Radiation-sensitive resin composition, cured film, pattern forming method, solid-state imaging element, and image display device

Abstract

The present invention provides a radiation-sensitive resin composition having good sensitivity and excellent temporal stability of sensitivity, a cured film, a pattern forming method, a solid-state imaging element, and an image display device. The radiation-sensitive resin composition of the present invention comprises a resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, an organic solvent, and water. In the radiation-sensitive resin composition, the photopolymerization initiator comprises an oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group, and the water content is 0.1 to 2% by mass relative to the mass of the radiation-sensitive resin composition.

Description

[0001] The present application is a divisional application of International Application No. PCT / JP2016 / 085914, National Application No. 201680070064.6, and Invention Name: “Radiation-Sensitive Resin Composition, Cured Film, Pattern Forming Method, Solid-State Imaging Element, and Image Display Device.” Technical Field

[0002] The present invention relates to a radiation-sensitive resin composition, a cured film, a pattern forming method, a solid-state imaging element, and an image display device. Background Art

[0003] A cured film is produced using a radiation-sensitive resin composition containing a resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and an organic solvent.

[0004] Oxime ester compounds and the like are known as photopolymerization initiators (see Patent Documents 1 to 4).

[0005] Furthermore, Patent Document 1 discloses an invention relating to a coloring composition comprising a compound (A) having an ethylenically unsaturated double bond, a pigment (B), a pigment dispersant (C), a photopolymerization initiator (D), and a solvent (E) containing a solvent (S) having a solubility in water exceeding 7.0% by weight, accounting for 25% or more of the total solvent weight, wherein the water content of the coloring composition is 0.3 to 2.0% by weight based on the total weight of the coloring composition. Furthermore, paragraph 0007 of Patent Document 1 states that the coloring composition described in Patent Document 1 contains an appropriate amount of water, thereby exhibiting high sensitivity and a fast development speed.

[0006] Furthermore, Patent Document 2 describes an invention relating to a coloring composition comprising a triarylmethane dye, a solvent, and a resin, wherein the water content of the coloring composition is 1060 ppm to 11000 ppm. Paragraph 0007 of Patent Document 2 states that adjusting the water content to this range can improve pixel brightness and heat resistance.

[0007] Furthermore, Patent Document 3 describes an invention relating to a coloring composition comprising at least an alkali-soluble resin, an organic solvent-soluble dye, a photosensitive compound, and a solvent, and having a water content of 1.0% by mass or less. Paragraph 0012 of Patent Document 3 states that by setting the water content of the coloring composition within the above range, it is possible to suppress detachment of fine patterns after development and the occurrence of interlocking shapes between the pattern and the substrate.

[0008] Previous technical literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 2008-268242

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 2013-199554

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. 2003-295427

[0013] Patent Document 4: Japanese Patent Application No. 2015-509074 Summary of the Invention

[0014] Technical issues to be solved by the invention

[0015] Regarding radiation-sensitive resin compositions, cured films may be produced using the prepared composition, or cured films may be produced using the prepared radiation-sensitive resin composition after long-term storage. Studies by the present inventors have revealed that long-term storage of radiation-sensitive resin compositions may increase or decrease their sensitivity compared to that immediately after production.

[0016] If the sensitivity of a radiation-sensitive resin composition varies, pattern size and other factors may vary when patterns are produced under the same exposure conditions. Therefore, if sensitivity varies, it may be time-consuming to adjust exposure conditions based on the radiation-sensitive resin composition used. Furthermore, if the sensitivity of the radiation-sensitive resin composition is low, the exposure dose required for pattern formation may increase, which may lead to increased time and running costs.

[0017] Therefore, there is a demand for the development of a radiation-sensitive resin composition having good sensitivity and excellent temporal stability of sensitivity.

[0018] Therefore, an object of the present invention is to provide a radiation-sensitive resin composition, a cured film, a pattern forming method, a solid-state imaging element, and an image display device having good sensitivity and excellent temporal stability of sensitivity.

[0019] Means for solving technical problems

[0020] As a result of intensive research, the present inventors have found that the above-mentioned object can be achieved by using a radiation-sensitive resin composition described below, and have thus completed the present invention.

[0021] <1> A radiation-sensitive resin composition comprising a resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, an organic solvent, and water.

[0022] In the radiation-sensitive resin composition,

[0023] The photopolymerization initiator includes an oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group.

[0024] The water content is 0.1 to 2% by mass based on the mass of the radiation-sensitive resin composition.

[0025] <2> according to <1> The radiation-sensitive resin composition, wherein the resin contains an alkali-soluble resin.

[0026] <3> according to <1> or <2> In the radiation-sensitive resin composition, the polymerizable compound is a multifunctional (meth)acrylate compound having an ethylenically unsaturated bond equivalent of 3.0 to 12.0 mmol / g.

[0027] <4> according to <1> ~ <3> The radiation-sensitive resin composition according to any one of the preceding claims, wherein the oxime ester compound has at least one group selected from a branched alkyl group having 7 or more carbon atoms and a cyclic alkyl group having 7 or more carbon atoms.

[0028] <5> according to <1> ~ <4> The radiation-sensitive resin composition according to any one of the preceding claims, wherein the oxime ester compound has a carbazole structure.

[0029] <6> according to <5> The radiation-sensitive resin composition, wherein the carbazole structure further has a ring-condensed structure on the benzene ring of the carbazole portion.

[0030] <7> according to <1> ~ <6> The radiation-sensitive resin composition according to any one of the preceding claims, wherein the oxime ester compound is an oxime ester compound containing a fluorine atom.

[0031] <8> according to <1> ~ <7> The radiation-sensitive resin composition according to any one of the preceding claims, wherein the oxime ester compound is a compound represented by formula (1),

[0032] [Chemical Formula 1]

[0033]

[0034] In formula (1), Ar 1 and Ar 2 Each independently represents an aromatic hydrocarbon ring which may have a substituent, R 1 ~R 3 Each independently represents an alkyl group or an aryl group; wherein, R 1 ~R 3 At least one of them is a branched alkyl group or a cyclic alkyl group, or R 1 ~R 3 、Ar 1 and Ar 2At least one of them has a branched alkyl group or a cyclic alkyl group.

[0035] <9> according to <1> ~ <8> The radiation-sensitive resin composition according to any one of the preceding claims, wherein the organic solvent is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, butyl acetate, ethyl 3-ethoxypropionate, propylene glycol monoethyl ether acetate, xylene, ethylbenzene, methyl isobutyl ketone, 2-butanol, and dipropylene glycol monomethyl ether.

[0036] <10> according to <1> ~ <9> The radiation-sensitive resin composition according to any one of the preceding claims, further comprising at least one selected from the group consisting of a coloring agent and inorganic particles.

[0037] <11> according to <1> ~ <10> The radiation-sensitive resin composition according to any one of the preceding claims, further comprising a phthalimide compound.

[0038] <12> according to <1> ~ <11> The radiation-sensitive resin composition according to any one of the preceding claims, further comprising an ultraviolet absorber.

[0039] <13> according to <1> ~ <12> The radiation-sensitive resin composition according to any one of the preceding claims, further comprising a thermosetting compound.

[0040] <14> according to <1> ~ <13> The radiation-sensitive resin composition according to any one of the preceding claims, wherein the photopolymerization initiator further contains a compound other than the oxime ester compound.

[0041] <15> according to <14> In the radiation-sensitive resin composition, the compound other than the oxime ester compound is at least one selected from the group consisting of an oxime ester compound having no branched alkyl group and no cyclic alkyl group, an alkylphenone compound, and an acylphosphine compound.

[0042] <16> A cured film, using <1> ~ <15> The radiation-sensitive resin composition according to any one of the above claims.

[0043] <17> according to <16> The cured film has a transmittance of light at a wavelength of 365 nm of 15% or less.

[0044] <18> A pattern forming method comprising: using <1> ~ <15> The step of forming a radiation-sensitive resin composition layer on a support using the radiation-sensitive resin composition described in any one of the preceding claims; exposing the radiation-sensitive resin composition layer in a pattern; and developing and removing unexposed portions to form a pattern.

[0045] <19> A solid-state imaging element having <16> or <17> The cured film.

[0046] <20> An image display device having <16> or <17> The cured film.

[0047] Effects of the Invention

[0048] The present invention can provide a radiation-sensitive resin composition having good sensitivity and excellent temporal stability of sensitivity, a cured film, a pattern forming method, a solid-state imaging element, and an image display device. DETAILED DESCRIPTION

[0049] Hereinafter, the contents of the present invention will be described in detail.

[0050] In the description of groups (atomic groups) in this specification, the description that does not describe substitution or unsubstitution includes groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, the so-called "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0051] In this specification, light refers to actinic rays or radiation. Furthermore, "actinic rays" or "radiation" include, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.

[0052] In this specification, the term "exposure" refers not only to exposure using the bright line spectrum of a mercury lamp, extreme ultraviolet light represented by an excimer laser, X-rays, EUV light, etc., but also includes drawing using particle beams such as electron beams and ion beams, unless otherwise specified.

[0053] In this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0054] In this specification, the total solid content refers to the total mass of the components obtained by removing the solvent from all the components of the composition.

[0055] In this specification, "(meth)acrylate" means both or either acrylate and methacrylate, "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid, "(meth)allyl" means both or either allyl and methallyl, and "(meth)acryloyl" means both or either acryloyl and methacryloyl.

[0056] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved.

[0057] In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by Tosoh Corporation) with a TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID (inner diameter) × 15.0 cm) column and a 10 mmol / L lithium bromide NMP (N-methylpyrrolidone) solution as the eluent.

[0058] <Radiation-sensitive resin composition>

[0059] The radiation-sensitive resin composition of the present invention comprises a resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, an organic solvent, and water. In the radiation-sensitive resin composition, the photopolymerization initiator comprises an oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group, and the water content is 0.1 to 2% by mass relative to the mass of the radiation-sensitive resin composition. Hereinafter, the radiation-sensitive resin composition is also referred to as a resin composition.

[0060] The resin composition of the present invention has the above-mentioned structure, thereby achieving good sensitivity and excellent temporal stability of sensitivity. Specifically, the resin composition of the present invention contains 0.1 to 2% by mass of water, thereby achieving good sensitivity and suppressing the increase or decrease in sensitivity over time. When the water content is above the above lower limit, the sensitivity is good. Furthermore, when the water content is below the above upper limit, the temporal stability of sensitivity is good.

[0061] On the other hand, when water is contained in a radiation-sensitive resin composition, the initial sensitivity is good, but the sensitivity tends to decrease over time. This is presumably because the photopolymerization initiator is decomposed by water.

[0062] The present inventors conducted detailed research on radiation-sensitive resin compositions containing water and discovered that by setting the water content to 2% by mass or less and using an oxime ester compound having at least one group selected from branched alkyl groups and cyclic alkyl groups (hereinafter referred to as oxime ester compound A) as a photopolymerization initiator, sensitivity reduction can be suppressed. Oxime ester compound A is believed to be less susceptible to water-induced decomposition because the at least one group selected from branched alkyl groups and cyclic alkyl groups inhibits nucleophilic attack by water on the oxime ester site.

[0063] Therefore, it is presumed that by using the oxime ester compound A and setting the water content of the resin composition to 0.1 to 2 mass %, a resin composition having good sensitivity, suppressed increase or decrease in sensitivity over time, and excellent temporal stability of sensitivity can be obtained.

[0064] The resin composition of the present invention has a water content of 0.1 to 2.0% by mass, with a lower limit of preferably 0.11% by mass or more, more preferably 0.12% by mass or more, and an upper limit of preferably 1.7% by mass or less, more preferably 1.5% by mass or less.

[0065] Furthermore, the resin composition of the present invention preferably contains 20 to 7000 parts by mass of water, more preferably 25 to 1500 parts by mass of water, and even more preferably 30 to 1000 parts by mass of water, relative to 100 parts by mass of the oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group.

[0066] Furthermore, the resin composition of the present invention preferably contains 4 to 500 parts by mass of water, more preferably 5 to 450 parts by mass, and even more preferably 10 to 300 parts by mass of water, based on 100 parts by mass of the photopolymerization initiator.

[0067] In the present invention, the water content in the resin composition is a value measured by the Karl Fischer method. The Karl Fischer method refers to a method for measuring the water content in a composition using a Karl Fischer reagent (composed of iodine, sulfur dioxide, an alkali, and a solvent such as an alcohol) that reacts selectively and quantitatively with water. This method includes coulometric titration and volumetric titration, but either method can be used.

