Compound, polymer, resist composition, resist film, and optical element

Abstract

Provided are: a compound capable of forming a cured film having good post-development liquid repellency (development resistance and liquid repellency) and coating film uniformity; a polymer containing a structural unit based on the compound; a resist composition containing at least one selected from the group consisting of the compound and the polymer; a resist film comprising a cured product containing a fluorine-containing component (A) that is at least one selected from the group consisting of the compound and the polymer; and an optical element having a partition wall that is the resist film. The present invention provides a compound represented by formula (A1). (EA1-)n1QA-NRaC(=O)-Rf-C(=O)NRb-QB(-EB1)n2 … (A1)

Description

Compound, polymer, resist composition, resist film, and optical element

[0001] The present invention relates to a compound, a polymer, a resist composition, a resist film, and an optical element, and in particular to a compound capable of forming a cured film that exhibits excellent liquid repellency after development (development resistance and liquid repellency) and coating uniformity, a polymer containing a structural unit based on the compound, a resist composition containing at least one compound selected from the group consisting of the compound and the polymer, a resist film made of a cured product containing a fluorine-containing component (A) that is at least one compound selected from the group consisting of the compound and the polymer, and an optical element having partition walls that are the resist film.

[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] In order to prevent color mixing between adjacent pixels of such color filters or organic EL elements, the upper surfaces of the partition walls must have ink-repellent properties, i.e., liquid repellency. Furthermore, the partition walls must have development resistance, i.e., properties that prevent the liquid repellency of the bank portions from decreasing even after a development process in which unnecessary portions are washed away with a solvent after exposure during pattern formation. Note that an alkaline aqueous solution is mainly used in the development process (hereinafter, the term "development" will be understood to mean "development with an alkaline aqueous solution").

[0004] Under these circumstances, compositions have been developed that contain a fluoropolyether group-containing compound, which can provide a low-haze film while maintaining liquid repellency and other properties (see, for example, Patent Document 1), and compositions that contain a fluorine-containing siloxane acrylate having a perfluoropolyether group, which has good compatibility with non-fluorine-based solvents and a low refractive index (see, for example, Patent Document 2).

[0005] International Publication No. WO 2022 / 270442 International Publication No. WO 2021 / 044639

[0006] However, it cannot be said that the fluorine compounds and compositions described in Patent Documents 1 and 2 are necessarily sufficient to form a cured film having good liquid repellency after development (development resistance and liquid repellency) and good coating uniformity.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a compound capable of forming a cured film that exhibits good liquid repellency after development (development resistance and liquid repellency) and coating uniformity; a polymer containing a structural unit based on the compound; a resist composition containing at least one member selected from the group consisting of the compound and the polymer; a resist film consisting of a cured product containing a fluorine-containing component (A) that is at least one member selected from the group consisting of the compound and the polymer; and an optical element having partition walls that are the resist film.

[0008] The present invention is based on the discovery that by using a resist composition containing a fluorine-containing component (A), which is at least one selected from the group consisting of specific fluorine-containing compounds and fluorine-containing polymers having a linking group with an amide bond, an alkali-soluble resin (B), a solvent (C), and a photosensitizer (D), it is possible to form a cured film with good liquid repellency (development resistance and liquid repellency) and coating uniformity after development. The linking group closest to the fluorine-containing group, such as perfluoropolyether, is inherently susceptible to hydrolysis under basic conditions due to the high electronegativity of the fluorine atom, so resist compositions using fluorine-containing components having fluorine-containing groups, such as perfluoropolyether, have low development resistance. Therefore, in the present invention, development resistance is improved by using an amide bond, which has high hydrolysis resistance, as the linking group. Furthermore, compounds having fluorine-containing groups, such as perfluoropolyethers, have low compatibility with other resins and solvents, so resist compositions using compounds having fluorine-containing groups, such as perfluoropolyethers, have poor uniformity when applied. Therefore, in the present invention, two or more highly polar bonds (in the present invention, this corresponds to an amide bond) are used as linking groups, thereby improving compatibility with other components and improving uniformity during coating.

[0009] The present invention provides the following means: [1] A compound represented by the following formula (A1): (E Ａ１ -) ｎ１ Q Ａ -NR ａ C(=O)-R ｆ -C(=O)NR ｂ -Q Ｂ (-E Ｂ１ ) ｎ２ ...(A1) (In the formula (A1), E Ａ１ represents a (meth)acryloyloxy group, a (meth)acrylamide group, or a group represented by any one of the following formulae (X1) to (X3), E Ａ１ When there are two or more, they may be the same or different, and n1 is Q Ａ E bound to Ａ１ represents the number of, and is an integer from 1 to 4; Ａrepresents a divalent to pentavalent group, and is (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of the saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) are substituted with a hydroxy group, ａ Is E Ｂ１ or a hydrogen atom, R ｆ has a number average molecular weight of 1,000 to 50,000, has one or more etheric oxygen atoms inserted between the carbon-carbon bonds of the fluoroalkylene group, and has two bond ends each independently represented by -CX １ X ２ - (where X １ represents a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms which may contain one or more etheric oxygen atoms, and X ２ represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 4 carbon atoms which may contain one or more etheric oxygen atoms; R ｂ Is E Ｂ１ or a hydrogen atom, Ｂ represents a divalent to pentavalent group, and is (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of the saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) are substituted with a hydroxy group, Ｂ１ Is E Ａ１ or an alkyl group having 1 to 15 carbon atoms; E Ｂ１ When there are two or more, they may be the same or different, and n2 is Q Ｂ E bound to Ｂ１ represents the number of , which is an integer from 1 to 4.) (In the formulas (X1) to (X3), S １ ~S ４are each independently a hydrogen atom, a halogen atom, or an optionally halogenated alkyl group having 1 to 4 carbon atoms. Ａ１ and E Ｂ１ are each independently a group represented by the following formula (C): ｃ =CH ２ ...(C) (wherein R ｃ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a halogen atom.) [3] R ｆ The compound according to the above [1] or [2], wherein R has a number average molecular weight of 1,000 to 50,000 and represents a group represented by the following formula (D): ｆ１ O-[(R ｆ２ O) ｍ１ (R ｆ３ O) ｍ２ (R ｆ４ O) ｍ３ (R ｆ５ O) ｍ４ ]-R ｆ６ - (D) (wherein, R ｆ１ and R ｆ６ each independently represents a fluoroalkylene group having 1 to 6 carbon atoms; R ｆ２ represents a fluoromethylene group; R ｆ３ represents a fluoroethylene group; R ｆ４ represents a fluoroalkylene group having 3 carbon atoms; R ｆ５ represents a fluoroalkylene group having 4 carbon atoms, and m1, m2, m3, and m4 each independently represent 0 or an integer of 1 or more.) [4] (E Ａ１ -) ｎ１ Q Ａ , Q Ｂ (-E Ｂ１ ) ｎ２ , R ａ , and R ｂ [5] The compound according to any one of the above [1] to [3], wherein R each independently has a molecular weight of 450 or less. ａ and R ｂare each independently a hydrogen atom. [6] A polymer comprising, as repeating units, a structural unit based on the compound according to any one of [1] to [5] above, and a structural unit based on a monomer represented by the following formula (B1) or a structural unit based on a monomer represented by the following formula (B2): (E Ａ２ -) ｅ Q Ｙ ...(B1) (In the formula (B1), E Ａ２ represents a (meth)acryloyloxy group or a (meth)acrylamide group, E Ａ２ When there are two or more, they may be the same or different, and e is Q Ｙ E bound to Ａ２ represents the number of, and is an integer from 1 to 4; Ｙ represents (I) a hydrogen atom, or (II) a group that does not contain a monovalent to tetravalent fluorine atom and is (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to carbon atoms of the group (i) or (ii) are substituted with a hydroxy group or a carboxyl group. (In the above formula (B2), S ５ ~S ９are each independently (I) a hydrogen atom, (II) a halogen atom, (III) a hydroxy group, (IV) a carboxyl group, (V) an amino group, or (VI) a group that does not contain a monovalent to tetravalent fluorine atom, and is also (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bond of a saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) are substituted with a hydroxy group or a carboxyl group.) [7] A resist composition comprising a fluorine-containing component (A), an alkali-soluble resin (B), a solvent (C), and a photosensitizer (D), wherein the fluorine-containing component (A) is at least one selected from the group consisting of the compound according to any one of items [1] to [5] above, and the polymer according to item [6] above. [8] A resist film comprising a cured product containing a fluorine-containing component (A) which is at least one selected from the group consisting of the compound according to any one of [1] to [5] above and the polymer according to [6] above. [9] 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 the resist film according to [8] above.

[0010] The present invention provides a compound capable of forming a cured film that exhibits excellent liquid repellency after development (development resistance and liquid repellency) and coating uniformity; a polymer containing a structural unit based on the compound; a resist composition containing at least one member selected from the group consisting of the compound and the polymer; a resist film comprising a cured product containing a fluorine-containing component (A) that is at least one member selected from the group consisting of the compound and the polymer; and an optical element having partition walls that are the resist film.

[0011] FIG. 2 shows film thickness measurement points in a sample used to evaluate the in-plane film thickness uniformity of a cured film formed from a resist composition of the present invention in the examples.

