １ ~S ５ Any one of the above is a single bond that bonds to *, and the above non-single bond S １ ~S ５are each independently a hydrogen atom, a halogen atom, or an optionally halogenated alkyl group of 1 to 4 carbon atoms, and ** represents the bond to X.] [5] The resist composition according to [4] above, wherein P represents a (meth)acryloyl group. [6] The resist composition according to any one of [1] to [5] above, wherein R represents (i) a hydrogen atom, or (ii) an organic group of 1 carbon atom that has a heteroatom, and the bond to L is a monovalent organic group that is a heteroatom or a carbon atom to which a heteroatom is directly bonded. [7] The resist composition according to any one of [1] to [6] above, wherein the polymer (A) is a copolymer that further includes a repeating unit of another monomer represented by the following formula (2): R1-P1... (2) [In formula (2), R1 represents a monovalent organic group of 0 to 13 carbon atoms that may have a heteroatom, and P1 represents a monovalent polymerizable group. [8] The resist composition according to [7] above, wherein the polymer (A) has a copolymerization ratio of the repeating unit of the monomer represented by formula (1) to the repeating unit of the other monomer represented by formula (2) of 99:1 to 50:50 in mass ratio. [9] A resist film consisting of a cured product containing the polymer (A) according to any one of [1] to [8] above.

[10] An optical element having a substrate, a plurality of pixels formed on a surface of the substrate, and partition walls located between the plurality of adjacent pixels, wherein the partition walls are resist films consisting of a cured product containing the polymer (A) according to any one of [1] to [8] above.

[0009] According to the present invention, there are provided resist compositions and the like that are capable of forming cured films with excellent oil repellency.

[0010] The definitions and meanings of terms and notations used in this specification are as follows. In this specification, "room temperature" means 25°C. In this specification, "repeating unit based on a monomer" is a collective term for an atomic group derived from one monomer molecule formed by polymerization of a monomer, and an atomic group obtained by chemically converting a portion of the atomic group. Hereinafter, "repeating unit based on a monomer" will also be simply referred to as "repeating unit" or "unit." Unless otherwise specified in this specification, % means % by mass. However, in this specification, a proportion based on mass (percentage, parts, etc.) is the same as a proportion based on weight (percentage, parts, etc.). Numerical ranges include ranges rounded to the nearest whole number. Furthermore, when a numerical range is expressed as "X to Y," it means "at least X and at most Y." In this specification, "(meth)acrylic acid" is a generic term meaning both acrylic acid and methacrylic acid, "(meth)acryloyl" is a generic term meaning both acryloyl and methacryloyl, "(meth)acrylate" is a generic term meaning both acrylate and methacrylate, and "(meth)acrylamide" is a generic term meaning both acrylamide and methacrylamide. In this specification, "halogen atom" means any of iodine atom, bromine atom, chlorine atom, and fluorine atom. In this specification, "solid content" refers to the non-volatile content excluding volatile substances such as solvents, and indicates components that remain without volatilization when the resist composition is dried, and includes those that are liquid, syrup-like, or wax-like at room temperature. The total solid content can also be calculated from the amount charged. In this specification, "mass average molecular weight (Mw)" means the mass average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as the mobile phase, converted based on standard polymethyl methacrylate (PMMA). The mass average molecular weight (Mw) value is used as an indicator of the molecular weight of a polymer or resin. A "side chain" is a group other than a hydrogen atom or a heteroatom (including a halogen atom) that is bonded to a carbon atom that constitutes the main chain of a polymer in which repeating units consisting of carbon atoms constitute the main chain.

[0011] [Resist Composition] The resist composition according to an embodiment of the present invention (hereinafter also referred to simply as "resist composition") comprises a combination of essential components and optional components. The essential components are contained in the resist composition and provide the main function of its performance. The optional components are used as needed. Examples of essential components include a polymer (A), an alkali-soluble resin (B), a solvent (C), and a photosensitizer (D). The optional components are not particularly limited and include, for example, a crosslinking agent (E). The resist composition of the present invention may be either a negative resist composition or a positive resist composition. When the resist composition of the present invention is a negative resist composition, in photolithography or the like, the portions not irradiated with light (unexposed portions) are selectively removed during alkaline development following exposure, resulting in the formation of partition walls made of a cured product of the resist composition. When the resist composition of the present invention is a positive resist composition, in photolithography or the like, the portions irradiated with light (exposed portions) are selectively removed during alkaline development following exposure, resulting in the formation of partition walls made of a cured product of the resist composition.

[0012] <Polymer (A)> The polymer (A) is not particularly limited as long as it has a repeating unit of a monomer represented by the following formula (1) (hereinafter, sometimes simply referred to as "monomer") and has a melting point of 20°C or higher, but is preferably a copolymer further having a repeating unit of another monomer represented by the following formula (2) (hereinafter, sometimes simply referred to as "another monomer"): R-L-X-P... (1) [In the formula (1), R is (i) a hydrogen atom or (ii) a monovalent organic group which is a C 0-3 organic group having a heteroatom and whose linkage to L is a heteroatom or a carbon atom to which a heteroatom is directly bonded, L is a divalent organic group having 14 to 40 carbon atoms, X is a single bond or a C 0-4 divalent organic group having a heteroatom, and P is a monovalent polymerizable group. R1-P1 (2) [In the formula (2), R1 represents a monovalent organic group having 0 to 13 carbon atoms which may have a heteroatom, and P1 represents a monovalent polymerizable group.]

[0013] When the polymer (A) has a melting point of 20°C or higher, i.e., is crystalline, the polymer (A) can migrate to the surface when added to a resist, forming a coating film with high oil repellency. The melting point of the polymer (A) is not particularly limited as long as it is 20°C or higher, but in order to maintain oil repellency even when temperature changes occur, it is preferably 24°C or higher, more preferably 28°C or higher, and particularly preferably 32°C or higher. In this specification, the "melting point" is a value measured using a differential scanning calorimeter, as in the examples described below.

[0014] <<Monomer>> The monomer is not particularly limited as long as it is represented by the formula (1), and examples thereof include (i) C １８ H ３７ -acrylate (R = hydrogen atom, L = -C １８ H ３６ -, X=-O-, P=acryloyl group), (ii) C １８ H ３７ -methacrylate (R = hydrogen atom, L = -C １８ H ３６ -, X=-O-, P=methacryloyl group), (iii) C ２２ H ４５ -acrylate (R = hydrogen atom, L = -C ２２ H ４４ -, X=-O-, P=acryloyl group), (iv) CF ３ -C １８ H ３６ - acrylate (R = CF ３ -, L=-C １８ H ３６ -, X=-O-, P=acryloyl group), (v) CF ３ -C ２２ H ４４ - acrylate (R = CF ３ -, L=-C ２２ H ４４ Suitable examples include monomers having crystallinity at 20° C. or higher, such as the compounds represented by the following structures: (X=—, X=—O—, P=acryloyl group), and compounds represented by the following structures. These may be used alone or in combination of two or more.

[0015] The molecular weight of the monomer is not particularly limited, but is preferably not more than 1000, more preferably not more than 800, and particularly preferably not more than 600. When the molecular weight of the monomer is not more than the upper limit, the compatibility of the polymer (A) with the resist resin can be improved.

[0016] (R) R in the formula (1) is (i) a hydrogen atom, or (ii) a monovalent organic group having 0 to 3 carbon atoms and containing a heteroatom, wherein the linking portion to L is a heteroatom or a carbon atom directly bonded to a heteroatom, and is preferably (i) a hydrogen atom, or (ii) a monovalent organic group having 1 carbon atom and containing a heteroatom, wherein the linking portion to L is a carbon atom directly bonded to a heteroatom. Specific examples of such R include a hydrogen atom, HO—, F—, Cl—, CH ３ O-, CF ３ -, CF ２ H-, CF ３ O-, CF ３ S-, SF ５ Among these, from the viewpoint of increasing the melting point and oil repellency of the polymer (A), a hydrogen atom, F—, CF ３ - is preferred.

[0017] (L) There are no particular restrictions on L in the formula (1) as long as it is a divalent organic group having 14 to 40 carbon atoms, but from the viewpoint of availability and improving the compatibility of the polymer (A) with the resist resin, it is preferably a divalent linear saturated hydrocarbon group having 14 to 40 carbon atoms, more preferably a linear saturated hydrocarbon group having 15 to 30 carbon atoms, and particularly preferably a divalent linear saturated hydrocarbon group having 16 to 24 carbon atoms. Specific examples of such L include -C １６ H ３２ -, -C １８ H ３６ -, -C ２０ H ４０ -, -C ２２ H ４４ -, -C ２４ H ４８ Among these, from the viewpoint of availability and improving the melting point of the polymer (A), -C １８ H ３６ -, -C ２２ H ４４- is preferred.

[0018] (X) X in the formula (1) is not particularly limited as long as it is a single bond or a divalent organic group having 0 to 4 carbon atoms and a hetero atom. From the viewpoint of increasing the melting point of the polymer (A), it is preferably a single bond or a divalent organic group having 0 to 2 carbon atoms and a hetero atom, and more preferably a single bond or a divalent organic group having 0 carbon atoms and a hetero atom. Specific examples of such X include a single bond, -O-, -OC ２ H ４ O-, -NH-, -N(CH ３ Among these, a single bond, —O—, and —NH— are preferred from the viewpoints of availability and improving the melting point of the polymer (A).

[0019] (P) P in the formula (1) is not particularly limited as long as it is a monovalent polymerizable group, and examples thereof include a group having a polymerizable unsaturated bond, a cyclic ether structure-containing group, a hydrolyzable silyl group, etc. Among these, from the viewpoint of increasing the melting point of the polymer (A), an ethylenic double bond-containing group is preferred, a (meth)acryloyl group or a group represented by the following formula (A) is more preferred, and a (meth)acryloyl group is most preferred. ...(A) [In the formula (A), S １ ~S ５ Any one of the above is a single bond that bonds to *, and the above non-single bond S １ ~S ５ are each independently a hydrogen atom, a halogen atom, or an optionally halogenated alkyl group having 1 to 4 carbon atoms, and ** represents the bonding site to X.] The optionally halogenated alkyl group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

[0020] The cyclic ether structure-containing group is not particularly limited and may be, for example, a three- or four-membered ring ether-containing group. Among these, epoxy-based polymerizable groups such as a glycidyl group and an oxetanyl group are preferred.

[0021] The hydrolyzable silane-containing group is not particularly limited, and examples thereof include a group represented by the following formula (B): —Si(R Ｈ ) ｄ X １ （４－ｃ－ｄ） ...(B) In formula (B), the symbols are as follows: R Ｈ is a monovalent hydrocarbon group having 1 to 6 carbon atoms. c is 1 or 2, d is 0 to 2, and c+d is 1 to 3. X １ is a hydrolyzable group. Ｈ and X １ When there are a plurality of, they may be different or the same.

[0022] R Ｈ is preferably a hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably a methyl group. In formula (B), c is more preferably 1, and d is more preferably 0 or 1, and particularly preferably d is 0. X １ Specific examples and preferred embodiments of the hydrolyzable group are as follows:

[0023] Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, and a group in which at least one hydrogen atom of an amino group has been substituted with an alkyl group. In view of the fact that a hydrolysis reaction results in a hydroxyl group (silanol group) and that a further intermolecular condensation reaction to form an Si—O—Si bond easily proceeds, an alkoxy group having 1 to 4 carbon atoms and a halogen atom are preferred, a methoxy group, an ethoxy group and a chlorine atom are more preferred, and a methoxy group and an ethoxy group are particularly preferred.