[0068] When the resin composition of the present invention is used to make a film with a thickness of 0.5 μm after drying, the transmittance of the film at a wavelength of 365 nm is preferably 15% or less, more preferably 10% or less, and even more preferably 7% or less. Since the transmittance of i-rays is low, the resin composition used in the manufacture of such a film having a spectrum tends to have low sensitivity. However, the resin composition of the present invention can obtain excellent sensitivity by being set to the above structure, and is therefore particularly suitable for the manufacture of a resin composition for a film with low transmittance at a wavelength of 365 nm. Furthermore, the resin composition of the present invention is particularly preferred as a resin composition for i-ray exposure.

[0069] Hereinafter, each component of the resin composition of the present invention will be described in detail.

[0070] Polymeric Compounds

[0071] The resin composition of the present invention contains a polymerizable compound with an ethylenically unsaturated bond. As a polymerizable compound with an ethylenically unsaturated bond, compounds having a group with an ethylenically unsaturated bond, etc. can be mentioned. As a group with an ethylenically unsaturated bond, vinyl, styryl, (meth) allyl, (meth) acryloyl, etc. can be mentioned, preferably (meth) acryloyl. The polymerizable compound is preferably a compound having more than one group with an ethylenically unsaturated bond, more preferably a compound having more than two such groups, further preferably more than three. The upper limit is, for example, preferably less than 15, more preferably less than 6.

[0072] The ethylenically unsaturated bond equivalent of the polymerizable compound is preferably 3.0 to 12.0 mmol / g. In the present invention, the ethylenically unsaturated bond equivalent (double bond equivalent) is defined by the valence of the ethylenically unsaturated bond relative to the molecular weight of the compound.

[0073] The polymerizable compound may be, for example, any chemical form such as a monomer, a prepolymer, i.e., a dimer, a trimer, an oligomer, or a mixture thereof, and a multimer thereof. Preferably, it is a monomer. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more. The polymerizable compound is preferably a 3-15 functional (meth)acrylate compound, more preferably a 3-6 functional (meth)acrylate compound. Furthermore, the polymerizable compound is preferably a functional (meth)acrylate compound having an ethylenically unsaturated bond equivalent of 3.0 to 12.0 mmol / g.

[0074] As specific examples of the polymerizable compound, reference can be made to the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-29760, and paragraphs 0254 to 0257 of JP-A-2008-292970, the contents of which are incorporated herein.

[0075] Preferred polymerizable compounds include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which their (meth)acryloyl groups are bonded via ethylene glycol or propylene glycol residues (for example, SR454, SR494, and SR499 commercially available from Sartomer Company, Inc.). Oligomers thereof can also be used. KAYARAD RP-1040 and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) can also be used.

[0076] The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Commercially available products include polyacid-modified acrylic oligomers such as M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd. Alternatively, Aronix TO-2349 (Toagosei Co., Ltd.) may be used.

[0077] The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. A polymerizable compound with an acid value of 0.1 mgKOH / g or greater exhibits excellent development and solubility characteristics, while an acid value of 40 mgKOH / g or less provides advantages in production and handling. Furthermore, the polymerizable compound exhibits excellent photopolymerization performance and curability.

[0078] As for the polymerizable compound, a compound having a caprolactone structure is also a preferred embodiment.

[0079] The polymerizable compound having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

[0080] The polymerizable compound may also be a polymerizable compound having an alkyleneoxy group. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and more preferably a tri- to hexafunctional (meth)acrylate compound having 4 to 20 ethyleneoxy groups.

[0081] Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethyleneoxy groups; DPCA-60 manufactured by Nippon Kayaku Co., Ltd., which is a hexafunctional acrylate having six oxypentylene groups; and TPA-330 manufactured by Nippon Kayaku Co., Ltd., which is a functional acrylate having three oxyisobutylene groups.

[0082] The following compounds can also be used as the polymerizable compound.

[0083] [Chemical Formula 2]

[0084]

[0085] Preferred polymerizable compounds include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and polyurethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a thioether structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-B-1-105238, are also preferably used.

[0086] Examples of commercially available products include polyurethane oligomers UAS-10 and UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by KYOEISHA CHEMICAL Co., Ltd.).

[0087] The content of the polymerizable compound is preferably 0.1 to 50% by mass relative to the total solid content of the resin composition. The lower limit is, for example, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is, for example, more preferably 45% by mass or less, and further preferably 40% by mass or less. The polymerizable compound may be used alone or in combination. When two or more are used in combination, the total amount preferably falls within the above range.

[0088] Photopolymerization Initiator

[0089] The resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator includes an oxime ester compound (oxime ester compound A) having at least one group selected from a branched alkyl group and a cyclic alkyl group.

[0090] (Oxime ester compound A)

[0091] The number of carbon atoms in the branched alkyl group of the oxime ester compound A is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more. The upper limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.

[0092] The number of carbon atoms in the cyclic alkyl group of the oxime ester compound A is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more. The upper limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.

[0093] The oxime ester compound A preferably has a carbazole structure. According to this embodiment, a resin composition with excellent sensitivity can be easily obtained. Moreover, the time stability of the sensitivity is also good. The carbazole structure preferably further has a structure formed by ring fusion on the benzene ring of the carbazole portion. On the benzene ring of the carbazole portion, preferably aromatic rings are fused, more preferably benzene rings are fused to form a naphthalene ring. As such a structure, for example, the following structure can be cited, preferably (CB-1). R represents a hydrogen atom or a substituent.

[0094] [Chemical Formula 3]

[0095]

[0096] The oxime ester compound A is preferably an oxime ester compound containing a fluorine atom. According to this embodiment, a resin composition with excellent sensitivity can be easily obtained. In addition, the temporal stability of the sensitivity is also good.

[0097] The oxime ester compound containing fluorine atoms preferably has a group containing fluorine atoms. The group containing fluorine atoms is preferably an alkyl group having fluorine atoms (hereinafter, also referred to as a fluorine-containing alkyl group) and / or a group containing an alkyl group having fluorine atoms (hereinafter, also referred to as a fluorine-containing group). As the fluorine-containing group, it is preferably selected from -OR X11 、-SR X11 、-CORX11 、-COOR X11 、-OCOR X11 、-NR X11 R X12 、-NHCOR X11 、-CONR X11 R X12 、-NHCONR X11 R X12 、-NHCOOR X11 、-SO2R X11 、-SO2OR X11 and -NHSO2R X11 At least one group in R X11 represents a fluorinated alkyl group, R X12 represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, an aryl group or a heterocyclic group. The fluorinated group is more preferably -OR X11 .

[0098] The number of carbon atoms in the alkyl group and the fluorinated alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group and the fluorinated alkyl group may be linear, branched, or cyclic, but are preferably linear or branched.

[0099] Regarding the fluorine-containing alkyl group, the fluorine atom substitution rate is preferably 40 to 100%, more preferably 50 to 100%, and even more preferably 60 to 100%. In addition, the fluorine atom substitution rate refers to the ratio (%) of the number of hydrogen atoms substituted by fluorine atoms to the total number of hydrogen atoms in the alkyl group.

[0100] The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring.

[0101] The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of condensed rings is preferably 2 to 8, more preferably 2 to 6, further preferably 3 to 5, and particularly preferably 3 to 4. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and even more preferably 3 to 20. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heteroatoms constituting the heterocyclic group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms, and more preferably nitrogen atoms.

[0102] The group containing fluorine atoms is preferably a fluorinated alkyl group and / or -OR X11 The group containing a fluorine atom preferably has a terminal structure represented by formula (1) or (2). * in the formula represents a connecting bond.

[0103] *-CHF2 (1)

[0104] *-CF3 (2)

[0105] Regarding the fluorine-atom-containing oxime ester compound, the total number of fluorine atoms in the compound is preferably 3 or more, more preferably 4 to 10.

[0106] In the present invention, the oxime ester compound is preferably a compound represented by formula (1). According to this embodiment, there is a tendency that the effects of the present invention can be particularly significantly achieved.

[0107] [Chemical Formula 4]

[0108]

[0109] In formula (1), Ar 1 and Ar 2 Each independently represents an aromatic hydrocarbon ring which may have a substituent, R 1 ~R 3 Each independently represents an alkyl group or an aryl group; wherein, R 1 ~R 3 At least one of them is a branched alkyl group or a cyclic alkyl group, or R 1 ~R 3 、Ar 1 and Ar 2 At least one of them has a branched alkyl group or a cyclic alkyl group.

[0110] In formula (1), Ar 1 and Ar 2 Each independently represents an aromatic hydrocarbon ring which may have a substituent. The aromatic hydrocarbon ring may be a single ring or a condensed ring. The number of carbon atoms constituting the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring. Among them, Ar is preferred. 1 and Ar 2 At least one of them is a benzene ring and the other is a naphthalene ring. 1 More preferably, it is a benzene ring. 2 It is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring.

[0111] As Ar 1 and Ar 2 The substituents that may be present include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR X1 、-SR X1 、-COR X1 、-COOR X1 、-OCOR X1 、-NR X1 R X2 、-NHCOR X1 、-CONR X1 R X2、-NHCONR X1 R X2 、-NHCOOR X1 、-SO2R X1 、-SO2OR X1 、-NHSO2R X1 etc. R X1 and R X2 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

[0112] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

[0113] Alkyl as a substituent, and R X1 and R X2 The number of carbon atoms in the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. In the alkyl group, some or all of the hydrogen atoms may be substituted with halogen atoms (preferably fluorine atoms). Furthermore, in the alkyl group, some or all of the hydrogen atoms may be substituted with the substituents described above.

[0114] an aryl group as a substituent, and R X1 and R X2 The number of carbon atoms in the aryl group represented is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a single ring or a condensed ring. In addition, some or all of the hydrogen atoms in the aryl group may be substituted with the above-mentioned substituents.

[0115] A heterocyclic group as a substituent, and R X1 and R X2 The heterocyclic group represented is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heteroatoms constituting the heterocyclic group are preferably nitrogen, oxygen, or sulfur atoms. In addition, some or all of the hydrogen atoms in the heterocyclic group may be substituted with the above-mentioned substituents.

[0116] In formula (1), Ar 1 The aromatic hydrocarbon ring represented by is preferably unsubstituted. 2 The aromatic hydrocarbon ring represented may be unsubstituted or may have a substituent. Preferably, it has a substituent. As a substituent, -COR X1 . R X1 An alkyl group, an aryl group, or a heterocyclic group is preferred, and an aryl group is more preferred. The aryl group may be substituted or unsubstituted. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.

[0117] In formula (1), R 1 ~R 3 R and R are independently an alkyl group or an aryl group. 1 Preferably, it is an alkyl group or an aryl group. 2 and R 3 Each independently is preferably an alkyl group.

[0118] The number of carbon atoms in the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched, or cyclic. The alkyl group may be unsubstituted or may have a substituent.

[0119] The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring, and may be unsubstituted or have a substituent.

[0120] In formula (1), R 1 ~R 3 At least one of them is a branched alkyl group or a cyclic alkyl group, or R 1 ~R 3 、Ar 1 and Ar 2 At least one of the carbon atoms has a branched or cyclic alkyl group. The branched alkyl group preferably has 3 or more carbon atoms, more preferably 5 or more carbon atoms, and even more preferably 7 or more carbon atoms. The upper limit is preferably 30 or less, more preferably 20 or less carbon atoms, and even more preferably 15 or less carbon atoms. The cyclic alkyl group preferably has 3 or more carbon atoms, more preferably 5 or more carbon atoms, and even more preferably 7 or more carbon atoms. The upper limit is preferably 30 or less carbon atoms, more preferably 20 or less carbon atoms, and even more preferably 15 or less carbon atoms.

[0121] In formula (1), R 3 Preferably, it is a branched alkyl group or a cyclic alkyl group, R 3 More preferred is a branched alkyl group.

[0122] In formula (1), R 1 Also preferred is an aryl group having a group containing a fluorine atom. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring. Examples of the group containing a fluorine atom include the above-mentioned alkyl group having a fluorine atom (fluorine-containing alkyl group) and a group containing an alkyl group having a fluorine atom (fluorine-containing group). The preferred range is also the same. The number of carbon atoms of the fluorine-containing alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4. The fluorine-containing alkyl group may be any of a linear, branched, or cyclic group, but a linear or branched chain is preferred. With respect to the fluorine-containing alkyl group, the substitution rate of fluorine atoms is preferably 40 to 100%, more preferably 50 to 100%, and further preferably 60 to 100%.