[0012] 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, "structural unit" 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, a "structural unit based on a monomer" will also be referred to simply as a "structural unit" or a "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, a numerical range expressed as "X to Y" means "X or more and Y or less." In this specification, "(meth)acryloyl" is a collective term meaning both acryloyl and methacryloyl, "(meth)acrylate" is a collective term meaning both acrylate and methacrylate, and "(meth)acrylamide" is a collective term meaning both acrylamide and methacrylamide. As used herein, the term "halogen atom" refers to any of an iodine atom, a bromine atom, a chlorine atom, and a fluorine atom. As used herein, the term "solid content" refers to the non-volatile content excluding volatile substances such as solvents, and refers to components that remain without volatilization when the resist composition is dried, including those that are liquid, syrup-like, or waxy at room temperature. The total solid content can also be calculated from the charge amount. As used herein, the term "mass average molecular weight (Mw)" refers to the mass average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as the mobile phase, converted relative to standard polymethyl methacrylate (PMMA). This value is used as an index of the molecular weight of a polymer or resin. As used herein, the term "number average molecular weight (Mn)" refers to the number average molecular weight (Mn) calculated by determining the number (average value) of fluorinated alkylene groups based on the terminal groups using 1H-NMR and 19F-NMR. The term "side chain" refers to a group other than a hydrogen atom or a halogen atom that is bonded to a carbon atom that constitutes the main chain of a polymer in which repeating units made of carbon atoms constitute the main chain.

[0013] [Compound] The compound of the present invention is represented by the following formula (A1): (E Ａ１ -) ｎ１ Q Ａ -NR ａ C(=O)-R ｆ -C(=O)NR ｂ -Q Ｂ (-E Ｂ１ ) ｎ２ ...(A1) (In the formula (A1), E Ａ１ represents a (meth)acryloyloxy group, a (meth)acrylamide group, or a group represented by any one of the following formulae (X1) to (X3), E Ａ１ When there are two or more, they may be the same or different, and n1 is Q Ａ E bound to Ａ１ represents the number of, and is an integer from 1 to 4; Ａ represents a divalent to pentavalent group, and is (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of the saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) are substituted with a hydroxy group, ａ Is, Q Ｂ (-E Ｂ１ ) ｎ２ (However, Q Ｂ is bonded to a nitrogen atom), E Ｂ１ or a hydrogen atom, R ｆ has a number average molecular weight of 1,000 to 50,000, has one or more etheric oxygen atoms inserted between the carbon-carbon bonds of the fluoroalkylene group, and has two bond ends each independently represented by -CX １ X ２ - (where X １ represents a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms which may contain one or more etheric oxygen atoms, and X ２ represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 4 carbon atoms which may contain one or more etheric oxygen atoms; R ｂ Is, Q Ｂ(-E Ｂ１ ) ｎ２ (However, Q Ｂ is bonded to a nitrogen atom), E Ｂ１ or a hydrogen atom; Ｂ represents a divalent to pentavalent group, and is (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of the saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to carbon atoms of the group (i) or (ii) are substituted with hydroxy groups, and Q Ｂ When there are two or more of E, they may be the same or different, Ｂ１ Is E Ａ１ or an alkyl group having 1 to 15 carbon atoms; E Ｂ１ When there are two or more, they may be the same or different, and n2 is Q Ｂ E bound to Ｂ１ represents the number of , which is an integer from 1 to 4.) (In the formulas (X1) to (X3), S １ ~S ４ are each independently a hydrogen atom, a halogen atom, or an optionally halogenated alkyl group having 1 to 4 carbon atoms.

[0014] <E Ａ１ > E in formula (A1) Ａ１ represents a (meth)acryloyloxy group, a (meth)acrylamide group, or a group represented by any one of formulas (X1) to (X3), preferably a group represented by the following formula (C), E Ａ１ When there are two or more of -O-C(=O)-CR, they may be the same or different. ｃ =CH ２ ...(C) (wherein R ｃrepresents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a halogen atom.) 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.

[0015] <n1> n1 in formula (A1) is Q Ａ E bound to Ａ１ and is an integer of 1 to 4. By setting n1 to 1 or 2, polymerization controllability can be improved when the present compound is used as a monomer. On the other hand, by setting n1 to 2 to 4, compatibility can be improved when the present compound is added to an organic solvent or a resist resin.

[0016] <Q Ａ and Q Ｂ Q in formula (A1) Ａ and Q Ｂ are each independently divalent to pentavalent and represent (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) are substituted with a hydroxy group. Ｂ When there are two or more of them, they may be the same or different. There are no particular limitations on the "saturated hydrocarbon group having 1 to 15 carbon atoms", and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isobutylene group, an isopentylene group, and a cyclohexyl group. Ａ and Q ＢFrom the viewpoint of improving the liquid repellency of the present compound, Q is preferably either (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, or (ii) a group in which a total of two or less bonds selected from the group consisting of ether bonds, amide bonds, urea bonds, urethane bonds, sulfide bonds, ester bonds, and amide bonds are inserted between the carbon-carbon bond of a saturated hydrocarbon group having 1 to 15 carbon atoms, and more preferably either (i) a saturated hydrocarbon group having 1 to 5 carbon atoms, or (ii) a group in which one bond selected from the group consisting of an ether bond, amide bond, urea bond, urethane bond, sulfide bond, ester bond, and amide bond is inserted between the carbon-carbon bond of a saturated hydrocarbon group having 1 to 5 carbon atoms. Ａ and Q Ｂ is (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bond of a saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) have been substituted with a hydroxy group, thereby improving the compatibility of the compound with organic solvents and resist resins.

[0017] <E Ｂ１ > E in formula (A1) Ｂ１ Is E Ａ１ or an alkyl group having 1 to 15 carbon atoms; E Ｂ１ When two or more of these are present, they may be the same or different. The "alkyl group having 1 to 15 carbon atoms" is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and a cyclohexyl group.

[0018] <R ａ and R ｂ R in formula (A1) ａ and R ｂ are each independently Ｂ (-E Ｂ１ ) ｎ２ (However, Q Ｂis bonded to a nitrogen atom), E Ｂ１ or a hydrogen atom, and preferably represents a hydrogen atom from the viewpoint of improving the liquid repellency of the compound.

[0019] <R ｆ R in formula (A1) ｆ has a number average molecular weight of 1,000 to 50,000, has one or more etheric oxygen atoms inserted between the carbon-carbon bonds of the fluoroalkylene group, and has two bond ends each independently represented by -CX １ X ２ - (However, X １ represents a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms which may contain one or more etheric oxygen atoms, and X ２ represents a fluoroalkyl group having 1 to 4 carbon atoms which may contain one or more hydrogen atoms, fluorine atoms, or etheric oxygen atoms.) The "fluoroalkyl group having 1 to 4 carbon atoms" is not particularly limited, and examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

[0020] R ｆ The number average molecular weight of is not particularly limited as long as it is 1,000 to 50,000, but from the viewpoint of improving compatibility with organic solvents and resist resins, it is preferably 1,000 to 30,000, more preferably 1,000 to 15,000, and particularly preferably 1,000 to 7,000.

[0021] R in formula (A1) ｆ preferably represents a group represented by the following formula (D): ｆ１ O-[(R ｆ２ O) ｍ１ (R ｆ３ O) ｍ２ (R ｆ４ O) ｍ３ (R ｆ５ O) ｍ４ ]-R ｆ６ - (D) R in formula (D) ｆ１ and R ｆ６ each independently represents a fluoroalkylene group having 1 to 6 carbon atoms; R ｆ２ represents a fluoromethylene group, and R ｆ３represents a fluoroethylene group, and R ｆ４ represents a fluoroalkylene group having 3 carbon atoms, and R ｆ５ represents a fluoroalkylene group having 4 carbon atoms, and m1, m2, m3, and m4 each independently represent 0 or an integer of 1 or more.

[0022] In addition, (R ｆ２ O) ~ (R ｆ５ The bonding order of m1 to m4 in formula (D) is arbitrary. ｆ２ O) ~ (R ｆ５ O), and does not represent the arrangement. For example, (R ｆ２ O) ｍ１ is (R ｆ２ O) is m1, and (R ｆ２ O) ｍ１ Similarly, (R ｆ２ O) ~ (R ｆ５ The order of the units R and O does not represent the bonding order of the units. ｆ１ ~R ｆ６ The fluoroalkylene group represented by the formula (R) may be linear, branched, or have a ring structure. ｆ２ O) ~ (R ｆ５ The position of —O— in each (R ｆ２ O) ~ (R ｆ５ O) may have two or more —O— groups.

