Composition for patterning and use of same

Abstract

Provided is a composition for patterning which enables use of an alkaline solution in development process carried out after exposure to light in the atmosphere and which has curing properties such that a sufficient thickness can be maintained in an exposed portion even after the development process.　A composition for patterning according to the present invention comprises a compound represented by general formula (1) and a resin. [In general formula (1), R1 and R2 each independently represent any one selected from the group consisting of a hydrogen atom, C1-6 alkyl groups, C2-6 alkenyl groups, aryl groups, and aralkyl groups, R3 represents any one group selected from the group consisting of C1-6 alkyl groups, C2-6 alkenyl groups, aryl groups, and aralkyl groups, R4 represents any one group selected from the group consisting of (meth)acryloyl groups, styryl groups, and C2-6 alkenyl groups, and X represents NH or O. n represents an arbitrary integer of 1-5.]

Description

Pattern-forming composition and its use

[0001] The present invention relates to a pattern-forming composition (particularly, a negative-tone pattern-forming composition) and uses thereof (for example, a composition for forming a wavelength conversion film for a display or a resist pattern film formed from the pattern-forming composition).

[0002] In photolithography, a pattern-forming film (sometimes simply referred to as a "resist film") made of a pattern-forming composition (sometimes simply referred to as a "resist composition") is formed on a substrate, selectively exposed to radiation such as light or an electron beam, and then developed to form a pattern of a predetermined shape (i.e., a resist pattern) in the resist film. The patterned resist film is called a resist pattern film. Pattern-forming compositions are classified into negative-type and positive-type compositions based on their reaction mechanism. Negative-type pattern-forming compositions are photopolymerizable and curable photosensitive resin compositions that become insoluble in a developer upon exposure (see, for example, Patent Documents 1 and 2). Positive-type pattern-forming compositions are photosensitive resin compositions in which the exposed portions become soluble in a developer (see, for example, Patent Document 3). Patent Document 1 describes a negative-type pattern-forming composition, an epoxy cationically polymerized UV-curable resin composition containing an epoxy compound and a photoacid generator. Patent Document 2 describes a radical polymerization composition containing a polymer having an acryloyl group, a polyfunctional acrylic monomer, and a photoradical initiator as a negative pattern-forming composition that can be developed in an alkaline environment. Patent Document 3 describes a photosensitive composition containing a binder resin made of a resin having a urea bond in its side chain as a positive pattern-forming composition.

[0003] International Publication No. 2008 / 007764 Japanese Patent Application Laid-Open No. 2004-302389 Japanese Patent Application Laid-Open No. 8-339082

[0004] Positive-tone pattern-forming compositions are generally known to have problems such as sensitivity, adhesion, and resist fragility. Conventional negative-tone pattern-forming compositions also have the problem that when a resist film formed using the composition is exposed to light under atmospheric conditions, it does not have sufficient curability, and when the resulting resist film is subsequently developed with a developer, the resulting resist film dissolves in the developer. In particular, when a resist film formed using a photoradical polymerization initiator as a photopolymerization initiator is exposed to light under atmospheric conditions and then developed with an aqueous alkaline solution, oxygen inhibition (i.e., termination of the polymerization reaction by oxygen in the atmosphere) during the curing process during the formation of the resist film results in insufficient curing, and the resulting resist film is easily dissolved in the developer. Furthermore, the negative-tone pattern-forming composition described in Patent Document 1 cannot be developed with an aqueous alkaline solution and requires development with an organic solvent, which presents undesirable issues in terms of handling and other factors. Therefore, there is a need for a pattern-forming composition (especially a negative-tone pattern-forming composition) that can be used in an alkaline solution for development after exposure under atmospheric conditions and that has curability that allows the exposed portion to maintain a sufficient thickness even after development. The higher the film retention rate (i.e., the ratio (%) of the film thickness after development to the film thickness immediately before development (original film thickness)), which is an index of thickness maintenance, the better, and specifically, it is desirable for it to be 50% or more, preferably 70% or more. Furthermore, it is desirable for a wavelength conversion film formed from a wavelength conversion film-forming composition prepared using the pattern-forming composition to have excellent conversion efficiency in addition to the film retention rate, even after exposure and development under atmospheric conditions as described above.

[0005] As a result of extensive research into solving the above problems, the inventors discovered that the above problems can be solved by a pattern-forming composition containing a specified compound and a resin, and thus completed the present invention.

[0006] That is, the present invention provides the following pattern-forming composition, etc.: [1] A pattern-forming composition containing a compound represented by the following general formula (1), a resin, and [In general formula (1), R １ and R ２ each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; R ３ represents any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; R ４ represents any one selected from the group consisting of a (meth)acryloyl group, a styryl group, and an alkenyl group having 2 to 6 carbon atoms, and X represents NH or O. n represents any integer from 1 to 5.] [2] R in the above general formula (1) １ and R ２ is a hydrogen atom, and R ３ is a methyl group, n is 1 to 4, and R ４ is a (meth)acryloyl group or a styryl group, and X is O. [3] The composition for pattern formation according to [1] or [2], wherein the general formula (1) is general formula (2). [In the formula, R ５represents a hydrogen atom or a methyl group.] [4] The pattern-forming composition according to any one of [1] to [3], wherein the resin contains an alkali-soluble resin. [5] The pattern-forming composition according to any one of [1] to [4], comprising: (A) a compound represented by general formula (1) above; (B) a compound having two or more polymerizable functional groups in the molecule, different from the compound represented by general formula (1) above; (C) a photopolymerization initiator; and (D) a resin. [6] The pattern-forming composition according to [5], wherein the polymerizable functional group in (B) is a (meth)acryloyl group. [7] The pattern-forming composition according to [5] or [6], wherein the (D) resin contains an alkali-soluble resin. [8] The pattern-forming composition according to any one of [5] to [7], further comprising (E) a thermal crosslinking agent. [9] The pattern-forming composition according to [8], wherein the (E) thermal crosslinking agent contains an epoxy-based crosslinking agent.

[10] The pattern-forming composition according to any one of [5] to [9], further comprising (F) a phosphor.

[11] The pattern-forming composition according to any one of [1] to

[10] , further comprising (G) light-scattering particles.

[12] The pattern-forming composition according to

[11] , wherein the (G) light-scattering particles are titanium oxide particles.

[13] The pattern-forming composition according to

[11] or

[12] , wherein the content of the (G) light-scattering particles is 1 mass % or more based on the solid content.

[14] The pattern-forming composition according to any one of [1] to

[13] , wherein a film formed from the composition has a haze value of 18% or more.

[15] The pattern-forming composition according to any one of

[10] to

[14] , wherein the pattern-forming composition is a composition for forming a wavelength conversion film.

[16] The pattern-forming composition according to

[15] , wherein the pattern-forming composition is a composition for forming a wavelength conversion film for display.

[17] A resist pattern film formed from the pattern-forming composition according to any one of [1] to

[16] .

[0007] According to the present invention, a pattern-forming composition (particularly a negative-tone pattern-forming composition) can be used in an alkaline solution for development after exposure under atmospheric conditions, and the curable pattern-forming composition has the ability to maintain a sufficient thickness in the exposed area even after development. Specifically, a high film residual ratio (specifically, 50% or more, preferably 70% or more) can be maintained. According to the present invention, a high film residual ratio can be maintained, particularly when a resist film formed using a photoradical polymerization initiator as a photopolymerization initiator is developed with an aqueous alkaline developer after exposure under atmospheric conditions. According to the present invention, an alkaline solution can be used for development, eliminating the need for development with an organic solvent and providing excellent handleability. According to the present invention, a resist pattern film can be formed from the pattern-forming composition, thereby providing a resist pattern film containing the pattern-forming composition. According to the present invention, a composition for forming a wavelength conversion film (i.e., a wavelength conversion film-forming composition) can be prepared by using the pattern-forming composition together with a phosphor. In this case, a wavelength-converting film formed from the composition for forming a wavelength-converting film can provide not only the above-mentioned high film retention rate but also high conversion efficiency even after exposure and development treatment under atmospheric conditions. Specifically, a wavelength-converting film can be formed that not only has the above-mentioned high film retention rate but also has a conversion efficiency of 30% or more. Therefore, the composition for forming a wavelength-converting film can also be used for displays.

[0008] The present invention will be described in more detail below. The pattern-forming composition of the present invention contains a compound represented by the following general formula (1) and a resin. [In general formula (1), R １ and R ２ each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; R ３ represents any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; R ４represents any one selected from the group consisting of a (meth)acryloyl group, a styryl group, and an alkenyl group having 2 to 6 carbon atoms, X represents NH or O, and n represents an integer of 1 to 5.

[0009] In the following description, the solid content refers to components other than the solvent that constitute the pattern-forming composition.

[0010] [Compound Represented by General Formula (1)] The compound represented by general formula (1) is a compound represented by the following formula. [In general formula (1), R １ and R ２ each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; R ３ represents any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; R ４ represents any one selected from the group consisting of a (meth)acryloyl group, a styryl group, and an alkenyl group having 2 to 6 carbon atoms, X represents NH or O, and n represents an integer of 1 to 5.

[0011] R １ , R ２ and R ３ Examples of the alkyl group having 1 to 6 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0012] R １ , R ２ and R ３ Examples of the alkenyl group having 2 to 6 carbon atoms represented by include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group (such as a cis-3-hexenyl group), and a cyclohexenyl group.

[0013] R １ , R２ and R ３ Examples of the aryl group represented by include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0014] R １ , R ２ and R ３ Examples of the aralkyl group represented by include a benzyl group, a 2-phenylethyl group, a 2-naphthylethyl group, and a diphenylmethyl group.

[0015] R １ and R ２ are each preferably any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. １ and R ２ are preferably both hydrogen atoms.

[0016] Also R ３ is preferably any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.

[0017] R ４ represents any one selected from the group consisting of a (meth)acryloyl group, a styryl group, and an alkenyl group having 2 to 6 carbon atoms. In this specification, the term "(meth)acryloyl group" refers to either an acryloyl group or a methacryloyl group. This also applies to (meth)acrylic acid, (meth)acrylate, and (meth)acryloyloxy group.

[0018] R ４Examples of the alkenyl group having 2 to 6 carbon atoms represented by the formula (I) include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group (such as a cis-3-hexenyl group), and a cyclohexenyl group, and an alkenyl group having 2 to 5 carbon atoms is preferred.

[0019] Among these, R ４ is preferably a (meth)acryloyl group or a styryl group, and more preferably a (meth)acryloyl group, because it can effectively function as a polymerizable group and the effects of the present invention can be more effectively achieved.

[0020] In general formula (I), n represents any integer from 1 to 5. Preferably, n is any integer from 1 to 4, more preferably 1 or 2, and even more preferably 1. The compound of general formula (I) has a plurality of polymerizable functional groups, and therefore can be cured by polymerization. In addition, the effect of intermolecular interactions is kept low, and therefore the compound is characterized by being less likely to become viscous.

[0021] X may be either NH or O, but is preferably O.

[0022] Specific examples of the compound represented by the general formula (1) include the following compounds.

[0023]

[0024] The compound represented by the above general formula (1) is preferably a compound represented by the following general formula (II), in view of the ease of availability of raw materials and the like, and from the viewpoint of more efficiently and / or effectively achieving the effects of the present invention.

[0025]

[0026] In general formula (II), R ５ represents a hydrogen atom or a methyl group. ５ When is a methyl group, it is IPEMA (isoprenyl methacrylate).

[0027] The pattern-forming composition of the present invention may contain only one type of compound represented by the general formula (1), or may contain two or more types of compounds.

[0028] In the pattern-forming composition of the present invention, the content of the compound represented by the general formula (1) is not particularly limited, but from the viewpoint of more effectively achieving the effects of the present invention, it is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more of the solid content, and is preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less of the solid content.

[0029] In the pattern-forming composition of the present invention, there is no particular limitation on the content of the compound represented by the general formula (1). As described below, the pattern-forming composition of the present invention may contain a compound having two or more polymerizable functional groups in the molecule and different from the compound represented by the general formula (1). In this case, if the compound represented by the general formula (1) is component (A) and the compound different from the compound represented by the general formula (1) is component (B), from the viewpoint of more effectively achieving the effects of the present invention, the content of the component (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to 100% by mass of the total of the components (A) and (B). Furthermore, the content of the component (A) is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, relative to 100% by mass of the total of the components (A) and (B).

[0030] [Resin (Base Polymer)] The resin may be selected from known resins used as binders in pattern-forming compositions, etc. In the present application, the resin may also be referred to as a "base polymer."

[0031] The resin can be appropriately selected from resins used as base polymers in pattern-forming compositions, and examples thereof include polyolefin resins such as polystyrene, polyethylene, polypropylene, polyester, polyimide, polyamide, and polymethylpentene; acrylic resins such as polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, and benzyl methacrylate-methacrylic acid copolymer, ethylene-vinyl acetate copolymer; polyvinyl butyrate; and cellulose ester resins such as triacetyl cellulose and nitrocellulose. The resin may be an alkali-soluble resin, as described below, or may contain both an alkali-soluble resin and another resin. Among these, acrylic resins are preferred, and methyl methacrylate-methacrylic acid copolymers are more preferred. Each of the resins may be commercially available, or those obtained by the reaction of unsaturated double bond groups may be synthesized according to a conventional method, such as radical polymerization using a polymerization initiator.

[0032] The average molecular weight of the resin is not particularly limited, but the weight average molecular weight (Mw) is usually 5,000 to 100,000, and preferably 7,000 to 50,000. In the present invention, the average molecular weight is a polystyrene-equivalent value determined by gel permeation chromatography.

[0033] The resin may be prepared by blending a polymerizable monomer and a photopolymerization initiator, and polymerizing the resulting resin after film formation. These may also be used in combination with the resin described above. The polymerizable monomer is not particularly limited as long as it is used together with a photopolymerization initiator and polymerizes upon irradiation with light, but an ethylenically unsaturated monomer that is a radically polymerizable compound is preferred. In the present invention, the ethylenically unsaturated monomer may be any of a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher functional monomer.

[0034] [Ethylenically Unsaturated Monomer] Examples of the ethylenically unsaturated monofunctional monomer include a mono(meth)acrylate represented by the following formula (M1), a mono(meth)acrylamide compound represented by the following formula (M2), and an amide compound represented by the following formula (M3).

[0035]

[0036] In formula (M1), R ｍ１ represents a hydrogen atom or a methyl group, and R ｍ２ represents a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The hydrocarbon group may be linear, branched, or cyclic. From the viewpoints of excellent ejection stability in the inkjet method and an excellent effect of improving external quantum efficiency, the R ｍ２ The number of carbon atoms is preferably not more than 10. The hydrocarbon group may be substituted, for example, may have an ether bond.

[0037] In formula (M2), R ｍ１ is the same as above. ｍ３ and R ｍ４ are each independently a hydrogen atom or a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The hydrocarbon group may be linear, branched, or cyclic. ｍ３ and R ｍ４ may be bonded to each other to form a ring. In view of excellent ejection stability in the ink jet method and an excellent effect of improving external quantum efficiency, ｍ３ and R ｍ４ The total number of carbon atoms is preferably not more than 10. The hydrocarbon group may be substituted, for example, may have an ether bond.