[0123] The oxime ester compound A preferably has a maximum absorption wavelength in the wavelength range of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength range of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 405 nm.

[0124] From the perspective of sensitivity, the molar absorptivity of the oxime ester compound A at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorptivity of the compound can be determined using a known method, but is preferably measured, for example, using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0125] Specific examples of the oxime ester compound A include the following compounds.

[0126] [Chemical Formula 5]

[0127]

[0128] In the resin composition of the present invention, the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 20% by mass relative to the total solid content of the resin composition. In the present invention, the photopolymerization initiator preferably contains 0.01% by mass or more of the oxime ester compound A, more preferably 0.02% by mass or more. The upper limit can be set to 100% by mass or less, and can also be set to 10% by mass or less.

[0129] In the resin composition of the present invention, the content of the oxime ester compound A is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 20% by mass relative to the total solids content of the resin composition. By setting the content within this range, a resin composition having good sensitivity and excellent temporal stability of sensitivity can be obtained.

[0130] The resin composition of the present invention may contain only one type of oxime ester compound A, or may contain two or more types. When containing two or more types, the total amount thereof is preferably within the above range.

[0131] (Other photopolymerization initiators)

[0132] The resin composition of the present invention may contain a photopolymerization initiator (other photopolymerization initiator) in addition to the above-mentioned oxime ester compound, and preferably further contains other photopolymerization initiators. By further containing other photopolymerization initiators, it is easy to produce a cured film with good sensitivity, adhesion, etc.

[0133] Examples of other photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds (e.g., acylphosphine oxide, etc.), hexaarylbiimidazoles, oxime compounds (e.g., oxime ester compounds not having a branched alkyl group or a cyclic alkyl group), organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, hydroxyacetophenone, etc. Furthermore, oxime compounds as other photopolymerization initiators are compounds other than oxime ester compounds having at least one selected from a branched alkyl group and a cyclic alkyl group.

[0134] From the perspective of exposure sensitivity, at least one compound selected from trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds (preferably oxime ester compounds without branched alkyl groups and cyclic alkyl groups), triaryl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds is preferred. More preferably, at least one compound selected from oxime ester compounds without branched alkyl groups and cyclic alkyl groups, alkylphenone compounds, and acylphosphine compounds is preferred. Specific examples of photopolymerization initiators can be found in, for example, paragraphs 0265 to 0268 of Japanese Patent Application Laid-Open No. 2013-29760, the contents of which are incorporated herein.

[0135] Other photopolymerization initiators can also preferably use hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds. More specifically, for example, the aminoacetophenone-based initiators described in Japanese Patent Laid-Open No. 10-291969 and the acylphosphine-based initiators described in Japanese Patent No. 4225898 can also be used. As hydroxyacetophenone-based initiators, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names, all manufactured by BASF) can be used. As aminoacetophenone-based initiators, commercially available products IRGACURE-907, IRGACURE-369 and IRGACURE-379 (trade names, all manufactured by BASF) can be used. As aminoacetophenone-based initiators, compounds described in Japanese Patent Application Laid-Open No. 2009-191179, which match the absorption wavelength of a light source such as 365 nm or 405 nm, can also be used. Furthermore, as acylphosphine-based initiators, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names, both manufactured by BASF) can be used.

[0136] Other photopolymerization initiators are preferably oxime compounds. Specific examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166.

[0137] Examples of the oxime compound include JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A-2000-66385, and compounds described in JP-A-2000-80068, JP-T-2004-534797, and JP-A-2006-342166.

[0138] Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by Changzhou TRONLY NEW ELECTRONIC MATERIALS CO., LTD.) and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Among them, IRGACURE-OXE01 and IRGACURE-OXE02 are preferred.

[0139] In addition, as oxime compounds other than those described above, compounds described in Japanese Patent Application Laid-Open No. 2009-519904 in which an oxime is linked to the N position of the carbazole ring, compounds described in U.S. Patent No. 7,626,957 in which a hetero substituent is introduced into the benzophenone site, compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and U.S. Patent Application Laid-Open No. 2009-292039 in which a nitro group is introduced into the pigment site, ketone oxime compounds described in International Publication No. WO2009 / 131189, compounds described in U.S. Patent No. 7,556,910 in which a triazine skeleton and an oxime skeleton are contained in the same molecule, and compounds described in Japanese Patent Application Laid-Open No. 2009-221114 in which an absorption maximum is observed at 405 nm and which have good sensitivity to a g-ray light source, etc. can be used. Preferably, for example, reference can be made to paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760, and the contents are incorporated into this specification. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. In addition, the N-O bond of the oxime may be an oxime compound in the (E) form, an oxime compound in the (Z) form, or a mixture of the (E) form and the (Z) form.

[0140] [Chemical Formula 6]

[0141]

[0142] In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

[0143] In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

[0144] Examples of monovalent non-metallic atomic groups include alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. Furthermore, these groups may have one or more substituents. Furthermore, the aforementioned substituents may be substituted with other substituents.

[0145] Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

[0146] In the general formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituents include the substituents described above.

[0147] In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group or an alkynylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituents include the substituents described above.

[0148] In the present invention, as other photopolymerization initiators, oxime compounds having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated into this specification.

[0149] In the present invention, as other photopolymerization initiators, oxime compounds having fluorine atoms can also be used. Specific examples of oxime compounds having fluorine atoms include compounds described in Japanese Patent Application Publication No. 2010-262028 and compound (C-3) described in Japanese Patent Application Publication No. 2013-164471. These contents are incorporated into this specification.

[0150] As other photopolymerization initiators, oxime compounds having a nitro group can be used. Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of JP-A-2014-137466, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

[0151] In the present invention, specific examples of the oxime compound preferably used are shown below, but the present invention is not limited to these.

[0152] [Chemical Formula 7]

[0153]

[0154] The oxime compound preferably has a maximum absorption wavelength in the wavelength range of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength range of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 405 nm.

[0155] From the perspective of sensitivity, the molar absorptivity of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorptivity of the compound can be measured using known methods. Specifically, for example, it is preferably measured using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) using ethyl acetate as a solvent at a concentration of 0.01 g / L.

[0156] The photopolymerization initiators may be used in combination of two or more types as needed.

[0157] The content of the other photopolymerization initiator is preferably 100 to 1300 parts by mass, more preferably 330 to 1000 parts by mass, relative to 100 parts by mass of the oxime ester compound A. When the content of the other photopolymerization initiator is within the above range, sensitivity can be adjusted and effects such as improved adhesion and pattern rectangularity can be achieved.

[0158] Furthermore, the composition can be made substantially free of other photopolymerization initiators. Substantially free of other photopolymerization initiators means that the content of other photopolymerization initiators is preferably 1% by mass or less, more preferably 0.1% by mass or less, and further preferably contains no other photopolymerization initiators relative to the mass of all photopolymerization initiators.

[0159] Thermosetting compounds

[0160] The resin composition of the present invention also preferably contains a thermosetting compound. By containing a thermosetting compound, the curability of the film after post-baking is improved, thereby being expected to improve various resistances such as solvent resistance. In the present invention, the so-called thermosetting compound refers to a compound that is cured by heating.

[0161] In the present invention, the thermosetting compound can be, for example, a compound having a thermosetting functional group. In the present invention, the thermosetting compound can be either a low molecular weight compound (e.g., a molecular weight of less than 1000) or a high molecular weight compound (e.g., a molecular weight of 1000 or greater, or a polymer having a weight average molecular weight of 1000 or greater). The thermosetting compound is preferably a high molecular weight compound, more preferably a compound having a molecular weight (weight average molecular weight) of 1000 to 100,000.

[0162] Examples of thermosetting compounds include compounds having an epoxy group (epoxy compounds), compounds having an oxetane group (oxetane compounds), compounds having a hydroxymethyl group (hydroxymethyl compounds), compounds having an alkoxymethyl group (alkoxymethyl compounds), and compounds having an oxetane group (blocked isocyanate compounds).

[0163] (Epoxy Compound)

[0164] The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The number of epoxy groups in one molecule is preferably 2 to 100. The upper limit can be, for example, 10 or less, or 5 or less.

[0165] The epoxy compound preferably has an epoxy equivalent (=molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / eq or less, more preferably 100 to 400 g / eq, and even more preferably 100 to 300 g / eq.

[0166] The epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 1000) or a high molecular weight compound (macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The epoxy compound is preferably an epoxy resin. The weight average molecular weight of the epoxy resin is preferably 1000 to 10000. The lower limit is preferably 1500 or more, and more preferably 2000 or more. The upper limit is preferably 9000 or less, and more preferably 8000 or less. Furthermore, the epoxy resin is preferably a compound that does not substantially have a molecular weight distribution. In addition, in the present invention, the so-called substantially no molecular weight distribution means that the dispersity of the compound (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.0 to 1.5, and more preferably 1.0 to 1.3.

[0167] The epoxy compound is preferably a compound having an aromatic ring and / or an aliphatic ring, and more preferably a compound having an aliphatic ring. The epoxy group is preferably bonded to the aromatic ring and / or the aliphatic ring via a single bond or a linking group. As a linking group, there can be mentioned a structure represented by an alkylene group, an arylene group, -O-, -NR'- (R' represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, preferably a hydrogen atom), a group selected from at least one of -SO2-, -CO-, -O- and -S-. In the case of a compound having an aliphatic ring, it is preferred that the epoxy group is directly bonded (single bond) to the aliphatic ring. In the case of a compound having an aromatic ring, the epoxy group is preferably bonded to the aromatic ring via a linking group. The linking group is preferably an alkylene group or a group consisting of a combination of an alkylene group and -O-.

[0168] Epoxy compounds may also be compounds having a structure in which two or more aromatic rings are linked via a hydrocarbon group. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. The epoxy group is preferably linked via the above-mentioned linking group.

[0169] When the epoxy compound is a low molecular weight compound, examples of the epoxy compound include compounds represented by the following formula (EP1).

[0170] [Chemical Formula 8]

[0171]

[0172] In formula (EP1), R EP1 ~R EP3 represent a hydrogen atom, a halogen atom, or an alkyl group, respectively. The alkyl group may have a cyclic structure and may have a substituent. EP1 With R EP2 、R EP2 With R EP3 They can be bonded to each other to form a ring structure. EP Indicates a single bond or n EP valent organic group. EP1 ~R EP3 Can also be used with Q EP Bonded to form a ring structure. EP represents an integer greater than 2, preferably 2 to 10, more preferably 2 to 6. EP In the case of a single bond, n EP is 2.

[0173] About R EP1 ~R EP3 , Q EP For details, reference can be made to paragraphs 0087 to 0088 of Japanese Patent Application Publication No. 2014-089408, which are incorporated herein. Specific examples of compounds represented by formula (EP1) include compounds described in paragraph 0090 of Japanese Patent Application Publication No. 2014-089408, which are incorporated herein.

[0174] Epoxy compounds that can be used include bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, aliphatic epoxy resins, and the like. Furthermore, epoxy compounds that can be used include compounds described in paragraphs 0034 to 0036 of Japanese Patent Application Laid-Open No. 2013-011869, paragraphs 0147 to 0156 of Japanese Patent Application Laid-Open No. 2014-043556, and paragraphs 0085 to 0092 of Japanese Patent Application Laid-Open No. 2014-089408. These contents are incorporated into this specification. Commercially available epoxy compounds can be used. For example, bisphenol A epoxy resins include jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, and jER1010 (all manufactured by Mitsubishi Chemical Corporation), EPCLON860, EPICLON1050, EPICLON1051, and EPICLON1055 (all manufactured by DIC Corporation), and the like. Examples of bisphenol F-type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, and jER4010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 830 and EPICLON 835 (all manufactured by DIC Corporation), and LCE-21 and RE-602S (all manufactured by Nippon Kayaku Co., Ltd.). Examples of phenol novolac-type epoxy resins include jER152, jER154, jER157S70, and jER157S65 (all manufactured by Mitsubishi Chemical Corporation), and EPICLON N-740, EPICLON N-770, and EPICLON N-775 (all manufactured by DIC Corporation). Examples of the cresol novolac epoxy resin include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, and EPICLON N-695 (all manufactured by DIC Corporation) and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, and ADEKA RESIN EP-4088S (manufactured by ADEKA CORPORATION), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, and CELLOXIDE 2085, EHPE 3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (manufactured by Daicel Corporation), and DENACOL EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase ChemteX Corporation). In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (all manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA CORPORATION), JER1031S (manufactured by Mitsubishi Chemical Corporation), etc.