[0023] R ｆ２ Specific examples of the group include -CF ２ -, -CHF-. ｆ３ Specific examples of the group include -CF ２ CF ２ -, -CHFCF ２ -, -CHFCHF-, -CH ２ CF ２ -, -CH ２ CHF- and the like. ｆ４ Specific examples of the group include -CF ２ CF ２ CF ２ -, -CF ２ CHFCF ２-、-CF ２ CH ２ CF ２ -、-CHFCF ２ CF ２ -、-CHFCHFCF ２ -、-CHFCHFCHF-、-CHFCH ２ CF ２ -、-CHFCH ２ CF ２ -、-CH ２ CF ２ CF ２ -、-CH ２ CHFCF ２ -、-CH ２ CH ２ CF ２ -、-CH ２ CF ２ CHF-、-CH ２ CHFCHF-、-CH ２ CH ２ CHF-、-CF(CF ３ )-CF ２ -、-CF(CHF ２ )-CF ２ -、-CF(CH ２ F)-CF ２ -、-CF(CH ３ )-CF ２ -、-CF(CF ３ )-CHF-、-CF(CHF ２ )-CHF-、-CF(CH ２ F)-CHF-、-CF(CH ３ )-CHF-、-CF(CF ３ )-CH ２ -、-CF(CHF ２ ) -CH ２ -、-CF(CH ２ F)-CH ２ -、-CF(CH ３ )-CH ２ -、-CH(CF ３ )-CF ２ -、-CH(CHF ２ )-CF ２ -、-CH(CH ２ F)-CF ２ -、-CH(CH ３ )-CF ２ -、-CH(CF３ )-CHF-, -CH(CHF ２ )-CHF-, -CH(CH ２ F)-CHF-, -CH(CH ３ )-CHF-, -CH(CF ３ )-CH ２ -, -CH(CHF ２ )-CH ２ -, -CH(CH ２ F)-CH ２ - etc. are exemplified. R ｆ５ Specific examples of include -CF ２ CF ２ CF ２ CF ２ -, -CHFCF ２ CF ２ CF ２ -, -CH ２ CF ２ CF ２ CF ２ -, -CF ２ CHFCF ２ CF ２ -, -CHFCHFCF ２ CF ２ -, -CH ２ CHFCF ２ CF ２ -, -CF ２ CH ２ CF ２ CF ２ -, -CHFCH ２ CF ２ CF ２ -, -CH[[ID=7!]] ２ CH ２ CF ２ CF ２ -, -CHFCF ２ CHFCF ２ -, -CH ２ CF ２ CHFCF ２ -, -CF ２ CHFCHFCF ２ -, -CHFCHFCHFCF ２ -, -CH ２ CHFCHFCF ２ -, -CF ２ CH ２ CHFCF ２ -, -CHFCH２ CHFCF ２ -, -CH ２ CH ２ CHFCF ２ -, -CF ２ CH ２ CH ２ CF ２ --, --CHFCH ２ CH ２ CF ２ -, -CH ２ CH ２ CH ２ CF ２ --, --CHFCH ２ CH ２ CHF-, -CH ２ CH ２ CH ２ CHF-, -cycloC ４ F ６ - etc.

[0024] R ｆ The higher the content of fluorine atoms in the group, the more improved the liquid repellency of the present compound, and therefore the fluoroalkylene group is preferably a perfluoroalkylene group.

[0025] <n2> n2 in formula (A1) is Q Ｂ E bound to Ｂ１ and is an integer of 1 to 4. By setting n2 to 1 or 2, it is possible to improve the polymerization controllability when the present compound is used as a monomer, and also to improve the liquid repellency of the present compound. On the other hand, by setting n2 to 2 to 4, it is possible to improve the compatibility when the present compound is added to an organic solvent or a resist resin.

[0026] (E Ａ１ -) ｎ１ Q Ａ The molecular weight of (E) in formula (A1) is not particularly limited, but is preferably 50 to 450, more preferably 90 to 400, and particularly preferably 90 to 300. Ａ１ -) ｎ１ Q Ａ When the molecular weight is equal to or greater than the lower limit, the compatibility of the compound with organic solvents and resist resins can be improved, and when the molecular weight is equal to or less than the upper limit, the liquid repellency of the compound can be improved.

[0027] Q in formula (A1) Ｂ (-E Ｂ１ ) ｎ２ The molecular weight of Q in formula (A1) is not particularly limited, but is preferably 50 to 450, more preferably 90 to 400, and particularly preferably 90 to 300. Ｂ (-E Ｂ１ ) ｎ２ When the molecular weight is equal to or greater than the lower limit, the compatibility of the compound with organic solvents and resist resins can be improved, and when the molecular weight is equal to or less than the upper limit, the liquid repellency of the compound can be improved.

[0028] R in formula (A1) ａ The molecular weight of R is not particularly limited, but from the viewpoint of improving the liquid repellency, it is preferably 450 or less, more preferably 300 or less, particularly preferably 150 or less, and most preferably 1, that is, R ａ is a hydrogen atom.

[0029] R in formula (A1) ｂ The molecular weight of R is not particularly limited, but from the viewpoint of improving the liquid repellency, it is preferably 450 or less, more preferably 300 or less, particularly preferably 150 or less, and most preferably 1, that is, R ｂ is a hydrogen atom.

[0030] These E Ａ１ , E Ｂ１ , R ａ , R ｂ The number of polymerizable groups in this compound can be changed by appropriately setting n1 and n2. When the total number of polymerizable groups is set to 2 or more, dense crosslinking can be formed, and development resistance can be improved when the compound is added to a resist composition. When the total number of polymerizable groups in the compound represented by formula (A1) is set to 1, molecular weight control becomes easy when the compound represented by formula (A1) is used for polymerization.

[0031] Specific examples of the compound represented by formula (A1) include the following compounds: However, the present invention is not limited to these compounds.

[0032] The compounds of the present disclosure described above have high water and oil repellency, lubricity, a low refractive index, and abrasion resistance, and can be used as additives that impart liquid repellency to resist materials, surface treatment agents for touch panels and displays, lens resins, etc.

[0033] [Polymer] The polymer of the present invention is a polymer having, as repeating units, a structural unit based on the compound of the present invention and a structural unit based on the monomer represented by formula (B1) or a structural unit based on the monomer represented by formula (B2). Ａ２ -) ｅ Q Ｙ ...(B1) In formula (B1), E Ａ２ represents a (meth)acryloyloxy group or a (meth)acrylamide group, E Ａ２ When there are two or more of them, they may be the same or different. Ａ２ In terms of improving copolymerizability with the compound of the present invention, it is preferable that e is a group equivalent to the polymerizable group contained in the compound of the present invention. Ｙ E bound to Ａ２ and is an integer of 1 to 4. e is not particularly limited as long as it is an integer of 1 to 4, but is preferably 1 or 2, more preferably 1, in order to improve molecular weight controllability during polymerization. Ｙrepresents (I) a hydrogen atom, or (II) a group that does not contain a monovalent to tetravalent fluorine atom, and is (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) are substituted with a hydroxy group or a carboxyl group. The "saturated hydrocarbon group having 1 to 15 carbon atoms" is not particularly limited, and examples thereof include primary hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; secondary hydrocarbon groups such as isobutyl and isopentyl; tertiary hydrocarbon groups such as t-butyl; and cyclic hydrocarbon groups such as cyclohexyl. From the viewpoint of improving the liquid repellency of the present compound, a saturated hydrocarbon group having 1 to 10 carbon atoms is preferred.

[0034] In formula (B2), S ５ ~S ９ are each independently (I) a hydrogen atom, (II) a halogen atom, (III) a hydroxy group, (IV) a carboxyl group, (V) an amino group, or (VI) a group that does not contain a monovalent to tetravalent fluorine atom, and is also (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to carbon atoms of the group (i) or (ii) are substituted with a hydroxy group or a carboxyl group.

[0035] Q Ｙ Examples of the compound represented by formula (B1) in which is a hydrogen atom include acrylic acid, methacrylic acid, acrylamide, methacrylamide, etc. Among these, acrylic acid and methacrylic acid are preferred from the viewpoint of improving the lyophilicity of ink in pattern-removed portions when a resist coating film containing the resulting polymer is developed.

[0036] Q ＹBy carrying out polymerization using a monomer represented by formula (B1), in which (i) is a saturated hydrocarbon group having 1 to 15 carbon atoms, it is expected that the liquid repellency of the resulting polymer will be improved. From the viewpoint of improving the liquid repellency of the polymer, a saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable, and one having 1 to 8 carbon atoms is even more preferable.

[0037] Such, Q Ｙ Examples of the monomer represented by formula (B1) in which (i) is a saturated hydrocarbon group having 1 to 15 carbon atoms include methyl acrylate, methyl methacrylate, ethyl methacrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate.

[0038] Q Ｙ (ii) by carrying out polymerization using a monomer represented by formula (B1), which is a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms, the compatibility of the obtained polymer with organic solvents and resist resins, and the uniformity of the coating film can be improved. Among these, from the viewpoint of further improving the compatibility of the obtained polymer with organic solvents and resist resins, and the uniformity of the coating film, it is preferred to use a monomer represented by formula (B1) Ｙ (ii) It is preferable to carry out the polymerization using a monomer represented by formula (B1), which is a group in which one or more of an amide bond, a urea bond, and a urethane bond are inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms.

[0039] Q Ｙ (ii) is a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms. Examples of the monomer represented by formula (B1) include 2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, diethylene glycol monomethyl ether methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol monoacetoacetate monomethacrylate, 2-(dimethylamino)ethyl methacrylate, and the compounds listed below.