[0038] In formula (M3), R ｍ５ represents a hydrogen atom or a methyl group, and R ｍ６represents a monovalent hydrocarbon group having an ethylenically unsaturated group. The hydrocarbon group may be linear, branched, or cyclic. From the viewpoints of excellent ejection stability in the ink-jet method and an excellent effect of improving external quantum efficiency, the R ｍ６ The number of carbon atoms is preferably not more than 10. The hydrocarbon group may be substituted, for example, may have an ether bond.

[0039] Specific examples of the mono(meth)acrylate represented by the formula (M1) include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, amyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, nonyl(meth)acrylate, dodecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, cyclohexyl(meth)acrylate, methoxyethyl(meth)acrylate, butoxyethyl(meth)acrylate, phenoxyethyl(meth)acrylate, nonylphenoxyethyl(meth)acrylate, glycidyl(meth)acrylate, and dimethylaminoethyl(meth)acrylate. acrylate, diethylaminoethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylbenzyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, and the like.

[0040] Specific examples of the mono(meth)acrylamide compound represented by the formula (M2) above include 4-(meth)acryloylmorpholine, (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-diisopropyl(meth)acrylamide.

[0041] Specific examples of the amide compound represented by the formula (M3) include N-vinylformamide, N-vinylacetamide, N-allylformamide, and N-allylacetamide.

[0042] In the present invention, among the above-mentioned monofunctional monomers, ethoxyethoxyethyl (meth)acrylate, N-vinylformamide, 4-(meth)acryloylmorpholine, N,N-dimethylacrylamide, and N,N-diethyl(meth)acrylamide are preferably used.

[0043] Examples of the ethylenically unsaturated bifunctional monomer include a di(meth)acrylate represented by the following formula (M4) and a di(meth)acrylamide compound represented by the following formula (M5).

[0044]

[0045] In formula (M4), a plurality of R ｍ７ each independently represents a hydrogen atom or a methyl group, R ｍ８ represents a divalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The divalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoint of excellent ejection stability and an excellent effect of improving external quantum efficiency, the number of carbon atoms in the divalent hydrocarbon group is preferably 10 or less. The divalent hydrocarbon group may be substituted, and may have, for example, an ether bond.

[0046] In formula (M5), a plurality of R ｍ９ each independently represents a hydrogen atom or a methyl group, and a plurality of R ｍ１０are each independently a hydrogen atom or a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The monovalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoints of excellent ejection stability in the inkjet method and an excellent effect of improving external quantum efficiency, the R ｍ１０ The number of carbon atoms in R is preferably 7 or less. The monovalent hydrocarbon group may be substituted, for example, may have an ether bond. ｍ１１ represents a divalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The divalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoint of excellent ejection stability and an excellent effect of improving external quantum efficiency, the number of carbon atoms in the divalent hydrocarbon group is preferably 10 or less. The divalent hydrocarbon group may be substituted, and may have, for example, an ether bond.

[0047] Specific examples of the di(meth)acrylate represented by the formula (M4) include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, (Meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalic acid ester diacrylate, di(meth)acrylate in which two hydroxyl groups of tris(2-hydroxyethyl)isocyanurate are substituted with (meth)acryloyloxy groups, di(meth)acrylate in which two hydroxyl groups of a diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol are substituted with (meth)acryloyloxy groups, bisphenol A Examples of such a di(meth)acrylate include a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, and two hydroxyl groups of the diol are substituted with (meth)acryloyloxy groups; a triol obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane, and two hydroxyl groups of the triol are substituted with (meth)acryloyloxy groups; and a di(meth)acrylate obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A, and two hydroxyl groups of the diol are substituted with (meth)acryloyloxy groups.

[0048] Specific examples of the di(meth)acrylamide compound represented by formula (M5) include N,N-[oxybis(2,1-ethanediyloxy-3,1-propanediyl)]bisacrylamide, etc. Commercially available di(meth)acrylamide compounds may be used, and specific examples thereof include FOM-03008 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

[0049] In the present invention, among the above-mentioned bifunctional monomers, dipropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate are preferably used.

[0050] Examples of the tri- or higher functional ethylenically unsaturated monomer include tri(meth)acrylates, tetra(meth)acrylates, and penta(meth)acrylates represented by the following formula (M6), and tri(meth)acrylamide compounds and tetra(meth)acrylamide compounds represented by the following formula (M7).

[0051]

[0052] In formula (M6), a plurality of R ｍ１２ each independently represents a hydrogen atom or a methyl group, R ｍ１３ represents a trivalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The trivalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoint of excellent ejection stability and an excellent effect of improving external quantum efficiency, the number of carbon atoms in the hydrocarbon group is preferably 10 or less, more preferably 5 or less. The trivalent hydrocarbon group may be substituted, and may have, for example, an ether bond.

[0053] In formula (M7), a plurality of R ｍ１４ each independently represents a hydrogen atom or a methyl group, and a plurality of R ｍ１５are each independently a hydrogen atom or a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The monovalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoints of excellent ejection stability in the inkjet method and an excellent effect of improving external quantum efficiency, the R ｍ１５ The number of carbon atoms in R is preferably 7 or less. The monovalent hydrocarbon group may be substituted, for example, may have an ether bond. ｍ１６ are each independently a divalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The divalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoint of excellent ejection stability and an excellent effect of improving external quantum efficiency, the number of carbon atoms in the divalent hydrocarbon group is preferably 10 or less. The divalent hydrocarbon group may be substituted, and may have, for example, an ether bond.

[0054] Specific examples of the tri(meth)acrylate represented by the formula (M6) include glycerin tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate.

[0055] Specific examples of the tetra(meth)acrylate include pentaerythritol tetraacrylate and ditrimethylolpropane tetraacrylate.

[0056] Specific examples of the penta(meth)acrylate include dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.

[0057] Specific examples of the tri(meth)acrylamide compound represented by formula (M7) include N,N-bis(2-acrylamidoethyl)acrylamide, etc. Commercially available products may be used as the tri(meth)acrylamide compound, and specific examples thereof include FOM-03007 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0058] Specific examples of the tetra(meth)acrylamide compound include N-[tris(3-acrylamidopropoxymethyl)methyl]acrylamide, N,N-1,2-ethanediylbis{N-[2-(acryloylamino)ethyl]acrylamide}, etc. Commercially available tetra(meth)acrylamide compounds may be used, and specific examples thereof include FOM-03006 and FOM-03009 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0059] In the present invention, among the above-mentioned trifunctional or higher functional monomers, glycerin tri(meth)acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferably used.

[0060] In the present invention, the alkali-soluble resin is a resin having an alkali-soluble group, specific examples of which include a phenolic hydroxy group, a carboxy group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid group, a boronic acid group, and an active methylene group.

[0061] The active methylene group is a methylene group (-CH ２ -) that has a carbonyl group at the adjacent position and is reactive with nucleophiles.

[0062] The active methylene group is more preferably a group represented by the following formula (b1).

[0063] (In the formula, R ｂ represents an alkyl group, an alkoxy group, or a phenyl group, and the dashed line represents a bond.

[0064] In the above formula (b1), R ｂ Examples of the alkyl group represented by include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferred. Specific examples of such alkyl groups include methyl, ethyl, n-propyl, and i-propyl groups. Of these, methyl, ethyl, and n-propyl groups are preferred.

[0065] In the above formula (b1), R ｂExamples of the alkoxy group represented by include alkoxy groups having 1 to 20 carbon atoms, and preferably alkoxy groups having 1 to 5 carbon atoms. Specific examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, and t-butoxy groups. Of these, methoxy, ethoxy, and n-propoxy groups are preferred.

[0066] Specific examples of the group represented by formula (b1) above include, but are not limited to, groups represented by the following formulae (b1-1) to (b1-5): In the structural formula, dashed lines represent bonds.

[0067]

[0068] Among the above alkali-soluble groups, alkali-soluble resins having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxy group and having a number average molecular weight of 2,000 to 50,000 are preferred.

[0069] As described above, the alkali-soluble resin preferably has a number-average molecular weight in the range of 2,000 to 50,000, but if the number-average molecular weight is 50,000 or less, development residues are less likely to be generated and the required sensitivity can be obtained, while if the number-average molecular weight is 2,000 or more, film loss in exposed areas is less likely to occur during development and sufficient curability can be obtained.

[0070] The alkali-soluble resin may have the above structure, and there are no particular limitations on the types of main chain skeleton and side chains of the polymer constituting the resin.

[0071] Examples of the alkali-soluble resin include acrylic resins, polyhydroxystyrene resins, polyimide precursors, polyimides, and polyesters.

[0072] In the present invention, an alkali-soluble resin made of a copolymer obtained by polymerizing a plurality of types of monomers can also be used. Furthermore, the alkali-soluble resin may be a blend of a plurality of types of alkali-soluble resins.

[0073] The alkali-soluble resin may be an acrylic polymer, which is an acrylic resin. In the present invention, the term "acrylic polymer" refers to a resin obtained by the polymerization reaction of a monomer having an unsaturated double bond group, resulting in the reaction of the unsaturated double bond group portion. Examples of alkali-soluble acrylic polymers include copolymers formed from monomers exhibiting alkali solubility, i.e., monomers having at least one alkali-soluble group selected from the above-mentioned group, and at least one monomer selected from the group of monomers copolymerizable with these monomers, as essential structural units. The number-average molecular weight of the alkali-soluble resin is preferably 2,000 to 50,000. A number-average molecular weight of 50,000 or less reduces the likelihood of residue formation.

[0074] The above-mentioned "monomer having at least one selected from alkali-soluble groups" includes a monomer having a carboxy group, a phenolic hydroxy group, and a monomer having an imide group. These monomers are not limited to those having one carboxy group or one phenolic hydroxy group, but may also have multiple carboxy groups or one phenolic hydroxy group.

[0075] Specific examples of the above-mentioned monomers are listed below, but are not limited to these. Examples of monomers having a carboxy group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

[0076] Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and 4-hydroxyphenyl methacrylate.

[0077] Examples of the monomer having an imide group include maleimide.

[0078] In the production of the alkali-soluble acrylic polymer, the ratio of the monomer having an alkali-soluble group and an unsaturated double bond group to all the monomers used in the production of the alkali-soluble acrylic polymer is preferably 5 to 90 mol %, more preferably 10 to 60 mol %, and most preferably 10 to 40 mol %. When the ratio of the monomer having an alkali-soluble group and an unsaturated double bond group is 10 mol % or more, sufficient alkali solubility can be obtained.

[0079] The alkali-soluble acrylic polymer may be copolymerized with a monomer having a hydroxyalkyl group and an unsaturated double bond group in order to further stabilize the pattern shape after curing.

[0080] Specific examples of monomers having a hydroxyalkyl group and an unsaturated double bond group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

[0081] In the production of the alkali-soluble acrylic polymer, the ratio of the monomer having a hydroxyalkyl group and an unsaturated double bond group is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass. When the ratio of the monomer having a hydroxyalkyl group and an unsaturated double bond group is 10% by mass or more, the effect of stabilizing the pattern shape of the copolymer is obtained. When this ratio is 60% by mass or less, the content of the alkali-soluble group falls within an appropriate range, and sufficient properties such as developability are obtained.

[0082] The alkali-soluble acrylic polymer may be further copolymerized with an N-substituted maleimide compound in order to increase the Tg of the copolymer.

[0083] Specific examples of the N-substituted maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. From the viewpoint of transparency, those not having an aromatic ring are preferred, and from the viewpoints of developability, transparency, and heat resistance, those having an alicyclic skeleton are more preferred, with cyclohexylmaleimide being even more preferred.

[0084] The proportion of N-substituted maleimide in the production of the alkali-soluble acrylic polymer is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass. When the proportion of N-substituted maleimide is 10% by mass or more, the Tg of the copolymer increases, and therefore the Tg of the final resist film also increases, resulting in sufficient heat resistance and light resistance. When the proportion is 60% by mass or less, sufficient transparency is obtained.

[0085] In the present invention, the alkali-soluble acrylic polymer may also be a copolymer containing a monomer other than the above-mentioned monomers (hereinafter referred to as "other monomers") as a constituent unit. Specifically, the other monomer may be any monomer copolymerizable with at least one selected from the group consisting of the above-mentioned monomers having a carboxy group and the monomers having a phenolic hydroxy group, and is not particularly limited as long as it does not impair the properties of the alkali-soluble acrylic polymer. Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds. Specific examples of the other monomers are listed below, but are not limited to these.

[0086] Specific examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, and methoxytriethylene glycol acrylate. acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, and the like.

[0087] Specific examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, and methoxytriethylene glycol methacrylate. Examples of the methacrylate include 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, and poly(ethylene glycol) ethyl ether methacrylate.

[0088] Specific examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide.

[0089] Specific examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0090] The styrene compound may be a styrene having no hydroxy group, specific examples of which include styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

[0091] In the production of the alkali-soluble acrylic polymer, the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 20% by mass or less. When the ratio of the other monomers is 80% by mass or less, the effects of the present invention can be sufficiently obtained.

[0092] The method for obtaining the alkali-soluble acrylic polymer is not particularly limited, but can be, for example, by polymerizing a monomer having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a group that generates a carboxylic acid upon the action of heat or acid, and a phenolic hydroxyl group upon the action of heat or acid; a monomer having a hydroxyalkyl group; and, optionally, a monomer having at least one group selected from a crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, or a blocked isocyanate group, and a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, or a blocked isocyanate group, at a temperature of 50 to 110°C in a solvent containing, optionally, other copolymerizable monomers; and, optionally, a polymerization initiator. The solvent used in this process is not particularly limited, as long as it dissolves the monomers that constitute the alkali-soluble acrylic polymer and the alkali-soluble acrylic polymer. Specific examples include the following solvents.

[0093] Examples of the solvent used in the above reaction include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, and 3-methyl-2-pentanone. Examples of suitable solvents include ethanol, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, and butyl lactate are preferred from the viewpoints of good film-forming properties and high safety. These may be used alone or in combination of two or more.

[0094] The alkali-soluble acrylic polymer thus obtained is usually in the form of a solution dissolved in a solvent.

[0095] Furthermore, the solution of the specific copolymer obtained as described above can be reprecipitated by adding diethyl ether, water, or the like under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the specific copolymer. This procedure can remove polymerization initiators and unreacted monomers coexisting with the specific copolymer, resulting in a purified powder of the specific copolymer. If the specific copolymer cannot be sufficiently purified in a single procedure, the obtained powder can be redissolved in a solvent and the above procedure can be repeated. In the present invention, the powder of the specific copolymer may be used as is, or the powder may be redissolved in an appropriate solvent, such as the solvent used in the polymerization reaction, and used in the form of a solution.

[0096] In addition, as the alkali-soluble resin, polyimide precursors such as polyamic acid, polyamic acid ester, and partially imidized polyamic acid, and polyimides such as carboxylic acid group-containing polyimides can also be used, and the type of these resins is not particularly limited as long as they are alkali-soluble.

[0097] The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensation of (a) a tetracarboxylic dianhydride and (b) a diamine compound.