[0024] The polymer (A) may be a polymer containing only one or more monomers represented by the formula (1) as repeating units, or a copolymer containing one or more monomers represented by the formula (1) as repeating units and one or more other monomers. The "different monomer" is not particularly limited as long as it is a monomer other than the monomer represented by the formula (1), but is preferably another monomer represented by the formula (2) from the viewpoint of improving the compatibility of the polymer (A) with the resist resin.

[0025] <Other Monomers> The other monomers are not particularly limited as long as they are represented by the formula (2), and examples thereof include methyl (meth)acrylate, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, and monomers represented by the following structural formula (R ２ represents a hydrogen atom or a methyl group, and the portion surrounded by a dotted line represents P1. These may be used alone or in combination of two or more.

[0026]

[0027] The molecular weight of the other monomer is not particularly limited, but is preferably not more than 500, more preferably not more than 300, and particularly preferably not more than 150. When the molecular weight of the other monomer is not more than the upper limit, the compatibility of the polymer (A) with the resist resin can be improved.

[0028] (R1) R1 in the formula (2) is not particularly limited as long as it is a monovalent organic group having 0 to 13 carbon atoms which may have a heteroatom, and examples thereof include CH ３ -O-, C ４ H ９ -O-, C １２ H ２５ -O-, HO-, HO-C ２ H ４ —O—, NCO—C ２ H ４ These may be used alone or in combination of two or more.

[0029] The molecular weight of R1 in the formula (2) is not particularly limited, but is preferably not more than 200, more preferably not more than 150, and particularly preferably not more than 100. When the molecular weight of R1 in the formula (2) is not more than the upper limit, the compatibility of the polymer (A) with the resist resin can be improved.

[0030] (P1) P1 in the formula (2) is not particularly limited as long as it is a monovalent polymerizable group, but from the viewpoint of increasing the melting point of the polymer (A), it is preferably a (meth)acryloyl group or a group represented by the formula (A), and more preferably a (meth)acryloyl group.

[0031] Details of the monovalent polymerizable group as P1 are the same as those of the monovalent polymerizable group as P in the formula (2).

[0032] The copolymerization ratio (mass ratio) ((1):(2)) of the repeating unit of the monomer represented by the formula (1) to the repeating unit of the other monomer represented by the formula (2) in the polymer (A) is not particularly limited, but from the viewpoint of increasing the melting point of the polymer (A), it is preferably 99:1 to 50:50, more preferably 98:2 to 60:40, and particularly preferably 97:3 to 70:30.

[0033] The copolymerization ratio (molar ratio) ((1):(2)) of the repeating units of the monomer represented by formula (1) to the repeating units of the other monomer represented by formula (2) in polymer (A) is not particularly limited, but from the viewpoint of increasing the melting point of polymer (A), it is preferably 97:3 to 30:70, more preferably 95:5 to 40:60, and particularly preferably 90:10 to 50:50. Furthermore, the total content of the repeating units of the monomer represented by formula (1) and the repeating units of the other monomer represented by formula (2) in 100 mol% of the total number of moles of repeating units constituting polymer (A) is not particularly limited, but from the viewpoint of increasing the oil repellency and melting point of polymer (A), it is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 100 mol%.

[0034] Such a polymer (A) can be obtained, for example, by copolymerizing one or more monomers represented by the formula (1) with one or more other monomers represented by the formula (2).

[0035] <Polymerization of Monomer> Polymerization of a monomer (homopolymerization of a monomer, copolymerization of a monomer with another monomer, etc.) is carried out using, for example, the following solvents, initiators, polymerization inhibitors, antioxidants, chain transfer agents, catalysts, etc.

[0036] (Solvent) The solvent for carrying out the polymerization (homopolymerization or copolymerization) is not particularly limited, and suitable examples include an organic solvent capable of dissolving a monomer, an organic solvent capable of dissolving a monomer and other monomers, water, etc. The solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or may contain both solvents.

[0037] The fluorine-based organic solvent is not particularly limited, and examples thereof include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and hydrochlorofluoroolefins. These may be used alone or in combination of two or more. The fluorinated alkane is not particularly limited, and for example, a compound having 4 to 8 carbon atoms is preferred. Commercially available fluorinated alkanes include, for example, C ６ F １３ H (manufactured by AGC, Asahiklin (registered trademark) AC-2000), C ６ F １３ C ２ H ５ (AGC, Asahiklin (registered trademark) AC-6000), C ２ F ５ CHFCHFCF ３ (Vertrel (registered trademark) XF, manufactured by Chemours). These may be used alone or in combination of two or more. The fluorinated aromatic compound is not particularly limited, and examples thereof include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis(trifluoromethyl)benzene, etc. These may be used alone or in combination of two or more. The fluoroalkyl ether is not particularly limited, and suitable examples include compounds having 4 to 12 carbon atoms. Commercially available fluoroalkyl ethers include, for example, CF ３ CH ２ OCF ２ CF ２ H (manufactured by AGC, Asahiklin (registered trademark) AE-3000), C ４ F ９ OCH ３ (3M Novec (registered trademark) 7100), C ４ F ９ O.C.２ H ５ (3M Novec (registered trademark) 7200), C ２ F ５ CF (OCH ３ ) C ３ F ７ (Novec (registered trademark) 7300, manufactured by 3M Company) and the like. These may be used alone or in combination of two or more. The fluorinated alkylamine is not particularly limited, and examples thereof include perfluorotripropylamine and perfluorotributylamine. These may be used alone or in combination of two or more. The fluoroalcohol is not particularly limited, and examples thereof include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol, and the like. These may be used alone or in combination of two or more. The hydrochlorofluoroolefin is not particularly limited, and examples thereof include 1-chloro-2,3,3-trifluoro-1-propene and 1-chloro-3,3-difluoro-1-propyne. These may be used alone or in combination of two or more.

[0038] The non-fluorine-based organic solvent is not particularly limited, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, and ester organic solvents. These may be used alone or in combination of two or more. The hydrocarbon organic solvent is not particularly limited, and examples thereof include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene. These may be used alone or in combination of two or more. The alcohol organic solvent is not particularly limited, and examples thereof include ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol. These may be used alone or in combination of two or more. The ketone organic solvent is not particularly limited, and examples thereof include methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone, and cyclohexanone. These may be used alone or in combination of two or more. The ether-based organic solvent is not particularly limited, and examples thereof include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dibutyl ether, diethylene glycol methyl ethyl ether, etc. These may be used alone or in combination of two or more.The ester-based organic solvent is not particularly limited, and examples thereof include methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, γ-butyrolactone, 3-methyl-3-methoxybutyl acetate, glycerin triacetate, etc. These may be used alone or in combination of two or more.

[0039] (Initiator) It is preferable to use an initiator when polymerizing the polymer (A) having repeating units of a monomer. The initiator is not particularly limited and can be appropriately selected depending on the polymerizable groups of the monomer and other monomers. Examples of initiators include organic peroxides, inorganic peroxides, azo compounds, etc. used in radical polymerization; organic acids, inorganic acids, Lewis acids, and thermal cationic polymerization initiators or photocationic polymerization initiators that generate these in the polymerization system that are used in cationic polymerization; and photoanionic polymerization initiators that generate organometallics and organic bases in the polymerization system that are used in anionic polymerization. These may be used alone or in combination of two or more. The organic peroxide is not particularly limited, and examples include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl-α-cumyl peroxide, etc. These may be used alone or in combination of two or more. The inorganic peroxide is not particularly limited, and examples thereof include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and percarbonate. These may be used alone or in combination of two or more. The azo compound is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, and 2,2'-azobis(2-amidinopropane) dihydrochloride. These may be used alone or in combination of two or more. In addition, commercially available products such as V-59 and V-65 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) can also be used as an azo polymerization initiator. The organic acid is not particularly limited and examples thereof include trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. The inorganic acid is not particularly limited and examples thereof include hydrochloric acid, nitric acid, sulfuric acid, tetrafluoroboric acid, fluoroantimonic acid, hexafluorophosphoric acid, etc.The Lewis acid is not particularly limited, and examples thereof include trichloroaluminum, ethylaluminum dichloride, and ethylaluminum sesquichloride. The thermal cationic polymerization initiator is not particularly limited, and examples thereof include benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate. The photocationic polymerization initiator is not particularly limited, and examples thereof include commercially available products such as WPI-113, WPI-116, and WPI-170 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The organic metal is not particularly limited, and examples thereof include n-butyllithium, sec-butyllithium, t-butyllithium, diethylzinc, and triethylaluminum. The photoanionic polymerization initiator is not particularly limited, and examples thereof include commercially available products such as WPBG-266, WPBG-300, and WPGB-345 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0040] (Polymerization inhibitor) When polymerizing the polymer (A) having a repeating unit of a monomer, a polymerization inhibitor may be used to control the molecular weight. In particular, when a monomer having two or more polymerizable groups in one molecule is used in the polymerization, adding such a polymerization inhibitor is preferable because it can suppress gelation and precipitation of the polymer (A). The polymerization inhibitor is not particularly limited, and examples include hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol (BHT), and the like. These may be used alone or in combination of two or more.

[0041] (Antioxidant) An antioxidant may be used to prevent oxidation during polymerization of the polymer (A) having repeating units of the monomer. The antioxidant is not particularly limited, and examples thereof include t-butyl-p-benzoquinone (TBQ).

[0042] (Chain Transfer Agent) When polymerizing the polymer (A) having repeating units of a monomer, a chain transfer agent that enables living radical polymerization may be used to control the molecular weight. Examples of the chain transfer agent are preferably reversible addition-fragmentation chain transfer agents, such as cyanomethyl dodecyl trithiocarbonate, 2-cyano-2-propyl benzodithioate, 2-(dodecylthiocarbonothioylthio)-2-methylpropanoic acid, and cyanomethyl methyl(phenyl)carbamodithioate. In particular, when a monomer having two or more polymerizable groups in one molecule is used in the polymerization, adding such a chain transfer agent is preferred because it can suppress gelation and precipitation of the polymer (A).

[0043] (Catalyst) A catalyst may be added during polymerization of the polymer (A) having repeating units of a monomer. The catalyst is not particularly limited, and examples thereof include tin compounds such as dibutyltin dilaurate (dibutyltin dilaurate (DBTDL)); basic catalysts such as 1,4-diazabicyclo[2.2.2]octane (DABCO); and the like. These may be used alone or in combination of two or more.

[0044] In the polymerization reaction, the order of addition of each material is not limited, and a reaction solution is prepared by adding a monomer, and if necessary, other monomers, an initiator, etc. to a reaction solvent. The reaction solution is heated preferably to 30 to 100°C and shaken or stirred preferably for 1 to 48 hours to allow the polymerization reaction to proceed.

[0045] The polymer (A) may be obtained by reacting a polymer having both a repeating unit of the monomer represented by formula (1) and a reactive group (z1) with a compound (z2) to form a partial structure. The reactive group (z1) is not particularly limited, and examples thereof include a hydroxy group, an amino group, an isocyanate group, and a mercapto group. The compound (z2) is not particularly limited, and examples thereof include (1) a compound having an isocyanate group, (2) a compound having a hydroxy group, (3) a compound having an amino group, (4) a compound having an acid anhydride group, and (5) a compound having an acyl chloride group. These may be used alone or in combination of two or more.

[0046] (1) Specific examples of compounds having an isocyanate group are not particularly limited, and include, for example, benzyl isocyanate, 1-adamantyl isocyanate, cyclohexyl isocyanate, tertiary butyl isocyanate, isopropyl isocyanate, ethyl isocyanate, butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, etc. These may be used alone or in combination of two or more.