[0040] Q Ｙ or (iii) by carrying out polymerization using a monomer represented by formula (B1) in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) are substituted with a hydroxy group or a carboxyl group, it is possible to improve the lyophilicity of the ink in the patterned portion when a resist coating film containing the obtained polymer is developed. Among these, from the viewpoint of further improving the lyophilicity of the ink in the patterned portion when a resist coating film containing the obtained polymer is developed, Q Ｙ is preferably a group represented by formula (B1) in which (iii) one or two hydrogen atoms bonded to the carbon atom of the group represented by (i) or (ii) are substituted with a carboxyl group.

[0041] Such, Q Ｙ (iii) is a group in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) are substituted with a hydroxy group or a carboxyl group. Examples of the monomer represented by formula (B1) include hydroxyethyl acrylate, hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, and the following compounds:

[0042] By carrying out polymerization using the monomer represented by formula (B1) as explained above, a polymer can be obtained that has good compatibility with organic solvents and resist resins while maintaining liquid repellency.

[0043] The monomer represented by formula (B2) is not particularly limited, but from the viewpoint of improving the liquid repellency of the polymer, S ５ ~S ９ are preferably all organic groups having 0 to 4 carbon atoms.

[0044] Examples of the monomer represented by formula (B2) include styrene, 4-chlorostyrene, pentafluorostyrene, 4-methylstyrene, 4-methoxystyrene, 4-aminostyrene, 4-vinylbenzoic acid, and 4-vinylphenol.

[0045] The mass average molecular weight (Mw) of the polymer of the present invention is not particularly limited, but is preferably 10,000 to 1,000,000, more preferably 20,000 to 700,000, and particularly preferably 50,000 to 500,000. When the mass average molecular weight (Mw) of the polymer of the present invention is at least the lower limit, the liquid repellency and development resistance when added to a resist can be improved, and when the mass average molecular weight (Mw) is at most the upper limit, the compatibility with organic solvents and resist resins can be improved.

[0046] The mass proportion of the structural units based on the compound of the present invention in the polymer of the present invention is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 15% by mass to 50% by mass. When the mass proportion of the structural units based on the compound of the present invention in the polymer of the present invention is equal to or greater than the lower limit, the liquid repellency can be improved, and when it is equal to or less than the upper limit, the compatibility with organic solvents and resist resins can be improved.

[0047] The fluorine atom content of the polymer of the present invention is not particularly limited, but is preferably 5 to 40 mass %, more preferably 10 to 30 mass %, and particularly preferably 15 to 25 mass %. When the fluorine atom content of the polymer of the present invention is equal to or greater than the lower limit, the liquid repellency can be improved, and when it is equal to or less than the upper limit, the compatibility with organic solvents and resist resins can be improved.

[0048] The polymers described above can be used as additives that impart liquid repellency to resist materials, water-repellent or oil-repellent agents for cloth and paper, surface treatment agents for touch panels and displays, and the like.

[0049] When the compound of the present invention is polymerized to obtain a homopolymer or copolymer of the compound of the present invention, the polymerization can be carried out using, for example, the following solvents, initiators, polymerization inhibitors, catalysts, etc. The polymer of the present invention can also be obtained by polymerization in the same manner.

[0050] (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 the compound of the present invention, an organic solvent capable of dissolving the compound of the present invention and the monomer represented by the formula (B1) or (B2), water, etc. The solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or may contain both solvents.

[0051] 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 ４F 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.

[0052] The non-fluorine-based organic solvent is not particularly limited, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ester organic solvents, and ether 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 acetone, 2-butanone, methyl isobutyl ketone, and cyclohexanone. 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.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.

[0053] (Initiator) It is preferable to use an initiator when polymerizing the compound of the present invention. The initiator is not particularly limited and can be appropriately selected depending on the polymerizable group of the compound of the present invention or the monomer represented by Formula (B1) or Formula (B2). 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.).

[0054] (Polymerization inhibitor) When polymerizing using the compound of the present invention, 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 for polymerization, adding such a polymerization inhibitor is preferable because it can suppress gelation and precipitation of the polymer. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, etc.

[0055] (Chain Transfer Agent) When polymerizing using the compound of the present invention, a chain transfer agent that enables living radical polymerization may be used in order 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 compound 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.

[0056] (Catalyst) A catalyst may be added during polymerization using the compound of the present invention. The catalyst is not particularly limited, and examples thereof include tin compounds such as dibutyltin dilaurate; basic catalysts; and the like. These may be used alone or in combination of two or more.

[0057] In the polymerization reaction, the order of addition of each material is not limited, and a reaction solution is prepared by adding the compound of the present invention, and, if necessary, the monomer represented by formula (B1) or (B2), an initiator, etc. to a reaction solvent. The reaction solution is heated preferably to 30 to 100°C, and is shaken or stirred preferably for 1 to 48 hours to allow the polymerization reaction to proceed.

[0058] The polymer of the present invention may be obtained by reacting a polymer having both a structural unit based on the compound of the present invention 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.

[0059] (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.

[0060] (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.

[0061] (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.

[0062] (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.

[0063] (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.

[0064] 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.

[0065] The equivalent ratio of [functional group of compound (z2)] / [reactive group (z1) of the polymer] 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.

[0066] The mass average molecular weight (Mw) of the polymer of the present invention is not particularly limited, but is preferably 10,000 to 1,000,000, more preferably 20,000 to 700,000, and particularly preferably 50,000 to 500,000. When the mass average molecular weight (Mw) of the polymer of the present invention is at least the lower limit, the liquid repellency and development resistance when added to a resist can be improved, and when it is at most the upper limit, the compatibility with organic solvents and resist resins can be improved.

[0067] The mass proportion of the structural units based on the compound of the present invention in the polymer of the present invention is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 15% by mass to 50% by mass. When the mass proportion of the structural units based on the compound of the present invention in the polymer of the present invention is equal to or greater than the lower limit, the liquid repellency can be improved, and when it is equal to or less than the upper limit, the compatibility with organic solvents and resist resins can be improved.

[0068] The fluorine atom content of the polymer of the present invention is not particularly limited, but is preferably 5 to 40 mass %, more preferably 10 to 30 mass %, and particularly preferably 15 to 25 mass %. When the fluorine atom content of the polymer of the present invention is equal to or greater than the lower limit, the liquid repellency can be improved, and when it is equal to or less than the upper limit, the compatibility with organic solvents and resist resins can be improved.

[0069] The polymers described above can be used as additives that impart liquid repellency to resist materials, water-repellent or oil-repellent agents for cloth and paper, surface treatment agents for touch panels and displays, and the like.

[0070] [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 as required and provide the main function of its performance. The optional components are used as needed. Examples of essential components include a fluorine-containing component (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 fluorine-containing component (A2) other than the fluorine-containing component (A), a crosslinking agent (E), etc. 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 that is performed 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 light-irradiated portion (exposed portion) is selectively removed during alkaline development that is carried out following exposure, and as a result, a partition wall made of a cured product of the resist composition is formed.

[0071] <Fluorine-containing component (A)> The fluorine-containing component (A) is not particularly limited as long as it is at least one selected from the group consisting of the compound of the present invention and the polymer of the present invention, but is preferably the polymer of the present invention. Preferred aspects of the compound of the present invention and the polymer of the present invention are the same as the preferred aspects described above.

[0072] The content of the fluorine-containing component (A) in the total solid content of the resist composition of the present invention is not particularly limited, but from the viewpoint of achieving both liquid repellency and coating uniformity, it is preferably from 0.01 to 2.0 mass%, more preferably from 0.05 to 1 mass%, and particularly preferably from 0.1 to 0.5 mass%.

[0073] <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).

[0074] In order to impart alkali solubility to the alkali-soluble resin (B), it is preferable that the alkali-soluble resin (B) has an alkali-soluble group in the structural 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 carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups. These may be used alone or in combination of two or more.

[0075] 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.

[0076] <<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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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).

[0084] The monomer (BM-3) is not particularly limited, and examples thereof include 2,2,2-triacryloyloxymethylethyl phthalate.

[0085] 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.

[0086] 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 40.0 to 60.0 mass %.

[0087] <<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.

[0088] (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.

[0089] (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, the polyimide resin is preferably a resin obtained by dehydrating and cyclizing a polyamic acid, which is a polyimide precursor obtained by reacting a tetracarboxylic dianhydride with a diamine, 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.

[0090] 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.

[0091] (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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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, carboxyl group-containing polymers, and urethane resins may also be used.

[0096] 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.

[0097] 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.

[0098] 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 %.

[0099] <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 improved. Furthermore, by containing the solvent (C), the fluorine-containing component (A) can be stably present in the composition. There are no particular restrictions on the solvent (C), so long as the resist composition can uniformly dissolve or disperse the essential components and optional components and the solvent (C) is not reactive with the components contained in the resist composition.

[0100] 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, 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 mono Examples of suitable esters include ethyl 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.

[0101] 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 %.

[0102] <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.

[0103] 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.

[0104] 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), ethanone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), which are classified as oxime esters; and 2,4-diethylthioxanthone, which is classified as thioxanthones, are preferred, and combinations of these with benzophenones, such as 4,4'-bis(diethylamino)benzophenone, are more preferred.

[0105] 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 %.

[0106] <<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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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 %.

[0112] 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.