[0098] The (a) tetracarboxylic acid dianhydride is not particularly limited, and specific examples thereof include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride; and 1,2-dimethyl-1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. Examples of the dianhydride include alicyclic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetracarboxylic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butane tetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0099] The (b) diamine compound is not particularly limited, and specific examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3,5-dicarboxyphenyl)ether, bis(4-amino-3-carboxyphenyl)sulfone, bis(4-amino-3,5-dicarboxyphenyl)sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, phenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxyphenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane; 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl)ether, bis(4-amino-3-hydroxyphenyl)ether, bis(4-amino-3,5-dihydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl)methane, bis(3-amino bis(4-amino-3-hydroxyphenyl)sulfone, bis(4-amino-3,5-dihydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,Diamine compounds having a phenolic hydroxy group, such as 5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]sulfone, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane, and 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane; Examples of the diamine compound include diamine compounds having a thiophenol group such as 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, and 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane; and diamine compounds having a sulfonic acid group such as 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis(4-aminobenzene-3-sulfonic acid)ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, and 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. Further, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3',5,5'-tetramethylbenzidine, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,Examples of diamine compounds include 4-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4-toluyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 2,2'-bis(trifluoromethyl)benzidine. These may be used alone or in combination of two or more.

[0100] When the polyamic acid is produced from (a) a tetracarboxylic dianhydride and (b) a diamine compound, the compounding ratio of the two compounds, i.e., the total number of moles of (b) a diamine compound / the total number of moles of (a) a tetracarboxylic dianhydride, is preferably 0.7 to 1.2. As in a normal polycondensation reaction, the closer this molar ratio is to 1, the greater the degree of polymerization of the polyamic acid produced and the greater the molecular weight.

[0101] Furthermore, when polymerization is carried out using an excess diamine compound, the terminal amino groups of the remaining polyamic acid can be protected by reacting them with a carboxylic acid anhydride. Examples of such carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

[0102] In the production of polyamic acid, the reaction temperature for the reaction between a diamine compound and a tetracarboxylic dianhydride can be selected from the range of typically -20 to 150°C, preferably -5 to 100°C. To obtain a high-molecular-weight polyamic acid, the reaction temperature is appropriately selected from the range of 5 to 40°C and the reaction time from 1 to 48 hours. To obtain a low-molecular-weight, partially imidized polyamic acid with high storage stability, it is more preferable to select a reaction temperature from 40 to 90°C and a reaction time from 10 hours or more. Furthermore, when protecting the terminal amino groups with an acid anhydride, the reaction temperature can be selected from the range of -20 to 150°C, preferably -5 to 100°C.

[0103] The reaction of the diamine compound with the tetracarboxylic dianhydride can be carried out in a solvent, and examples of the solvent that can be used include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Examples of suitable solvents include diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These may be used alone or in combination of two or more. Furthermore, even if a solvent does not dissolve polyamic acid, it may be mixed with the above solvent to the extent that the polyamic acid produced by the polymerization reaction does not precipitate.

[0104] The solution containing the polyamic acid thus obtained can be used as it is for preparing a negative-type photosensitive resin composition (also referred to as a "negative-type pattern-forming composition" in the present application.) The polyamic acid can also be recovered and used by precipitation and isolation in a poor solvent such as water, methanol, or ethanol.

[0105] The alkali-soluble resin may be any polyimide. The polyimide used in the present invention is a polyimide precursor such as the polyamic acid described above that is chemically or thermally imidized to 50% or more.

[0106] The polyimide preferably has a group selected from a carboxy group and a phenolic hydroxy group to impart alkali solubility. Methods for introducing the carboxy group or the phenolic hydroxy group into the polyimide include a method using a monomer having a carboxy group or a phenolic hydroxy group, a method of capping the amine end with an acid anhydride having a carboxy group or a phenolic hydroxy group, and a method of imidizing a polyimide precursor such as a polyamic acid to an imidization rate of 99% or less.

[0107] Such polyimides can be obtained by synthesizing a polyimide precursor such as the polyamic acid described above, followed by chemical imidization or thermal imidization. Chemical imidization is typically carried out by adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting the solution at room temperature to 100°C. Thermal imidization is typically carried out by heating a polyimide precursor solution at a temperature of 180 to 250°C while dehydrating it.

[0108] Furthermore, as the alkali-soluble resin, a phenol novolac resin can also be used.

[0109] Furthermore, polyester polycarboxylic acids can also be used as the alkali-soluble resin. Polyester polycarboxylic acids can be obtained from acid dianhydrides and diols by the method described in International Publication No. 2009 / 051186. Examples of acid dianhydrides include the above-mentioned (a) tetracarboxylic dianhydrides. Examples of diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol; alicyclic diols such as hydrogenated bisphenol A, hydrogenated bisphenol F, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; and aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0110] The alkali-soluble resin of the present invention may be a copolymer further having a self-crosslinking group, or further having a group (hereinafter also referred to as a crosslinking group) that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxy group, an amide group, and an amino group.

[0111] Specific examples of the self-crosslinking group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group, and a blocked isocyanate group.

[0112] Specific examples of the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a vinyl group, and a blocked isocyanate group.

[0113] When such a self-crosslinking group or crosslinkable group is contained in the alkali-soluble resin, the content thereof is preferably 0.1 to 0.9 per repeating unit in the alkali-soluble resin, and from the viewpoints of developability and solvent resistance, it is more preferably 0.1 to 0.8.

[0114] When the alkali-soluble resin further has a repeating unit having at least one selected from the crosslinkable group and the self-crosslinkable group, for example, in the case of an alkali-soluble acrylic polymer, it is sufficient to copolymerize an unsaturated compound that has radical polymerizability and further has at least one selected from the crosslinkable group and the self-crosslinkable group.

[0115] Specific examples of the radically polymerizable unsaturated compound having an N-alkoxymethyl group include N-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, and N-methylolacrylamide.

[0116] Specific examples of the radically polymerizable monomer having a hydroxymethylamide group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

[0117] Specific examples of the radically polymerizable monomer further having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.

[0118] Specific examples of radically polymerizable unsaturated compounds further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate are preferred. These may be used alone or in combination of two or more.

[0119] Examples of the radically polymerizable unsaturated compound further having an oxetanyl group include (meth)acrylic acid esters having an oxetanyl group. Specific examples of such monomers include 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, and 2-(acryloyloxymethyl)-4-trifluoromethyloxetane. Among these, 3-(methacryloyloxymethyl)-3-ethyl-oxetane and 3-(acryloyloxymethyl)-3-ethyl-oxetane are preferred.

[0120] Specific examples of the radically polymerizable monomer further having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

[0121] Specific examples of the radically polymerizable monomer having a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.

[0122] In the alkali-soluble resin of the present invention, the content of the structural unit derived from an unsaturated compound having radical polymerizability and having at least one group selected from the above-mentioned crosslinkable group and the above-mentioned self-crosslinkable group is preferably 10 to 70 mass %, more preferably 20 to 60 mass %, of all repeating units contained in the alkali-soluble resin. When the content of this structural unit is 10 mass % or more, the heat resistance and surface hardness of the cured film are improved. On the other hand, when the content of this structural unit is 70 mass % or less, the storage stability of the radiation-sensitive resin composition is improved.

[0123] When the alkali-soluble resin of the present invention is used in combination with the polymerizable monomer, it is preferable that the alkali-soluble resin has a substituent capable of reacting with the polymerizable monomer. Examples of the substituent capable of reacting with the polymerizable monomer include a radically polymerizable group such as an ethylenically unsaturated group. Here, the radically polymerizable group refers to a group that initiates a polymerization reaction in the presence of a radical, and the reaction proceeds in a chain reaction.

[0124] The method for obtaining an alkali-soluble resin having a substituent reactive with a polymerizable monomer is not particularly limited as long as it can obtain a resin with stable properties, but examples include a method of copolymerizing a monomer having a substituent reactive with a polymerizable monomer, and a method of synthesizing an alkali-soluble resin that does not have a substituent reactive with a polymerizable monomer, and then adding a compound having a substituent reactive with a polymerizable monomer by thermal reaction. When the alkali-soluble resin is an alkali-soluble acrylic polymer and an ethylenically unsaturated group is incorporated, the former method may cause the substituent reactive with the polymerizable monomer to react during the polymerization process, leading to the risk of gelation, so the latter method is preferred.

[0125] Specific methods for incorporating ethylenically unsaturated groups into alkali-soluble resins include, for example, adding glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, or the like to an alkali-soluble acrylic polymer synthesized using a radically polymerizable monomer having a carboxy group or a phenolic hydroxyl group. In this case, by reducing the molar ratio of the monomer to be added relative to the carboxy group or phenolic hydroxyl group in the resin, it is possible to introduce a substituent reactive with the polymerizable monomer while maintaining the alkali-solubility of the resin derived from the carboxy group or phenolic hydroxyl group. Another example includes, for example, adding a monomer having a substituent reactive with a polymerizable monomer capable of thermally reacting with the thermally reactive group in the resin to an alkali-soluble acrylic polymer obtained by copolymerizing a radically polymerizable monomer having a thermally reactive group. Specific examples include adding (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, or the like to an alkali-soluble acrylic polymer copolymerized with glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, or the like.

[0126] Examples of methods for incorporating a cationically polymerizable group into an alkali-soluble resin include a method of synthesizing an alkali-soluble resin by radical polymerization using a compound having an unsaturated compound that has radical polymerizability and further has at least one type of cationically polymerizable group selected from the above-mentioned cationically polymerizable groups.

[0127] In the alkali-soluble resin of the present invention, the proportion of repeating units having a substituent reactive with a polymerizable monomer is preferably 5 to 60 mass %, more preferably 10 to 50 mass %, and even more preferably 10 to 40 mass %, of all repeating units contained in the alkali-soluble resin. When the content of this structural unit is 5 mass % or more, the heat resistance and chemical resistance of the cured film are improved. On the other hand, when the content of this structural unit is 60 mass % or less, the pattern formability of the radiation-sensitive resin composition is improved.

[0128] In the present invention, the alkali-soluble resin may be a mixture of a plurality of types of alkali-soluble resins.

[0129] When the alkali-soluble resin is used, the content thereof is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to 100% by mass of the total of the polymerizable monomer and the alkali-soluble resin, from the viewpoint of film-forming properties, and the upper limit of the content thereof is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, from the viewpoint of pattern-forming properties.

[0130] The content of the resin (corresponding to the component (D) described later) is preferably 25% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 85% by mass or less, and even more preferably 35% by mass or more and 80% by mass or less, of the solid content.

[0131] In the present invention, in addition to the compound represented by the general formula (1) and the resin, a compound having two or more polymerizable functional groups in its molecule and different from the compound represented by the general formula (1) and a photopolymerization initiator may be included. In this case, for convenience, the above components are referred to as components (A) to (D). In this application, the compound represented by the general formula (1) is referred to as "(A) the compound represented by the general formula (1)" or simply "(A)," the compound having two or more polymerizable functional groups in its molecule and different from the compound represented by the general formula (1) is referred to as "(B) the compound having two or more polymerizable functional groups in its molecule and different from the compound represented by the general formula (1)" or simply "(B)," the photopolymerization initiator is referred to as "(C) the photopolymerization initiator" or simply "(C)," and the resin is referred to as "(D) resin" or simply "(D)." Therefore, the compound represented by the general formula (1) directly corresponds to "(A) the compound represented by the general formula (1)," and the resin is referred to as "(D) resin."

[0132] "(B) A compound having two or more polymerizable functional groups in its molecule and different from the compound represented by general formula (1)" Here, the compound (B) having two or more polymerizable functional groups in its molecule and different from the compound represented by general formula (1) refers to a compound having two or more polymerizable functional groups in its molecule (excluding the compound represented by general formula (1)). The polymerizable functional group is preferably a radically polymerizable functional group. The radically polymerizable functional group is particularly preferably a radically polymerizable functional group that undergoes a polymerization reaction due to radicals from a photopolymerization initiator. Specific examples of (B) include radically polymerizable functional groups such as a (meth)acryloyl group and a vinyl group. Of these, a (meth)acryloyl group is preferred. Examples of (B) include polyvalent (meth)acrylic acid esters having two or more (meth)acryloyloxy groups in their molecules. The polyvalent (meth)acrylic acid ester may be a hydroxyl group-containing polyvalent (meth)acrylic acid ester. The composition of the present invention may contain only one type of (B), or two or more types of (B).

[0133] As the polyhydric (meth)acrylic acid ester, a (meth)acrylic acid ester of a polyhydric alcohol such as a diol or triol can be used, and more specifically, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexamethylene di(meth)acrylate, neopentyl glycol di(meth)acrylate, Examples of the di(meth)acrylate include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, glycerin di(meth)acrylate, hydrogenated bisphenol A or hydrogenated bisphenol F di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and trimethylolpropane tri(meth)acrylate.

[0134] Examples of hydroxyl group-containing polyvalent (meth)acrylic acid esters include glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, and dipentaerythritol monohydroxypenta(meth)acrylate.

[0135] Among these, from the viewpoint of more effectively achieving the effects of the present invention, polyhydric (meth)acrylic acid esters are preferred as (B), and 1,6-hexamethylene di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and pentaerythritol tri(meth)acrylate are more preferred.

[0136] When the composition contains the component (B), from the viewpoint of more effectively achieving the effects of the present invention, the content of the component (B) in the composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to 100% by mass of the total of the components (A) and (B). The upper limit of the content can be appropriately set depending on the application of the composition, and is, for example, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, of the solid content.

[0137] When the composition of the present invention contains the component (B), from the viewpoint of more effectively achieving the effects of the present invention, the total content of the components (A) and (B) in the composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the solid content. The upper limit of this content can be appropriately set depending on the application of the composition, but is, for example, preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, based on the solid content.

[0138] [(C) Photopolymerization Initiator] The photopolymerization initiator (C) is not particularly limited as long as the object of the present invention can be achieved. In the present invention, it is preferable to use a photoradical polymerization initiator as the photopolymerization initiator (C). In particular, in consideration of compatibility with general methods for producing wavelength conversion members formed from a pattern-forming composition and a wavelength conversion film-forming composition using the composition, it is preferable to use a photoradical polymerizable compound. Furthermore, according to the present invention, even when a photoradical polymerization initiator is used as the photopolymerization initiator (C), a cured film with excellent insolubility in a developer can be formed as a wavelength conversion film without being inhibited by oxygen in the curing process.

[0139] As the photoradical polymerization initiator, a molecular cleavage type or hydrogen abstraction type photoradical polymerization initiator is preferably used.

[0140] Examples of molecular cleavage type photoradical polymerization initiators include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide. Other molecular cleavage type photoradical polymerization initiators that may be used in combination include, for example, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0141] Examples of the hydrogen abstraction type photoradical polymerization initiator include benzophenone, 4-phenylbenzophenone, isophthalphenone, and 4-benzoyl-4'-methyl-diphenyl sulfide. A molecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator may be used in combination.

[0142] The photoradical polymerization initiator can also be obtained as a commercially available product. Examples of such commercially available products include acylphosphine oxide compounds such as Omnirad (registered trademark; the same applies hereinafter) TPO-H, Omnirad TPO-L, and Omnirad 819 manufactured by IGM Resin; alkylphenone compounds such as Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG; intramolecular hydrogen abstraction compounds such as Omnirad MBF and Omnirad 754; and Irgacure (registered trademark; the same applies hereinafter) manufactured by BASF Japan Ltd. OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, TR-PBG-304 and TR-PBG-305 manufactured by Changzhou Strong Electronic New Materials Co., Ltd., and NCI-730, NCI-831, and NCI-930 manufactured by ADEKA Corporation.