[0047] (2) Specific examples of compounds having a hydroxy group are not particularly limited, and include, for example, ethanol, 1-butanol, 1-hexanol, 1-dodecanol, cyclohexanol, phenol, benzyl alcohol, 2-ethoxyethanol, 2-(2-ethoxyethoxy)ethanol, 2-methyl-1,3-propanediol, trimethylolethane, allyl alcohol, 3-butenol, 2-butenol, cis-2-penten-1-ol, trans-2-hexen-1-ol, propargyl alcohol, acetamidomethanol, N-propionylethanolamine, etc. These may be used alone or in combination of two or more.

[0048] (3) Specific examples of the compound having an amino group are not particularly limited and include, for example, propylamine, butylamine, hexylamine, dodecylamine, cyclohexylamine, aniline, benzylamine, diethylamine, allylamine, N-allylmethylamine, propargylamine, N-acetylethylenediamine, etc. These may be used alone or in combination of two or more.

[0049] (4) Specific examples of compounds having an acid anhydride group are not particularly limited and include, for example, acetic anhydride, propionic anhydride, butyric anhydride, decanoic anhydride, benzoic anhydride, etc. These may be used alone or in combination of two or more.

[0050] (5) Specific examples of compounds having an acyl chloride group are not particularly limited, and include, for example, acetyl chloride, propionyl chloride, butyric acid chloride, methoxyacetyl chloride, decanoic acid chloride, N-acetylglycinoyl chloride, etc. These may be used alone or in combination of two or more.

[0051] The combination of the reactive group (z1) and the compound (z2) is not particularly limited, but a combination in which (z1) is a hydroxy group and (z2) is (1) a compound having an isocyanate group is preferred.

[0052] The equivalent ratio of [functional group of compound (z2)] / [reactive group (z1) of polymer (A)] is not particularly limited, but from the viewpoint of reducing the remaining amount of excess compound (z2), it is preferably 1.5 or less, more preferably 1.3 or less, and particularly preferably 1.1 or less.

[0053] The weight average molecular weight (Mw) of the polymer (A) having repeating units of a monomer is not particularly limited, but is preferably 2,000 to 1,000,000, more preferably 3,000 to 700,000, and particularly preferably 4,000 to 400,000. When the weight average molecular weight (Mw) of the polymer (A) having repeating units of a monomer is at least the lower limit, the liquid repellency can be improved, and when it is at most the upper limit, the compatibility with organic solvents and resist resins can be improved.

[0054] The fluorine atom content of the polymer (A) having repeating units of a monomer is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, particularly preferably 10% by mass or less, and most preferably 0% by mass. When the fluorine atom content of the polymer (A) having repeating units of a monomer is not more than the upper limit, compatibility of the polymer (A) with the resist resin can be improved, and this is also desirable from the viewpoint of reducing the environmental load.

[0055] There are no particular restrictions on the content of the polymer (A) in the total solid content of the resist composition of the present invention, but from the viewpoint of improving oil repellency, it is preferably from 0.01 to 3.0 mass%, more preferably from 0.05 to 2.0 mass%, and particularly preferably from 0.1 to 1.0 mass%.

[0056] <Alkali-soluble resin (B)> The alkali-soluble resin (B) is a resin that is a main component of the partition walls used in pixel portions, etc., and is soluble in a developer (usually an alkali developer) used in a development step. The alkali-soluble resin (B) contains at least one of an alkali-soluble resin (BP) and an alkali-soluble monomer (BM).

[0057] In order to impart alkali solubility, the alkali-soluble resin (B) preferably has an alkali-soluble group in the repeating unit of the resin and / or at the end of its main chain. The alkali-soluble group refers to a functional group that increases solubility in an alkaline solution by interacting with or reacting with an alkali, and specific examples thereof include acidic groups. Preferred alkali-soluble groups include a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. These may be used alone or in combination of two or more.

[0058] In negative resist compositions, the alkali-soluble resin (BP) is polymerized by radicals generated from the photosensitizer (D) during exposure in photolithography or the like, and hardens. The hardened portions are insoluble in alkaline developer. Therefore, the unexposed portions are selectively removed in alkaline developer. As a result, the cured film in the exposed portions can be formed into partition walls that separate a predetermined area into multiple compartments. In positive resist compositions, the alkali-soluble resin (BP) becomes more alkaline soluble due to the acid generated by activation of the photosensitizer (D) during exposure in photolithography or the like. Therefore, the exposed portions dissolve in developer (usually alkaline developer) during development and are selectively removed. The portions not irradiated with light (unexposed portions) become partition walls. As a result, the cured film in the unexposed portions can be formed into partition walls that separate a predetermined area into multiple compartments. Note that some alkali-soluble resins (BP) become insoluble in developer when combined with a photosensitizer (D) before exposure.

[0059] <<Alkali-Soluble Resin (B) in Negative Resist Composition>> In the negative resist composition, the alkali-soluble resin (BP) is preferably a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. The acidic group is not particularly limited, and examples thereof include a carboxy group, a phenolic hydroxyl group, a sulfo group, and a phosphate group. These may be used alone, or two or more types may be used in combination. The ethylenic double bond is not particularly limited, and examples thereof include addition-polymerizable double bonds such as (meth)acryloyl groups, allyl groups, vinyl groups, vinyloxy groups, and vinyloxyalkyl groups. These may be used alone, or two or more types may be used in combination. Some or all of the hydrogen atoms in the ethylenic double bond may be substituted with alkyl groups such as methyl groups.

[0060] The alkali-soluble resin (BP) is not particularly limited, and examples thereof include a resin (BP-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, a resin (BP-2) in which an acidic group and an ethylenic double bond have been introduced into an epoxy resin, etc. These may be used alone or in combination of two or more.

[0061] The epoxy resin mentioned above means a compound having two or more epoxy groups (i.e., polyepoxide), which is a compound used as a base compound for curable epoxy resins.

[0062] The resin (BP-1) is not particularly limited, and examples thereof include vinyl resins having a side chain with an acidic group and a side chain with an ethylenic double bond.

[0063] The resin (BP-2) is not particularly limited, and examples thereof include a resin obtained by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond, followed by a reaction with a polycarboxylic acid or an anhydride thereof. The epoxy resin used is not particularly limited, and examples thereof include conventionally known epoxy resins used as the main chain of negative photosensitive resins, such as the epoxy resins described in WO 2010 / 013816. These may be used alone, or two or more types may be used in combination.

[0064] The acid value of the alkali-soluble resin (BP) in the negative resist composition is not particularly limited, but from the viewpoint of making it easier for the alkali-soluble resin (BP) on the substrate to be washed away from the partition walls in the development step, it is preferably 10 to 300 mgKOH / g, more preferably 20 to 200 mgKOH / g, and particularly preferably 30 to 150 mgKOH / g. The mass average molecular weight (Mw) of the alkali-soluble resin (BP) in the negative resist composition is not particularly limited, but from the viewpoint of solubility in a developer, it is preferably 1,000 or more and less than 40,000, more preferably 3,000 or more and less than 20,000.

[0065] As the alkali-soluble resin (BP), it is preferable to use resin (BP-2) from the viewpoints that peeling of the cured film during development is suppressed, thereby enabling a high-resolution dot pattern to be obtained, that the linearity of the pattern when the dots are linear is good, and that a smooth cured film surface is easily obtained.

[0066] The alkali-soluble monomer (BM) is not particularly limited, and examples thereof include a monomer (BM-3) having an acidic group and an ethylenic double bond. The acidic group and the ethylenic double bond are the same as those of the alkali-soluble resin (BP). The acid value of the alkali-soluble monomer (BM) is also preferably in the same range as that of the alkali-soluble resin (BP).

[0067] The monomer (BM-3) is not particularly limited, and examples thereof include 2,2,2-triacryloyloxymethylethyl phthalate.

[0068] The alkali-soluble resin (B) contained in the negative resist composition may use either a single type, or a combination of two or more types.

[0069] There are no particular restrictions on the amount of alkali-soluble resin (B) contained in the total solids of the negative resist composition, but from the perspective of improving the developability of the resist resin composition, it is preferably from 1.0 to 90.0 mass %, more preferably from 20.0 to 75.0 mass %, and particularly preferably from 30.0 to 65.0 mass %.

[0070] <<Alkali-Soluble Resin (B) in Positive Resist Composition>> The alkali-soluble resin (B) contained in the positive resist composition is a known alkali-soluble resin used in positive resist compositions. There are no particular restrictions on the alkali-soluble resin (B), and examples include acrylic resins, polyimide resins, and novolac phenolic resins. These may be used alone, or two or more may be used in combination.

[0071] (Acrylic resin) The acrylic resin is not particularly limited, and examples thereof include N-substituted maleimide having a high Tg, benzyl methacrylate, copolymers of acrylic acid, acrylic resins containing phenolic hydroxyl groups, and acrylic resins having sulfonamide groups. These may be used alone or in combination of two or more. Specific examples of acrylic resins are not particularly limited, and examples include alkali-soluble resins described in Japanese Patent No. 6177495, Japanese Patent No. 5447384, Japanese Patent No. 4770985, Japanese Patent No. 4600477, Japanese Patent No. 5444749, and International Publication No. 2019 / 156000. These may be used alone or in combination of two or more.

[0072] (Polyimide Resin) The polyimide resin is not particularly limited, and examples thereof include polyimide resins, polyimide precursors, and copolymers having two or more of these repeating units. These may be used alone or in combination of two or more. The polyimide resin is not particularly limited, and examples thereof include resins obtained by reacting tetracarboxylic acids, tetracarboxylic dianhydrides, tetracarboxylic diester dichlorides, etc. with diamines, diisocyanate compounds, trimethylsilylated diamines, etc. These may be used alone or in combination of two or more. Such polyimide resins have tetracarboxylic acid residues and diamine residues. Furthermore, preferred polyimide resins are resins obtained by dehydrating and cyclizing polyamic acid, which is a type of polyimide precursor obtained by reacting tetracarboxylic dianhydrides with diamines, through heat treatment. During this heat treatment, a solvent that forms an azeotrope with water, such as m-xylene, may be added. The polyimide resin may be a resin obtained by adding a dehydrating condensation agent such as a carboxylic acid anhydride or dicyclohexylcarbodiimide, or a base such as triethylamine as a ring-closing catalyst, and then subjecting the resulting resin to dehydration and ring-closing through chemical heat treatment. Alternatively, the polyimide resin may be obtained by adding a weakly acidic carboxylic acid compound and then subjecting the resulting resin to dehydration and ring-closing through heat treatment at a low temperature of 100°C or lower.

[0073] The polyimide precursor is not particularly limited, and examples thereof include polyamic acid, polyamic acid ester, polyamic acid amide, polyisoimide, etc. These may be used alone or in combination of two or more. Polyamic acid can be obtained by reacting a tetracarboxylic acid, a tetracarboxylic acid dianhydride, a tetracarboxylic acid diester dichloride, etc. with a diamine, a diisocyanate compound, a trimethylsilylated diamine, etc. Polyisoimide can be obtained, for example, by dehydrating and cyclizing the polyamic acid obtained by the above method by heating or chemical treatment with an acid or a base, etc.

[0074] (Novolac-type phenolic resin) The novolac-type phenolic resin is preferably an unmodified or modified novolac-type phenolic resin produced by polycondensation of a phenol and an aldehyde, and further adding various modifiers as required.