[0113] <<Fluorine-Containing Component (A2) Other Than Fluorine-Containing Component (A)>> The resist composition according to an embodiment of the present invention may contain, as an optional component, a fluorine-containing component (A2) other than the fluorine-containing component (A). By including a fluorine-containing component (A2) other than the fluorine-containing component (A) in the resist composition, improved liquid repellency can be expected. The fluorine-containing component (A2) other than the fluorine-containing component (A) is not particularly limited, and examples include the polymer (A) described in Japanese Patent No. 5152332.

[0114] There are no particular restrictions on the amount of the fluorine-containing component (A2) other than the fluorine-containing component (A) in the total solids content of the resist composition of the present invention, but from the perspective of achieving both liquid repellency and coating uniformity, it is preferably from 0.01 to 1.0 mass%, more preferably from 0.05 to 0.5 mass%, and particularly preferably from 0.1 to 0.3 mass%.

[0115] <<Crosslinking Agent (E)>> The resist composition according to an embodiment of the present invention may 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.

[0116] (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.

[0117] 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.

[0118] 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.

[0119] (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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] The crosslinking agent (E) is preferably a compound having two or more epoxy groups in one molecule.

[0125] 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%.

[0126] (Crosslinking Accelerator (F)) The resist composition of the present invention may contain a crosslinking accelerator (F) as an optional component that accelerates crosslinking.

[0127] 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).

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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 %.

[0132] (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.

[0133] 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 structural 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.

[0134] There are no particular restrictions on the content of the colorant (G) in the total solid content of the resist composition of the present invention, but from the viewpoints of providing the resist composition with excellent sensitivity and the formed partition walls with excellent light-shielding properties, it is preferably 15.0 to 65.0 mass %, and more preferably 20.0 to 50.0 mass %.

[0135] (Silane Coupling Agent (H)) The resist composition of the present invention may contain a silane coupling agent (H) as necessary. By including 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.

[0136] There are no particular restrictions on the amount of the silane coupling agent (H) in the total solids content 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 liquid 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%.

[0137] (Fine Particles (I)) The resist composition of the present invention may contain fine particles (I) as necessary. The fine particles (I) referred to here refer to powder 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.

[0138] 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.

[0139] 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.

[0140] 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 ink 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 %.

[0141] (Phosphate Compound (J)) The resist composition of the present invention may 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.

[0142] 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%.

[0143] (Thiol Compound (K)) The resist composition of the present invention may optionally contain a thiol compound (K). 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 ethylenic double bonds in 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 resist composition is cured is low and a uniform network is easily obtained, among other advantages.

[0144] 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.

[0145] 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.

[0146] 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 of such esters include trimethylolpropane 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.

[0147] 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.

[0148] 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 %.

[0149] (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, within a range that does not impair the effects of the present invention.

[0150] <Method for Producing Resist Composition> As a method for producing a resist composition, a method of mixing a fluorine-containing component (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 is preferred. Mixing is carried out using a stirrer at a temperature of 20 to 30°C for a time of 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. Furthermore, prior to this mixing, a solution obtained by diluting or dissolving any of the fluorine-containing component (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 prepared and used for mixing.

[0151] The resist composition of the present invention can be used, like a conventional resist composition, to protect a substrate or change the affinity of the 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. A cured film obtained using the resist composition of the present invention can be used as a member for an optical element, for example, in which a cured film of a conventional resist composition is used, and contains the above-mentioned fluorine-containing component (A).

[0152] [Resist film] The resist film of the present invention is not particularly limited as long as it is made of a cured product containing a fluorine-containing component (A) which is at least one selected from the group consisting of the compound of the present invention and the polymer of the present invention, but it is preferably made of a cured product containing a fluorine-containing component (A) which is the polymer of the present invention. Preferred aspects of the compound of the present invention and the polymer of the present invention are the same as the preferred aspects described above.

[0153] [Optical Element] The optical element of the present invention has a substrate, a plurality of pixels formed on the surface of the substrate, and a partition wall located between adjacent pixels, the partition wall being the resist film of the present invention. The optical element is not particularly limited, and examples thereof include an organic EL element, a color filter, an organic TFT array, and the like. 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.

[0154] <Partition Walls and Their Manufacturing Method> The partition walls are partition walls formed to provide compartments on a substrate, and are preferably made of a cured film obtained by applying, drying, and curing the resist composition of the present invention. The partition walls are suitably used in optical element applications, 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] <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).

[0162] <<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.

[0163] 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.

[0164] 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.

[0165] The ink repellency of a cured film formed from a resist composition according to an embodiment of the present invention can be evaluated, for example, by the contact angles of water and PGMEA (propylene glycol monomethyl ether acetate: an organic solvent commonly used as an ink solvent). 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 PGMEA of the partition walls is preferably 40 degrees or more, and more preferably 45 degrees or more. Furthermore, the difference between the advancing contact angle and the receding contact angle of the PGMEA of the partition walls is preferably 30 degrees or less, and more preferably 25 degrees or less.

[0166] <<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.

[0167] <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.

[0168] <<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.

[0169] <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.

[0170] <<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.

[0171] 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 with 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. Aqueous inks contain 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. Oil-based inks contain an organic solvent as a solvent and, as a binder resin component, a resin soluble in an 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.

[0172] 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 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 of the upper surfaces of the partition walls, and examples include plasma ashing and light ashing. Furthermore, to improve the quality of liquid crystal panels manufactured using the color filters, photospacers may be formed on the partition walls (e.g., black matrix) if necessary.

[0173] <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.

[0174] 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.

[0175] The structures of the "raw materials," "fluorine-containing monomers," and "comparative monomers" described in the following examples are average compositions determined by 19F NMR. For example, ２ CF ２ CF ２ CF ２ OCF ２ CF ２ O) ｍ１１ "The base is CF ２ CF ２ CF ２ CF ２ OCF ２ CF ２ It indicates that an average of m11 O groups are connected, and "(CF ２ O) ｍ１２ (CF２ CF ２ O) ｍ１３ "The base is CF ２ Average of 12 O groups and CF ２ CF ２ This indicates that an average of m 13 O groups are linked in random order.

[0176] [Synthesis Example 1: Raw material 2 (HOCOCF ２ O(CF2O) ７ (CF ２ CF ２ O) ９ CF ２ Synthesis of (HOCH2COOH)] In a 200 mL glass flask, sodium bicarbonate (Junsei Chemical Co., Ltd., 2.26 g), potassium bromide (Junsei Chemical Co., Ltd., 0.16 g), raw material 1 (HOCH2COOH), ２ CF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ CH ２ OH (10.0 g)) and acetonitrile (Junsei Chemical Co., Ltd., 10.43 g) were added and a nitrogen atmosphere was created. TEMPO (TCI, 0.060 g) was added, and then an aqueous solution of sodium perchlorate (Junsei Chemical Co., Ltd., 20.64 g) was added dropwise over 10 minutes. After the addition was complete, the mixture was stirred at 50°C for 3 hours. Then, a 2M aqueous solution of hydrochloric acid was added, and the mixture was stirred at room temperature, and the aqueous layer was removed. The organic layer was dissolved in an AE-3000, separated with saturated saline, and concentrated to obtain raw material 2 (10.40 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ9.59 (s, 2H) 19FNMR (400MHz, (CD ３ ) ２ CO): δ -47.67 (m, 6F), -49.45 (m, 6F), -51.18 (m, 2F), -74.49 (s, 2F), -76.29 (s, 2F), -84.62 (m, 20F), -86.48 (m, 16F)

[0177]

[0178] [Synthesis Example 2: Raw material 3 (CH ３ OCOCF ２O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ COOCH ３ Synthesis of Raw Material 3 (5.8 g) was obtained by adding AC-2000 (AGC, 16.56 g), methanol (Junsei Chemical, 3.07 g), and Raw Material 2 (10.40 g) to a 100 mL glass flask and refluxing overnight. The mixture was then concentrated and subjected to silica gel column chromatography (AE-3000) to obtain Raw Material 3 (5.8 g). ３ ) ２ CO): δ4.08 (s, 6H) 19FNMR (400MHz, (CD ３ ) ２ CO): δ -47.78 (m, 6F), -49.40 (m, 6F), -51.13 (m, 2F), -73.79 (s, 2F), -75.54 (s, 2F), -84.50 (m, 20F), -86.40 (m, 16F)

[0179]

[0180] [Synthesis Example 3: Raw material 4 (HOCH ２ CH ２ NHCOCF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ CONHCH ２ CH ２ Synthesis of Raw Material 4 (OH)] A 100 mL glass flask was charged with AE-3000 (AGC, 6 g), tetrahydrofuran (Junsei Chemical, 2.0 g), and Raw Material 3 (5.8 g), and ethanolamine (TCI, 0.49 g) was added and stirred at room temperature for 1 hour. The mixture was then separated with a 2 M aqueous hydrochloric acid solution and concentrated to obtain Raw Material 4 (6.0 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ3.65 (t, 4H), 3.54 (t, 4H) 19FNMR (400MHz, (CD ３ ) ２CO): δ -47.68 (m, 6F), -49.44 (m, 6F), -51.19 (m, 2F), -74.22 (s, 2F), -76.00 (s, 2F), -84.51 (m, 20F), -86.45 (m, 16F)