[0143] In addition to these, the oxime ester compounds include oxime ester compounds such as those described in JP-T-2004-534797, JP-A-2000-80068, WO 2012 / 45736, WO 2015 / 36910, JP-A-2006-36750, JP-A-2008-179611, WO 2009 / 131189, WO 2012-526185, WO 2012-519191, WO 2006 / 18973, WO 2008 / 78678, and WO 2011-132215.

[0144] When a photoradical polymerization initiator is used as the photopolymerization initiator, a chain transfer agent may be used in combination. By using a chain transfer agent, the reaction rate of the photoradical reaction can be increased.

[0145] The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to 100% by mass of the polymerizable monomer, from the viewpoint of the curability of the composition. The upper limit of the content is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, from the viewpoint of film-forming property and the transparency, heat resistance, and light resistance of the cured film.

[0146] When a polymerizable monomer and a photopolymerization initiator are blended, an alkali-soluble resin may be further blended. By blending a polymerizable monomer, a photopolymerization initiator, and an alkali-soluble resin into the pattern-forming composition of the present invention, it can be used as a composition for forming a resist film.

[0147] [(E) Thermal Crosslinking Agent] The present invention may contain a thermal crosslinking agent as a further component (referred to as component (E) for convenience). In the present application, the thermal crosslinking agent is also referred to as "(E) thermal crosslinking agent" or simply "(E)". More specifically, for example, a compound having a structure capable of forming a crosslinked structure upon thermal reaction with a thermally reactive site (e.g., a carboxyl group and / or a phenolic hydroxy group) of the alkali-soluble resin may be mentioned. The thermal crosslinking agent is not particularly limited as long as it can achieve the object of the present invention. As the (E) thermal crosslinking agent, for example, a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group (for convenience, also referred to as "(E1) a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group" or simply "E1") or a crosslinkable compound represented by the following formula (1) (for convenience, also referred to as "(E2) a crosslinkable compound represented by the following formula (1)" or simply "E2") is preferred. These crosslinking agents can be used alone or in combination of two or more.

[0148] When exposed to high temperatures during thermal curing, the above-mentioned (E1) undergoes a crosslinking reaction via a dehydration condensation reaction. Examples of such compounds include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine, and phenoplast compounds.

[0149] Specific examples of alkoxymethylated glycolurils include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (high condensation type, trade names: Beckamin (registered trademark) J-300S, P-955, N) manufactured by DIC Corporation.

[0150] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123) and Sanwa Chemical Co., Ltd. (trade names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).

[0151] Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine, etc. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) and butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506, 508) manufactured by Mitsui Cytec Co., Ltd., and methoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, MX-035) and butoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, MX-302) manufactured by Sanwa Chemical Co., Ltd.

[0152] The compound may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, or a benzoguanamine compound in which the hydrogen atom of the amino group has been substituted with a methylol group or an alkoxymethyl group. For example, the compound may be a high molecular weight compound produced from a melamine compound or a benzoguanamine compound as described in U.S. Patent No. 6,323,310. Commercially available melamine compounds include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available benzoguanamine compounds include Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0153] Specific examples of the phenoplast-based compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6-bis(hydroxmethyl)phenol], 2,6-bis(methoxymethyl)phenol], 2,6-bis(methoxymethyl)cresol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(methoxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-methoxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4'-methylenebis[2-methyl-6-methoxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol], 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol], and the like. These are also commercially available, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Organic Chemicals Co., Ltd.).

[0154] Furthermore, as the (E1), polymers produced using an acrylamide compound or methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, or N-butoxymethylmethacrylamide, can also be used.

[0155] Examples of such polymers include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. The weight-average molecular weight of such polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

[0156] The first photosensitive resin composition of the present invention may contain, as the above-mentioned (E2), a crosslinkable compound represented by the following formula (1): (wherein k is an integer of 2 to 10, m is an integer of 0 to 4, R １１ represents a k-valent organic group)

[0157] The compound (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by formula (1). Specific examples thereof include compounds represented by formulas E2-1 and E2-2 below and the commercially available products shown below.

[0158] Commercially available products include Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 (trade names manufactured by Daicel Corporation), alicyclic epoxy resins such as Denacol EX-252 (trade name manufactured by Nagase ChemteX Corporation), CY175, CY177, and CY179 (trade names manufactured by Huntsman Corporation), Araldite CY-182, CY-192, and CY-184 (trade names manufactured by Huntsman Corporation), Epiclon 200 and 400 (trade names manufactured by DIC Corporation), and Epicoat 871 and 872 (trade names manufactured by Mitsubishi Chemical Corporation). Examples of such crosslinkable compounds include ED-5661, ED-5662 (trade names, manufactured by Celanese Coatings Co., Ltd.), and the like. These crosslinkable compounds may be used alone or in combination of two or more.

[0159] Among these, from the viewpoints of process resistance such as heat resistance, solvent resistance, and long-term baking resistance, as well as transparency, compounds having a cyclohexene oxide structure and represented by formulas E2-1 and E2-2, Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 are preferred.

[0160] Furthermore, as the thermal crosslinking agent (E), for example, compounds other than those shown as (E1) and (E2) above that can form a crosslinked structure by thermal reaction with a thermally reactive site (e.g., a carboxyl group and / or a phenolic hydroxy group) of an alkali-soluble resin can also be used. Specific examples of the epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane; VESTANAT B1358 / 100; VESTAGON BF; Examples of the isocyanate compound include Takenate (registered trademark) B-1540 (all isocyanurate-modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, Takenate (registered trademark) B-7075 (all isocyanurate-modified polyisocyanates, manufactured by Mitsui Chemicals, Inc.).

[0161] Furthermore, as the (E) thermal crosslinking agent, for example, a polymer having two or more structures capable of forming a crosslinked structure by a thermal reaction with a thermally reactive site (e.g., a carboxyl group and / or a phenolic hydroxy group) of the alkali-soluble resin can be used. Specific examples include polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate; polymers produced using compounds having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane; compounds having an isocyanate group such as 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Resonac Corporation) and 2-isocyanatoethyl acrylate (Karenz AOI [registered trademark], manufactured by Resonac Corporation); and polymers produced using compounds having a blocked isocyanate group such as 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karenz MOI-BM [registered trademark], manufactured by Resonac Corporation) and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Resonac Corporation). These compounds may be used alone or in combination to produce a polymer, or may be combined with other compounds to produce a polymer.

[0162] When the alkali-soluble resin has a group reactive with at least one group selected from the group consisting of groups represented by a hydroxy group, a carboxyl group, an amide group, and an amino group, a compound having two or more groups represented by a hydroxy group, a carboxyl group, an amide group, or an amino group can be used as the thermal crosslinking agent (E).

[0163] These crosslinkable compounds may be used alone or in combination of two or more.

[0164] When a thermal crosslinking agent (E) is selected as the crosslinking agent in the first photosensitive resin composition of the present invention, the content is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of the alkali-soluble resin. If the content of the crosslinking compound is low, the density of the crosslinks formed by the crosslinking compound is insufficient, and the effect of improving heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation may not be obtained. On the other hand, if the content exceeds 50 parts by mass, uncrosslinked crosslinking compound is present, which reduces heat resistance, solvent resistance, resistance to long-term baking, etc. after pattern formation, and also deteriorates the storage stability of the photosensitive resin composition. To avoid this, it is preferable to keep the content at 50 parts by mass or less.

[0165] [(F) Phosphor] The present invention may contain a phosphor as an additional component (referred to as component (F) for convenience). In the present application, this thermal crosslinking agent is also referred to as "(F) phosphor" or simply "(F)". The (F) phosphor is not particularly limited as long as it can achieve the object of the present invention. It is sufficient that the (F) phosphor is suitable as a phosphor while maintaining the desired film remaining ratio even when a wavelength conversion film is formed, exposed to air, and developed. A phosphor that can exhibit better properties as a phosphor is preferred. For example, when forming a wavelength conversion film for a micro LED display, a phosphor that can exhibit better properties as a micro LED display, such as wavelength conversion efficiency, color purity, and light resistance, while maintaining the desired film remaining ratio, is preferred.

[0166] The (F) phosphor can be appropriately selected from conventionally known inorganic phosphors, organic dyes, quantum dots, etc., but organic dyes are preferred. Examples of organic dyes include compounds having a condensed aryl ring such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, and indene, and derivatives thereof; furan, pyrrole, thiophene, silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine, pyrazine, naphthacene, and the like. Compounds having a heteroaryl ring such as pyridine, quinoxaline, and pyrrolopyridine, and derivatives thereof; stilbene compounds such as 1,4-distyrylbenzene, 4,4'-bis(2-(4-diphenylaminophenyl)ethenyl)biphenyl, and 4,4'-bis(N-(stilben-4-yl)-N-phenylamino)stilbene; aromatic acetylene compounds; tetraphenylbutadiene compounds; aldazine compounds; pyrromethene compounds; diketopyrrolo[3,4-c]pyrrole compounds; and coumarin. Coumarin-based compounds such as Coumarin 6, Coumarin 7, Coumarin 153, and compounds disclosed in Patent Document 7; azole-based compounds such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, and triazole, and metal complexes thereof; cyanine-based compounds such as indocyanine green; xanthene-based compounds and thioxanthene-based compounds such as fluorescein, eosin, and rhodamine; polyphenylene-based compounds, naphthalimide-based compounds, phthalocyanine-based compounds, and metal complexes thereof complexes, porphyrin compounds and metal complexes thereof; oxazine compounds such as Nile Red and Nile Blue; helicene compounds; aromatic amine compounds such as N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine; and organometallic complex compounds such as iridium (Ir), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re), but are not limited to these.

[0167] In addition, perylene-based compounds can also be suitably used as the organic dye used as the phosphor (F) in the pattern-forming composition of the present invention. A perylene-based compound is a compound having a perylene skeleton, and preferred perylene-based compounds include, but are not limited to, the compound represented by the following formula (2) (Oracet (registered trademark) FL Red 305, manufactured by BASF), Lumogen (registered trademark) F Yellow 083 (manufactured by BASF), Solvent Green 5, and the compound represented by the following formula (Y1). The compound represented by the following formula (2) (Oracet (registered trademark) FL Red 305, manufactured by BASF) and the compound represented by the following formula (Y1) are more preferred.

[0168]

[0169] A compound represented by the following formula (Y1): [In the formula, R Ａ and R Ｂ are each independently a group represented by the following formula (2) or (3): (G １ is O or NR Ｅ and A １ is an ethylene group or a propylene group, n is an integer from 1 to 10, and R Ｃ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkylcarbonyl group, an optionally substituted alkenylcarbonyl group, an optionally substituted arylcarbonyl group or an optionally substituted heteroarylcarbonyl group, and R Ｅ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, and the dashed line represents a bond. (G ２ is O or NR Ｅand L ２ is a single bond or an alkylene group which may have a substituent, R Ｄ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkylcarbonyl group, an optionally substituted alkenylcarbonyl group, an optionally substituted arylcarbonyl group, an optionally substituted heteroarylcarbonyl group, or OR Ｆ and R Ｅ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group, R Ｆ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkylcarbonyl group, an optionally substituted alkenylcarbonyl group, an optionally substituted arylcarbonyl group or an optionally substituted heteroarylcarbonyl group, and G ２ NR Ｅ Katsu L ２ is a single bond, R Ｄ and R Ｅ may be bonded to each other to form a ring together with the nitrogen atom, ２ is a single bond, R Ｄ is OR Ｆ It will not be like this, ２ When R is an alkylene group which may have a substituent, Ｄ cannot be a hydrogen atom, and R Ｄ is an alkyl group which may have a substituent, L ２ is a single bond, and the dashed line is a bond.)

[0170] G １ is preferably O. １is preferably an ethylene group. n is preferably an integer of 1 to 8, more preferably an integer of 1 to 6.

[0171] R Ｃ The alkyl group represented by the formula (I) may be either linear or branched, and specific examples thereof include alkyl groups having 1 to 40 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, a decyl group, and an eicosanyl group, and an alkyl group having 1 to 20 carbon atoms is preferred.

[0172] The above R Ｃ The alkyl group represented by the formula (I) may have a substituent. Examples of the substituent include a halogen atom, a cycloalkyl group, an aryl group, a heteroaryl group, a hydroxy group, a cyano group, and a nitro group, which will be described later. When the alkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0173] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0174] R Ｃ Examples of the cycloalkyl group represented by the formula (I) include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups, and preferably cycloalkyl groups having 3 to 8 carbon atoms.

[0175] The above R Ｃ The cycloalkyl group represented by the following formula (I) may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the above-mentioned alkyl groups, the alkenyl groups described below, the alkynyl groups described below, the aryl groups described below, the heteroaryl groups described below, a hydroxy group, a cyano group, and a nitro group. When the cycloalkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0176] Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, an isobutynyl group, an s-butynyl group, and a t-butynyl group.

[0177] R ＣExamples of the alkenyl group represented by the formula (I) include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, an s-butenyl group, and a t-butenyl group.

[0178] The above R Ｃ The alkenyl group represented by the formula (I) may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the aryl group described below, the heteroaryl group described below, a hydroxy group, a cyano group, and a nitro group. When the alkenyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0179] R Ｃ The aryl group represented by the formula (I) may be any of a monocyclic aryl group, a fused ring aryl group, and a polycyclic aryl group, and specific examples thereof include a phenyl group as the monocyclic aryl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, a triphenylenyl group, and the like as the fused ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group as the polycyclic aryl group, and an aryl group having 6 to 14 carbon atoms is preferred.

[0180] The above R Ｃ The aryl group represented by the formula (I) may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, halogenated alkyl groups described below, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups described below, hydroxy groups, cyano groups, and nitro groups. When the aryl group has a substituent, the number of substituents is preferably 1 to 6, and more preferably 1 to 3.

[0181] Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

[0182] R ＣThe heteroaryl group represented by the formula (I) may be either a monocyclic heteroaryl group or a fused-ring heteroaryl group. Examples of the monocyclic heteroaryl group include a pyrrolyl group, a thienyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, and a pyrazyl group. Examples of the fused-ring heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.