[0175] (Oxetane compound)

[0176] The oxetanyl compound is preferably a compound having two or more oxetanyl groups in one molecule. The number of oxetanyl groups in one molecule is preferably 2 to 100. The upper limit can be, for example, 10 or less, or 5 or less.

[0177] Specific examples of the compound having two or more oxetanyl groups in one molecule include ARONOXETANE OXT-121, OXT-221, OX-SQ, and PNOX (all manufactured by TOAGOSEI CO., LTD.), ETERNACOLL (registered trademark) OXMA, and ETERNACOLL (registered trademark) OXBP (manufactured by UBE INDUSTRIES, LTD.).

[0178] (Alkoxymethyl compounds, hydroxymethyl compounds)

[0179] Examples of the alkoxymethyl compound and the hydroxymethyl compound include compounds in which an alkoxymethyl group or a hydroxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring.

[0180] Preferred compounds having an alkoxymethyl group or a hydroxymethyl group bonded to a nitrogen atom include alkoxymethylated melamine, hydroxymethylated melamine, alkoxymethylated benzoguanamine, hydroxymethylated benzoguanamine, alkoxymethylated glycoluril, hydroxymethylated glycoluril, alkoxymethylated urea, and hydroxymethylated urea. Reference can also be made to paragraphs 0134 to 0147 of JP-A-2004-295116 and paragraphs 0095 to 0126 of JP-A-2014-089408, the contents of which are incorporated herein.

[0181] Preferred structures of the compound in which an alkoxymethyl group or a hydroxymethyl group is bonded to a nitrogen atom include compounds represented by the following formulae (8-1) to (8-4).

[0182] [Chemical Formula 9]

[0183]

[0184] Examples of the compound in which an alkoxymethyl group or a hydroxymethyl group is bonded to a carbon atom forming an aromatic ring include compounds represented by the following general formulae (4) and (5).

[0185] [Chemical Formula 10]

[0186]

[0187] (In formula (4), X represents a single bond or a monovalent to tetravalent organic group, R 11 、R 12 Each independently represents a hydrogen atom or a monovalent organic group, n is an integer of 1 to 4, and p and q are each independently an integer of 0 to 4.

[0188] [Chemical Formula 11]

[0189]

[0190] (In formula (5), the two Ys may each independently contain an oxygen atom or a fluorine atom in a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 13 ~R 16 Each independently represents a hydrogen atom or a monovalent organic group, m and n each independently represent an integer of 1 to 3, and p and q each independently represent an integer of 0 to 4.

[0191] As commercially available products of alkoxymethyl compounds and hydroxymethyl compounds, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (all manufactured by Mitsui Cyanamid Co., Ltd.), NIKALAC MX-750, -032, -706, -708, -40, -31, -270, -280, -290, -750LM, NIKALAC MS-11, NIKALAC MW-30HM, -100LM, -390 (all manufactured by SANWA CHEMICAL CO., LTD.), etc. can be preferably used.

[0192] (Blocked isocyanate compound)

[0193] There are no particular limitations on blocked isocyanate compounds, but from the perspective of curability, compounds having two or more blocked isocyanate groups per molecule are preferred. The blocked isocyanate group in the present invention is a group that can generate an isocyanate group by heat, and preferably, for example, a group that allows a blocking agent to react with an isocyanate group and protect the isocyanate group. Furthermore, the blocked isocyanate group is preferably a group that can generate an isocyanate group by heat at 90 to 260°C.

[0194] The skeleton of the blocked isocyanate compound is not particularly limited and may be an aliphatic, alicyclic or aromatic polyisocyanate. Specific examples of the skeleton can be found in paragraph 0144 of JP-A-2014-238438, the contents of which are incorporated herein.

[0195] As the parent structure of blocked isocyanate compound, biuret type, isocyanurate type, adduct type, 2 functional prepolymer type etc. can be enumerated. As the blocking agent (Rlockingagent) of the block structure forming blocked isocyanate compound, oxime compound, lactam compound, phenolic compound, alcohol compound, amine compound, active methylene compound, pyrazole compound, thiol compound, imidazole compound, imide compound etc. can be enumerated. Among these, especially preferably the blocking agent selected from oxime compound, lactam compound, phenolic compound, alcohol compound, amine compound, active methylene compound, pyrazole compound. As the concrete example of blocking agent, it is possible to refer to the record of 0146 sections of Japanese Patent Laid-Open No. 2014-238438 Gazette, this content is incorporated in this specification.

[0196] Blocked isocyanate compounds are commercially available, and preferably used are, for example, CORONATE APSTABLE M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS-50 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Desmodule BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.), etc.

[0197] The content of the thermosetting compound is preferably 0 to 10% by mass relative to the total solid content of the resin composition of the present invention, with a lower limit of preferably 1% by mass or more and an upper limit of preferably 5% by mass or less, more preferably 3% by mass or less.

[0198] The resin composition of the present invention can also be configured to contain substantially no thermosetting compounds. Furthermore, in the present invention, "substantially no thermosetting compounds" means, for example, that the content of the thermosetting compounds relative to the total solids content of the resin composition of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and even more preferably no thermosetting compounds.

[0199] "fat"

[0200] The resin composition of the present invention comprises a resin. For example, the resin may be incorporated into the composition for purposes such as dispersing a pigment or as an adhesive. Furthermore, a resin primarily used to disperse a pigment in a composition is also referred to as a dispersant. However, this application of the resin is merely an example, and the resin may also be used for purposes other than this. Furthermore, in the present invention, a resin is a material distinct from a free-radically polymerizable compound and a thermophilic compound.

[0201] The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 5,000 or more.

[0202] In the resin composition of the present invention, the content of the resin is preferably 1 to 90% by mass of the total solid content of the resin composition. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less. The resin composition of the present invention may contain only one resin or two or more. When containing two or more resins, the total amount is preferably within the above range.

[0203] (Alkali-soluble resin)

[0204] The resin composition of the present invention preferably contains an alkali-soluble resin as the resin. The inclusion of an alkali-soluble resin improves developability and pattern forming properties. Furthermore, the alkali-soluble resin can be used as a dispersant or binder. Furthermore, the alkali-soluble resin is a material different from free radical polymerizable compounds and thermosetting compounds.

[0205] The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 5000 to 100,000, and the number average molecular weight (Mn) is preferably 1000 to 20,000.

[0206] The alkali-soluble resin may be a linear organic high molecular weight polymer, and can be appropriately selected from alkali-soluble resins having at least one group promoting alkali solubility in the molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain).

[0207] As alkali-soluble resins, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic acid / acrylamide copolymer resins are preferred from the perspective of heat resistance. From the perspective of controlling developability, acrylic resins, acrylamide resins, and acrylic acid / acrylamide copolymer resins are preferred. Groups that promote alkali solubility (hereinafter also referred to as acid groups) include, for example, carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups, with carboxyl groups being preferred. The acid groups may be one or more.

[0208] For example, a method based on a known free radical polymerization method can be applied to the production of the alkali-soluble resin. Polymerization conditions such as temperature, pressure, type and amount of free radical initiator, and type of solvent when producing the alkali-soluble resin by free radical polymerization can be easily set by those skilled in the art, and the conditions can be determined experimentally.

[0209] As the alkali-soluble resin, a polymer having a carboxyl group on the side chain is preferred, and examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolac resins, acidic cellulose derivatives having carboxyl groups on the side chains, and resins obtained by adding anhydrides to polymers having hydroxyl groups. In particular, copolymers of (meth)acrylic acid and other monomers copolymerizable therewith are preferred as alkali-soluble resins. Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylates, aryl (meth)acrylates, vinyl compounds, and the like. Examples of the alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, tolyl (meth)acrylate, naphthyl (meth)acrylate, and cyclohexyl (meth)acrylate. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomers, and polymethyl methacrylate macromonomers. Furthermore, as other monomers, N-substituted maleimide monomers described in Japanese Patent Application Laid-Open No. 10-300922 can also be used. For example, there can be mentioned N-phenylmaleimide, N-cyclohexylmaleimide, etc. In addition, these other monomers copolymerizable with (meth)acrylic acid may be only one kind or two or more kinds.

[0210] Alkali-soluble resins preferably include benzyl (meth)acrylate / (meth)acrylic acid copolymers, benzyl (meth)acrylate / (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate copolymers, and benzyl (meth)acrylate / (meth)acrylic acid / multi-component copolymers composed of other monomers. Furthermore, copolymers obtained by copolymerizing 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymers described in Japanese Patent Application Laid-Open No. 7-140654, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymers, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymers, and 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymers can also be preferably used. Examples of commercially available products include Acrybase FF-426 and FFS-6824 (manufactured by FUJIKURA KASEI CO., LTD.).

[0211] Furthermore, the alkali-soluble resin may be an alkali-soluble resin having a polymerizable group. Examples of the polymerizable group include a (meth)allyl group and a (meth)acryloyl group. Alkali-soluble resins having a polymerizable group include those having a polymerizable group on a side chain. Examples of the alkali-soluble resin having a polymerizable group include DIANAL NR series (manufactured by MITSUBISHI RAYON CO., LTD.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), VISCOAT R-264, KS Resist 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMERP series (for example, ACA230AA), PLACCEL CF200 series (both manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and ACRYCURE RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.).

[0212] The alkali-soluble resin also preferably includes a polymer obtained by polymerizing monomer components containing a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as "ether dimers").

[0213] [Chemical Formula 12]

[0214]

[0215] In the general formula (ED1), R 1 and R 2 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[0216] [Chemical Formula 13]

[0217]

[0218] In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Specific examples of the general formula (ED2) can be found in Japanese Patent Application Laid-Open No. 2010-168539.

[0219] Specific examples of ether dimers can be found in paragraph 0317 of Japanese Patent Application Laid-Open No. 2013-29760, the contents of which are incorporated herein. The ether dimers may be one or more. The structure derived from the ether dimer may be copolymerized with other monomers.

[0220] The alkali-soluble resin may include a structural unit derived from a compound represented by the following formula (X).

[0221] [Chemical Formula 14]

[0222]

[0223] In formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 2 to 10 carbon atoms, and R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1 to 15.

[0224] In the above formula (X), the alkylene group represented by R2 preferably has 2 to 3 carbon atoms. Furthermore, the alkyl group represented by R3 has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group represented by R3 may contain a benzene ring. Examples of the alkyl group represented by R3 containing a benzene ring include benzyl and 2-phenyl(iso)propyl.

[0225] Specific examples of the alkali-soluble resin include the following resins.

[0226] [Chemical Formula 15]

[0227]

[0228] Regarding the alkali-soluble resin, reference can also be made to paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (paragraphs 0685 to 0700 of the corresponding US Patent Application Publication No. 2012 / 0235099), the contents of which are incorporated herein. In addition, the copolymer (B) described in paragraphs 0029 to 0063 of JP-A-2012-32767 and the alkali-soluble resin used in the examples, the binder resin described in paragraphs 0088 to 0098 of JP-A-2012-208474 and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP-A-2012-137531 and the binder resin used in the examples, the binder resin described in paragraphs 0132 to 0143 of JP-A-2013-024934 and the binder resin used in the examples, the binder resin described in paragraphs 0092 to 0098 of JP-A-2011-242752 and the binder resin used in the examples, and the binder resin described in paragraphs 0030 to 0072 of JP-A-2012-032770 can also be used. These contents are incorporated into this manual.

[0229] The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or higher, and even more preferably 70 mgKOH / g or higher. The upper limit is more preferably 400 mgKOH / g or lower, even more preferably 200 mgKOH / g or lower, particularly preferably 150 mgKOH / g or lower, and even more preferably 120 mgKOH / g or lower.

[0230] The content of the alkali-soluble resin is preferably 1 to 90% by mass relative to the total solid content of the resin composition. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less. The resin composition of the present invention may contain only one alkali-soluble resin or may contain two or more. When containing two or more, the total amount is preferably within the above range.