[0181]

[0182] Synthesis Example 4: Fluorine-containing monomer 1 (CH ２ =C(CH ３ ) COOCH ２ CH ２ NHCOCF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ CONHCH ２ CH ２ OCOC (CH ３ ) = CH ２ Synthesis of Fluorine-Containing Monomer 1] A 100 mL glass flask was charged with AC-2000 (AGC, 12 g) and Raw Material 4 (6.0 g), and triethylamine (TCI, 0.72 g), 4-dimethylaminopyridine (TCI, 0.040 g), and methacrylic anhydride (TCI, 1.10 g) were added and stirred at room temperature for 1 hour. Thereafter, methanol (TCI, 0.10 g) was added and stirred at room temperature for 1 hour. The resulting reaction solution was subjected to silica gel column chromatography (AE-3000: ethyl acetate = 1:1) to obtain Fluorine-Containing Monomer 1 (6.1 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ6.04 (s, 2H), 5.58 (s, 2H), 4.24 (t, 4H), 3.69 (t, 4H), 1.90 (s, 6H) 19FNMR (400MHz, (CD ３ ) ２ CO): δ -47.72 (m, 6F), -49.47 (m, 6F), -51.26 (m, 2F), -74.24 (s, 2F), -76.02 (s, 2F), -84.58 (m, 20F), -86.53 (m, 16F)

[0183]

[0184] [Synthesis Example 5: Raw material 5 ((HOCH ２ ) ２ CHNHCOCF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ CONHCH (CH ２ OH) ２ Synthesis of Raw Material 5] A 100 mL glass flask was charged with AE-3000 (AGC, 14 g), methanol (Junsei Chemical, 7.0 g), and Raw Material 3 (7.0 g). 2-amino-1,3-propanediol (TCI, 0.75 g) was added and the mixture was stirred at room temperature for 1 hour. The mixture was then separated with a 2 M aqueous hydrochloric acid solution and concentrated to obtain Raw Material 5 (6.9 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ3.65 (m, 2H), 3.54 (d, 8H) 19FNMR (400MHz, (CD ３ ) ２ CO): δ -47.67 (m, 6F), -49.46 (m, 6F), -51.20 (m, 2F), -74.24 (s, 2F), -76.02 (s, 2F), -84.49 (m, 20F), -86.47 (m, 16F)

[0185]

[0186] Synthesis Example 6: Fluorine-containing monomer 2(((CH ２ =CHCOOCH ２ ) ２ C(CH ３ ) NHCOOCH ２ ) ２ CHNHCOCF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ CONHCH (CH ２ OCONHC (CH ３ ) (CH ２ OCOCH=CH ２ ) ２ ) ２Synthesis of Fluorine-Containing Monomer 2] A 100 mL glass flask was charged with 1,3-bistrifluoromethylbenzene (TCI, 20 g), tetrahydrofuran (Junsei Chemical, 4.0 g), Raw Material 5 (6.9 g), butylhydroxytoluene (BHT) (Junsei Chemical, 0.012 g), dibutyltin dilaurate (DBTDL) (TCI, 0.072 g), and 1,1-(bisacryloyloxymethyl)ethyl isocyanate (Karenz BEI, Resonac, 5.75 g), and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was concentrated and subjected to silica gel column chromatography (AE-3000:ethyl acetate=3:1) to obtain Fluorine-Containing Monomer 2 (12.1 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ6.40 (d, 8H), 6.15 (m, 8H), 5.90 (d, 8H), 4.34 (m, 16H), 4.24 (m, 8H), 3.67 (m, 2H), 1.45 (s, 12H) 19F NMR (400MHz, (CD ３ ) ２ CO): δ-47.65 (m, 6F), -49.42 (m, 6F), -51.17 (m, 2F), -74.23 (s, 2F), -76.00 (s, 2F), -84.48 (m, 20F), -86.45 (m, 16F)

[0187]

[0188] [Synthesis Example 7: Raw material 6 ((HOCH ２ CH ２ ) ２ NHCOCF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ CONH (CH ２ CH ２ OH) ２Synthesis of Raw Material 6 (6.8 g) was obtained by adding AE-3000 (AGC, 14 g), methanol (Junsei Chemical, 7.0 g), and Raw Material 3 (7.0 g) to a 100 mL glass flask, adding diethanolamine (TCI, 0.92 g) and stirring at room temperature for 1 hour. The mixture was then separated with a 2 M aqueous hydrochloric acid solution and concentrated to obtain Raw Material 6 (6.8 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ3.64 (t, 8H), 3.52 (t, 8H) 19FNMR (400MHz, (CD ３ ) ２ CO): δ-47.65 (m, 6F), -49.42 (m, 6F), -51.17 (m, 2F), -74.21 (s, 2F), -76.03 (s, 2F), -84.50 (m, 20F), -86.45 (m, 16F)

[0189]

[0190] Synthesis Example 8: Fluorine-containing monomer 3 ((CH ２ C(CH ３ ) COOCH ２ CH ２ ) ２ NHCOCF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ CONH (CH ２ CH ２ OCOC (CH ３ ) CH ２ ) ２Synthesis of Fluorine-Containing Monomer 3] A 100 mL glass flask was charged with 1,3-bistrifluoromethylbenzene (TCI, 20 g), tetrahydrofuran (Junsei Chemical, 4.0 g), Raw Material 6 (6.8 g), butylhydroxytoluene (BHT) (Junsei Chemical, 0.0088 g), dibutyltin dilaurate (DBTDL) (TCI, 0.050 g), and 1,1-(bisacryloyloxymethyl)ethyl isocyanate (Karenz BEI, Resonac, 4.02 g), and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was concentrated and subjected to silica gel column chromatography (AE-3000:ethyl acetate=2:1) ​​to obtain Fluorine-Containing Monomer 3 (10.1 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ6.05 (s, 4H), 5.56 (s, 4H), 4.34 (t, 8H), 3.67 (t, 8H), 1.90 (s, 12H) 19FNMR (400MHz, (CD ３ ) ２ CO): δ-47.63 (m, 6F), -49.40 (m, 6F), -51.13 (m, 2F), -74.20 (s, 2F), -76.01 (s, 2F), -84.49 (m, 20F), -86.47 (m, 16F)

[0191]

[0192] [Synthesis Example 9: Raw material 7 (HOCH ２ CH ２ NHCOCF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ CONH (CH ２ ) １１ CH ３Synthesis of Raw Material 7] A 100 mL glass flask was charged with AE-3000 (AGC, 20 g), tetrahydrofuran (Junsei Chemical, 5.0 g), and Raw Material 3 (10.0 g), and dodecylamine (TCI, 1.06 g) was added and stirred at room temperature for 1 hour. Then, 2-ethanolamine (TCI, 0.35 g) was added and stirred at room temperature for 1 hour. After completion of the reaction, the mixture was separated with a 2 M aqueous hydrochloric acid solution and subjected to silica gel column chromatography (AE-3000: ethyl acetate = 10:1) to obtain Raw Material 7 (4.6 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ3.96 (t, 2H), 3.78 (t, 1H), 3.68 (m, 4H), 3.44 (q, 2H), 1.66 (m, 2H), 1.35 (m, 16H), 0.92 (t, 3H) 19F NMR (400MHz, (CD ３ ) ２ CO): δ-47.65 (m, 6F), -49.48 (m, 6F), -51.17 (m, 2F), -74.23 (s, 2F), -76.01 (s, 2F), -84.50 (m, 20F), -86.47 (m, 16F)

[0193]

[0194] Synthesis Example 10: Fluorine-containing monomer 4 (CH ２ C(CH ３ ) COOCH ２ CH ２ NHCOCF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ CONH (CH ２ ) １１ CH ３Synthesis of Fluorine-Containing Monomer 4 (4.2 g) AE-3000 (manufactured by AGC, 10 g) and Raw Material 7 (4.6 g) were placed in a 100 mL glass flask, and triethylamine (manufactured by TCI, 0.28 g) and methacrylic anhydride (manufactured by TCI, 0.42 g) were added and stirred at room temperature for 1 hour. Thereafter, the mixture was separated into saturated aqueous sodium bicarbonate and saturated saline, and subjected to silica gel column chromatography (AE-3000:ethyl acetate=10:1) to obtain Fluorine-Containing Monomer 4 (4.2 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ6.04 (s, 1H), 5.58 (s, 1H), 4.34 (t, 2H), 3.68 (m, 4H), 3.44 (q, 2H), 1.66 (m, 2H), 1.35 (m, 16H), 0.92 (t, 3H) 19FNMR (400MHz, (CD ３ ) ２ CO): δ -47.64 (m, 6F), -49.47 (m, 6F), -51.15 (m, 2F), -74.24 (s, 2F), -76.02 (s, 2F), -84.48 (m, 20F), -86.49 (m, 16F)

[0195]