[0183] The above R Ｃ The heteroaryl group represented by the formula (I) may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cyano groups, and nitro groups. When the heteroaryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0184] R ＣExamples of the alkylcarbonyl group represented by the formula (I) include a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an i-propylcarbonyl group, a c-propylcarbonyl group, an n-butylcarbonyl group, an i-butylcarbonyl group, an s-butylcarbonyl group, a t-butylcarbonyl group, a c-butylcarbonyl group, a 1-methyl-c-propylcarbonyl group, a 2-methyl-c-propylcarbonyl group, an n-pentylcarbonyl group, a 1-methyl-n-butylcarbonyl group, a 2-methyl-n-butylcarbonyl group, a 3-methyl-n-butylcarbonyl group, a 1,1-dimethyl-n-butylcarbonyl group, a 2- ... Methyl-n-propylcarbonyl group, 1,2-dimethyl-n-propylcarbonyl group, 2,2-dimethyl-n-propylcarbonyl group, 1-ethyl-n-propylcarbonyl group, c-pentylcarbonyl group, 1-methyl-c-butylcarbonyl group, 2-methyl-c-butylcarbonyl group, 3-methyl-c-butylcarbonyl group, 1,2-dimethyl-c-propylcarbonyl group, 2,3-dimethyl-c-propylcarbonyl group, 1-ethyl-c-propylcarbonyl group, 2-ethyl-c-propylcarbonyl group, n-hexylcarbonyl group, 1-methyl-n -pentylcarbonyl group, 2-methyl-n-pentylcarbonyl group, 3-methyl-n-pentylcarbonyl group, 4-methyl-n-pentylcarbonyl group, 1,1-dimethyl-n-butylcarbonyl group, 1,2-dimethyl-n-butylcarbonyl group, 1,3-dimethyl-n-butylcarbonyl group, 2,2-dimethyl-n-butylcarbonyl group, 2,3-dimethyl-n-butylcarbonyl group, 3,3-dimethyl-n-butylcarbonyl group, 1-ethyl-n-butylcarbonyl group, 2-ethyl-n-butylcarbonyl group, 1,1,2-trimethyl-n-propyl carbonyl group, 1,2,2-trimethyl-n-propylcarbonyl group, 1-ethyl-1-methyl-n-propylcarbonyl group, 1-ethyl-2-methyl-n-propylcarbonyl group, c-hexylcarbonyl group, 1-methyl-c-pentylcarbonyl group, 2-methyl-c-pentylcarbonyl group, 3-methyl-c-pentylcarbonyl group, 1-ethyl-c-butylcarbonyl group, 2-ethyl-c-butylcarbonyl group, 3-ethyl-c-butylcarbonyl group, 1,2-dimethyl-c-butylcarbonyl group, 1,3-dimethyl-c-butylcarbonyl group, 2,2-dimethyl-c-butylcarbonyl group, 2,3-dimethyl-c-butylcarbonyl group, 2,4-dimethyl-c-butylcarbonyl group, 3,3-dimethyl-c-butylcarbonyl group, 1-n-propyl-c-propylcarbonyl group, 2-n-propyl-c-propylcarbonyl group, 1-i-propyl-c-propylcarbonyl group, 2-i-propyl-c-propylcarbonyl group, 1,2,2-trimethyl-c-propylcarbonyl group, 1 Examples of alkylcarbonyl groups include alkylcarbonyl groups having 2 to 11 carbon atoms, such as a 2,3-trimethyl-c-propylcarbonyl group, a 2,2,3-trimethyl-c-propylcarbonyl group, a 1-ethyl-2-methyl-c-propylcarbonyl group, a 2-ethyl-1-methyl-c-propylcarbonyl group, a 2-ethyl-2-methyl-c-propylcarbonyl group, and a 2-ethyl-3-methyl-c-propylcarbonyl group, and alkylcarbonyl groups having 2 to 6 carbon atoms are preferred.

[0185] The above R Ｃ The alkylcarbonyl group represented by the following formula (I) may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, cycloalkyl groups, aryl groups, heteroaryl groups, hydroxy groups, cyano groups, and nitro groups. When the alkylcarbonyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0186] R ＣExamples of the alkenylcarbonyl group represented by the formula (I) include an ethenylcarbonyl group, a 1-propenylcarbonyl group, a 2-propenylcarbonyl group, a 1-methyl-1-ethenylcarbonyl group, a 1-butenylcarbonyl group, a 2-butenylcarbonyl group, a 3-butenylcarbonyl group, a 2-methyl-1-propenylcarbonyl group, a 2-methyl-2-propenylcarbonyl group, a 1-ethylethenylcarbonyl group, a 1-methyl-1-propenylcarbonyl group, a 1-methyl-2-propenylcarbonyl group, a 1-pentenylcarbonyl group, a 2-pentenylcarbonyl group, a 3-pentenylcarbonyl group, a 4-pentenylcarbonyl group, a 1-n -propylethenylcarbonyl group, 1-methyl-1-butenylcarbonyl group, 1-methyl-2-butenylcarbonyl group, 1-methyl-3-butenylcarbonyl group, 2-ethyl-2-propenylcarbonyl group, 2-methyl-1-butenylcarbonyl group, 2-methyl-2-butenylcarbonyl group, 2-methyl-3-butenylcarbonyl group, 3-methyl-1-butenylcarbonyl group, 3-methyl-2-butenylcarbonyl group, 3-methyl-3-butenylcarbonyl group, 1,1-dimethyl-2-propenylcarbonyl group, 1-i-propylethenylcarbonyl group, 1,2-dimethyl-1-propenylcarbonyl group, 1,2-dimethyl-2-propenylcarbonyl group, 1-c-pentenylcarbonyl group, 2-c-pentenylcarbonyl group, 3-c-pentenylcarbonyl group, 1-hexenylcarbonyl group, 2-hexenylcarbonyl group, 3-hexenylcarbonyl group, 4-hexenylcarbonyl group, 5-hexenylcarbonyl group, 1-methyl-1-pentenylcarbonyl group, 1-methyl-2-pentenylcarbonyl group, 1-methyl-3-pentenylcarbonyl group, 1-methyl-4-pentenylcarbonyl group, 1-n-butylethenylcarbonyl group, 2-methyl-1-pentenylcarbonyl group, 2-methyl-2-pentenylcarbonyl group, 2-methyl-3-pentenylcarbonyl group, 2-methyl-4-pentenylcarbonyl group, 2-n-propyl-2-propenylcarbonyl group, 3-methyl-1-pentenylcarbonyl group, 3-methyl-2-pentenylcarbonyl group, 3-methyl-3-pentenylcarbonyl group, 3-methyl-4-pentenylcarbonyl group, 3-ethyl-3-butenylcarbonyl group nyl group, 4-methyl-1-pentenylcarbonyl group, 4-methyl-2-pentenylcarbonyl group, 4-methyl-3-pentenylcarbonyl group, 4-methyl-4-pentenylcarbonyl group, 1,1-dimethyl-2-butenylcarbonyl group, 1,1-dimethyl-3-butenylcarbonyl group, 1,2-dimethyl-1-butenylcarbonyl group, 1,2-dimethyl-2-butenylcarbonyl group, 1,2-dimethyl-3-butenylcarbonyl group, 1-methyl-2-ethyl-2-propenylcarbonyl a 1-s-butylethenylcarbonyl group, a 1,3-dimethyl-1-butenylcarbonyl group, a 1,3-dimethyl-2-butenylcarbonyl group, a 1,3-dimethyl-3-butenylcarbonyl group, a 1-i-butylethenylcarbonyl group, a 2,2-dimethyl-3-butenylcarbonyl group, a 2,3-dimethyl-1-butenylcarbonyl group, a 2,3-dimethyl-2-butenylcarbonyl group, a 2,3-dimethyl-3-butenylcarbonyl group, a 2-i-propyl-2-propenylcarbonyl group, a 3,3-dimethyl-1-butenylcarbonyl group, 1-ethyl-1-butenylcarbonyl group, 1-ethyl-2-butenylcarbonyl group, 1-ethyl-3-butenylcarbonyl group, 1-n-propyl-1-propenylcarbonyl group, 1-n-propyl-2-propenylcarbonyl group, 2-ethyl-1-butenylcarbonyl group, 2-ethyl-2-butenylcarbonyl group, 2-ethyl-3-butenylcarbonyl group, 1,1,2-thiazolinone trimethyl-2-propenylcarbonyl group, 1-t-butylethenylcarbonyl group, 1-methyl-1-ethyl-2-propenylcarbonyl group, 1-ethyl-2-methyl-1-propenylcarbonyl group, 1-ethyl-2-methyl-2-propenylcarbonyl group, 1-i-propyl-1-propenylcarbonyl group, 1-i-propyl-2-propenylcarbonyl group, 1-methyl-2-c-pentenylcarbonyl group, 1-methyl -3-c-pentenylcarbonyl group, 2-methyl-1-c-pentenylcarbonyl group, 2-methyl-2-c-pentenylcarbonyl group, 2-methyl-3-c-pentenylcarbonyl group, 2-methyl-4-c-pentenylcarbonyl group, 2-methyl-5-c-pentenylcarbonyl group, 2-methylene-c-pentylcarbonyl group, 3-methyl-1-c-pentenylcarbonyl group, 3-methyl-2-c-pentenylcarbonyl group Examples of alkenylcarbonyl groups include alkenylcarbonyl groups having 3 to 11 carbon atoms, such as an alkenyl group, a 3-methyl-3-c-pentenylcarbonyl group, a 3-methyl-4-c-pentenylcarbonyl group, a 3-methyl-5-c-pentenylcarbonyl group, a 3-methylene-c-pentylcarbonyl group, a 1-c-hexenylcarbonyl group, a 2-c-hexenylcarbonyl group, and a 3-c-hexenylcarbonyl group, and alkenylcarbonyl groups having 3 to 6 carbon atoms are preferred.

[0187] The above R Ｃ The alkenylcarbonyl group represented by the following formula (I) may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, aryl groups, heteroaryl groups, hydroxy groups, cyano groups, and nitro groups. When the alkenylcarbonyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0188] R ＣExamples of the arylcarbonyl group represented by the formula (I) include arylcarbonyl groups having 7 to 16 carbon atoms, such as a benzoyl group, a naphthoyl group, and an anthracenyl group, and an arylcarbonyl group having 7 to 11 carbon atoms is preferred.

[0189] The above R Ｃ The arylcarbonyl group represented by the following formula (I) may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cyano groups, and nitro groups. When the arylcarbonyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0190] R Ｃ Examples of the heteroarylcarbonyl group represented by the formula (I) include heteroarylcarbonyl groups having 4 to 12 carbon atoms, such as a pyrrolylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, an imidazolylcarbonyl group, a pyrazolylcarbonyl group, a thiazolylcarbonyl group, an oxazolylcarbonyl group, a pyridylcarbonyl group, a pyrazylcarbonyl group, an indolylcarbonyl group, an isoindolylcarbonyl group, a benzimidazolylcarbonyl group, a quinolylcarbonyl group, an isoquinolylcarbonyl group, and a quinoxalylcarbonyl group, and a heteroarylcarbonyl group having 4 to 10 carbon atoms is preferred.

[0191] The heteroarylcarbonyl group may have a substituent. Examples of the substituent include the halogen atom, the alkyl group, the halogenated alkyl group, the alkenyl group, the alkynyl group, the aryl group, the heteroaryl group, a cyano group, and a nitro group. When the heteroarylcarbonyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0192] R Ｅ The alkyl group represented by the formula (I) may be either linear or branched, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, and an alkyl group having 1 to 6 carbon atoms is preferred.

[0193] The above RＥ The alkyl group represented by the formula (I) may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the cycloalkyl group described below, the aryl group described below, the heteroaryl group described below, a hydroxy group, a cyano group, and a nitro group. When the alkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0194] R Ｅ Examples of the cycloalkyl group represented by the formula (I) include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups, and preferably cycloalkyl groups having 3 to 8 carbon atoms.

[0195] The above R Ｅ The cycloalkyl group represented by the following formula (I) may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the above-mentioned alkyl groups, the alkenyl groups described below, the alkynyl groups described below, the aryl groups described below, the heteroaryl groups described below, a hydroxy group, a cyano group, and a nitro group. When the cycloalkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0196] R Ｅ Examples of the alkenyl group represented by the formula (I) include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, an s-butenyl group, and a t-butenyl group.

[0197] The above R Ｅ The alkenyl group represented by the formula (I) may have a substituent. Examples of the substituent include a halogen atom, an aryl group, a heteroaryl group, a hydroxy group, a cyano group, and a nitro group, which will be described later. When the alkenyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0198] R ＥThe aryl group represented by the formula (I) may be any of a monocyclic aryl group, a fused ring aryl group, and a polycyclic aryl group, and specific examples thereof include a phenyl group as the monocyclic aryl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, a triphenylenyl group, and the like as the fused ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group as the polycyclic aryl group, and an aryl group having 6 to 14 carbon atoms is preferred.

[0199] The above R Ｅ The aryl group represented by the formula (I) may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups described below, hydroxy groups, cyano groups, nitro groups, and pentafluorosulfanyl groups. When the aryl group has a substituent, the number of substituents is preferably 1 to 6, and more preferably 1 to 3.

[0200] R Ｅ The heteroaryl group represented by the formula (I) may be either a monocyclic heteroaryl group or a fused-ring heteroaryl group. Examples of the monocyclic heteroaryl group include a pyrrolyl group, a thienyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, and a pyrazyl group. Examples of the fused-ring heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.

[0201] The above R Ｅ The heteroaryl group represented by the formula (I) may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cyano groups, nitro groups, and pentafluorosulfanyl groups. When the heteroaryl group has a substituent, the number of substituents is preferably 1 to 6, and more preferably 1 to 3.

[0202] G ２ is O or NR Ｅ and O or NH is preferred.

[0203] L２ The alkylene group represented by the formula (I) may be linear, branched, or cyclic, and specific examples include alkylene groups having 1 to 20 carbon atoms such as methylene, methylmethylene, dimethylmethylene, ethylene, 1,2-dimethylethylene, tetramethylethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene, with alkylene groups having 1 to 14 carbon atoms being preferred.

[0204] The above L ２ The alkylene group represented by the formula (I) may have a substituent. Examples of the substituent include the halogen atoms, cycloalkyl groups, aryl groups, heteroaryl groups, alkylcarbonyloxy groups described below, hydroxy groups, cyano groups, nitro groups, and oxo groups. When the alkylene group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0205] Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, a c-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, a c-butylcarbonyloxy group, a 1-methyl-c-propylcarbonyloxy group, a 2-methyl-c-propylcarbonyloxy group, an n-pentylcarbonyloxy group, an ethyl ... nyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n-propylcarbonyloxy group, c-pentylcarbonyloxy group, 1-methyl-c-butylcarbonyloxy group, 2-methyl-c-butylcarbonyloxy group oxy group, 3-methyl-c-butylcarbonyloxy group, 1,2-dimethyl-c-propylcarbonyloxy group, 2,3-dimethyl-c-propylcarbonyloxy group, 1-ethyl-c-propylcarbonyloxy group, 2-ethyl-c-propylcarbonyloxy group, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group dimethyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, c-hexylcarbonyloxy group, 1-methyl-c-pentylcarbonyloxy group, 2-methyl-c-pentylcarbonyloxy group, 3-methyl-c-pentylcarbonyloxy group, 1-ethyl-c-butylcarbonyloxy group, 2-ethyl-c-butylcarbonyloxy group, 3-ethyl-c-butylcarbonyloxy group, 1,2-dimethyl-c-butylcarbonyloxy group, 1,3-dimethyl-c-butylcarbonyloxy group, 2,2-dimethyl-c-butylcarbonyloxy group, 2,3-dimethyl-c-butylcarbonyloxy group, 2,4-dimethyl-c-butylcarbonyloxy group, 3,3-dimethyl-c-butyl Examples of alkylcarbonyloxy groups having 2 to 11 carbon atoms include a carbonyloxy group, a 1-n-propyl-c-propylcarbonyloxy group, a 2-n-propyl-c-propylcarbonyloxy group, a 1-i-propyl-c-propylcarbonyloxy group, a 2-i-propyl-c-propylcarbonyloxy group, a 1,2,2-trimethyl-c-propylcarbonyloxy group, a 1,2,3-trimethyl-c-propylcarbonyloxy group, a 2,2,3-trimethyl-c-propylcarbonyloxy group, a 1-ethyl-2-methyl-c-propylcarbonyloxy group, a 2-ethyl-1-methyl-c-propylcarbonyloxy group, a 2-ethyl-2-methyl-c-propylcarbonyloxy group, and a 2-ethyl-3-methyl-c-propylcarbonyloxy group, and alkylcarbonyloxy groups having 2 to 6 carbon atoms are preferred.