[0231] (Dispersant)

[0232] The resin composition of the present invention can contain a dispersant as a resin. Examples of dispersants include polymer dispersants [for example, resins having an amino group (polyamidoamine and its salts, etc.), oligoimide resins, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic acid copolymers, and naphthalenesulfonic acid formaldehyde condensates]. Polymer dispersants can be further classified into linear polymers, terminal modified polymers, grafted polymers, and block polymers based on their structure. In addition, as polymer dispersants, resins having an acid value of 60 mgKOH / g or more (more preferably an acid value of 60 mgKOH / g or more and 300 mgKOH / g or less) can also be preferably cited.

[0233] As the terminal modified polymer, for example, there can be enumerated the polymer with phosphate group at the terminal, the polymer with sulfonic acid group at the terminal, the polymer with partial skeleton of organic pigment or heterocycle in Japanese Unexamined Patent Publication No. 9-77994 publication etc., which are put down in writing in Japanese Unexamined Patent Publication No. 3-112992, Japanese Unexamined Patent Publication No. 2003-533455 publication etc., which are put down in writing in Japanese Unexamined Patent Publication No. 2002-273191 publication etc., and the polymer etc. which are put down in writing in Japanese Unexamined Patent Publication No. 9-77994 publication etc. Also, the dispersion stability of the polymer formed by introducing more than 2 anchoring sites (partial skeleton of acidic group, basic group, organic pigment or heterocycle etc.) for pigment surface at the polymer terminal is also excellent, and is therefore preferred.

[0234] Examples of the graft polymer include reaction products of poly(lower alkylene imine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, etc., reaction products of polyallylamine and polyester described in JP-A-9-169821, etc., reaction products of poly(alkylene imine) and polyester described in JP-A-10-339949, JP-A-2004-37 Copolymers of a macromonomer and a monomer containing a nitrogen atom as described in Japanese Patent Application Publication No. 986, etc., graft polymers having a partial skeleton of an organic pigment or a heterocyclic ring as described in Japanese Patent Application Publication No. 2003-238837, Japanese Patent Application Publication No. 2008-9426, Japanese Patent Application Publication No. 2008-81732, etc., copolymers of a macromonomer and a monomer containing an acid group as described in Japanese Patent Application Publication No. 2010-106268, etc., etc.

[0235] As the block polymer, those described in JP-A-2003-49110, JP-A-2009-52010, and the like are preferred.

[0236] The resin (dispersant) may also be a graft copolymer containing a repeating unit represented by any one of the following formulas (1) to (4).

[0237] [Chemical Formula 16]

[0238]

[0239] In formulas (1) to (4), W 1 、W 2 、W 3 and W 4 Each independently represents an oxygen atom or NH, X 1 、X 2 、X 3 、X 4 and X 5 Each independently represents a hydrogen atom or a monovalent organic group, Y 1 、Y 2 、Y 3 and Y 4 Each independently represents a divalent linking group, Z 1 、Z 2 、Z 3 and Z 4 Each independently represents a monovalent organic group, R 3 represents an alkylene group, R 4 represents a hydrogen atom or a monovalent organic group, n, m, p and q each independently represent an integer of 1 to 500, j and k each independently represent an integer of 2 to 8, in formula (3), when p is 2 to 500, there are multiple R 3 They may be the same or different from each other. In formula (4), when q is 2 to 500, there are multiple X 5 and R 4 They can be the same as or different from each other.

[0240] W 1 、W 2 、W 3 and W 4 Preferably, X is an oxygen atom. 1 、X 2 、X 3 、X 4 and X 5 It is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably each of which is independently a hydrogen atom or a methyl group, and particularly preferably a methyl group. 1 、Y 2 、Y 3 and Y 4 Each independently represents a divalent linking group, and the linking group is not particularly limited in structure. 1 、Z 2 、Z3 and Z 4 The structure of the monovalent organic group represented by is not particularly limited, and specific examples thereof include alkyl, hydroxy, alkoxy, aryloxy, heteroaryloxy, alkylthioether, arylthioether, heteroarylthioether, and amino groups. 1 、Z 2 、Z 3 and Z 4 The organic groups represented by preferably have a steric repulsive effect, particularly from the viewpoint of improving dispersibility, and are preferably each independently an alkyl group or an alkoxy group having 5 to 24 carbon atoms. Among them, they are particularly preferably each independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

[0241] In formulae (1) to (4), n, m, p, and q each independently represent an integer of 1 to 500. Furthermore, in formulae (1) and (2), j and k each independently represent an integer of 2 to 8. From the viewpoint of dispersion stability and developability, j and k in formulae (1) and (2) are preferably integers of 4 to 6, and most preferably 5.

[0242] In formula (3), R 3 represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, there are multiple R 3 They can be the same as or different from each other.

[0243] In formula (4), R 4 represents a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited in structure. 4 , preferably a hydrogen atom, an alkyl group, an aryl group and a heteroaryl group, more preferably a hydrogen atom or an alkyl group. 4 When it is an alkyl group, it is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and particularly preferably a linear alkyl group having 1 to 6 carbon atoms. In formula (4), when q is 2 to 500, there are multiple X in the graft copolymer. 5 and R 4 They can be the same as or different from each other.

[0244] Regarding the graft copolymer, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein. Specific examples of the graft copolymer include the following resins. Furthermore, the resins described in paragraphs 0072 to 0094 of JP-A-2012-255128 are also included, the contents of which are incorporated herein.

[0245] [Chemical Formula 17]

[0246]

[0247] Furthermore, oligoimine-based dispersants containing nitrogen atoms in at least one of the main chain and side chains can be used as resins (dispersants). Preferred oligoimine-based dispersants include a resin comprising repeating units having a partial structure X containing a functional group with a pKa of 14 or less, and a side chain containing a side chain Y having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and side chains. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.

[0248] Regarding oligoimine-based dispersants, reference may be made to paragraphs 0102 to 0174 of JP-A-2012-255128, which are incorporated herein. Specific examples of oligoimine-based dispersants include resins described in paragraphs 0168 to 0174 of JP-A-2012-255128.

[0249] Dispersants are commercially available. Specific examples thereof include Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylate), 110, 111 (copolymers containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymers), BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) manufactured by BYK Chemie; EFKA 4047, 4050 to 4165 (polyurethane), EFKA 4330 to 4340 (blocked copolymers), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) manufactured by EFKA; and Ajinomoto Fine-Techno Co., Inc.'s "Ajisper PB821, PB822, PB880, PB881," KYOEISHA CHEMICAL CO., LTD.'s "Floren TG-710 (polyurethane oligomer), POLYFLOW No. 50E, No. 300 (acrylic copolymer)," Kusumoto Chemicals Ltd.'s "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725," Kao Corporation's "DEMOL RN, N (naphthalenesulfonic acid formaldehyde condensate), MS, C, SN-B (aromatic sulfonic acid formaldehyde condensate), Homogenol L-18 (polymeric polycarboxylic acid), EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether), ACETAMIN 86 (stearylamine acetate)” manufactured by The Lubrizol Corporation; SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional portion at the terminal), 24000, 28000, 32000, 38500 (graft-type polymer)”; Nikkol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) manufactured by NIKKO CHEMICALS CO., LTD.; Hinoact T-8000E manufactured by Kawaken Fine Chemicals Co., Ltd.; Shin-Etsu Chemical Co., Ltd.Polymer dispersants such as "Organosiloxane Polymer KP341" manufactured by KOREA ELECTRONICS, "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450" manufactured by MORISHITA & CO., LTD., "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" manufactured by SAN NOPCO LIMITED, "Adeka pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA CORPORATION, and "Ionet S-20" manufactured by Sanyo Chemical Industries, Ltd. Furthermore, the resins described above for the alkali-soluble resins can also be used.

[0250] These dispersants can be used alone or in combination. More than two kinds of dispersants can also be used. Dispersant can also use the above-mentioned alkali-soluble resin. As alkali-soluble resin, (meth) acrylic acid copolymer, itaconic acid, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer etc. and the acidic cellulose derivative with carboxylic acid on the side chain, the resin that anhydride-modified is formed in the polymer with hydroxyl, especially preferred (meth) acrylic acid copolymer. And, also preferably the alkali-soluble resin containing polymerizable group of the N-substituted maleimide monomer copolymer described in Japanese Unexamined Patent Publication No. 10-300922, the ether dimer copolymer described in Japanese Unexamined Patent Publication No. 2004-300204, and Japanese Unexamined Patent Publication No. 7-319161.

[0251] The content of the dispersant is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and even more preferably 10 to 60 parts by mass, relative to 100 parts by mass of the pigment.

[0252] Pigment Derivatives

[0253] The resin composition of the present invention may contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a portion of an organic pigment is substituted with an acidic group, a basic group, or a phthalimidomethyl group. From the perspective of pigment dispersibility and dispersion stability, the pigment derivative is preferably one having an acidic group or a basic group.

[0254] Examples of the organic pigment used to constitute the pigment derivative include pyrrolopyrrole pigments, diketopyrrolopyrrole pigments, quinacridone pigments, anthraquinone pigments, dianthraquinone pigments, benzisoindole pigments, thiazine indigo pigments, azo pigments, quinophthalone pigments, phthalocyanine pigments, naphthalocyanine pigments, dioxazine pigments, perylene pigments, perinone pigments, benzimidazolone pigments, benzothiazole pigments, benzimidazole pigments, and benzoxazole pigments.

[0255] Furthermore, as the acidic group possessed by the pigment derivative, sulfonic acid groups, carboxylic acid groups and their salts are preferred, carboxylic acid groups and sulfonic acid groups are more preferred, and sulfonic acid groups are particularly preferred. As the basic group possessed by the pigment derivative, amino groups are preferred, and tertiary amino groups are particularly preferred.

[0256] As specific examples of pigment derivatives, reference can be made to paragraphs 0111 to 0175 of JP-A-2015-063593, the contents of which are incorporated herein.

[0257] When the resin composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, relative to the mass of the pigment.

[0258] Color Colorants

[0259] The resin composition of the present invention can contain a colorant. In the present invention, the so-called colorant refers to a colorant other than a white colorant and a black colorant. The colorant is preferably a colorant having a maximum absorption in the range of a wavelength of more than 400nm and less than 650nm. In the present invention, the colorant can be a pigment or a dye. The average particle size (r) of the pigment preferably satisfies 20nm≤r≤300nm, more preferably satisfies 25nm≤r≤250nm, and particularly preferably satisfies 30nm≤r≤200nm. The "average particle size" mentioned here refers to the average particle size of the secondary particles formed by the aggregation of the primary particles of the pigment. In addition, with respect to the particle size distribution of the secondary particles of the usable pigment (hereinafter referred to as "particle size distribution"), the secondary particles within (average particle size ± 100) nm account for more than 70% by mass of the whole, preferably more than 80% by mass. In addition, with respect to the particle size distribution of the secondary particles, the scattering intensity distribution can be used for measurement. The average particle size of the primary particles can be determined by observing with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), measuring the sizes of 100 particles at a portion where the particles are not aggregated, and calculating the average value.

[0260] The pigment is preferably an organic pigment, and the following pigments can be mentioned, but the present invention is not limited to these.

[0261] Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118 , 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. (above, yellow pigment),

[0262] CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (above, orange pigments),

[0263] CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146 6, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red pigment),

[0264] CI Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigments),

[0265] CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (the above are purple pigments),

[0266] CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigments).

[0267] Furthermore, as green pigments, zinc phthalocyanine halides can also be used, wherein the average number of halogen atoms in the molecule is 10 to 14, the average number of bromine atoms is 8 to 12, and the average number of chlorine atoms is 2 to 5. Specific examples include compounds described in WO2015 / 118720.

[0268] Furthermore, as the yellow colorant, quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A-2013-54339 and quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-26228 can also be used.

[0269] Furthermore, as a blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

[0270] These organic pigments can be used alone or in combination of two or more.

[0271] The organic pigment is preferably at least one selected from a green pigment and a yellow pigment, and more preferably a combination of a green pigment and a yellow pigment. The green pigment is preferably at least one selected from CI Pigment Green 7, 36, 58, and 59. Furthermore, the aforementioned zinc phthalocyanine halide pigment is also preferred. The yellow pigment is preferably at least one selected from CI Pigment Yellow 139, 150, and 185. Furthermore, the aforementioned quinophthalone pigment is also preferred.