[0196] Synthesis Example 11: Comparative Monomer 1 (CH ２ C(CH ３ ) COOCH ２ CH ２ NHCOOCH ２ CF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ CH ２ OCONHCH ２ CH ２ OCOC (CH ３ ) CH ２Synthesis of Comparative Monomer 1] A 100 mL glass flask was charged with 1,3-bistrifluoromethylbenzene (TCI, 20 g), Raw Material 1 (10.0 g), butylhydroxytoluene (BHT) (Junsei Chemical, 0.012 g), dibutyltin dilaurate (DBTDL) (TCI, 0.073 g), and 2-isocyanatoethyl methacrylate (Karenz MOI, Resonac, 1.97 g), and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was concentrated and subjected to silica gel column chromatography (AE-3000: ethyl acetate = 3:1) to obtain Comparative Monomer 1 (11.5 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ6.12 (s, 2H), 5.61 (s, 2H), 5.25 (m, 2H), 4.48 (t, 4H), 4.25 (m, 4H), 3.54 (q, 4H), 1.95 (s, 3H) 19F NMR (400MHz, (CD ３ ) ２ CO): δ-47.65 (m, 6F), -49.47 (m, 6F), -51.13 (m, 2F), -74.20 (s, 2F), -76.00 (s, 2F), -84.50 (m, 20F), -86.45 (m, 16F)

[0197]

[0198] Synthesis Example 12: Comparative Monomer 2 (CH ２ C(CH ３ ) COOCH ２ CH ２ OCOCF ２ O (CF ２ O) ７ (CF ２ CF ２ O) ９ CF ２ COOCH ２ CH ２ OCOC (CH ３ ) CH ２Synthesis of Comparative Monomer 2] A 100 mL glass flask was charged with 1,3-bistrifluoromethylbenzene (TCI, 20 g), BHT (Junsei Chemical, 0.063 g), and Raw Material 3 (10.0 g). 2-Hydroxyethyl methacrylate (TCI, 7.45 g) was added and the mixture was refluxed and stirred for 10 hours. After completion of the reaction, the mixture was concentrated and separated into AC-2000 and saturated brine. After drying and concentration with sodium sulfate, silica gel column chromatography (AE-3000: ethyl acetate = 10:1) was performed to obtain Comparative Monomer 2 (8.8 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ6.10 (s, 2H), 5.60 (s, 1H), 4.61 (m, 4H), 4.43 (m, 4H), 1.92 (s, 6H) 19FNMR (400MHz, (CD ３ ) ２ CO): δ -47.63 (m, 6F), -49.45 (m, 6F), -51.15 (m, 2F), -74.21 (s, 2F), -76.00 (s, 2F), -84.48 (m, 20F), -86.44 (m, 16F)

[0199]

[0200] [Synthesis Example 13: Raw material 9 (CF ３ OCF ２ CF ２ O (CF ２ CF ２ CF ２ CF ２ OCF ２ CF ２ O) １３ CF ２ CF ２ CF ２ CONHCH ２ CH ２ Synthesis of (C1H-OH)] In a 100 mL glass flask, AE-3000 (AGC, 20 g), tetrahydrofuran (Junsei Chemical, 3 g), and raw material 8 (CF ３ OCF ２ CF ２ O (CF ２ CF ２ CF ２ CF ２ OCF ２ CF ２ O)１３ CF ２ CF ２ CF ２ COOCH ３ (10.0 g)) was charged, 2-aminoethanol (TCI, 0.17 g) was added, and the mixture was stirred at room temperature for 1 hour. After that, the mixture was separated with a 2 M aqueous hydrochloric acid solution and concentrated to obtain Raw Material 9 (10.06 g). 1H NMR (400 MHz, (CD ３ ) ２ CO): δ3.76 (t, 2H), 3.53 (q, 2H) 19FNMR (400MHz, (CD ３ ) ２ CO): δ-52.00 (t, 3F), -79.34 (m, 56F), -84.57 (m, 54F), -86.70 (q, 2F), -115.92 (t, 2F), -121.70 (m, 52F), -122.56 (m, 2F)

[0201]

[0202] Synthesis Example 14: Comparative Monomer 3 (CF ３ OCF ２ CF ２ O (CF ２ CF ２ CF ２ CF ２ OCF ２ CF ２ O) １３ CF ２ CF ２ CF ２ CONHCH ２ CH ２ OCOC (CH ３ ) = CH ２ Synthesis of Comparative Monomer 3] A 100 mL glass flask was charged with AC-2000 (AGC, 20 g) and Raw Material 9 (10.2 g), and triethylamine (TCI, 0.35 g), 4-dimethylaminopyridine (TCI, 0.029 g), and methacrylic anhydride (TCI, 0.52 g) were added and stirred at room temperature for 1 hour. Thereafter, methanol (TCI, 0.20 g) was added and stirred at room temperature for 1 hour. The resulting reaction solution was subjected to silica gel column chromatography (AE-3000: ethyl acetate = 100:2) to obtain Comparative Monomer 3 (9.36 g). 1H NMR (400 MHz, (CD３ ) ２ CO): δ6.14 (s, 1H), 5.67 (s, 1H), 4.39 (t, 2H), 3.80 (q, 2H), 2.00 (s, 3H) 19FNMR (400MHz, (CD ３ ) ２ CO): δ-52.01 (t, 3F), -79.32 (m, 56F), -84.44 (m, 54F), -86.70 (q, 2F), -115.99 (t, 2F), -121.68 (m, 52F), -122.51 (m, 2F)

[0203]

[0204] Fluorine-containing component (A1): A component synthesized by the following method was used. Each of the raw materials (unit: g) shown in Table 1 was polymerized at 70°C for 24 hours while stirring under a nitrogen atmosphere. In Table 1, "V-59" means "2,2'-azobis(2-methylbutyronitrile)" and "SR solvent" means "1,3-bis(trifluoromethyl)benzene". The polymer was reprecipitated using hexane, filtered, and then dried to obtain fluorine-containing component (A1). Thereafter, the resultant was diluted with propylene glycol monomethyl ether acetate (PGMEA) to obtain a PGMEA solution of fluorine-containing component (A1) (fluorine-containing component (A1) concentration: 10% by mass; hereinafter also referred to as "fluorine-containing component (A1) solution").

[0205] Fluorine-containing components (A2), (A3), (A5) to (A8), (A10), and (A11): Fluorine-containing components (A2), (A3), (A5) to (A8), (A10), and (A11) were obtained by the same procedure as for fluorine-containing component (A1), except that the raw materials and blending amounts were changed as shown in Table 1. Thereafter, the resulting mixture was diluted with propylene glycol monomethyl ether acetate (PGMEA) to obtain a PGMEA solution of fluorine-containing components (A2), (A3), (A5) to (A8), (A10), and (A11) (fluorine-containing component (A2), (A3), (A5) to (A8), (A10), and (A11) concentration: 10 mass%; hereinafter, also referred to as "fluorine-containing component (A2), (A3), (A5) to (A8), (A10), and (A11) solution").

[0206] Fluorine-containing component (A4) The fluorine-containing component (A4) refers to fluorine-containing monomer 1. Fluorine-containing monomer 1 (5 g) was diluted with methyl ethyl ketone to obtain a fluorine-containing component (A4) solution with a concentration of 10% by mass.

[0207] Fluorine-containing component (A9): Fluorine-containing component (A9) refers to Comparative Monomer 1. Comparative Monomer 1 (5 g) was diluted with methyl ethyl ketone to obtain a fluorine-containing component (A9) solution with a concentration of 10 mass %.

[0208] [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%, 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%, 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%, acid value 60 mg KOH / g B4: Copolymer of N-phenylmaleimide, benzyl methacrylate, and acrylic acid (Mw 6,200, solid content 20%)

[0209] [Solvent (C)] EDM: diethylene glycol ethyl methyl ether (boiling point 176°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)

[0210] [Photosensitizer (D)] D1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one D2: EAB: 4,4'-bis(diethylamino)benzophenone D3: OXE02: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(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)

[0211] [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]

[0212] <Examples 1 to 15: Preparation of resist compositions> Resist compositions were prepared by stirring (approximately 30 minutes) the raw materials in the proportions shown in Table 2 until homogeneous. Each of the prepared resist compositions was evaluated using the methods described below. Examples 1 to 11 are working examples, and Examples 12 to 15 are comparative examples.

[0213] <Measurement Conditions and Evaluation Conditions> <<Mass Average Molecular Weight (Mw) and Fluorine Atom Content (% by mass) of Fluorine-Containing Component (A)>> The mass average molecular weight (Mw) and fluorine atom content (% by mass) of fluorine-containing component (A) were measured by the following method. Note that the mass average molecular weight (Mw) and fluorine atom content (% by mass) of fluorine-containing components (A4) and (A9) were not measured because their structures could be identified by NMR.

[0214] (Weight-average molecular weight (Mw) of fluorine-containing component (A)) Gel permeation chromatography (GPC) of several types of monodisperse PMMA with different degrees of polymerization, commercially available as standard samples for molecular weight measurement, was measured using a commercially available GPC measurement device (manufactured by Tosoh Corporation, device name: HLC-8320GPC), 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, and then GPC of the sample was measured using the GPC measurement device. The weight-average molecular weight (Mw) of the sample was determined by computer analysis of the GPC spectrum of the sample using the calibration curve. The results are shown in Table 1.

[0215] (Fluorine atom content (mass %) of fluorine-containing component (A)) The fluorine atom content was calculated by 19F NMR measurement using 1,4-bis(trifluoromethyl)benzene as a standard substance. The results are shown in Table 1.