[0206] R Ｄ The alkyl group represented by the formula (I) may be either linear or branched, and specific examples thereof include alkyl groups having 1 to 40 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, a decyl group, and an eicosanyl group, and an alkyl group having 1 to 20 carbon atoms is preferred.

[0207] The above R ＤThe alkyl group represented by the formula (I) may have a substituent. Examples of the substituent include a halogen atom, a cycloalkyl group, an aryl group, a heteroaryl group, a hydroxy group, a cyano group, a nitro group, an oxo group, and an epoxy group. When the alkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0208] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0209] R Ｄ Examples of the cycloalkyl group represented by the formula (I) include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups, and preferably cycloalkyl groups having 3 to 8 carbon atoms.

[0210] The above R Ｄ The cycloalkyl group represented by the following formula (I) may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the above-mentioned alkyl groups, the alkenyl groups described below, the alkynyl groups described below, the aryl groups described below, the heteroaryl groups described below, a hydroxy group, a cyano group, and a nitro group. When the cycloalkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0211] Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, an isobutynyl group, an s-butynyl group, and a t-butynyl group.

[0212] R Ｄ Examples of the alkenyl group represented by the formula (I) include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, an s-butenyl group, and a t-butenyl group.

[0213] The above R Ｄ The alkenyl group represented by the formula (I) may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the aryl group described below, the heteroaryl group described below, a hydroxy group, a cyano group, and a nitro group. When the alkenyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0214] R ＤThe aryl group represented by the formula (I) may be any of a monocyclic aryl group, a fused ring aryl group, and a polycyclic aryl group, and specific examples thereof include a phenyl group as the monocyclic aryl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, a triphenylenyl group, and the like as the fused ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group as the polycyclic aryl group, and an aryl group having 6 to 14 carbon atoms is preferred.

[0215] The above R Ｄ The aryl group represented by the formula (I) may have a substituent. Examples of the substituent include the halogen atoms, the alkyl groups, the halogenated alkyl groups described below, the alkenyl groups, the alkynyl groups, the aryl groups, the heteroaryl groups described below, a hydroxy group, a cyano group, a nitro group, and a pentafluorosulfanyl group. When the aryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0216] Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

[0217] R Ｄ The heteroaryl group represented by the formula (I) may be either a monocyclic heteroaryl group or a fused-ring heteroaryl group. Examples of the monocyclic heteroaryl group include a pyrrolyl group, a thienyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, and a pyrazyl group. Examples of the fused-ring heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.

[0218] The above R Ｄ The heteroaryl group represented by the formula (I) may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cyano groups, and nitro groups. When the heteroaryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0219] R ＤExamples of the alkylcarbonyl group represented by the formula (I) include a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an i-propylcarbonyl group, a c-propylcarbonyl group, an n-butylcarbonyl group, an i-butylcarbonyl group, an s-butylcarbonyl group, a t-butylcarbonyl group, a c-butylcarbonyl group, a 1-methyl-c-propylcarbonyl group, a 2-methyl-c-propylcarbonyl group, an n-pentylcarbonyl group, a 1-methyl-n-butylcarbonyl group, a 2-methyl-n-butylcarbonyl group, a 3-methyl-n-butylcarbonyl group, a 1,1-dimethyl-n-butylcarbonyl group, a 2- ... Methyl-n-propylcarbonyl group, 1,2-dimethyl-n-propylcarbonyl group, 2,2-dimethyl-n-propylcarbonyl group, 1-ethyl-n-propylcarbonyl group, c-pentylcarbonyl group, 1-methyl-c-butylcarbonyl group, 2-methyl-c-butylcarbonyl group, 3-methyl-c-butylcarbonyl group, 1,2-dimethyl-c-propylcarbonyl group, 2,3-dimethyl-c-propylcarbonyl group, 1-ethyl-c-propylcarbonyl group, 2-ethyl-c-propylcarbonyl group, n-hexylcarbonyl group, 1-methyl-n -pentylcarbonyl group, 2-methyl-n-pentylcarbonyl group, 3-methyl-n-pentylcarbonyl group, 4-methyl-n-pentylcarbonyl group, 1,1-dimethyl-n-butylcarbonyl group, 1,2-dimethyl-n-butylcarbonyl group, 1,3-dimethyl-n-butylcarbonyl group, 2,2-dimethyl-n-butylcarbonyl group, 2,3-dimethyl-n-butylcarbonyl group, 3,3-dimethyl-n-butylcarbonyl group, 1-ethyl-n-butylcarbonyl group, 2-ethyl-n-butylcarbonyl group, 1,1,2-trimethyl-n-propyl carbonyl group, 1,2,2-trimethyl-n-propylcarbonyl group, 1-ethyl-1-methyl-n-propylcarbonyl group, 1-ethyl-2-methyl-n-propylcarbonyl group, c-hexylcarbonyl group, 1-methyl-c-pentylcarbonyl group, 2-methyl-c-pentylcarbonyl group, 3-methyl-c-pentylcarbonyl group, 1-ethyl-c-butylcarbonyl group, 2-ethyl-c-butylcarbonyl group, 3-ethyl-c-butylcarbonyl group, 1,2-dimethyl-c-butylcarbonyl group, 1,3-dimethyl-c-butylcarbonyl group, 2,2-dimethyl-c-butylcarbonyl group, 2,3-dimethyl-c-butylcarbonyl group, 2,4-dimethyl-c-butylcarbonyl group, 3,3-dimethyl-c-butylcarbonyl group, 1-n-propyl-c-propylcarbonyl group, 2-n-propyl-c-propylcarbonyl group, 1-i-propyl-c-propylcarbonyl group, 2-i-propyl-c-propylcarbonyl group, 1,2,2-trimethyl-c-propylcarbonyl group, 1 Examples of alkylcarbonyl groups include alkylcarbonyl groups having 2 to 11 carbon atoms, such as a 2,3-trimethyl-c-propylcarbonyl group, a 2,2,3-trimethyl-c-propylcarbonyl group, a 1-ethyl-2-methyl-c-propylcarbonyl group, a 2-ethyl-1-methyl-c-propylcarbonyl group, a 2-ethyl-2-methyl-c-propylcarbonyl group, and a 2-ethyl-3-methyl-c-propylcarbonyl group, and alkylcarbonyl groups having 2 to 6 carbon atoms are preferred.

[0220] The above R Ｄ The alkylcarbonyl group represented by the following formula (I) may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, cycloalkyl groups, aryl groups, heteroaryl groups, hydroxy groups, cyano groups, and nitro groups. When the alkylcarbonyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0221] R ＤExamples of the alkenylcarbonyl group represented by the formula (I) include an ethenylcarbonyl group, a 1-propenylcarbonyl group, a 2-propenylcarbonyl group, a 1-methyl-1-ethenylcarbonyl group, a 1-butenylcarbonyl group, a 2-butenylcarbonyl group, a 3-butenylcarbonyl group, a 2-methyl-1-propenylcarbonyl group, a 2-methyl-2-propenylcarbonyl group, a 1-ethylethenylcarbonyl group, a 1-methyl-1-propenylcarbonyl group, a 1-methyl-2-propenylcarbonyl group, a 1-pentenylcarbonyl group, a 2-pentenylcarbonyl group, a 3-pentenylcarbonyl group, a 4-pentenylcarbonyl group, a 1-n -propylethenylcarbonyl group, 1-methyl-1-butenylcarbonyl group, 1-methyl-2-butenylcarbonyl group, 1-methyl-3-butenylcarbonyl group, 2-ethyl-2-propenylcarbonyl group, 2-methyl-1-butenylcarbonyl group, 2-methyl-2-butenylcarbonyl group, 2-methyl-3-butenylcarbonyl group, 3-methyl-1-butenylcarbonyl group, 3-methyl-2-butenylcarbonyl group, 3-methyl-3-butenylcarbonyl group, 1,1-dimethyl-2-propenylcarbonyl group, 1-i-propylethenylcarbonyl group, 1,2-dimethyl-1-propenylcarbonyl group, 1,2-dimethyl-2-propenylcarbonyl group, 1-c-pentenylcarbonyl group, 2-c-pentenylcarbonyl group, 3-c-pentenylcarbonyl group, 1-hexenylcarbonyl group, 2-hexenylcarbonyl group, 3-hexenylcarbonyl group, 4-hexenylcarbonyl group, 5-hexenylcarbonyl group, 1-methyl-1-pentenylcarbonyl group, 1-methyl-2-pentenylcarbonyl group, 1-methyl-3-pentenylcarbonyl group, 1-methyl-4-pentenylcarbonyl group, 1-n-butylethenylcarbonyl group, 2-methyl-1-pentenylcarbonyl group, 2-methyl-2-pentenylcarbonyl group, 2-methyl-3-pentenylcarbonyl group, 2-methyl-4-pentenylcarbonyl group, 2-n-propyl-2-propenylcarbonyl group, 3-methyl-1-pentenylcarbonyl group, 3-methyl-2-pentenylcarbonyl group, 3-methyl-3-pentenylcarbonyl group, 3-methyl-4-pentenylcarbonyl group, 3-ethyl-3-butenylcarbonyl group nyl group, 4-methyl-1-pentenylcarbonyl group, 4-methyl-2-pentenylcarbonyl group, 4-methyl-3-pentenylcarbonyl group, 4-methyl-4-pentenylcarbonyl group, 1,1-dimethyl-2-butenylcarbonyl group, 1,1-dimethyl-3-butenylcarbonyl group, 1,2-dimethyl-1-butenylcarbonyl group, 1,2-dimethyl-2-butenylcarbonyl group, 1,2-dimethyl-3-butenylcarbonyl group, 1-methyl-2-ethyl-2-propenylcarbonyl a 1-s-butylethenylcarbonyl group, a 1,3-dimethyl-1-butenylcarbonyl group, a 1,3-dimethyl-2-butenylcarbonyl group, a 1,3-dimethyl-3-butenylcarbonyl group, a 1-i-butylethenylcarbonyl group, a 2,2-dimethyl-3-butenylcarbonyl group, a 2,3-dimethyl-1-butenylcarbonyl group, a 2,3-dimethyl-2-butenylcarbonyl group, a 2,3-dimethyl-3-butenylcarbonyl group, a 2-i-propyl-2-propenylcarbonyl group, a 3,3-dimethyl-1-butenylcarbonyl group, 1-ethyl-1-butenylcarbonyl group, 1-ethyl-2-butenylcarbonyl group, 1-ethyl-3-butenylcarbonyl group, 1-n-propyl-1-propenylcarbonyl group, 1-n-propyl-2-propenylcarbonyl group, 2-ethyl-1-butenylcarbonyl group, 2-ethyl-2-butenylcarbonyl group, 2-ethyl-3-butenylcarbonyl group, 1,1,2-thiazolinone trimethyl-2-propenylcarbonyl group, 1-t-butylethenylcarbonyl group, 1-methyl-1-ethyl-2-propenylcarbonyl group, 1-ethyl-2-methyl-1-propenylcarbonyl group, 1-ethyl-2-methyl-2-propenylcarbonyl group, 1-i-propyl-1-propenylcarbonyl group, 1-i-propyl-2-propenylcarbonyl group, 1-methyl-2-c-pentenylcarbonyl group, 1-methyl -3-c-pentenylcarbonyl group, 2-methyl-1-c-pentenylcarbonyl group, 2-methyl-2-c-pentenylcarbonyl group, 2-methyl-3-c-pentenylcarbonyl group, 2-methyl-4-c-pentenylcarbonyl group, 2-methyl-5-c-pentenylcarbonyl group, 2-methylene-c-pentylcarbonyl group, 3-methyl-1-c-pentenylcarbonyl group, 3-methyl-2-c-pentenylcarbonyl group Examples of alkenylcarbonyl groups include alkenylcarbonyl groups having 3 to 11 carbon atoms, such as an alkenyl group, a 3-methyl-3-c-pentenylcarbonyl group, a 3-methyl-4-c-pentenylcarbonyl group, a 3-methyl-5-c-pentenylcarbonyl group, a 3-methylene-c-pentylcarbonyl group, a 1-c-hexenylcarbonyl group, a 2-c-hexenylcarbonyl group, and a 3-c-hexenylcarbonyl group, and alkenylcarbonyl groups having 3 to 6 carbon atoms are preferred.

[0222] The above R Ｄ The alkenylcarbonyl group represented by the following formula (I) may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, aryl groups, heteroaryl groups, hydroxy groups, cyano groups, and nitro groups. When the alkenylcarbonyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0223] R ＤExamples of the arylcarbonyl group represented by the formula (I) include arylcarbonyl groups having 7 to 16 carbon atoms, such as a benzoyl group, a naphthoyl group, and an anthracenyl group, and an arylcarbonyl group having 7 to 11 carbon atoms is preferred.

[0224] The above R Ｄ The arylcarbonyl group represented by the following formula (I) may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cyano groups, and nitro groups. When the arylcarbonyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0225] R Ｄ Examples of the heteroarylcarbonyl group represented by the formula (I) include heteroarylcarbonyl groups having 4 to 12 carbon atoms, such as a pyrrolylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, an imidazolylcarbonyl group, a pyrazolylcarbonyl group, a thiazolylcarbonyl group, an oxazolylcarbonyl group, a pyridylcarbonyl group, a pyrazylcarbonyl group, an indolylcarbonyl group, an isoindolylcarbonyl group, a benzimidazolylcarbonyl group, a quinolylcarbonyl group, an isoquinolylcarbonyl group, and a quinoxalylcarbonyl group, and a heteroarylcarbonyl group having 4 to 10 carbon atoms is preferred.

[0226] The heteroarylcarbonyl group may have a substituent. Examples of the substituent include the halogen atom, the alkyl group, the halogenated alkyl group, the alkenyl group, the alkynyl group, the aryl group, the heteroaryl group, a cyano group, and a nitro group. When the heteroarylcarbonyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0227] R Ｅrepresents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and examples of these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, and heteroaryl groups, as well as the substituents of these groups, include R Ｅ Examples of the groups include the same as those exemplified in the above.

[0228] R Ｆ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted alkylcarbonyl group, an optionally substituted alkenylcarbonyl group, an optionally substituted arylcarbonyl group or an optionally substituted heteroarylcarbonyl group, and examples of these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkylcarbonyl groups, alkenylcarbonyl groups, arylcarbonyl groups and heteroarylcarbonyl groups, as well as the substituents of these groups, include those listed above for R Ｄ The groups include the same as those exemplified in the above.

[0229] In addition, in formula (2), G ２ NR Ｅ Katsu L ２ is a single bond, R Ｄ and R Ｅ may be bonded to each other to form a ring together with the nitrogen atom, and L ２ is a single bond, R Ｄ is OR Ｆ It will not become L ２ When R is an alkylene group which may have a substituent, Ｄ cannot be a hydrogen atom, and R Ｄ is an alkyl group which may have a substituent, L ２ is a single bond.

[0230] The above R Ａ and R Ｂmay be the same or different, but are preferably the same group.

[0231] The above R Ａ and R Ｂ The bonding positions of the above to the perylene structure are not particularly limited, but the bonding positions are preferably those represented by the following formulae (Y1a) to (Y1c).

[0232] (In the formula, R Ａ and R Ｂ is the same as above.)