[0075] The phenols used to produce the novolac phenolic resin are not particularly limited, and examples thereof include cresols such as phenol, o-cresol, p-cresol, and m-cresol; xylenols such as 3,5-xylenol, 2,5-xylenol, 2,3-xylenol, and 3,4-xylenol; trimethylphenols such as 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,4,5-trimethylphenol, and 3,4,5-trimethylphenol; t-butylphenols such as 2-t-butylphenol, 3-t-butylphenol, and 4-t-butylphenol; methoxyphenols such as 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, and 3,5-dimethoxyphenol. phenols; ethylphenols such as 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,3-diethylphenol, 3,5-diethylphenol, 2,3,5-triethylphenol, and 3,4,5-triethylphenol; chlorophenols such as o-chlorophenol, m-chlorophenol, p-chlorophenol, and 2,3-dichlorophenol; resorcinols such as resorcinol, 2-methylresorcinol, 4-methylresorcinol, and 5-methylresorcinol; catechols such as 5-methylcatechol; pyrogallols such as 5-methylpyrogallol; bisphenols such as bisphenol A, B, C, D, E, and F; methylolated cresols such as 2,6-dimethylol-p-cresol; naphthols such as α-naphthol and β-naphthol; and the like. These may be used alone or in combination of two or more.

[0076] The aldehydes used to produce the novolac phenolic resin are not particularly limited, and examples thereof include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, furfural, glyoxal, n-butylaldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, etc. These may be used alone or in combination of two or more.

[0077] Among novolac phenolic resins, novolac phenolic resins using cresols, xylenols, or the like as phenols are preferred from the viewpoints of availability and low metal impurities, and novolac phenolic resins using cresols are more preferred.

[0078] In addition to the above, examples of the alkali-soluble resin (B) contained in the positive resist composition include polyhydroxystyrene, polyhalogenated hydroxystyrene, N-(4-hydroxyphenyl)methacrylamide copolymer, and hydroquinone monomethacrylate copolymer. These may be used alone or in combination of two or more. Various alkali-soluble polymeric compounds such as sulfonylimide polymers, carboxy group-containing polymers, and urethane resins may also be used.

[0079] There are no particular restrictions on the mass average molecular weight (Mw) of the alkali-soluble resin (B) contained in the positive resist composition, but from the perspective of excellent solubility in a developer after exposure, it is preferably 500 to 20,000, more preferably 3,000 to 10,000, and even more preferably 3,000 to 8,000.

[0080] The alkali-soluble resin (B) contained in the positive resist composition may use either a single type, or a combination of two or more types.

[0081] There are no particular restrictions on the amount of alkali-soluble resin (B) within the total solids content of the positive resist composition, but, from the perspective of improving the developability of the positive resist composition, it is preferably within a range from 10.0 to 90.0 mass %, more preferably from 30.0 to 80.0 mass %, and even more preferably from 40.0 to 75.0 mass %.

[0082] <Solvent (C)> The resist composition according to an embodiment of the present invention contains a solvent (C). By containing the solvent (C) in the resist composition according to an embodiment of the present invention, the composition's coatability onto a substrate and adhesion to the substrate surface are superior. Furthermore, by containing the solvent (C), the polymer (A) can be stably present in the composition. There are no particular restrictions on the solvent (C), so long as the solvent (C) allows the resist composition to uniformly dissolve or disperse the essential components and optional components and is not reactive with the other components contained in the resist composition.

[0083] Specific examples of the solvent (C) are not particularly limited, and include, for example, alcohols such as water, ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; cellosolves such as 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol; carbitols such as 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, and 2-(2-butoxyethoxy)ethanol; methyl acetate, ethyl acetate, n-butyl acetate (butyl acetate), ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol. Examples of suitable esters include diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, butyl lactate, γ-butyrolactone, 3-methyl-3-methoxybutyl acetate, and glycerin triacetate; diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dibutyl ether, and diethylene glycol methyl ethyl ether. Other examples include chain hydrocarbons such as n-butane and n-hexane; cyclic saturated hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as toluene, xylene, and benzyl alcohol. These may be used alone or in combination of two or more.

[0084] There are no particular restrictions on the content of the solvent (C) in the resist composition of the present invention, but from the viewpoint of ensuring coatability, it is preferably from 10.0 to 95.0 mass %, more preferably from 20.0 to 90.0 mass %, and particularly preferably from 30.0 to 85.0 mass %.

[0085] <Photosensitizer (D)> <<Photosensitizer (D) in Negative Resist Composition>> As the photosensitizer (D) in the negative resist composition, any known compound used as a photosensitizer for negative resist compositions can be used, and a compound that generates radicals in response to light (photopolymerization initiator) is preferred.

[0086] The photosensitizer (D) in the negative resist composition is not particularly limited, and examples thereof include various compounds classified into α-diketones, acyloins, acyloin ethers, thioxanthones, benzophenones, acetophenones, quinones, aminobenzoic acids, peroxides, oxime esters, aliphatic amines, etc. These may be used alone or in combination of two or more. When benzophenones, aminobenzoic acids, or aliphatic amines are used, it is preferable to use them together with other radical initiators, from the viewpoint of exerting a sensitizing effect.

[0087] Among the photosensitizers (D) in negative resist compositions, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, which are classified as acetophenones; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime), and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone O-acetyloxime, which are classified as oxime esters; and 2,4-diethylthioxanthone, which is classified as thioxanthone, are preferred, and combinations of these with benzophenones, such as 4,4'-bis(diethylamino)benzophenone, are more preferred.

[0088] There are no particular restrictions on the amount of photosensitizer (D) contained in the total solids of the negative resist composition, but from the perspective of ensuring good photocurability and developability of the negative resist composition, it is preferably from 0.1 to 50.0 mass %, more preferably from 0.5 to 30.0 mass %, and even more preferably from 1.0 to 15.0 mass %.

[0089] <<Photosensitizer (D) in Positive Resist Composition>> As the photosensitizer (D) in the positive resist composition, a known photosensitizer used in a positive resist composition can be used. There are no particular restrictions on the photosensitizer (D) in the positive resist composition, and suitable examples include compounds having a quinone diazide group. There are no particular restrictions on the compound having a quinone diazide group, and examples include known compounds having a quinone diazide group that are used in combination with an acrylic resin, a novolac phenolic resin, a polyimide, a polybenzoxazole, a polyamide imide, a precursor of any of these, or a resin made of a polymer thereof. These may be used alone, or two or more may be used in combination.

[0090] The photosensitizer (D) in the positive resist composition is not particularly limited, and examples include a complete condensate or partial condensate of compound α and compound β having a quinonediazide group, which are condensable with each other, as described below.

[0091] Compound α has a functional group capable of undergoing a condensation reaction. The functional group capable of undergoing a condensation reaction is not particularly limited, and examples thereof include a sulfo group and a chlorosulfo group. Examples of compound α include sulfonic acids such as 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid, benzoquinone diazide sulfonic acid, naphthoquinone diazide sulfonic acid, and anthraquinone diazide sulfonic acid, as well as sulfonyl chlorides thereof. These may be used alone or in combination of two or more. Specific examples of sulfonyl chlorides include 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide-4-sulfonyl chloride, and 1,2-benzoquinone diazide-4-sulfonyl chloride. These may be used alone or in combination of two or more.

[0092] Compound β has a functional group capable of undergoing a condensation reaction with compound α. The functional group capable of undergoing a condensation reaction with compound α is not particularly limited, and examples thereof include a hydroxyl group and an amino group. These may be used alone or in combination of two or more. Among these, a hydroxyl group is preferred. Compound β is preferably a compound having an aromatic ring, from the viewpoint of excellent heat resistance of the resulting partition wall. The number of aromatic rings in the aromatic compound is preferably 1 to 6, and particularly preferably 2 to 4, from the viewpoint of heat resistance and the ability to introduce a large number of hydroxyl groups. Compound β is particularly preferably an aromatic compound in which at least one hydrogen atom bonded to the aromatic ring is substituted with a hydroxyl group. The number of hydroxyl groups in one molecule is preferably 1 to 10, and particularly preferably 2 to 4.Specific examples of compound β are not particularly limited, and include, for example, phenols such as phenol, 4-methylphenol, and 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-α,α-dimethylbenzyl}phenol; polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone; trisphenol-type compounds such as tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-[α,α-dimethyl-α-(4'-hydroxyphenyl)benzyl]ethane, and 1,3,5-tris(4-hydroxyphenyldimethylbenzyl)benzene; and bisphenol-type compounds such as 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane and 2-(3,4-dihydro- polynuclear branched compounds, such as 1-[1,1-bis(4-hydroxyphenyl)ethyl]-4-[1',1'-bis(4'-hydroxyphenyl)ethyl]benzene; condensed phenol compounds, such as 2-bis[1,1-bis(4-hydroxyphenylcyclohexyl)]-2-bis[1',1'-bis(4'-hydroxyphenylcyclohexyl)]propane; 1,1'-spirobi[1H-indene]-5,5',6,6'-tetraol, 2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman, pentacyclo[19,3,1,1]. ３，７ , 1 ９，１３ , 1 １５，１９ ]octacosa-1,3,5,7,9,11,13,15,17,19,21,23-dodecaene-4,6,10,12,16,18,22,24-octaol; etc. These may be used alone or in combination of two or more.

[0093] The photosensitizer (D) in the positive resist composition may be a mixture of compounds having different numbers of quinonediazide groups per molecule. The average number of quinonediazide groups per molecule in the entire photosensitizer (D) is not particularly limited, but is preferably 1 to 4, and more preferably 2.5 to 3.

[0094] There are no particular restrictions on the amount of photosensitizer (D) contained in the total solids content of the positive resist composition, but from the standpoint of achieving excellent developability for the positive resist composition, obtaining sufficient sensitivity as a positive resist composition, and preventing precipitation of components, it is preferably from 0.1 to 50.0 mass %, more preferably from 1.0 to 40.0 mass %, and even more preferably from 10.0 to 30.0 mass %.

[0095] There are no particular restrictions on the content of optional components in the total solid content of the resist composition of the present invention, but in order to avoid impairing the effects of the present invention, the content is preferably 70 mass % or less, more preferably 60 mass % or less, and particularly preferably 50 mass % or less.

[0096] <<Polymer (A2) Other Than Polymer (A)>> The resist composition according to an embodiment of the present invention may or may not contain a polymer (A2) other than the polymer (A) as an optional component. By including a polymer (A2) other than the polymer (A) in the resist composition, improved oil repellency can be expected. The polymer (A2) other than the polymer (A) is not particularly limited, and examples include the polymer (A) described in Japanese Patent No. 5152332.

[0097] There are no particular restrictions on the amount of the polymer (A2) other than the polymer (A) in the total solids content of the resist composition of the present invention, but from the perspective of achieving both oil repellency and compatibility with the resist composition, it is preferably from 0.01 to 1.0 mass%, more preferably from 0.05 to 0.5 mass%, and even more preferably from 0.1 to 0.3 mass%.

[0098] <<Crosslinking Agent (E)>> The resist composition according to an embodiment of the present invention may or may not include a crosslinking agent (E) as an optional component that promotes crosslinking. By including the crosslinking agent (E) in the resist composition, the curability of the resist composition is superior, and it is possible to form partition walls that have a stable shape after crosslinking.

[0099] (Crosslinking agent (E) in negative resist composition) The crosslinking agent (E) in the negative resist composition is a compound that has two or more ethylenic double bonds in one molecule and does not have an acidic group. By including the crosslinking agent (E) in the negative resist composition, the curability of the negative resist composition during exposure is improved, and a cured film can be efficiently formed.

[0100] The crosslinking agent (E) in the negative resist composition is not particularly limited, and examples thereof include diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, urethane acrylate, tris-(2-acryloxyethyl)isocyanurate, etc. These may be used alone or in combination of two or more.