[0216] <<Preparation of Evaluation Samples>> Using the resist compositions listed in Table 2, cured films were formed on glass substrates to prepare Evaluation Sample 1 and Evaluation Sample 2. Evaluation Sample 1 was prepared using the following Preparation Method 1 or Preparation Method 2 as listed in Table 2, and Evaluation Sample 2 was prepared using the following Preparation Method 3 or Preparation Method 4 as listed in Table 2.

[0217] (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 glass substrate that had been subjected to post-exposure treatment was immersed in an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 80 seconds for development treatment. Thereafter, it was washed with water and dried. (4) The dried substrate was heated on a hot plate (at 230°C for 30 minutes) to prepare a glass substrate with the entire coating film cured.

[0218] (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 coating film was developed by immersing it in an aqueous solution of tetramethylammonium hydroxide (0.4% by mass) for 40 seconds. Thereafter, it was washed with water and dried. (3) After drying, 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.

[0219] (Preparation Method 3) (1) A glass substrate (manufactured by AGC, dimensions 100 mm x 100 mm x 0.7 mm) was subjected to ultrasonic cleaning in ethanol (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 (at 300 rpm for 10 seconds) onto the surface of the glass substrate using a spinner (Mikasa Co., Ltd., IH-DX2). Next, the substrate was dried on a hot plate (at 100°C for 2 minutes) to form a coating film with a thickness of 1.3 μm. (2) The surface of the coating film was exposed under the following conditions. Lamp and irradiation conditions: UV light from an ultra-high pressure mercury lamp was irradiated onto the entire surface at the same time. Light of 330 nm or less was blocked, and the exposure dose was 250 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.

[0220] (Preparation Method 4) A coating film was prepared by carrying out only the operations (1) and (3) of Preparation Method 3.

[0221] <<Post-development liquid repellency (static contact angle)>> Using the prepared evaluation sample 1, the contact angle (static contact angle) of the substrate surface with PGMEA was measured by the θ / 2 method. The larger the contact angle, the better the post-development liquid repellency (development resistance and liquid repellency). The evaluation criteria are shown below. The evaluation results are shown in Table 2. A: 45° or more B: 40° or more and less than 45° C: 35° or more and less than 40° D: Less than 35°

[0222] <Coating Film Uniformity> Using the prepared Evaluation Sample 2, the film thickness was measured at ten measurement points P1 to P10 shown in FIG. 1 . Specifically, the film thickness was measured at six points (P1 to P6) from one vertex 21 of the cured substrate 20 toward the substrate center C, starting at position P1, 20 mm from the vertex 21 toward the center C, at 10 mm intervals up to the center C (P6). Furthermore, the substrate was tilted at a 45° angle from the center C to the line connecting the aforementioned measurement points, and the film thickness was measured at four points (P7 to P10) at 10 mm intervals along a line drawn perpendicular to one side of the glass substrate (Evaluation Sample 1) 20, up to position P10, 10 mm from the side toward the center C. The film thickness measurements at the ten points were used to calculate the in-plane uniformity of the coating film according to the following formula: (Coating Film Uniformity) = (Maximum Film Thickness - Minimum Film Thickness) / (2 × Average Film Thickness) × 100. A fully automatic microprofile measuring instrument ET4000A (manufactured by Kosaka Laboratory Co., Ltd.) was used to measure the film thickness. The cured coating film at each measurement point was scraped with a spatula to expose the glass substrate, and the height of the step between the glass substrate and the cured coating film was recorded as the film thickness. The results were evaluated as follows. The evaluation was performed according to the following criteria. The evaluation results are shown in Table 2. A: 3% or less B: More than 3% and less than 5% C: More than 5%

[0223]

[0224]

[0225] As can be seen from the results shown in Tables 1 and 2, Examples 1 to 11, which used resist compositions containing the compounds of the present invention or the polymers of the present invention, are capable of forming cured films that are excellent in both post-development liquid repellency (development resistance and liquid repellency) and coating uniformity, compared to Examples 12 to 15.

Claims

1. A compound represented by the following formula (A1): (E Ａ１ -) ｎ１ Q Ａ -NR ａ C(=O)-R ｆ -C(=O)NR ｂ -Q Ｂ (-E Ｂ１ ) ｎ２ (In the above formula (A1), E Ａ１ represents a (meth)acryloyloxy group, a (meth)acrylamide group, or a group represented by any one of the following formulae (X1) to (X3), E Ａ１ When there are two or more, they may be the same or different, and n1 is Q Ａ E bound to Ａ１ represents the number of, and is an integer from 1 to 4; Ａ represents a divalent to pentavalent group, (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) are substituted with a hydroxy group, ａ Is, E Ｂ１ or a hydrogen atom; R ｆ has a number average molecular weight of 1,000 to 50,000, has one or more ether oxygen atoms inserted between the carbon-carbon bonds of the fluoroalkylene groups, and has two bond ends each independently represented by -CX １ X ２ - (wherein X １ represents a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms which may contain one or more etheric oxygen atoms; X ２ represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 4 carbon atoms which may contain one or more ethereal oxygen atoms; R ｂ Is, E Ｂ１ or a hydrogen atom; Q Ｂ represents a divalent to pentavalent group, (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to the carbon atom of the group (i) or (ii) are substituted with a hydroxy group, Ｂ１ Is, E Ａ１ or an alkyl group having 1 to 15 carbon atoms; E Ｂ１ When there are two or more, they may be the same or different, and n2 is Q Ｂ E bound to Ｂ１ represents the number of, and is an integer from 1 to 4.) (In the above formulas (X1) to (X3), S １ ~S ４ are each independently a hydrogen atom, a halogen atom, or an optionally halogenated alkyl group having 1 to 4 carbon atoms.

2. E Ａ１ and E Ｂ１ Each of the groups independently represents a group represented by the following formula (C): ｃ =CH ２ (In the above formula (C), R ｃ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a halogen atom.

3. R ｆ The compound according to claim 1 or 2, wherein R has a number average molecular weight of 1,000 to 50,000 and represents a group represented by the following formula (D): ｆ１ O-[(R ｆ２ O) ｍ１ (R ｆ３ O) ｍ２ (R ｆ４ O) ｍ３ (R ｆ５ O) ｍ４ ]-R ｆ６ - (D) (wherein, R ｆ１ and R ｆ６ each independently represents a fluoroalkylene group having 1 to 6 carbon atoms; R ｆ２ represents a fluoromethylene group; R ｆ３ represents a fluoroethylene group; R ｆ４ represents a fluoroalkylene group having 3 carbon atoms; R ｆ５ represents a fluoroalkylene group having 4 carbon atoms, and m1, m2, m3, and m4 each independently represent 0 or an integer of 1 or more.

4. (E Ａ１ -) ｎ１ Q Ａ , Q Ｂ (-E Ｂ１ ) ｎ２ , R ａ , and R ｂ The compound according to claim 1 or 2, wherein each of the following independently has a molecular weight of 450 or less.

5. R ａ and R ｂ The compound according to claim 1 or 2, wherein each is independently a hydrogen atom.

6. A polymer comprising, as repeating units, a structural unit based on the compound according to claim 1 and a structural unit based on a monomer represented by the following formula (B1) or a structural unit based on a monomer represented by the following formula (B2). Ａ２ -) ｅ Q Ｙ ... (B1) (In the above formula (B1), E Ａ２ represents a (meth)acryloyloxy group or a (meth)acrylamide group; E Ａ２ When there are two or more, they may be the same or different, and e is Q Ｙ E bound to Ａ２ represents the number of, and is an integer from 1 to 4; Ｙ represents (I) a hydrogen atom, or (II) a group that does not contain a mono- to tetravalent fluorine atom, and is (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to carbon atoms of the group (i) or (ii) are substituted with a hydroxyl group or a carboxyl group. (In the above formula (B2), S ５ ~S ９ are each independently (I) a hydrogen atom, (II) a halogen atom, (III) a hydroxy group, (IV) a carboxyl group, (V) an amino group, or (VI) a group that does not contain a monovalent to tetravalent fluorine atom, and is (i) a saturated hydrocarbon group having 1 to 15 carbon atoms, (ii) a group in which a bond selected from the group consisting of an ether bond, an amide bond, a urea bond, a urethane bond, a sulfide bond, an ester bond, and an amino bond is inserted between the carbon-carbon bonds of a saturated hydrocarbon group having 1 to 15 carbon atoms, or (iii) a group in which one or two hydrogen atoms bonded to carbon atoms of the group (i) or (ii) are substituted with a hydroxy group or a carboxyl group.

7. A resist composition comprising a fluorine-containing component (A), an alkali-soluble resin (B), a solvent (C), and a photosensitizer (D), wherein the fluorine-containing component (A) is at least one member selected from the group consisting of the compound recited in claim 1 and the polymer recited in claim 6.

8. A resist film comprising a cured product containing a fluorine-containing component (A) which is at least one member selected from the group consisting of the compound according to claim 1 and the polymer according to claim 6.

9. An optical element having a substrate, a plurality of pixels formed on a surface of said substrate, and partition walls positioned between adjacent ones of said plurality of pixels, said partition walls being the resist film according to claim 8.

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