[0233] The group represented by the above formula (2) is preferably a group represented by any one of the following formulae (2-1) to (2-4). (In the formula, R Ｃ and n is the same as above.)

[0234] The group represented by the above formula (3) is preferably a group represented by any one of the following formulas (3-1) to (3-2). (wherein m is an integer from 1 to 20. R Ｄ is the same as above.)

[0235] Specific examples of the phosphor represented by the above formula (Y1) include phosphors represented by the following formulas (Y1-1) to (Y1-13).

[0236]

[0237]

[0238] The compound represented by the formula (Y1) can be synthesized by referring to known methods, but the synthesis method is not particularly limited as long as the target compound can be obtained.

[0239] [(G) Light-Scattering Particles] The pattern-forming composition of the present invention may contain light-scattering particles as a further component (referred to as component (G) for convenience). In the present application, the thermal crosslinking agent is also referred to as "(G) light-scattering particles" or simply "(G)." The light-scattering particles have the function of scattering light that has entered a wavelength-conversion film formed from a composition for forming a wavelength-conversion film produced using the pattern-forming composition, thereby essentially extending the optical path length in the wavelength-conversion film and improving the light absorptance, and of re-scattering light that has been reflected at the interface of the wavelength-conversion film and returned to the wavelength-conversion film, thereby improving the luminous efficiency.

[0240] The light-scattering particles can be appropriately selected depending on the purpose, and may be organic or inorganic fine particles. Among these, inorganic fine particles with a high refractive index are preferred in terms of enhancing the scattering performance of the particles.

[0241] The light-scattering particles can be appropriately selected depending on the purpose, and may be organic or inorganic fine particles. Among these, inorganic fine particles with a high refractive index are preferred in terms of enhancing the scattering performance of the particles.

[0242] Examples of the organic fine particles include polymethyl methacrylate beads, acrylic-styrene copolymer beads, melamine beads, polycarbonate beads, styrene beads, cross-linked polystyrene beads, polyvinyl chloride beads, and benzoguanamine-melamine formaldehyde beads.

[0243] The inorganic fine particles include inorganic oxide particles made of at least one oxide selected from silicon, zirconium, titanium, indium, zinc, antimony, cerium, niobium, tungsten, etc. Specific examples of the inorganic oxide particles include SiO ２ , ZrO ２ , TiO ２ (hereinafter, also referred to as titanium oxide particles), BaTiO ３ , In ２ O ３ , ZnO, Sb ２ O ３ , ITO, CeO ２ , Nb ２ O ５and W.O. ３ Among these, TiO ２ , BaTiO ３ , ZrO ２ , CeO ２ and Nb ２ O ５ is preferred, and TiO ２ More preferably, TiO ２ Among these, the rutile type is more preferable than the anatase type because it has a lower catalytic activity, which results in a higher durability of the film, and furthermore, it has a higher refractive index.

[0244] These particles may be surface-treated. When surface treatment is performed, specific examples of the surface treatment material include different inorganic oxides such as silicon oxide and zirconium oxide, metal hydroxides such as aluminum hydroxide, organosiloxanes, and organic acids such as stearic acid. These surface treatment materials may be used alone or in combination.

[0245] The average particle diameter of the light-scattering particles is more than 50 nm and less than 300 nm. From the viewpoint of wavelength conversion efficiency, the lower limit of the average particle diameter is preferably 60 nm or more, more preferably 70 nm or more. In addition to the viewpoint of wavelength conversion efficiency, when considering patterning characteristics, an average particle diameter of more than 100 nm is more preferable from the viewpoint of low total light reflectance at i-line (365 nm). If the average particle diameter is too large, sedimentation tends to occur, so from the viewpoint of storage stability of the composition, the upper limit of the average particle diameter is preferably 290 nm or less, more preferably 200 nm or less. The average particle diameter of the light-scattering particles is the average particle diameter determined by observation with a transmission electron microscope.

[0246] Commercially available light-scattering particles may be used, and specific examples of titanium oxide particles include, but are not limited to, PT-401M (rutile type, average particle diameter 70 nm), PT-401L (rutile type, average particle diameter 130 nm), and PT-501R (rutile type, average particle diameter 180 nm). Note that the average particle diameter of the light-scattering particles exemplified above may vary by ±10 nm.

[0247] In consideration of wavelength conversion efficiency, the content of the (G) light scattering particles is preferably 0.1 to 20 mass % of the solid content, more preferably 0.2 to 15 mass %, and even more preferably 0.3 to 10 mass %.

[0248] Furthermore, the pattern-forming composition of the present invention may further contain various known additives, such as a light stabilizer, an antioxidant, a surfactant, a polymer dispersant, a flame retardant, a clarifying agent, an ultraviolet absorber, and a filler, as necessary.

[0249] Examples of antioxidants include hindered phenol-based antioxidants, phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. These may be used alone or in combination of two or more. Commercially available antioxidants may also be used, including Irganox 245 and Irganox 1010 manufactured by BASF Japan Ltd., and Adeka STAB AO-20, Adeka STAB AO-30, Adeka STAB AO-40, Adeka STAB AO-50, Adeka STAB AO-60, Adeka STAB AO-80, and Adeka STAB AO-330 manufactured by ADEKA Corporation, but are not limited thereto. When an antioxidant is used, its amount is not particularly limited, but is preferably 0.1 to 5.0 mass %, more preferably 0.3 to 1.5 mass %, of the solid content of the composition for forming a wavelength conversion film.

[0250] The surfactant is preferably a fluorine-based surfactant, more preferably a nonionic fluorine-based surfactant. Specific examples thereof include the Ftergent series manufactured by Neos Corporation, such as 212M, 215M, 250, 222F, FTX-218, and DFX-18, but are not limited to these. When a surfactant is used, the amount thereof is not particularly limited, but is preferably 0.01 to 1 mass %, more preferably 0.01 to 0.5 mass %, of the solid content of the pattern-forming composition.

[0251] The polymer dispersant is a polymer compound having a weight-average molecular weight of 750 or more and having functional groups that have affinity for light-scattering particles. The polymer dispersant has the function of dispersing light-scattering particles. The polymer dispersant adsorbs to the light-scattering particles via the functional groups that have affinity for the light-scattering particles, and disperses the light-scattering particles in the composition due to electrostatic and / or steric repulsion between the polymer dispersants. The polymer dispersant is preferably bonded to the surface of the light-scattering particles and adsorbed to the light-scattering particles, but may also be free in the pattern-forming composition.

[0252] The functional group having an affinity for light-scattering particles includes an acidic functional group, a basic functional group, and a nonionic functional group. The acidic functional group has a dissociable proton and may be neutralized with a base such as an amine or hydroxide ion, while the basic functional group may be neutralized with an acid such as an organic acid or an inorganic acid.

[0253] Examples of the acidic functional group include a carboxy group (-COOH), a sulfo group (-SO3H), a sulfate group (-OSO3H), a phosphonic acid group (-PO(OH)2), a phosphoric acid group (-OPO(OH)2), a phosphinic acid group (-PO(OH)-), and a mercapto group (-SH).

[0254] Examples of basic functional groups include primary amino groups, secondary amino groups, tertiary amino groups, ammonium groups, and imino groups, as well as nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole, and triazole.

[0255] Examples of the nonionic functional group include a hydroxy group, an ether group, a thioether group, a sulfinyl group (—SO—), a sulfonyl group (—SO—), a carbonyl group, a formyl group, an ester group, a carbonate ester group, an amide group, a carbamoyl group, a ureido group, a thioamide group, a thioureido group, a sulfamoyl group, a cyano group, an alkenyl group, an alkynyl group, a phosphine oxide group, and a phosphine sulfide group.

[0256] The polymeric dispersant may be a polymer (homopolymer) of a single monomer or a copolymer (copolymer) of multiple types of monomers. The polymeric dispersant may be a random copolymer, a block copolymer, or a graft copolymer. When the polymeric dispersant is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer. Specific examples of polymeric dispersants include acrylic resins, polyester resins, polyurethane resins, polyamide resins, polyethers, phenolic resins, silicone resins, polyurea resins, amino resins, epoxy resins, polyethyleneimines, polyallylamine, polyimides, and the like.

[0257] As the polymer dispersant, commercially available products can be used, such as the DISPERBYK series and BYK series manufactured by BYK, the Efka series manufactured by BASF, the Solsperse series manufactured by Lubrizol Corporation, the AJISPER PB series manufactured by Ajinomoto Fine-Techno Co., Ltd., the TEGO series manufactured by Evonik Chemicals, and the DISPARLON series manufactured by Kusumoto Chemicals Co., Ltd.

[0258] Specific examples of the commercially available products include DISPERBYK-130, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, and DISPERBYK-1, all manufactured by BYK. 84, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2022, DISPER BYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164; EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4061, EFKA4080, EFKA4300, EFKA4310, EFKA4320, EFKA4330, EFKA4340, EFKA4560, EFKA4585, EFKA5207, EFKA1501, EFKA1502, EFKA1503, and EFKA PX-4701 manufactured by BASF;Solsperse 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 11200, Solsperse 13940, Solsperse 16000, Solsperse 17000, Solsperse 18000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, and Solsperse 280 manufactured by Lubrizol 00, Solsperse 32000, Solsperse 32500, Solsperse 32550, Solsperse 32600, Solsperse 33000, Solsperse 34750, Solsperse 35100, Solsperse 35200, Solsperse 36000, Solsperse 37500, Solsperse 38500, Solsperse 39000, Solsperse 41000, Solsperse 54000, Solsperse 71000 and Solsperse 76500; Examples of such dispersants include Ajisper PB821, Ajisper PB822, Ajisper PB881, PN411, and PA111 manufactured by Ajinomoto Fine-Techno Co., Ltd.; TEGO Dispers 650, TEGO Dispers 660C, TEGO Dispers 662C, TEGO Dispers 670, TEGO Dispers 685, TEGO Dispers 700, TEGO Dispers 710, and TEGO Dispers 760W manufactured by Evonik Chemicals; and Disparlon AQ-320, Disparlon AQ-330, Disparlon AQ-340, Disparlon AQ-360, and Disparlon AQ-380 manufactured by Kusumoto Chemicals Co., Ltd.

[0259] When a polymer dispersant is used, the amount of the polymer dispersant to be added is not particularly limited, but is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, based on the light scattering particles.

[0260] Furthermore, the pattern-forming composition of the present invention may contain a solvent, if necessary.Specific examples thereof include aromatic or halogenated aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene; aliphatic hydrocarbons such as n-heptane, n-hexane, and cyclohexane; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; ethyl acetate, normal hexyl acetate, ethyl lactate, γ-butyrolactone, and propylene carbonate. ester-based solvents such as ethyl 3-ethoxypropionate, diisopropyl malonate, and ethyl 3-ethoxypropionate; halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, 1,2-dichloroethane, and chloroform; amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; alcohol-based solvents such as methanol, ethanol, isopropanol, n-propanol, cyclohexanol, diacetone alcohol, and 2-benzooxyethanol; ethylene glycol mononitrate, diisopropyl malonate, diisopropyl malonate, and ethyl 3-ethoxypropionate; Examples of suitable organic solvents include glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol diglycidyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate; glycol solvents such as ethylene glycol, propylene glycol, hexylene glycol, 3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, and 1,4-butanediol; nitrile solvents such as acetonitrile; and sulfur-containing solvents such as dimethyl sulfoxide.These may be used alone or in combination of two or more.

[0261] The (F) phosphor may exist as a solvate. The solvate is not particularly limited as long as it is a solvate of the (F) phosphor and a solvent. Examples of solvents that can form a solvate include dichloromethane, chloroform, acetonitrile, diethyl ether, ethyl acetate, methanol, ethanol, cyclohexane, toluene, acetone, N,N-dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran.

[0262] When the pattern-forming composition contains a solvent, the solids concentration of the composition cannot be generally defined because it varies depending on the intended thickness of the resist film, the coating method, etc., but is usually 10 to 70 mass %, and preferably 15 to 60 mass %.

[0263] The upper limit of the viscosity of the pattern-forming composition at 25° C. is 10,000 mPa·s or less, and preferably 1,000 mPa·s or less. In consideration of storage stability, the lower limit is preferably 5 mPa·s or more, and more preferably 10 mPa·s or more. In the present invention, viscosity refers to a value measured using an EMS viscometer.

[0264] The pattern-forming composition of the present invention can be prepared by mixing the components, including (E) a thermal crosslinking agent, (F) a phosphor, (G) light-scattering particles, other additives such as a surfactant, and a solvent, which are used as needed, in any order.

[0265] The pattern-forming composition of the present invention described above can be applied to a substrate, for example, and the solvent can be evaporated by heating or the like, if necessary, followed by irradiation with active energy rays (e.g., ultraviolet light) if necessary, to obtain a resist film or a wavelength conversion film. Examples of application methods include methods using a reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, bar bar roll blade coater, two-stream coater, rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater, inkjet, etc.

[0266] Heating can be carried out using a general heating device such as an oven, a hot plate, etc. The heating conditions are not particularly limited as long as a film can be formed, but heating at 60 to 200°C for 2 minutes to 2 hours is preferred, and heating at 80 to 200°C for 15 minutes to 1 hour is more preferred. Heat curing may also be carried out in stages.

[0267] The ultraviolet light irradiation is not particularly limited as long as it can form a film, but light sources such as mercury lamps, metal halide lamps, xenon lamps, and LEDs can be used, and light from which light other than the target exposure wavelength has been removed can be irradiated by combining a bandpass filter as needed. The wavelength of the irradiated light is preferably 200 to 440 nm, and particularly preferably includes light with a wavelength of 300 to 400 nm. The exposure dose is 10 to 4,000 mJ / cm. ２ is preferred.

[0268] The heating step and the ultraviolet light exposure step may be combined in any order, for example, heating may be performed before ultraviolet light irradiation, ultraviolet light irradiation may be performed before heating, or heating may be performed after ultraviolet light irradiation, and then heating may be performed again.

[0269] The thickness of the wavelength conversion film formed from the wavelength conversion film-forming composition produced using the pattern-forming composition is not particularly limited, but is usually 1 to 50 μm, preferably 2 to 30 μm, and more preferably 3 to 20 μm. The haze of the wavelength conversion film is not particularly limited, but is preferably 18% or more, more preferably 30% or more, and more preferably 40% or more, from the viewpoint of increasing the amount of light that can be absorbed by the phosphor by scattering incident light within the film. The upper limit of the haze value is not particularly limited, but is usually about 95%. In the present invention, the haze value is a value measured in accordance with ASTM D1003-61. In the present invention, the haze value can be measured, for example, under conditions for measuring a 10 μm-thick wavelength conversion film formed from a composition containing 3% by mass of titanium oxide particles.

[0270] The substrate may be appropriately selected from those used as base substrates for forming this type of film, but a glass substrate or polymer plate having a transmittance of 50% or more for light in the visible region of 400 to 800 nm is preferred. Specific examples of glass include soda-lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Specific examples of polymers include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

[0271] In the present invention, when a coating film (resist film) is formed using a composition containing each of the above components (A) to (C) and an alkali-soluble resin as component (D) (i.e., a negative pattern-forming composition), a mask having a predetermined pattern is attached to the formed coating film, and the film is irradiated with light such as ultraviolet light, and developed with an alkaline developer, whereby the unexposed areas are washed out, and the remaining patterned film is heated at 80 to 140°C for 0.5 to 10 minutes as necessary, thereby obtaining a relief pattern with sharp end faces.