[0272] As dye, there is no particular restriction, known dye can be used. As chemical structure, pyrazole azo system, aniline azo system, triarylmethane system, anthraquinone system, anthrapyridone system, benzylidene system, oxonol system, pyrazolotriazole azo system, pyridone azo system, cyanine system, phenothiazine system, pyrrolopyrazole azoimine system, xanthene (xanthene) system, phthalocyanine system, benzopyran system, indigo system, methylene pyrrole system and other dyes can be used. And, also can preferably use the azo compound of putting down in writing in Japanese Unexamined Patent Publication No. 2012-158649 publication, the azo compound of putting down in writing in Japanese Unexamined Patent Publication No. 2011-184493 publication, the azo compound of putting down in writing in Japanese Unexamined Patent Publication No. 2011-145540 publication.

[0273] Furthermore, as the dye, an acid dye and / or its derivative may be preferably used.

[0274] In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be effectively used.

[0275] Specific examples of the acid dye are given below, but the present invention is not limited thereto. For example, the following dyes and derivatives of these dyes can be given.

[0276] Acid mordant blue K (acid alizarin violet N),

[0277] Acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40-45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1,

[0278] Acid Chrome Violet K,

[0279] Acid Fuchsin; Acid Green 1, 3, 5, 9, 16, 25, 27, 50,

[0280] Acid orange: 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95

[0281] Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274,

[0282] Acid violet: 6B, 7, 9, 17, 19,

[0283] Acid yellow: 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243

[0284] Food Yellow 3

[0285] In addition, azo, xanthene, and phthalocyanine acid dyes other than those mentioned above are also preferred. Acid dyes such as CI Solvent Blue 44 and 38, CI Solvent Orange 45, Rhodamine B, and Rhodamine 110, and derivatives of these dyes are also preferably used.

[0286] Among them, the dye is preferably a colorant selected from the group consisting of triarylmethane, anthraquinone, azomethine, benzyl, oxonol, cyanine, phenothiazine, pyrrolopyrazole azoimine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo, aniline azo, pyrazolotriazole azo, pyridone azo, anthrapyridone, and methylene pyrrole.

[0287] In the present invention, the color colorant can also use a pigment polymer. The pigment polymer is preferably a dye used by dissolving in a solvent, but the pigment polymer can form particles. When the pigment polymer is a particle, it is usually used in a state dispersed in a solvent. The pigment polymer in a particle state can be obtained, for example, by emulsion polymerization, and the compounds and manufacturing methods described in Japanese Patent Application Laid-Open No. 2015-214682 can be cited as specific examples. Regarding the pigment polymer, there are more than two pigment structures in one molecule, preferably more than three pigment structures. The upper limit is not particularly limited and can also be set to 100 or less. The pigment structure in one molecule can be the same pigment structure or different pigment structures. In addition, in the present invention, the so-called different pigment structures include not only pigment structures with different pigment skeletons, but also pigment structures with the same pigment skeleton and different types of substituents bonded to the pigment skeleton.

[0288] The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30000 or less, and even more preferably 20000 or less.

[0289] The pigment structure possessed by the pigment polymer can be a structure derived from a pigment compound having absorption in the visible region (preferably a wavelength range of 400 to 700 nm, more preferably a range of 400 to 650 nm), or a structure derived from a pigment compound having absorption in the infrared region (preferably a compound having a maximum absorption wavelength in the range of 700 to 1200 nm). For example, a triarylmethane dye structure, a xanthene dye structure, an anthraquinone dye structure, a cyanine dye structure, a squarylium dye structure, a quinophthalone dye structure, a phthalocyanine dye structure, a subphthalocyanine dye structure, an azo dye structure, a pyrazolotriazole dye structure, a dipyrromethene dye structure, an isoindoline dye structure, a thiazole dye structure, a benzimidazolone dye structure, a perinone dye structure, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, a diimmonium dye structure, a naphthalocyanine dye structure, a rylene dye structure, a dibenzofuranone dye structure, a merocyanine dye structure, a chroconium dye structure, and an oxonol dye structure can be mentioned. Furthermore, pigment structures derived from thiazole compounds described in JP-A-2012-158649, pigment structures derived from azo compounds described in JP-A-2011-184493, and pigment structures derived from azo compounds described in JP-A-2011-145540 can also be preferably used.

[0290] The dye multimer contains at least one of a repeating unit represented by formula (A), a repeating unit represented by formula (B), and a repeating unit represented by formula (C), or preferably is represented by formula (D).

[0291] [Chemical Formula 18]

[0292]

[0293] In formula (A), X 1 represents the main chain of the repeating unit, L 1 represents a single bond or a divalent linking group, D 1 The details of formula (A) can be found in paragraphs 0138 to 0152 of JP-A-2013-29760, which are incorporated herein by reference.

[0294] In formula (B), X 2 represents the main chain of the repeating unit, L 2 represents a single bond or a divalent linking group, D 2 Indicates that it can be used with Y 2 Pigment structure of ionically bonded or coordinately bonded groups, Y 2 Indicates that it can be used with D 2 Ionically bonded or coordinately bonded groups. For details of formula (B), reference can be made to paragraphs 0156 to 0161 of JP-A-2013-29760, the contents of which are incorporated herein.

[0295] In formula (C), L 3 represents a single bond or a divalent linking group, D 3 represents a pigment structure, and m represents 0 or 1. For details of formula (C), reference can be made to paragraphs 0165 to 0167 of JP-A-2013-29760, the contents of which are incorporated herein.

[0296] In formula (D), L 4 represents a (n+k) valence linking group, L 41 and L 42 Each independently represents a single bond or a divalent linking group, D 4 Indicates pigment structure, P 4 represents a substituent; n represents 2 to 15, k represents 0 to 13, and n+k represents 2 to 15. When n is 2 or more, multiple D 4 They can be different from each other or the same as each other. When k is greater than 2, multiple P 4 They can be different from each other or the same as each other.

[0297] As L 4Examples of the (n+k)-valent linking group include the linking groups described in paragraphs 0071 and 0072 of JP-A-2008-222950 and the linking groups described in paragraph 0176 of JP-A-2013-029760.

[0298] P 4 The substituents represented by the present invention include acid groups, curing groups, etc. As curing groups, free radical polymerizable groups such as groups having ethylenically unsaturated bonds, epoxy groups, oxazoline groups, hydroxymethyl groups, etc. As groups having ethylenically unsaturated bonds, vinyl groups, (meth)allyl groups, (meth)acryloyl groups, etc. As acid groups, carboxyl groups, sulfonic acid groups, and phosphoric acid groups can be mentioned. 4 The substituent represented may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound.

[0299] D 4 The dye structure represented is a structure obtained by removing one or more arbitrary atoms of the dye compound, and a part of the dye compound may be bonded to L. 4 The structure formed by the above-mentioned structure can also be a polymer chain containing repeating units having a pigment structure (a structure formed by removing one or more arbitrary atoms possessed by a pigment compound) on the main chain or side chain. There is no particular regulation on the above-mentioned polymer chain as long as it contains a pigment structure, but it is preferably one selected from (meth) acrylic resins, styrene resins and (meth) acrylic / styrene resins. There is no particular regulation on the repeating units of the polymer chain, but examples include repeating units represented by formula (A), repeating units represented by formula (C), etc. Furthermore, the total amount of repeating units having a pigment structure among all the repeating units constituting the polymer chain is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%.

[0300] In addition, n and k in one dye multimer (D) are integers, but in the present invention, the dye multimer may contain a plurality of compounds having different n and k in formula (D). Therefore, the average values ​​of n and k in compound A may not be integers.

[0301] The dye multimer represented by formula (D) preferably has a structure represented by formula (D-1).

[0302] [Chemical Formula 19]

[0303]

[0304] In formula (D-1), L 4represents a (n+k)-valent linking group. n represents 2 to 15, and k represents 0 to 13. 4 Indicates pigment structure, P 4 Represents a substituent. 41 and B 42 Each independently represents a single bond, -O-, -S-, -CO-, -NR-, -O2C-, -CO2-, -NROC- or -CONR-. R represents a hydrogen atom, an alkyl group or an aryl group. 41 and C 42 Each independently represents a single bond or a divalent linking group. S represents a sulfur atom. When n is 2 or more, multiple D 4 They can be different from each other or the same as each other. When k is greater than 2, multiple P 4 They may be different from each other or the same as each other. n+k represents 2 to 15.

[0305] L in formula (D-1) 4 、D 4 and P 4 With L in formula (D) 4 、D 4 and P 4 Same meaning.

[0306] B in formula (D-1) 41 and B 42 Each independently represents a single bond, -O-, -S-, -CO-, -NR-, -O2C-, -CO2-, -NROC-, or -CONR-, preferably a single bond, -O-, -CO-, -O2C-, -CO2-, -NROC-, or -CONR-, more preferably a single bond, -O-, -CO-, -O2C-, or -CO2-. R represents a hydrogen atom, an alkyl group, or an aryl group.

[0307] C in formula (D-1) 41 and C 42 Each independently represents a single bond or a divalent linking group. Preferred divalent linking groups include alkylene groups, arylene groups, and combinations thereof. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms. The alkylene group may be linear, branched, or cyclic. The arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 12 carbon atoms.

[0308] As the pigment multimer, compounds described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, and the like can also be used.

[0309] The content of the colorant is preferably 0 to 70% by mass relative to the total solid content of the resin composition. The upper limit is more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less. The lower limit can also be, for example, 1% by mass or more.

[0310] Inorganic Particles

[0311] The resin composition of the present invention may contain inorganic particles. Examples of the inorganic particles include black pigments and transparent particles. Specific examples of the inorganic particles include titanium oxide, titanium oxynitride, silicon oxide, cesium tungsten oxide, indium tin oxide, vanadium oxynitride, carbon black, titanium black, aluminum oxide, and zirconium oxide. Black pigments are preferred, for example. Compositions containing black pigments generally have low sensitivity, but according to the present invention, even resin compositions containing black pigments can achieve excellent sensitivity, significantly enhancing the effects of the present invention.

[0312] (Black pigment)

[0313] There are no particular limitations on the black pigment, and known pigments can be used. Examples include carbon black, titanium black (titanium oxynitride, etc.), graphite, and vanadium oxynitride. Carbon black, titanium black, and vanadium oxynitride are preferred, with titanium black being particularly preferred. Titanium black refers to black particles containing titanium atoms. Preferred are low-valent titanium oxide and titanium oxynitride. The surface of the titanium black particles can be modified as needed to improve dispersibility, suppress cohesion, etc. They can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and can also be treated with a water-repellent substance as described in Japanese Patent Application Laid-Open No. 2007-302836.

[0314] Titanium black is typically titanium black particles, and preferably, the primary particle size and average primary particle size of each particle are small. Specifically, particles having an average primary particle size of 10 nm to 45 nm are preferred. In addition, the particle size, i.e., particle diameter, in the present invention refers to the diameter of a circle having an area equal to the projected area of ​​the outer surface of the particle. The projected area of ​​the particle can be obtained by measuring the area obtained by photography in an electron micrograph and correcting the photographic magnification.

[0315] The specific surface area of ​​titanium black is not particularly limited, but the water repellency after the surface treatment of titanium black with a water repellent becomes a predetermined performance, and the value measured by the BET (Brunauer, Emmett, Teller) method is preferably 5 m 2 / g and above and 150m 2 / g or less, more preferably 20m 2 / g or above and 120m 2Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade names, manufactured by Mitsubishi Materials Corporation) and Tilack D (trade name, manufactured by AKO KASEI CO., LTD.).

[0316] Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, wherein the ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion is adjusted to a range of 0.20 to 0.50, can be cited. For details about such dispersions, reference can be made to paragraphs 0020 to 0105 of Japanese Patent Application Laid-Open No. 2012-169556, which is incorporated herein by reference.

[0317] (Transparent particles)

[0318] Examples of transparent particles include titanium oxide (TiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), silicon oxide (SiO2), and tin oxide (SnO2). Furthermore, indium oxide (In2O3) and indium tin oxide (tin-doped indium oxide, ITO), an inorganic compound of tin oxide (SnO2), are also preferred as transparent particles. Antimony tin oxide (ATO), zinc oxide (ZnO), aluminum-doped zinc oxide (Al-doped ZnO), fluorine-doped tin dioxide (F-doped SnO2), niobium-doped titanium dioxide (Nb-doped TiO2), and cesium tungsten oxide are also preferred. Silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles can also be used. For information on cesium tungsten oxide, reference can be made to paragraphs 0025-0029 of International Publication No. WO2014 / 142259, the contents of which are incorporated herein.