[0101] Among these, from the viewpoint of photoreactivity, compounds having a large number of ethylenic double bonds, such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, urethane acrylate, and tris-(2-acryloxyethyl)isocyanurate, are preferred.

[0102] (Crosslinking Agent (E) in Positive Resist Composition) The crosslinking agent (E) in the positive resist composition is not particularly limited, and examples include amino resins, epoxy compounds, oxazoline compounds, polyisocyanate compounds, polycarbodiimide compounds, etc. These may be used alone, or two or more types may be used in combination.

[0103] The amino resin is not particularly limited, and examples thereof include compounds in which some or all of the amino groups of melamine-based compounds, guanamine-based compounds, urea-based compounds, etc. are hydroxymethylated; compounds in which some or all of the hydroxyl groups of the hydroxymethylated compounds are etherified with methanol, ethanol, n-butyl alcohol, 2-methyl-1-propanol, etc. (e.g., hexamethoxymethylmelamine); etc. These may be used alone or in combination of two or more.

[0104] The epoxy compound is not particularly limited, and examples thereof include glycidyl ethers such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenolmethane epoxy resin, and brominated epoxy resin; alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis(2,3-epoxycyclopentyl)ether, and epoxy compounds having a cycloalkene oxide structure; glycidyl esters such as diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, and diglycidyl phthalate; glycidyl amines such as tetraglycidyldiaminodiphenylmethane and triglycidyl paraaminophenol; and heterocyclic epoxy resins such as triglycidyl isocyanurate. These may be used alone or in combination of two or more. Specific examples of the epoxy compound include, but are not limited to, 2-[4-(2,3-epoxypropoxy)phenyl-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl]ethyl]phenyl]propane)]. These may be used alone or in combination of two or more.

[0105] The oxazoline compound is not particularly limited, and examples thereof include copolymers of polymerizable monomers such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, and 2-isopropenyl-4-methyl-2-oxazoline. These may be used alone or in combination of two or more.

[0106] The crosslinking agent (E) may be a crosslinkable compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups. The crosslinkable compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups is not particularly limited, and examples thereof include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds. These may be used alone or in combination of two or more.

[0107] The crosslinking agent (E) is preferably a compound having two or more epoxy groups in one molecule.

[0108] There are no particular restrictions on the content of the crosslinking agent (E) in the total solid content of the resist composition of the present invention, but from the viewpoint of achieving better ink affinity within dots, including the side surfaces of the partition walls, when the resist composition is used to form partition walls, the content is preferably 2.0 to 70.0 mass%, more preferably 3.0 to 60.0 mass%, and particularly preferably 5.0 to 50.0 mass%.

[0109] (Crosslinking Accelerator (F)) The resist composition of the present invention may or may not contain a crosslinking accelerator (F) as an optional component that accelerates crosslinking.

[0110] The crosslinking accelerator (F) is a compound that has the effect of forming a crosslinked structure in the resist composition upon heating. There are no particular limitations on the crosslinking accelerator (F), and examples include a compound that reacts with the crosslinking agent (E) by itself to form a crosslinked structure through crosslinking, and a compound that does not crosslink by itself but has a catalytic effect on the crosslinking agent (E).

[0111] When a compound having two or more ethylenic double bonds and no acidic group per molecule is used as the crosslinking agent (E), the crosslinking accelerator (F) that forms the crosslinked structure is not particularly limited, and examples include polythiols. These may be used alone or in combination of two or more. During exposure, radicals generated from the photosensitizer (D) generate radicals of a thiol compound, which then act on the ethylenic double bonds of the alkali-soluble resin (B), etc., resulting in a so-called ene-thiol reaction. Unlike typical radical polymerization of ethylenic double bonds, this ene-thiol reaction is not inhibited by oxygen and therefore has high chain transfer properties. Furthermore, since crosslinking occurs simultaneously with polymerization, the shrinkage rate when the cured product is obtained is low and a uniform network is easily obtained.

[0112] When an epoxy compound is used as the crosslinking agent (E), the crosslinking accelerator (F) that forms the crosslinked structure is not particularly limited, and examples thereof include polyamines, polythiols, and polycarboxylic acid anhydrides. These may be used alone or in combination of two or more. The polyamines are not particularly limited, and examples thereof include ethylenediamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, polyoxyalkylenepolyamine, isophoronediamine, menthenediamine, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane. These may be used alone or in combination of two or more. The polythiols are not particularly limited, and examples thereof include polyether polythiol. The polycarboxylic acid anhydrides are not particularly limited, and examples thereof include succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride. These may be used alone or in combination of two or more. The catalytic agent is not particularly limited, and examples thereof include curing catalysts such as tertiary amines, imidazoles, Lewis acids, onium salts, dicyandiamides, organic acid dihydrazides, and phosphines. These may be used alone or in combination of two or more. Specific examples of the catalytic agent are not particularly limited, and examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, tris(dimethylaminomethyl)phenol, boron trifluoride-amine complex, dicyandiamide, diphenyliodonium hexafluorophosphate, and triphenylsulfonium hexafluorophosphate. These may be used alone or in combination of two or more.

[0113] When the crosslinking agent (E) is a compound having two or more epoxy groups in one molecule, the crosslinking accelerator (F) is not particularly limited, and suitable examples thereof include 2-methylimidazole and 4-methyl-2-phenylimidazole.

[0114] There are no particular restrictions on the content of the crosslinking accelerator (F) in the total solid content of the resist composition of the present invention, but it is preferably from 0.1 to 10.0 mass %, and more preferably from 0.5 to 3.0 mass %.

[0115] (Colorant (G)) When the resist composition of the present invention is used to form a black matrix, which is a lattice-shaped black portion surrounding the three color pixels of R, G, and B in a color filter of a liquid crystal display element, it may contain a colorant (G) as necessary. The colorant (G) is not particularly limited, and examples thereof include carbon black, aniline black, anthraquinone-based black pigments, metal oxides such as titanium black, metal particles such as silver-tin alloys, perylene-based black pigments, lactam black-based pigments, benzofuranone-based pigments, xanthene-based pigments, triarylmethane-based pigments, and the like. Specific examples include C.I. Pigment Black 1, 6, 7, 12, 20, and 31. Furthermore, a mixture of an organic pigment such as a red pigment, a blue pigment, or a green pigment and an inorganic pigment can also be used as the colorant (G). These pigments may be used alone or in combination of two or more. Among these, carbon black is preferred from the viewpoint of its light-blocking properties. The carbon black may be surface-treated with a resin or the like. In order to adjust the color tone of the black colorant, carbon black can be used in combination with a blue pigment, a purple pigment, or the like.

[0116] When the resist composition of the present invention contains a dispersible material such as the colorant (G), it may further contain a polymeric dispersant, a dispersing aid, or the like to improve its dispersibility. These can be contained in the resist composition in a content range that does not impair the effects of the present invention. The polymeric dispersant is not particularly limited, and examples thereof include urethane-based, polyimide-based, alkyd-based, epoxy-based, polyester-based, melamine-based, phenol-based, acrylic-based, polyether-based, vinyl chloride-based, vinyl chloride-vinyl acetate copolymer-based, polyamide-based, and polycarbonate-based dispersants. These dispersants may be used alone or in combination of two or more. Among these, urethane-based and polyester-based dispersants are preferred. The polymeric dispersant may have repeating units derived from ethylene oxide and / or propylene oxide. These dispersants may be used alone or in combination of two or more. The dispersing aid is not particularly limited, and examples thereof include phthalocyanine pigment derivatives and metal phthalocyanine sulfonamide compounds.

[0117] When the resist composition of the present invention contains a colorant (G), there are no particular restrictions on the amount of colorant (G) contained in the total solid content of the resist composition of the present invention, but from the standpoint of imparting excellent sensitivity to the resist composition and providing excellent light-shielding properties to the formed partition walls, the amount is preferably 15.0 to 65.0 mass %, and more preferably 20.0 to 50.0 mass %.

[0118] (Silane Coupling Agent (H)) The resist composition of the present invention may or may not contain a silane coupling agent (H) as necessary. By containing the silane coupling agent (H), the cured film formed will have better substrate adhesion. The silane coupling agent (H) is not particularly limited, and examples include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, and polyoxyalkylene chain-containing triethoxysilane. These may be used alone, or two or more types may be used in combination.

[0119] There are no particular restrictions on the amount of the silane coupling agent (H) in the total solids of the resist composition of the present invention, but from the standpoint of achieving both excellent substrate adhesion of a cured film formed from the resist composition and excellent oil repellency of the cured film, it is preferably from 0.1 to 20.0 mass%, and more preferably from 1.0 to 10.0 mass%.

[0120] (Fine Particles (I)) The resist composition of the present invention may or may not contain fine particles (I) as necessary. The fine particles (I) referred to here refer to particles having an average particle diameter of 5 μm or less. By including the fine particles (I), it is possible to prevent thermal sagging of the partition walls formed using the resist composition.

[0121] The fine particles (I) are not particularly limited, and examples thereof include inorganic fine particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO); and organic fine particles such as polyethylene and polymethyl methacrylate (PMMA). These may be used alone or in combination of two or more. Among these, inorganic fine particles are preferred from the viewpoint of heat resistance, and are more preferred than silica or zirconia from the viewpoint of easy availability and dispersion stability. Furthermore, when the resist composition contains a colorant (G) and a polymer dispersant, taking into account the adsorption ability of the polymer dispersant, the fine particles (I) are preferably negatively charged. Furthermore, taking into account the exposure sensitivity of the resist composition, it is preferable that the fine particles (I) do not absorb light irradiated during exposure, and it is particularly preferable that they do not absorb the i-line (365 nm), h-line (405 nm), and g-line (436 nm), which are the main emission wavelengths of ultra-high pressure mercury lamps.

[0122] The average particle size of the fine particles (I) is not particularly limited, but is preferably 1 μm or less, more preferably 200 nm or less, and particularly preferably 5 to 100 nm, in order to improve the surface smoothness of the partition walls.

[0123] There are no particular restrictions on the content of the fine particles (I) in the total solid content of the resist composition of the present invention, but from the standpoint of the effect of suppressing a decrease in oil repellency and the storage stability of the resist composition, it is preferably 5.0 to 35.0 mass %, and more preferably 10.0 to 30.0 mass %.

[0124] (Phosphate Compound (J)) The resist composition of the present invention may or may not contain a phosphate compound (J) as necessary. By containing the phosphate compound (J), adhesion to the substrate can be improved. The phosphate compound is not particularly limited, and examples thereof include mono(meth)acryloyloxyethyl phosphate, di(meth)acryloyloxyethyl phosphate, tris(meth)acryloyloxyethyl phosphate, etc. These may be used alone or in combination of two or more.

[0125] There are no particular restrictions on the amount of phosphoric acid compound (J) contained in the total solids of the resist composition of the present invention. However, from the standpoint of ensuring good adhesion between a cured film formed from the resulting resist composition and a substrate, the amount is preferably from 0.1 to 10.0 mass%, and more preferably from 0.3 to 1.0 mass%.

[0126] (Thiol Compound (K)) The resist composition of the present invention may or may not contain a thiol compound (K) as necessary. The thiol compound (K) is a polyfunctional thiol compound having two or more mercapto groups in one molecule. In particular, when the resist composition is a negative resist composition, containing a thiol compound (K) will cause a so-called ene-thiol reaction, in which radicals generated from the photosensitizer (D) during exposure generate radicals of the thiol compound, which then act on the ethylenic double bonds of the alkali-soluble resin (B) or the like. Unlike typical radical polymerization of ethylenic double bonds, this ene-thiol reaction is not inhibited by oxygen and therefore exhibits high chain transfer properties. Furthermore, since crosslinking occurs simultaneously with polymerization, the shrinkage rate when the cured product is obtained is low and a uniform network is easily obtained, among other advantages.