[0272] Examples of the alkaline developer include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants known for use in developers can also be added to these developers.

[0273] Among the above, an aqueous solution of 0.1 to 2.58 mass % tetraethylammonium hydroxide is generally used as a developer for photoresists, and the composition of the present invention can also be developed satisfactorily using this alkaline developer without causing problems such as swelling.

[0274] The developing method may be any of the puddle method, dipping method, and swing immersion method, etc. The developing time is usually 15 to 180 seconds.

[0275] After development, the photosensitive resin film is washed with running water and then air-dried using compressed air or compressed nitrogen or by spinning, thereby removing moisture from the substrate and obtaining a patterned film. In the above, the washing time is usually about 20 to 120 seconds.

[0276] Subsequently, the resulting pattern-forming film (resist film) is post-baked for thermal curing, thereby obtaining a film having a good relief pattern and excellent heat resistance, transparency, flattening properties, low water absorption, chemical resistance, etc. A hot plate, an oven, etc. can be used to heat the pattern-forming film.

[0277] A typical post-baking method involves treating the film at a heating temperature selected from the range of 140 to 270° C. for 5 to 30 minutes on a hot plate or for 30 to 90 minutes in an oven. Post-baking under these conditions allows a cured film having a good pattern shape to be obtained.

[0278] The resist film obtained from the composition of the present invention has a curability that allows the exposed portion to maintain a sufficient thickness even when subjected to a development treatment after exposure in the atmosphere. In particular, the resist film has a curability that allows the exposed portion to maintain a sufficient thickness when subjected to a development treatment using an alkaline aqueous solution, even when a photoradical polymerization initiator is used as the photopolymerization initiator. Therefore, the resist film can be suitably used as a pattern-forming composition (particularly a negative-tone pattern-forming composition).

[0279] The wavelength conversion film obtained from the composition of the present invention has excellent wavelength conversion efficiency, light resistance retention, and curability, and can therefore be suitably used as a wavelength conversion film (color conversion film) for displays such as micro LED displays, organic EL displays, and liquid crystal displays, as well as for lighting.

[0280] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0281] [Molecular Weight Measurement] In the present examples, the molecular weight of the polymer was measured using a GPC system manufactured by JASCO Corporation as the apparatus and Shodex (registered trademark) KF-804L and 803L as the columns under the following conditions: Column oven: 40°C Flow rate: 1 mL / min Eluent: tetrahydrofuran

[0282] The meanings of the abbreviations used in the examples are as follows: MMA: methyl methacrylate MAA: methacrylic acid MAIB: 2,2'-azobis(isobutyrate) dimethyl IPEMA: isoprenyl methacrylate manufactured by Kuraray Co., Ltd. [Acrylic crosslinker 1 (component (B))] V260: Viscoat V260 (trade name) manufactured by Osaka Organic Chemical Industry Ltd. [Photopolymerization initiator 1 (component (C))] NCI-930: NCI-930 (trade name) manufactured by ADEKA Corporation [Photopolymerization initiator 2 (component (C))] Omnirad 184: Omnirad 184 (trade name) manufactured by IGM Resin [Resin (component (D))] P1: acrylic polymer (alkali-soluble resin) described in Reference Synthesis Example 1 below. [Epoxy-based crosslinking agent 1 (component (E))] GT-401: Epolead (registered trademark) GT-401 manufactured by Daicel Corporation [Phosphor (component (F))] FL-305: Oracet (registered trademark) FL Red 305 (trade name) [Light-scattering particles (component (G))] PT-401L: High-purity titanium dioxide (rutile type, average particle diameter 130 nm) manufactured by Ishihara Sangyo Kaisha, Ltd. [Particle dispersant] AQ-320: Disparlon AQ-320 (trade name) manufactured by Kusumoto Chemicals Co., Ltd. [Surfactant] DFX-18: Futergent DFX-18 (trade name) manufactured by Neos Corporation [Solvent] CPN: Cyclopentanone PGMEA: Propylene glycol monomethyl ether acetate

[0283] Reference Synthesis Example 1 Synthesis of alkali-soluble resin P1 80.0 g of MMA, 20.0 g of MAA, and 7.0 g of MAIB were dissolved in 160.5 g of CPN, and the mixture was allowed to react for 20 hours at 100° C. to obtain an acrylic polymer P1 solution (solid content concentration: 40% by mass). The resulting acrylic polymer P1 had an Mn of 5,022 and an Mw of 8,070.

[0284] [Preparation Example 1] Preparation of Light-Scattering Particle Dispersion [CPN Dispersion of Component G] Light-scattering particles PT-401L and particle dispersant AQ-320 in an amount of 20% by weight in terms of solid content relative to the light-scattering particles PT-401L were added to a 1000 mL polypropylene container, and CPN was further added to adjust the solid content concentration to 36% by weight. A slurry was obtained by dispersing and stirring at 1,500 rpm for 30 minutes. Next, the entire amount of the slurry was transferred to a slurry tank, and then, using a bead mill device Labo Ministar DMS65 manufactured by Ashizawa Finetech Co., Ltd., the mixture was filled with 60% by volume of zirconia beads having a diameter of 0.2 mm. Ten passes were performed at a liquid feed rate of 60 mL / min and a disk peripheral speed of 8 m / s to obtain a light-scattering particle dispersion. The particle size distribution of the resulting dispersion was measured using a Nanotrac UPA (manufactured by Microtrac). CPN was used as the dilution liquid, and the 50% cumulative diameter (D50) of the particles in the dispersion liquid was calculated on a volume basis from the scattering that occurred when laser light was irradiated onto the diluted sample using analysis software Microtrac DMS manufactured by Nikkiso Co., Ltd., and was found to be 185 nm.

[0285] [Examples 1 to 7, Comparative Examples 1 and 2, and Reference Examples 1 to 6] Preparation of Compositions for Forming Patterns Compositions for forming wavelength conversion films were prepared by mixing the components according to the compositions shown in Tables 1 to 6 and filtering the resulting mixtures using a polytetrafluoroethylene (PTFE) filter with a pore size of 5.0 μm. The composition ratios in Tables 1 to 6 represent mass ratios of the solid content.

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292] [Film Thickness Measurement] The film thickness of each resist pattern film formed using each pattern-forming composition obtained in Examples 1 to 7, Comparative Examples 1 and 2, and Reference Examples 1 to 6 was measured as follows: The film thickness of each coating film obtained by the methods described in the optical property evaluation and lithography property evaluation below was measured using an interference film thickness meter F20-EXR manufactured by Filmetrics, Inc., from the spectrum in the wavelength range of 1000 nm to 1600 nm.

[0293] [Evaluation of Optical Properties] The optical properties shown in Tables 7 and 9 of the wavelength conversion films formed with the compositions for forming a wavelength conversion film obtained in Examples 1 to 3, Comparative Example 1, and Reference Examples 1 to 4 were evaluated as follows: The compositions for forming a wavelength conversion film of Examples 1 to 3, Comparative Example 1, and Reference Examples 1 to 4 were applied to a quartz substrate using a spin coater, and then prebaked on a hot plate at 110°C for 90 seconds to obtain coating film samples with a film thickness of 11 µm. Thereafter, the compositions were cured with 200 mJ / cm using an EYE UV curing device manufactured by EYE GRAPHICS CO., LTD. ２ The coating film was irradiated with ultraviolet light having a wavelength of 480 nm or less, and then post-baked at 230°C for 10 minutes to obtain a coating film sample with a thickness of 10 μm. Next, the coating film sample was placed on a blue LED light (emission peak wavelength 450 nm) manufactured by CCS Inc., the LED light was turned on, and the light emitted through the coating film sample was measured using a USR-45 spectroradiometer manufactured by Ushio Inc., and the result was reported as Result (1). Similarly, the light emitted from only the LED light, excluding the coating film sample, was measured in the same manner, and the result was reported as Result (2). From the obtained spectral irradiance spectrum, the number of photons of light with a wavelength of 480 nm or less in Result (2) was taken as the "excitation light photon number." Similarly, the number of photons of light with a wavelength of 480 nm or less in Result (1) was taken as the "transmitted light photon number." Similarly, the number of photons of light with a wavelength exceeding 480 nm in Result (1) was taken as the "emission photon number." The "blue light absorptance" and "conversion efficiency" were calculated using the following formulas. Blue light absorption rate = (number of excitation light photons - number of transmitted light photons) ÷ number of excitation light photons Conversion efficiency = number of emitted photons ÷ number of excitation light photons

[0294] [Evaluation of Lithography Properties] The lithography properties shown in Tables 7 to 10 of the resist pattern films formed using the pattern-forming compositions obtained in Examples 1 to 7, Comparative Examples 1 and 2, and Reference Examples 1 to 6 were evaluated as follows. For Examples 1 to 7, Comparative Examples 1 and 2, and Reference Examples 1 to 6, each composition was applied using a spin coater onto a silicon substrate treated with hexamethyldisilazane, and then prebaked on a hot plate at a temperature of 110°C for 90 seconds to form a coating film with a thickness of 13 µm. After measuring the thickness of the coating film (film thickness after prebaking), the coating film was exposed to ultraviolet light using a PLA-600FA ultraviolet irradiation device manufactured by Canon Inc., with a light intensity of 3.4 mW / cm at 365 nm. ２ of ultraviolet light at 200 mJ / cm ２ The coating film was irradiated through a photomask having 5 mm x 6 mm square light-transmitting portions spaced 5 mm x 6 mm apart for an exposure dose of 1000 sq m. The coating film was immersed in a 0.045 mass % potassium hydroxide aqueous solution for 4 minutes and 30 seconds while being penetrated, and then washed with running ultrapure water for 30 seconds. The coating film was then dried by air blowing to obtain a coating film sample having a pattern formed thereon. In all of Examples 1 to 7, Comparative Examples 1 and 2, and Reference Examples 1 to 6, no coating film was observed on the substrate in the light-shielded areas during ultraviolet light irradiation, and the film had been removed by the development treatment, while the coating film remained in the exposed areas. Next, the film thickness of the coating film sample after development was measured, and the "remaining film ratio" was calculated using the film thickness after development and the film thickness after pre-baking according to the following formula: Remaining film ratio = film thickness after development ÷ film thickness after pre-baking

[0295] The optical properties and lithography properties of the resist pattern films formed using the pattern-forming compositions obtained in Examples 1 to 7, Comparative Examples 1 and 2, and Reference Examples 1 to 6 are shown in Tables 7 to 10.

[0296]

[0297]

[0298]

[0299]

[0300] According to the results of the examples, which are embodiments of the present invention, it was found that in Examples 1 to 7, in which IPEMA was used as the pattern-forming composition, the residual film rate exceeded 50%. In Examples 1 to 2 and 4 to 7, the residual film rate exceeded 70%. Furthermore, in Examples 1 to 3, in which an (F) phosphor was included in the composition, the conversion efficiency exceeded 30% and the residual film rate exceeded 50%. In Examples 1 and 2, the conversion efficiency exceeded 35% and the residual film rate exceeded 70%. Furthermore, in Comparative Examples 1 to 2 and Reference Examples 1 to 6, the residual film rate was 0%. Furthermore, since a photoradical polymerization initiator was used as the photopolymerization initiator in Examples 1 to 7, it was confirmed that the pattern-forming composition of the present invention can provide a composition capable of forming a resist pattern film that is excellent in solubility in a developer in a development process after exposure under atmospheric conditions, and that the resist pattern film can be provided. Furthermore, the results of Examples 1 to 3 also confirmed that a composition capable of forming a wavelength conversion film (i.e., a wavelength conversion film-forming composition) and the wavelength conversion film can be provided. Therefore, it was confirmed that the pattern-forming composition according to the present invention can also be used as a composition for forming a wavelength-converting film, and that a wavelength-converting film formed from the composition for forming a wavelength-converting film can provide high curability and high conversion efficiency. Therefore, it was found that the pattern-forming composition according to the present invention can also be used as an excellent composition for forming a wavelength-converting film.

[0301] According to the present invention, the composition can be suitably used as a pattern-forming composition (particularly a negative-tone pattern-forming composition) that has excellent curability even when developed after exposure to air. Therefore, it is expected to be useful as a wide variety of materials, for example, as materials for forming cured films such as protective films, planarizing films, and insulating films in various displays such as thin film transistor (TFT) liquid crystal display devices, organic EL devices, and touch panel devices, particularly as materials for forming interlayer insulating films in TFT liquid crystal devices, protective films for color filters, array planarizing films, interlayer insulating films in capacitive touch panels, insulating films in organic EL devices, and structural sheets as optical property adjusting layers on display surfaces. Furthermore, the wavelength conversion film obtained from the composition of the present invention has excellent wavelength conversion efficiency, light resistance, and curability, and is therefore expected to be useful as a wavelength conversion film (color conversion film) for displays and lighting, such as micro LED displays, organic EL displays, and liquid crystal displays.

Claims

1. A pattern-forming composition comprising a compound represented by the following general formula (1), a resin, and [In general formula (1), R １ and R ２ each independently represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; R ３ represents any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; R ４ represents any one selected from the group consisting of a (meth)acryloyl group, a styryl group, and an alkenyl group having 2 to 6 carbon atoms, and X represents NH or O. n represents any integer from 1 to 5.

2. R in the above general formula (1) １ and R ２ is a hydrogen atom, R ３ is a methyl group, n is 1 to 4, and R ４ 2. The composition for pattern formation according to claim 1, wherein: is a (meth)acryloyl group or a styryl group; and X is O.

3. The pattern-forming composition according to claim 1, wherein the general formula (1) is general formula (2). [In the formula, R ５ represents a hydrogen atom or a methyl group.

4. The pattern-forming composition according to claim 1, wherein the resin contains an alkali-soluble resin.

5. The pattern-forming composition according to claim 1, comprising: (A) a compound represented by the above general formula (1); (B) a compound having two or more polymerizable functional groups in the molecule and different from the compound represented by the above general formula (1); (C) a photopolymerization initiator; and (D) a resin.

6. The pattern-forming composition according to claim 5, wherein the polymerizable functional group in (B) is a (meth)acryloyl group.

7. The pattern-forming composition according to claim 5, wherein the resin (D) contains an alkali-soluble resin.

8. The pattern-forming composition according to claim 5, further comprising (E) a thermal crosslinking agent.

9. The pattern-forming composition according to claim 8, wherein the thermal crosslinking agent (E) contains an epoxy-based crosslinking agent.

10. The pattern-forming composition according to claim 5, further comprising (F) a phosphor.

11. The pattern-forming composition according to claim 1, further comprising (G) light-scattering particles.

12. The pattern-forming composition according to claim 11, wherein the light-scattering particles (G) are titanium oxide particles.

13. The pattern-forming composition according to claim 11, wherein the content of the light-scattering particles (G) is 1% by mass or more based on the solid content.

14. The pattern-forming composition according to claim 1, wherein a film formed from said composition has a haze value of 18% or more.

15. The pattern-forming composition according to claim 10, which is a composition for forming a wavelength conversion film.

16. The pattern-forming composition according to claim 15, which is a composition for forming a wavelength conversion film for a display.

17. A resist pattern film made from the pattern-forming composition according to any one of claims 1 to 16.

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