[0319] The average particle size of the transparent particles is preferably 1 to 200 nm, more preferably 10 to 100 nm. The average particle size of the transparent particles is determined by observing the dispersed particles with a transmission electron microscope and based on the obtained photographs. The projected area of ​​the particles is determined, and the equivalent circle diameter is determined based on the projected area as the average particle size (usually, more than 300 particles are measured to determine the average particle size). The primary particle size of the transparent particles is preferably 1 to 100 nm, more preferably 1 to 60 nm. The refractive index of the transparent particles is preferably 1.6 to 2.8, more preferably 1.7 to 2.7, and most preferably 1.8 to 2.7. The specific surface area of ​​the transparent particles is preferably 10 to 2000 m 2 / g, more preferably 20 to 1800 m 2 / g, and most preferably 40 to 1500 m2 / g. The transparent particles may be crystalline or amorphous, and may be monodisperse particles. As long as the specified particle size is met, they may also be agglomerated particles. The shape is most preferably spherical, but may be a beaded shape, a shape with a ratio of major diameter to minor diameter of 1 or more, or an irregular shape. Commercially available particles may preferably be used as transparent particles. For example, the TTO series (TTO-51(A), TTO-51(C), etc.) manufactured by ISHIHARA SANGYOKAISHA, LTD., TTO-S, V series (TTO-S-1, TTO-S-2, TTO-V-3, etc.), MT series (MT-01, MT-05, etc.) manufactured by TAYCA CORPORATION, etc. may be used. In addition, as commercially available products containing cesium tungsten oxide dispersions, YMF-02A, YMS-01A-2, YMF-10A-1, etc. manufactured by Sumitomo Metal Mining Co., Ltd. may be cited.

[0320] The content of the inorganic particles is preferably 0 to 70% by mass relative to the total solid content of the resin composition. The upper limit is more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less. The lower limit can also be, for example, 1% by mass or more.

[0321] Phthalimide Compounds

[0322] The resin composition of the present invention preferably contains a phthalimide compound. In particular, when a green pigment (wherein a zinc phthalocyanine halide pigment) is used as a colorant, the phthalimide compound is contained, thereby being able to produce a cured film in which the generation of needle-shaped foreign matter, etc. is suppressed. The phthalimide compound is preferably a compound represented by the following general formula (PI).

[0323] [Chemical Formula 20]

[0324]

[0325] In formula (PI), A 1 ~A 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group.

[0326] Examples of the halogen atom include a chlorine atom, a bromine atom and a fluorine atom, and a chlorine atom or a fluorine atom is preferred.

[0327] The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.

[0328] Preferred A 1 ~A 4At least one of the atoms is selected from chlorine atoms and bromine atoms, more preferably a bromine atom. 1 ~A 4 All are selected from chlorine atoms and bromine atoms, more preferably A 1 ~A 4 All are bromine atoms.

[0329] In the resin composition of the present invention, the content of the phthalimide compound is preferably 0.001 to 5% by mass relative to the total solid content in the resin composition. The lower limit is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.15% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 1% by mass or less, further preferably 0.9% by mass or less, and particularly preferably 0.8% by mass or less. The phthalimide compound may be one or more. When comprising two or more, the total amount is preferably within the above range.

[0330] Organic Solvents

[0331] The resin composition of the present invention contains an organic solvent. There are no particular limitations on the organic solvent as long as it satisfies the solubility of the components and the coating properties of the composition. However, the organic solvent is preferably selected in consideration of the coating properties and safety of the composition.

[0332] Examples of the organic solvent include the following. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-Alkoxypropionic acid alkyl esters (e.g., 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (e.g., 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc.)), 2-alkoxypropionic acid alkyl esters (e.g., 2-alkoxypropionic acid methyl ester, 2-alkoxypropionic acid ethyl ester, 2-alkoxypropionic acid propyl ester, etc. (e.g., 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, etc.) 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2-alkoxy-2-methylpropionic acid ethyl ester (for example, 2-methoxy-2-methylpropionic acid methyl ester, 2-ethoxy-2-methylpropionic acid ethyl ester), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers, for example, diglyme, Examples of preferred ketones include tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of preferred aromatic hydrocarbons include toluene and xylene.

[0333] The organic solvent may be used alone or in combination of two or more. The organic solvent is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, butyl acetate, ethyl 3-ethoxypropionate, propylene glycol monoethyl ether acetate, xylene, ethylbenzene, methyl isobutyl ketone, 2-butanol, and dipropylene glycol monomethyl ether.

[0334] In the present invention, the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0335] The organic solvent content is preferably such that the total solids content of the resin composition is 25 to 80% by mass. The lower limit is preferably 30% by mass or greater, more preferably 35% by mass or greater. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less.

[0336] Curing accelerator

[0337] In order to promote the reaction of the polymerizable compound or lower the curing temperature, the resin composition of the present invention may be added with a curing accelerator. As a curing accelerator, a polyfunctional thiol compound (polyfunctional thiol compound) having two or more thiol groups in the molecule may be mentioned. In order to improve stability, odor, resolution, developability, adhesion, etc., a polyfunctional thiol compound may be added. The polyfunctional thiol compound is preferably a secondary alkyl thiol, and is particularly preferably a compound having a structure represented by the following general formula (T1).

[0338] General formula (T1)

[0339] [Chemical Formula 21]

[0340]

[0341] (In formula (T1), n ​​represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)

[0342] In the general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, and particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), with the compound represented by formula (T2) being particularly preferred. These polyfunctional thiol compounds can be used alone or in combination of multiples.

[0343] [Chemical Formula 22]

[0344]

[0345] Furthermore, as a curing accelerator, methylol compounds (for example, compounds exemplified as crosslinking agents in paragraph 0246 of Japanese Patent Application Laid-Open No. 2015-34963), amines, phosphonium salts, amidine salts, amide compounds (for example, curing agents described in paragraph 0186 of Japanese Patent Application Laid-Open No. 2013-41165), base generating agents (for example, ionic compounds described in Japanese Patent Application Laid-Open No. 2014-55114), cyanate compounds ( For example, compounds described in paragraph 0071 of Japanese Patent Application Laid-Open No. 2012-150180), alkoxysilane compounds (for example, alkoxysilane compounds having an epoxy group described in Japanese Patent Application Laid-Open No. 2011-253054), onium salt compounds (for example, compounds exemplified as acid generators in paragraph 0216 of Japanese Patent Application Laid-Open No. 2015-34963, compounds described in Japanese Patent Application Laid-Open No. 2009-180949), etc.

[0346] When the resin composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass, based on the total solid content of the resin composition.

[0347] Inhibitors

[0348] The resin composition of the present invention may contain a polymerization inhibitor to prevent unnecessary thermal polymerization of the crosslinking compound during the production or storage period of the composition. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, primary cerium salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solids content of the resin composition.

[0349] Surfactants

[0350] From the viewpoint of further improving coating properties, the resin composition of the present invention may contain various surfactants. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.

[0351] By including a fluorinated surfactant in the resin composition, the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid to which a resin composition containing a fluorinated surfactant is applied, the surface tension between the coated surface and the coating liquid decreases, the wettability of the coated surface is improved, and the coating properties of the coated surface are improved. Therefore, it is further preferable to form a film of uniform thickness with small thickness unevenness.

[0352] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorine-based surfactants with a fluorine content within this range are effective from the perspectives of uniformity of coating film thickness and liquid conservation, and also have good solubility in the composition.

[0353] Examples of the fluorine-based surfactant include Megaface F171, Megaface F172, Megaface F173, Megaface F176, Megaface F177, Megaface F141, Megaface F142, Megaface F143, Megaface F144, Megaface R30, Megaface F437, Megaface F475, Megaface F479, Megaface F482, Megaface F554, Megaface F780, and RS-72-K (all manufactured by DIC Corporation), FLUORAD FC430, FLUORAD FC431, and FLUORAD FC171 (all manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, and Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTIONS INC.), etc. Fluorine-based surfactants can also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Laid-Open No. 2015-117327. Block polymers can also be used as fluorine-based surfactants. Specific examples include compounds described in Japanese Patent Application Laid-Open No. 2011-89090.

[0354] Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds containing the following repeating units: repeating units derived from (meth)acrylate compounds having fluorine atoms; and repeating units derived from (meth)acrylate compounds having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups). The following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[0355] [Chemical Formula 23]

[0356]

[0357] The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, for example, 14,000.

[0358] Furthermore, fluorinated polymers having ethylenically unsaturated groups on their side chains can also be used as fluorinated surfactants. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, such as Megaface RS-101, RS-102, RS-718K, and RS-72-K manufactured by DIC Corporation.

[0359] Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearate, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 manufactured by BASF), and SOLSPERSE 20000 (manufactured by The Lubrizol Corporation). Furthermore, NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. and Pionin D-6112-W and D-6315 manufactured by Takemoto Oil & Fat Co., Ltd. can also be used.

[0360] Specific examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by MORISHITA & CO., LTD.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers POLYFLOW No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), and W001 (manufactured by Yusho Co., Ltd.).

[0361] Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.) and Sandetto BL (manufactured by Sanyo Chemical Industries, Ltd.).

[0362] Examples of the silicone surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie).

[0363] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, relative to the total solid content of the resin composition of the present invention.

[0364] Ultraviolet absorbers

[0365] The resin composition of the present invention may contain a UV absorber. Compositions containing UV absorbers tend to have reduced i-ray transmittance. Therefore, when a resin composition containing a UV absorber is exposed to i-rays, sensitivity may be low. However, according to the present invention, even a resin composition containing a UV absorber can achieve excellent sensitivity, thereby significantly achieving the effects of the present invention.

[0366] Examples of the UV absorber include salicylate-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, substituted acrylonitrile-based UV absorbers, and triazine-based UV absorbers. Commercially available UV absorbers may also be used. Examples of commercially available UV absorbers include UV503 (DAITO CHEMICAL CO., LTD.) and TINUVIN 477 (manufactured by BASF).

[0367] The content of the ultraviolet absorber is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, relative to the total solid content of the resin composition of the present invention.

[0368] Silane coupling agent

[0369] The resin composition of the present invention may contain a silane coupling agent in order to improve substrate adhesion.

[0370] The so-called silane coupling agent refers to a compound having a hydrolyzable group and other functional groups in the molecule. In addition, the hydrolyzable group such as alkoxy is bonded to the silicon atom.

[0371] A hydrolyzable group is a substituent that is directly bonded to a silicon atom and is capable of forming a siloxane bond through a hydrolysis reaction and / or a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, and alkenyloxy groups. When a hydrolyzable group has carbon atoms, the number of carbon atoms is preferably 6 or less, more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferred.

[0372] Furthermore, in order to improve the adhesion of the cured film, the silane coupling agent preferably does not contain fluorine atoms and silicon atoms (except for silicon atoms to which a hydrolyzable group is bonded), and preferably does not contain fluorine atoms, silicon atoms (except for silicon atoms to which a hydrolyzable group is bonded), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms.

[0373] In the present invention, the silane coupling agent is a compound different from the above-mentioned polymerizable compound and thermosetting compound, that is, a compound having a hydrolyzable group and other functional groups in its molecule.

[0374] The silane coupling agent preferably has a group represented by the following formula (Z): * represents a bonding position.

[0375] Formula (Z)*-Si(R z1 ) 3-m (R z2 ) m

[0376] R z1 represents an alkyl group, R z2 represents a hydrolyzable group, and m represents an integer of 1 to 3. z1 The number of carbon atoms in the alkyl group represented by is preferably 1 to 5, more preferably 1 to 3. z2 The hydrolyzable groups represented are as defined above.

[0377] The silane coupling agent preferably has a curable functional group. As the curable functional group, it is preferably one or more selected from the group consisting of (meth)acryloyloxy, epoxy, oxetanyl, isocyanate, hydroxyl, amino, carboxyl, thiol, alkoxysilyl, methylol, vinyl, (meth)acrylamide, styryl and maleimide, and more preferably one or more selected from the group consisting of (meth)acryloyloxy, epoxy and oxetanyl. The curable functional group may be directly bonded to the silicon atom or bonded to the silicon atom via a linking group.

[0378] The molecular weight of the silane coupling agent is not particularly limited, but is preferably 100 to 1000 from the viewpoint of operability, and is preferably 270 or more, more preferably 270 to 1000 from the viewpoint of further excellent effects of the present invention.