[0127] When the negative resist composition contains the thiol compound (K), it can be sufficiently cured even with a low exposure dose as described above, and therefore developability is improved, which can contribute to achieving both substrate adhesion in the exposed area and reduced residue in the unexposed area. Furthermore, when the thiol compound (K) is contained, photocuring is sufficiently carried out even in the upper layer portion including the upper surface of the partition wall, which is particularly susceptible to reaction inhibition by oxygen.

[0128] The number of mercapto groups in one molecule of the thiol compound (K) is not particularly limited, but is preferably 2 to 10, more preferably 3 to 8, and particularly preferably 3 to 5. The mercapto group equivalent (hereinafter also referred to as SH equivalent) of the thiol compound (K), expressed as [molecular weight / number of mercapto groups], is not particularly limited, but is preferably 40 to 1,000, more preferably 40 to 500, and particularly preferably 40 to 250, from the viewpoint of curability at low exposure doses.

[0129] Specific examples of the thiol compound (K) are not particularly limited, and include, for example, tris(2-mercaptopropanoyloxyethyl)isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tristhioglycolate, pentaerythritol tristhioglycolate, pentaerythritol tetrakisthioglycolate, dipentaerythritol hexathioglycolate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, dipentaerythritol hexa ... tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tri Examples include methylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptobutyrate), trimethylolpropane tris(2-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, triphenolmethane tris(3-mercaptopropionate), triphenolmethane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), 2,4,6-trimercapto-S-triazine, and 1,4-bis(3-mercaptobutyryloxy)butane. These may be used alone or in combination of two or more.

[0130] There are no particular restrictions on the amount of mercapto groups in the thiol compound (K) relative to 1 mole of ethylenic double bonds in the total solids of the resist composition of the present invention, but from the standpoint of ensuring good photocurability and developability of the resist composition even at a low exposure dose, it is preferably 0.0001 to 1.0 mole, more preferably 0.0005 to 0.5 mole, and particularly preferably 0.001 to 0.5 mole.

[0131] There are no particular restrictions on the amount of thiol compound (K) contained in the total solids of the resist composition of the present invention, but from the viewpoint of ensuring good photocurability and developability of the resist composition even at low exposure doses, it is preferably from 1.0 to 20.0 mass %, and more preferably from 3.0 to 15.0 mass %.

[0132] (Other Additives) The resist composition of the present invention may optionally contain one or more other additives selected from the group consisting of thickeners, plasticizers, antifoaming agents, leveling agents, anti-cising agents, and ultraviolet absorbers, as long as the effects of the present invention are not impaired.

[0133] <Method for Producing Resist Composition> A preferred method for producing a resist composition is to mix a polymer (A), an alkali-soluble resin (B), a solvent (C), a photosensitizer (D), and, if necessary, a crosslinking agent (E), a crosslinking accelerator (F), a colorant (G), a silane coupling agent (H), fine particles (I), a phosphate compound (J), a thiol compound (K), and other additives. Mixing is carried out using a stirrer at a temperature of 20 to 30°C for 0.1 to 6 hours, preferably 0.2 to 2 hours, and more preferably 0.3 to 1 hour, and the resulting composition is used as is. Alternatively, prior to this mixing, a solution prepared by diluting or dissolving any of the polymer (A), the alkali-soluble resin (B), the photosensitizer (D), the crosslinking agent (E), the crosslinking accelerator (F), the colorant (G), the silane coupling agent (H), fine particles (I), the phosphate compound (J), the thiol compound (K), and other additives with a solvent (C) may be used for mixing.

[0134] [Cured Film] The resist composition of the present invention can be used, like a typical resist composition, to protect a substrate or change the affinity of a substrate surface with other substances, and is suitable, for example, as a pattern-forming material for photolithography, etc., an antifouling coating agent, an antifingerprint agent, a water- and oil-repellent agent, a release agent, etc. The cured film obtained using the resist composition of the present invention can be used as a member for which a cured film of a typical resist composition is used, for example, as a member for an optical element, and contains the polymer (A) described above.

[0135] [Optical Element] The optical element of the present invention is a resist film having a substrate, a plurality of pixels formed on the surface of the substrate, and partition walls located between adjacent pixels, the partition walls being made of a cured product containing the polymer (A) described above. The optical element is not particularly limited, and examples thereof include organic EL elements, color filters, organic TFT arrays, thin-film solar cells, etc. Details of the optical element are described in, for example, International Publication No. 2015 / 190294, International Publication No. 2016 / 010077, International Publication No. 2013 / 031736, and JP-A No. 2015-172742.

[0136] <Partition Walls and Their Manufacturing Method> The partition walls are formed to provide compartments on a substrate, and are made of a cured film obtained by applying, drying, and curing the resist composition of the present invention. The partition walls are suitable for use in optical elements, and when the resist composition contains a colorant (G), the resulting partition walls can be used as a black matrix. The partition walls are used, for example, as partition walls for optical elements having a plurality of pixels on a substrate and partition walls located between adjacent pixels.

[0137] There are no particular limitations on the method for producing partition walls for optical elements using the resist composition of the present invention, and examples thereof include the following methods.

[0138] When the resist composition is a negative resist composition, the resist composition is applied onto a substrate to form a coating film (coating film forming step), the coating film is then dried to form a film (pre-baking step), and only the portions of the film that will become partition walls are exposed to light (exposure step), and then the non-exposed portions of the coating film are removed to form partition walls consisting of the exposed portions of the coating film (development step).Then, if necessary, the formed partition walls etc. are further crosslinked and cured by heating (post-baking step), thereby producing partition walls.

[0139] When the resist composition is a positive resist composition, the resist composition is applied onto a substrate to form a coating film (coating film forming step), the coating film is then dried to form a film (pre-baking step), and only the portions of the film that do not become partition walls are exposed to light (exposure step), and then the exposed portions of the coating film are removed to form partition walls consisting of the non-exposed portions of the coating film (development step). Next, if necessary, the formed partition walls etc. are further crosslinked and cured by heating (post-baking step), thereby producing partition walls.

[0140] The material of the substrate is not particularly limited, and examples thereof include glass plates, thermoplastic plastic sheets such as polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, polymethacrylic resin, and acrylic resin, and cured sheets of thermosetting resins such as epoxy resin and unsaturated polyester. Among these, from the viewpoint of heat resistance, heat-resistant plastics such as glass plates and polyimides are preferred, and transparent substrates are also preferred.

[0141] The shape of the substrate and the surface on which the partition walls are formed are not particularly limited and are appropriately selected depending on the application. When the substrate is plate-shaped, it may be flat, or may have a curvature entirely or partially. The thickness of the substrate can be appropriately selected depending on the application of the partition walls, and is generally preferably 0.5 to 10 mm.

[0142] It is preferable that the surface of the substrate to be coated with the resist composition is cleaned in advance by alcohol cleaning, ultraviolet / ozone cleaning, or the like.

[0143] <Method for manufacturing optical element> The optical element of the present invention can be obtained by forming partition walls on a substrate by the above-described manufacturing method, and then, for example, subjecting the exposed surface of the substrate in a region surrounded by the substrate and the partition walls to an ink-philic treatment (ink-philic treatment step), and then injecting ink into the region by an inkjet method to form the pixels (ink injection step).

[0144] <<Ink-Friendly Treatment Step>> The method of the ink-friendliness treatment is not particularly limited, and examples thereof include cleaning treatment with an alkaline aqueous solution, ultraviolet cleaning treatment, ultraviolet / ozone cleaning treatment, excimer cleaning treatment, corona discharge treatment, and oxygen plasma treatment. These may be used alone or in combination of two or more. The alkaline aqueous solution cleaning treatment is a wet treatment in which the substrate surface is cleaned using an alkaline aqueous solution (potassium hydroxide, tetramethylammonium hydroxide aqueous solution, etc.). The ultraviolet cleaning treatment is a dry treatment in which the substrate surface is cleaned using ultraviolet rays. The ultraviolet / ozone cleaning treatment is a dry treatment in which the substrate surface is cleaned using a low-pressure mercury lamp emitting light at 185 nm and 254 nm. The excimer cleaning treatment is a dry treatment in which the substrate surface is cleaned using a xenon excimer lamp emitting light at 172 nm. The corona discharge treatment is a dry treatment in which a corona discharge is generated in the air using high-frequency high voltage to clean the substrate surface. Oxygen plasma treatment is a dry process that mainly takes place in a vacuum, where oxygen is excited using a high-frequency power source or the like as a trigger, and then a highly reactive "plasma state" is created using the oxygen to clean the substrate surface.

[0145] Among these, dry treatment methods such as ultraviolet / ozone cleaning treatment are preferred from the viewpoint of simplicity. Ultraviolet / ozone can be generated using a commercially available device. The substrate on which the partition walls are formed is placed inside the ultraviolet / ozone device, and the treatment is carried out in air at room temperature for about 1 to 10 minutes within a range that does not impair the ink repellency of the partition walls, thereby making the substrate ink-philic. The treatment time may be adjusted to suit the individual ultraviolet / ozone device so as to be within a range that does not impair the ink repellency of the partition walls.

[0146] By performing the ink affinity treatment, development residue remaining on the dots can be sufficiently removed after the formation of the partition walls, thereby making it possible to sufficiently impart ink affinity to the dots, and to prevent the white void phenomenon in color display devices and the like using the obtained optical element.

[0147] The ink repellency of a cured film formed from a resist composition according to an embodiment of the present invention can be evaluated by the contact angle with a liquid such as water, hexadecane, or PGMEA (propylene glycol monomethyl ether acetate). More specifically, the ink repellency can be evaluated by the static contact angle. When an optical element is manufactured using a substrate having partition walls, the upper surface of the partition walls is required to have sufficient ink repellency even after the ink-affinity treatment. Furthermore, the static contact angle of the partition walls with hexadecane is preferably 30 degrees or more, and particularly preferably 35 degrees or more.

[0148] <<Ink Injection Step>> This is a step of forming pixels by injecting ink into the dots obtained after the ink affinity treatment step using an inkjet method. This step can be carried out in the same manner as a normal method using an inkjet device commonly used in inkjet methods. The inkjet device used to form such pixels is not particularly limited, and inkjet devices using various methods can be used, such as a method of continuously ejecting charged ink and controlling it with a magnetic field, a method of intermittently ejecting ink using a piezoelectric element, or a method of heating ink and ejecting it intermittently by utilizing the resulting bubble.

[0149] <Organic EL element> The organic EL element has a plurality of pixels and partition walls located between adjacent pixels on a substrate, the partition walls being formed from the resist composition of the present invention, and the pixels being formed by an inkjet method.

[0150] <<Manufacturing of Organic EL Devices>> Before forming partition walls using the resist composition of the present invention, a transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by sputtering or the like, and the transparent electrode is etched into a desired pattern as needed. Next, partition walls (cured product) are formed using the resist composition of the present invention, and the dots are treated to be ink-philic. Then, solutions of a hole transport material and a light-emitting material are sequentially applied to the dots by an inkjet method, and the dots are dried to form a hole transport layer and a light-emitting layer. Thereafter, electrodes such as aluminum are formed by vapor deposition or the like, thereby obtaining pixels of an organic EL device.

[0151] <Color filter> The color filter has a plurality of pixels on a substrate and partition walls located between adjacent pixels, the partition walls being formed from the resist composition of the present invention, and the pixels being formed by an inkjet method. In the color filter, the partition walls are preferably black matrices having an optical density of about 2 to 7.

[0152] <<Manufacturing of Color Filters>> As described above, a color filter can be manufactured by forming partition walls (e.g., a black matrix) on a substrate, and then applying ink to the openings of the partition walls using an inkjet method to form pixels. The formation of the partition walls, the ink-philic treatment of the dots, and the ink injection using the inkjet method are as described above. The shape of the pixels formed in the color filter can be any known arrangement, such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type.

[0153] The ink used to form pixels mainly contains a coloring component, a binder resin component, and a solvent, and may be either an aqueous ink or an oil-based ink. As the coloring component, it is preferable to use a pigment or dye that has excellent heat resistance, light resistance, etc. As the binder resin component, a transparent resin that has excellent heat resistance is preferable, and examples thereof include acrylic resin, melamine resin, and urethane resin. These may be used alone or in combination of two or more. An aqueous ink contains water as a solvent and, if necessary, a water-soluble organic solvent, and as a binder resin component, a water-soluble resin and / or a water-dispersible resin, and, if necessary, various auxiliary agents. An oil-based ink contains an organic solvent as a solvent and, as a binder resin component, a resin soluble in the organic solvent, and, if necessary, various auxiliary agents. After the ink is injected by the inkjet method, it is preferable to dry, heat-cure, and / or UV-cure as necessary.

[0154] After forming pixels in the openings of the partition walls, a protective film can be formed, if necessary, using an overcoat coating liquid. This improves the surface smoothness of the color filter and prevents eluates from the partition walls and pixels from reaching the liquid crystal layer adjacent to the protective film. In this case, it is preferable to remove the liquid repellency (oil repellency) of the upper surfaces of the partition walls before forming the protective film. This prevents the upper surfaces of the partition walls from repelling the coating liquid for the protective film. There are no particular limitations on the method for removing the liquid repellency (oil repellency) of the upper surfaces of the partition walls, and examples of such methods include plasma ashing and light ashing. Furthermore, to improve the quality of liquid crystal panels manufactured using color filters, photospacers may be formed on the partition walls (e.g., black matrix) if necessary.

[0155] <Manufacturing an Organic TFT Array> An organic TFT array can be manufactured through the following steps (1) to (3). (1) A partition wall is formed on a transparent substrate such as glass using the resist composition of the present invention. Next, the dots are treated to be ink-philic, and then a solution of a gate electrode material is applied to the dots using an inkjet method to form gate electrodes. (2) After the gate electrode is formed, a gate insulating film is formed thereon. Next, a partition wall is formed on the gate insulating film using the positive resist composition of the present invention. After the dots are treated to be ink-philic, a solution of a source / drain electrode material is applied to the dots using an inkjet method to form source / drain electrodes. (3) After the source / drain electrodes are formed, a partition wall is formed using the resist composition of the present invention so as to surround a region including a pair of source / drain electrodes. Next, the dots are treated to be ink-philic, and then a solution of an organic semiconductor is applied to the dots using an inkjet method to form an organic semiconductor layer between the source / drain electrodes. In each of steps (1) to (3), a partition wall using the resist composition of the present invention may be formed and used in only one step, or a partition wall using the resist composition of the present invention may be formed and used in two or more steps.

[0156] The present invention will be specifically described below based on examples, but the present invention is not limited to the following examples, and various modifications are possible within the scope of the gist of the present invention.

[0157] [CF ３ -C ２２ H ４４ -OC(=O)-CH=CH ２ Synthesis of Intermediate 1] <Synthesis of Intermediate 1> 1,20-eicosanediol (5.01 g, 15.93 mmol) and DMF (30.04 g, 25.81 mmol) were placed in a nitrogen-purged 50 mL three-neck flask and heated to 70°C, after which pyridine (2.55 g, 32.20 mmol) was added. After a homogeneous solution was obtained, trityl chloride (4.45 g, 16.00 mmol) was added and the mixture was stirred at 70°C for 2 hours. After completion of the reaction, the reaction solution was returned to room temperature and poured into water (200 mL) to precipitate a solid, which was then collected by filtration. Acetone (100 mL) and ethyl acetate (100 mL) were added to the collected solid, and the mixture was stirred and filtered to obtain filtrate A. The obtained filtrate A was concentrated under reduced pressure, and hexane (100 mL) was added, followed by filtering again to obtain filtrate B. The obtained filtrate B was concentrated under reduced pressure to obtain a crude product of Intermediate 1. The crude product was purified by silica gel column chromatography (hexane:ethyl acetate=5:1 (mass ratio)) to obtain intermediate 1 (4.17 g, 47% yield). １ H NMR (CDCl ３ , 400MHz) δ, 7.45 to 7.49 (6H, m), 7.29 to 7.34 (6H, m), 7.22 to 7.27 (3H, m), 3.61 to 3.71 (2H, t), 3.03 to 3.09 (2H, t), 1.20 to 1.70 (36H, m)

[0158]

[0159] <Synthesis of Intermediate 2> Intermediate 1 (4.17 g, 7.49 mmol), toluene (13.02 g, 141.3 mmol), 4-dimethylaminopyridine (1.32 g, 10.8 mmol), and tosyl chloride (1.78 g, 9.15 mmol) were placed in a nitrogen-purged 100 mL recovery flask and stirred at 90°C for 18 hours. After completion of the reaction, the reaction solution was returned to room temperature and subjected to suction filtration, and the obtained filtrate was concentrated under reduced pressure to obtain a crude product of Intermediate 2. The crude product was purified by silica gel column chromatography (hexane:ethyl acetate=10:1 (mass ratio)) to obtain Intermediate 2 (3.40 g, 78.9% yield). １ H NMR (CDCl ３ , 400MHz) δ, 7.41 to 7.47 (6H, m), 7.26 to 7.32 (6H, m), 7.19 to 7.24 (3H, m), 3.49 to 3.55 (2 H, t), 3.00-3.06 (2H, t), 1.71-1.80 (2H, q), 1.56-1.66 (2H, q), 1.21-1.47 (32H, m)

[0160]

[0161] <Synthesis of Intermediate 3> Intermediate 2 (56.05 g, 97.43 mmol), magnesium (3.60 g, 148 mmol), and tetrahydrofuran (50 mL, 614 mmol) were placed in a nitrogen-purged 1000 mL four-necked recovery flask and heated under reflux with stirring. Dibromoethane (0.4 mL, 5 mmol) was then added and the mixture was heated under reflux with stirring for 3 hours. After the reaction was completed, tetrahydrofuran (50 mL, 614 mmol) was added and the mixture was returned to room temperature to obtain reaction solution A. Separately, copper(I) bromide (1.43 g, 9.97 mmol), 1,1,1-trifluoro-3-iodopropane (27.56 g, 116.9 mmol), and tetrahydrofuran (250 mL, 3070 mmol) were placed in a nitrogen-purged 1000 mL four-necked recovery flask and stirred. The mixture was then cooled to -10 °C to obtain reaction solution B. Reaction Solution A was added dropwise to Reaction Solution B over 1.5 hours using a cannula. After the addition of Reaction Solution A was completed, the solution was gradually warmed to room temperature and stirred for 18 hours. After the reaction was completed, the reaction mixture was quenched by adding an aqueous ammonium chloride solution (300 mL), and the organic layer was concentrated by liquid separation with ethyl acetate (300 mL). Hexane was added to the concentrated organic layer, and the mixture was filtered through Celite. The filtrate was concentrated under reduced pressure to obtain a crude product of Intermediate 3. The crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 20:1 (mass ratio)) to obtain a mixture of Intermediate 3 (45.91 g, 73.99% yield). １ H NMR (CDCl ３ , 400MHz) δ7.44-7.50 (6H, m), 7.29-7.34 (6H, m), 7.22-7.27 (3H, m), 3.04-3.09 (2 H, t), 2.01 to 2.15 (2H, m) 1.80 to 1.89 (2H, q), 1.60 to 1.68 (2H, q), 1.21 to 1.47 (36H, m)

[0162]

[0163] <Synthesis of Intermediate 4> Intermediate 3 (34.21 g, 53.71 mmol), methanol (50 mL, 1240 mmol), dichloromethane (100 mL, 1560 mmol), and p-toluenesulfonic acid monohydrate (2.53 g, 14.7 mmol) were placed in a 300 mL recovery flask and stirred at room temperature for 18 hours. After the reaction was completed, triethylamine (16.10 g, 159.1 mmol) was added and the mixture was concentrated under reduced pressure to obtain a crude product of Intermediate 4. The crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 5:1 (mass ratio)) to obtain Intermediate 4 (2.54 g, 8.93% yield). １ H NMR (CDCl ３ , 400MHz) δ 3.62 to 3.71 (2H, t), 2.00 to 2.15 (2H, m), 1.52 to 1.62 (2H, m), 1.24 to 1.42 (38H, m)

[0164]

[0165] <CF ３ -C ２２ H ４４ -OC(=O)-CH=CH ２ Synthesis of Intermediate 4 (2.54 g, 6.44 mmol), chloroform (21 g, 175.12 mmol), 4-dimethylaminopyridine (0.095 g, 0.78 mmol), and triethylamine (1.08 g, 10.00 mmol) were placed in a 200 mL recovery flask, stirred, and cooled to 10°C. After cooling, acrylic chloride (0.8 mL, 10.07 mmol) was added, and the mixture was stirred for 1 hour while returning to room temperature. After completion of the reaction, saturated aqueous sodium bicarbonate (30 mL) was added, and the mixture was separated with chloroform. The organic layer was concentrated to obtain a crude product of the target product. The crude product of the target product was purified by silica gel column chromatography (hexane:ethyl acetate=10:1 (mass ratio)) and CF ３ -C ２２ H ４４ -OC(=O)-CH=CH ２ (1.21 g, 42.1% yield). １ H NMR (CDCl ３, 400MHz) δ6.34-6.44 (1H, d), 6.08-6.16 (1H, m), 5.79-5.83 (1H, d), 4.12-4.19 (2 H, t), 1.98-2.12 (2H, m), 1.61-1.71 (2H, m), 1.49-1.59 (2H, m), 1.20-1.46 (36H, m)

[0166]

[0167] [CF ３ -C １８ H ３６ -OC(=O)-CH=CH ２ Synthesis of ３ -C １８ H ３６ Synthesis of —OH> ３ -C ２２ H ４４ -OC(=O)-CH=CH ２ In the synthesis of intermediates 1 to 4, 1,16-hexadecanediol was used instead of 1,20-eicosanediol, and the synthesis was carried out in the same manner to obtain CF ３ -C １８ H ３６ It should be noted that this compound can also be synthesized by known methods such as those disclosed in Chem. Mater. 2015, 27, 7433-7446.

[0168] [CF ３ -C １８ H ３６ -OC(=O)-CH=CH ２ Synthesis of Intermediate 4 (6.00 g, 17.8 mmol), chloroform (53.4 g, 448.7 mmol), 4-dimethylaminopyridine (0.22 g, 1.82 mmol), and triethylamine (2.69 g, 27.0 mmol) were placed in a 300 mL recovery flask, stirred, and cooled to 10°C. After cooling, acrylic chloride (2.16 mL, 27.0 mmol) was added, and the mixture was stirred for 1 hour while returning to room temperature. After completion of the reaction, saturated aqueous sodium bicarbonate (70 mL) was added, and the mixture was separated with chloroform. The organic layer was concentrated to obtain a crude product of the target product. The crude product of the target product was purified by silica gel column chromatography (hexane:ethyl acetate=10:1 (mass ratio)) and purified by CF ３-C １８ H ３６ -OC(=O)-CH=CH ２ (4.53 g, 64.9% yield). １ H NMR (CDCl ３ , 400MHz) δ6.34-6.44 (1H, d), 6.08-6.16 (1H, m), 5.79-5.83 (1H, d), 4.12-4.19 (2 H, t), 1.98-2.12 (2H, m), 1.61-1.71 (2H, m), 1.49-1.59 (2H, m), 1.20-1.46 (28H, m)

[0169]

[0170] [Preparation of Polymer (A1)] A polymer synthesized by the following method was used. Each raw material (unit: g) shown in Table 1 was polymerized at 50°C for 24 hours while stirring under a nitrogen atmosphere. In Table 1, "DBTDL" means "dibutyltin dilaurate," "BHT" means "butylhydroxytoluene," "TBQ" means "t-butyl-p-benzoquinone," "MEK" means "methyl ethyl ketone," "Karenz AOI" means "2-isocyanatoethyl acrylate," and "V-65" means "2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)." The polymer was reprecipitated using methanol, filtered, and then dried to obtain Polymer (A1). The polymer was then diluted with butyl acetate to obtain a butyl acetate solution of Polymer (A1) (Polymer (A1) concentration: 10% by mass; hereinafter also referred to as "Polymer (A1) solution").

[0171] [Preparation of Polymers (A2) to (A5) and Polymers (A7) to (A12)] Polymers (A2) to (A5) and polymers (A7) to (A12) were obtained using the same procedure as for polymer (A1), except that the raw materials and blending amounts were changed as shown in Table 1. These were then diluted with butyl acetate to obtain butyl acetate solutions of polymers (A2) to (A5) and polymers (A7) to (A12) (polymer (A2) to (A5) and polymers (A7) to (A12) concentration: 10 mass%; hereinafter also referred to as "polymer (A2) to (A5) solutions and polymer (A7) to (A12) solutions").

[0172] [Preparation of Polymer (A6)] Of the raw materials (unit: g) shown in Table 1, C １８ H ３７ While stirring under a nitrogen atmosphere, hydroxyethyl acrylate, hydroxyethyl acrylate, V-65, and MEK were polymerized at 50°C for 24 hours. Then, the mixture was stirred at 70°C for 5 hours to decompose the V-65. After returning this solution to room temperature, Karenz AOI, DBTDL, BHT, and TBQ were added as shown in Table 1, and the temperature was raised to 40°C. The mixture was stirred for 24 hours to react Karenz AOI with the hydroxy group derived from hydroxyethyl acrylate. The polymer was reprecipitated using methanol, filtered, and then dried to obtain polymer (A6). The polymer was then diluted with butyl acetate to obtain a butyl acetate solution of polymer (A6) (polymer (A6) concentration: 10% by mass; hereinafter, also referred to as "polymer (A6) solution").

[0173] [Preparation of Polymer (A13)] Each raw material (unit: g) shown in Table 1 was polymerized at 50°C for 24 hours while stirring under a nitrogen atmosphere. After polymerization, the polymerization solution was concentrated and vacuum dried to obtain Polymer (A13). Thereafter, the solution was diluted with butyl acetate to obtain a butyl acetate solution of Polymer (A13) (Polymer (A13) concentration: 10 mass%; hereinafter also referred to as "Polymer (A13) solution").

[0174] [Alkali-soluble materials (B)] B1: Resin in which a carboxy group and an ethylenic double bond have been introduced into a bisphenol A type epoxy resin. Solid content 68% by mass, acid value 100 mg KOH / g B2: Resin in which a carboxy group and an ethylenic double bond have been introduced into a bisphenol A type epoxy resin. Solid content 68% by mass, acid value 30 mg KOH / g B3: Resin in which a carboxy group and an ethylenic double bond have been introduced into a biphenol type epoxy resin. Solid content 68% by mass, acid value 60 mg KOH / g B4: Copolymer of N-phenylmaleimide, benzyl methacrylate, and acrylic acid (Mw 6,200, solid content 20% by mass)

[0175] [Solvent (C)] EDEGAC: diethylene glycol monoethyl ether acetate (boiling point 217°C) PGME: propylene glycol monomethyl ether (boiling point 120°C) PGMEA: propylene glycol monomethyl ether acetate (boiling point 146°C)

[0176] [Photosensitizer (D)] D1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one D2: EAB: 4,4'-bis(diethylamino)benzophenone D3: OXE02: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone O-acetyloxime D4: ((mono to tetra)esters of 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-α,α-dimethylbenzyl}phenol and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid)

[0177] [Crosslinking agent (E)] E1: a 70:30 mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, E2: tris-(2-acryloxyethyl) isocyanurate, E3: 2-[4-(2,3-epoxypropoxy)phenyl-2-[4-[1,1-bis[4-[2,3-epoxypropoxy]phenyl]ethyl]phenyl]propane]

[0178] [Examples 1 to 17: Preparation of resist compositions] Resist compositions were prepared by stirring (for about 30 minutes) the raw materials in the proportions shown in Table 2 until they were homogeneous. Each of the prepared resist compositions was evaluated using the methods described below. Examples 1 to 14 are working examples, and Examples 15 to 17 are comparative examples.

[0179] [Measurement Conditions and Evaluation Conditions] <Mass Average Molecular Weight (Mw) of Polymer (A)> Gel permeation chromatography (GPC) spectra of several monodisperse PMMAs with different degrees of polymerization, commercially available as standard samples for molecular weight measurement, were measured using a commercially available GPC measurement device (manufactured by Tosoh Corporation, device name: HLC-8320GPC) with a differential refractive index detector, and a calibration curve was created based on the relationship between the molecular weight of PMMA and retention time. The sample was diluted to 1.0% by mass with tetrahydrofuran and passed through a 0.5 μm filter, after which the GPC spectrum of the sample was measured using the differential refractive index detector on the GPC measurement device. The mass average molecular weight (Mw) of the sample was determined using the calibration curve by computer analysis of the GPC spectrum of the sample. The results are shown in Table 1.

[0180] <Melting Point of Polymer (A)> Using a Photo-DSC 204 F1 Phoenix manufactured by NETZSCH, the melting point of each polymer (A) was measured as follows. 8 mg of polymer (A) was placed in an aluminum pan and placed in the sample holder of a differential scanning calorimeter. Under a nitrogen atmosphere, the following procedure was repeated twice: "Hold at -50°C for 2 minutes, then heat to 230°C at a heating rate of 10°C / min, hold at 230°C for 2 minutes, and then cool to -50°C at a heating rate of 10°C / min." The melting peak was determined from the DSC curve during the second heating run, and the peak end, i.e., the temperature at which the polymer (A) was completely melted, was recorded in Table 1 as the "polymer melting point (°C)." A peak with a heat of fusion of 20.0 J / g or more was considered to be a melting peak.

[0181] <Preparation of Evaluation Samples> Evaluation samples were prepared by forming cured films on glass substrates using the resist compositions listed in Table 2. The evaluation samples were prepared using the following Preparation Method 1 or Preparation Method 2 as listed in Table 2.

[0182] (Preparation Method 1) (1) A glass substrate (manufactured by AGC, dimensions 75 mm x 75 mm x 0.7 mm) was subjected to ultrasonic cleaning in ethanol (for 30 seconds). Next, ultraviolet / ozone cleaning (apparatus: PL7-200 manufactured by Sen Engineering Co., Ltd.) was performed for 5 minutes. After the cleaning, a resist composition was spin-coated (for 10 seconds at a rotation speed of 280 rpm) using a spinner (IH-DX2 manufactured by Mikasa Co., Ltd.) onto the surface of the glass substrate. Next, the substrate was dried on a hot plate (for 2 minutes at 100°C) to form a coating film with a thickness of 1.5 μm. (2) The surface of the coating film was exposed under the following conditions. Lamp and irradiation conditions: The entire surface was irradiated with UV light from an ultra-high pressure mercury lamp. Light of 330 nm or less was blocked, and the exposure dose was 40 mJ / cm. ２ (3) The substrate was heated on a hot plate (at 230° C. for 30 minutes) to prepare a glass substrate on which the entire surface of the coating film was cured.

[0183] (Preparation Method 2) (1) A coating film having a thickness of 1.5 μm was formed in the same manner as in (Preparation Method 1) (1). (2) The substrate was heated on a hot plate (at 230° C. for 30 minutes) to prepare a glass substrate on which the entire coating film was cured.

[0184] <Oil repellency (against hexadecane)> Using the prepared evaluation samples, the contact angle (static contact angle) of the substrate surface with hexadecane was measured by the θ / 2 method. The larger the contact angle, the better the oil repellency. The evaluation criteria are shown below. The evaluation results are shown in Table 2. A: 40° or more B: 35° or more and less than 40° C: 25° or more and less than 35° D: Less than 25°

[0185]

[0186]

[0187] As can be seen from the results shown in Tables 1 and 2, Examples 1 to 14, which used resist compositions containing a predetermined polymer (A), alkali-soluble resin (B), solvent (C), and photosensitizer (D), were able to form cured films with excellent oil repellency compared to Examples 15 to 17. Furthermore, Examples 13 and 14 were superior in terms of oil repellency to the other Examples (Examples 1 to 12). This is because the polymers (A) (A9 and A10) had trifluoromethyl groups at the ends of their long-chain alkyl side chains.

Claims

1. A resist composition comprising: a polymer (A) having a repeating unit of a monomer represented by the following formula (1) and having a melting point of 20°C or higher; an alkali-soluble resin (B); a solvent (C); and a photosensitizer (D): R-L-X-P...(1) [In the formula (1), R is (i) a hydrogen atom, or (ii) a monovalent organic group having 0 to 3 carbon atoms and containing a heteroatom, the linking point to L being a heteroatom or a carbon atom directly bonded to a heteroatom, L is a divalent organic group having 14 to 40 carbon atoms, X is a single bond or a divalent organic group having 0 to 4 carbon atoms and containing a heteroatom, and P is a monovalent polymerizable group.] 2. The resist composition according to claim 1, wherein said L is a divalent, linear, saturated hydrocarbon group.

3. The resist composition according to claim 1, wherein L is a divalent organic group having 16 to 24 carbon atoms.

4. The resist composition according to claim 1, wherein P is a (meth)acryloyl group or a group represented by the following formula (A): ...(A) [In the formula (A), S １ ~S ５ Any one of the above is a single bond that bonds to *, and the above non-single bond S １ ~S ５ are each independently a hydrogen atom, a halogen atom, or an optionally halogenated alkyl group having 1 to 4 carbon atoms, and ** is the bond to X.

5. The resist composition according to claim 4, wherein P is a (meth)acryloyl group.

6. The resist composition according to claim 1, wherein R is (i) a hydrogen atom, or (ii) a monovalent organic group having one carbon atom and a heteroatom, and the linking point with L is a heteroatom or a carbon atom directly bonded to a heteroatom.

7. The resist composition according to claim 1, wherein the polymer (A) is a copolymer further having a repeating unit of another monomer represented by the following formula (2): R1-P1... (2) [In the formula (2), R1 is a monovalent organic group having 0 to 13 carbon atoms which may have a heteroatom, and P1 is a monovalent polymerizable group.] 8. The resist composition according to claim 7, wherein the polymer (A) has a copolymerization ratio of the repeating unit of the monomer represented by formula (1) to the repeating unit of the other monomer represented by formula (2) of 99:1 to 50:50 in mass ratio.

9. A resist film comprising a cured product containing the polymer (A) according to any one of claims 1 to 8.

10. An optical element having a substrate, a plurality of pixels formed on the surface of said substrate, and partition walls located between adjacent pixels, wherein said partition walls are a resist film made of a cured product containing the polymer (A) described in any one of claims 1 to 8.

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