[0379] One preferred embodiment of the silane coupling agent is a silane coupling agent X represented by formula (W).

[0380] Formula (W)R z3 -Lz-Si(R z1 ) 3-m (R z2 ) m

[0381] R z1 represents an alkyl group, R z2 Represents a hydrolyzable group, R z3 represents a curable functional group, Lz represents a single bond or a divalent linking group, and m represents an integer of 1 to 3.

[0382] R z1 The alkyl group represented by is as defined above. z2 The hydrolyzable groups represented are as defined above.

[0383] Lz represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, and -NR 12 -、-CONR 12 -、-CO-、-CO2-、-SO2NR 12 -, -O-, -S-, -SO2- or a combination thereof.

[0384] The number of carbon atoms in the alkylene group is preferably 1 to 20. The alkylene group may be linear or branched. The alkylene group and the arylene group may be unsubstituted or have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group.

[0385] Lz is preferably at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms and an arylene group having 6 to 12 carbon atoms, or a combination of these groups and a alkylene group selected from the group consisting of -NR12 -、-CONR 12 -、-CO-、-CO2-、-SO2NR 12 -, -O-, -S- and -SO2-, more preferably an alkylene group having 2 to 10 carbon atoms, -CO2-, -O-, -CO-, -CONR 12 -, or a group consisting of a combination of these groups. 12 represents a hydrogen atom or a methyl group.

[0386] m represents 1 to 3, preferably 2 to 3, and more preferably 3.

[0387] Examples of the silane coupling agent X include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602), N-β-aminoethyl-γ-aminopropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-602), γ-aminopropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903), γ-aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903), 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903), and 1,2-dimethacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903). Co., Ltd., trade name: KBM-503), glycidoxyoctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name: KBM-4803), and the like.

[0388] A preferred embodiment of the silane coupling agent is a silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom.

[0389] Regarding the silane coupling agent Y, it is sufficient to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms or substituents. These can be the same atom or substituent, or different atoms or substituents. The atoms or substituents that can be bonded include hydrogen atoms, halogen atoms, hydroxyl groups, alkyl groups having 1 to 20 carbon atoms, alkenyl groups, alkynyl groups, aryl groups, amino groups that can be substituted by alkyl and / or aryl groups, silyl groups, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups, etc. These substituents can be further substituted by silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, amino groups that can be substituted by alkyl and / or aryl groups, halogen atoms, sulfonamide groups, alkoxycarbonyl groups, amide groups, urea groups, ammonium groups, alkylammonium groups, carboxyl groups or salts thereof, sulfonyl groups or salts thereof, etc.

[0390] In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.

[0391] The silane coupling agent Y may contain a group represented by formula (Z).

[0392] Regarding the silane coupling agent Y, there is at least one nitrogen atom in the molecule, preferably the nitrogen atom exists in the form of a secondary amino group or a tertiary amino group, that is, it is preferred that the nitrogen atom has at least one organic group as a substituent. In addition, as the structure of the amino group, it can exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or it can exist as a substituted amino group such as aniline. Here, as the organic group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a combination thereof can be mentioned. They can also have a substituent, and as the substituent that can be introduced, a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, a sulfonamido group, an alkoxycarbonyl group, a carbonyloxy group, an amide group, an urea group, an alkyleneoxy group, an ammonium group, an alkylammonium group, a carboxyl group or a salt thereof, a sulfo group, etc. can be mentioned.

[0393] Furthermore, the nitrogen atom is preferably bonded to the curable functional group via an arbitrary organic linking group. Preferred organic linking groups include substituents that can be introduced into the above-mentioned nitrogen atom and the organic group bonded to the above-mentioned nitrogen atom.

[0394] The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.

[0395] Regarding the curable functional group, it is sufficient as long as there is at least one curable functional group in one molecule of the silane coupling agent Y. It can also adopt a form having two or more curable functional groups. From the viewpoint of sensitivity and stability, it is preferably a form having 2 to 20 curable functional groups, more preferably 4 to 15 curable functional groups, and most preferably a form having 6 to 10 curable functional groups in the molecule.

[0396] Examples of the silane coupling agent Y include compounds represented by the following formula (Y).

[0397] Formula(Y)(R y3 ) n -LN-Si(R y1 ) 3-m (R y2 ) m

[0398] R y1 represents an alkyl group, R y2 Represents a hydrolyzable group, R y3 represents a curable functional group,

[0399] LN represents a linking group having a (n+1) valence of a nitrogen atom,

[0400] m represents an integer of 1 to 3, and n represents an integer of 1 or greater.

[0401] R in formula (Y) y1 、R y2 、R y3 and m and R of formula (W) z1 、R z2 、R z3 and m have the same meanings and the preferred ranges are also the same.

[0402] In formula (Y), n represents an integer greater than or equal to 1. The upper limit is, for example, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The lower limit is, for example, preferably 2 or more, more preferably 4 or more, and even more preferably 6 or more. Furthermore, n can also be 1.

[0403] LN in formula (Y) represents a group having a nitrogen atom.

[0404] Examples of the group containing a nitrogen atom include at least one selected from the following formulas (LN-1) to (LN-4), or a group consisting of a combination of the following formulas (LN-1) to (LN-4) and at least one selected from an alkylene group, an arylene group, -CO-, -CO2-, -O-, -S-, and -SO2-. The alkylene group may be linear or branched. The alkylene group and the arylene group may be unsubstituted or have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group.

[0405] [Chemical Formula 24]

[0406]

[0407] In the formula, * represents a connecting bond.

[0408] Specific examples of the silane coupling agent Y include the following compounds: wherein Et represents an ethyl group. In addition, compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703 are also included, and the contents thereof are incorporated herein.

[0409] [Chemical Formula 25]

[0410]

[0411] The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but may be within the above-mentioned range (preferably 270 or more).

[0412] The content of the silane coupling agent is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 1.0 to 6% by mass relative to the total solids content in the resin composition of the present invention. The silane coupling agent may be used alone or in combination of two or more. When two or more are used in combination, the total amount is preferably within the above range.

[0413] Other additives

[0414] In the resin combination of the present invention, as required, various additives, such as fillers, adhesion promoters, antioxidants, anti-agglomerating agents, etc. can be coordinated. As these additives, the additives described in paragraphs 0155 to 0156 of Japanese Patent Application Laid-Open No. 2004-295116 can be enumerated, and these contents are incorporated into this specification. As antioxidants, for example, phenolic compounds, phosphorus compounds (such as compounds described in paragraph 0042 of Japanese Patent Application Laid-Open No. 2011-90147), thioether compounds, etc. can be used. As commercially available products, for example, the ADEKASTAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330, etc.) manufactured by ADEKA CORPORATION can be enumerated. Antioxidants can be used in combination with two or more. The resin composition of the present invention may contain the photosensitizer and light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of JP-A-2004-295116.

[0415] The resin composition may contain metal elements depending on the raw materials used. However, from the perspective of suppressing the occurrence of defects, the content of Group II elements (calcium, magnesium, etc.) in the resin composition is preferably 50 ppm or less, and more preferably 0.01 to 10 ppm. Furthermore, the total amount of inorganic metal salts in the resin composition is preferably 100 ppm or less, and more preferably 0.5 to 50 ppm.

[0416] <Method for Preparing Resin Composition>

[0417] The resin composition of the present invention can be prepared by mixing the aforementioned components. When preparing the resin composition, each component can be mixed at one time, or each component can be dissolved / dispersed in a solvent and then mixed in sequence. In addition, the order of input and working conditions during mixing are not particularly limited. For example, all components can be dissolved / dispersed in a solvent at the same time to prepare the composition, or each component can be appropriately prepared into two or more solutions / dispersions as needed, and mixed to prepare the composition during use (during coating).

[0418] When preparing resin combination, in order to remove foreign matter, reduce defect etc., preferably filter with filter.As filter, as long as be the filter used for filtering purposes etc. in the past, then can be used without particular restriction.For example, can enumerate the filter of the raw materials such as polyolefin resin (comprising high density, ultra-high molecular weight polyolefin resin) such as polyamide resin, polyethylene, polypropylene (PP) etc. using fluororesin such as polytetrafluoroethylene (PTFE), nylon (such as nylon-6, nylon-6,6).In these raw materials, preferably polypropylene (comprising high-density polypropylene) and nylon.

[0419] The pore size of the filter is preferably between 0.01 and 7.0 μm, preferably between 0.01 and 3.0 μm, and more preferably between 0.05 and 0.5 μm. This range allows for the reliable removal of fine foreign matter that could hinder the preparation of a uniform composition or the formation of a smooth membrane in subsequent steps. Furthermore, it is preferred to use a fibrous filter material. Examples of such filter materials include polypropylene fibers, nylon fibers, and glass fibers. Specifically, filter elements from the SBP series (e.g., SBP008), TPR series (e.g., TPR002, TPR005), and SHPX series (e.g., SHPX003) manufactured by ROKI GROUP CO., LTD. can be used.

[0420] When using filters, different filters may be combined. In this case, filtration with the first filter may be performed only once or twice or more.

[0421] Furthermore, first filters having different pore sizes within the above range may be combined. The pore size here can refer to the nominal value specified by the filter manufacturer. Commercially available filters can be selected from various filters offered by, for example, Pall Corporation (DFA4201NXEY, etc.), ADVANTEC TOYO KAISHA, LTD., Nihon Entegris KK (formerly Nippon Mykrolis Corporation), or KITZ MICRO FILTER CORPORATION.

[0422] The second filter may be formed of the same material as that of the first filter.

[0423] For example, only the dispersion may be filtered using a first filter, and after mixing other components, a second filtration may be performed.

[0424] In the resin composition of the present invention, the viscosity can be adjusted for use in order to adjust the film surface state (flatness, etc.) and adjust the film thickness. The viscosity value can be appropriately selected as needed, for example, it can be set to 0.3mPa·s to 50mPa·s at 25°C, preferably 0.5mPa·s to 20mPa·s. As a measurement method, for example, a viscometer RE85L (rotor: 1°34'×R24, measurement range: 0.6 to 1200mPa·s) manufactured by TOKI SANGYO CO., LTD. can be used and the temperature can be adjusted to 25°C for measurement.

[0425] <Cured Film>

[0426] Next, the cured film of the present invention will be described.

[0427] The cured film of the present invention is formed using the resin composition of the present invention. The cured film of the present invention can be used in various devices such as solid-state imaging devices such as CCDs (charge coupled devices) and CMOSs ​​(complementary metal oxide semiconductors), and image display devices.

[0428] The cured film of the present invention can be used in color filters, light-shielding films, transparent films, etc. For example, by using a resin composition containing a color colorant, a cured film suitable for color filters, etc. can be manufactured. Furthermore, by using a resin composition containing a black pigment, a cured film suitable for light-shielding films, etc. can be manufactured. Furthermore, by using a resin composition that does not contain both a color colorant and a black pigment, a cured film suitable for transparent films (transparent pixels), etc. can be manufactured. The cured film of the present invention may have a pattern or may be a film without a pattern (flat film).

[0429] The thickness of the cured film of the present invention can be adjusted appropriately depending on the intended purpose. The film thickness is preferably 0.3 to 10 μm. The lower limit can be 0.4 μm or greater, or 0.5 μm or greater. The upper limit is more preferably 7 μm or less, further preferably 5 μm or less, and particularly preferably 3 μm or less.

[0430] The cured film of the present invention has a transmittance of light having a wavelength of 365 nm of preferably 15% or less, more preferably 10% or less, and further preferably 7% or less.

[0431] When the cured film of the present invention is used for liquid crystal display devices, the voltage holding ratio of the liquid crystal display element having the cured film is preferably 70% or more, more preferably 90% or more. Known methods for obtaining a high voltage holding ratio can be appropriately introduced. Typical methods include using high-purity raw materials (for example, reducing ionic impurities) and controlling the amount of acidic functional groups in the composition. The voltage holding ratio can be measured, for example, by the method described in paragraph 0243 of Japanese Patent Application Publication No. 2011-008004 and paragraphs 0123 to 0129 of Japanese Patent Application Publication No. 2012-224847.

[0432] <Pattern Formation Method>

[0433] Next, the pattern forming method of the present invention will be described.

[0434] The pattern forming method of the present invention comprises: forming a radiation-sensitive resin composition layer on a support using the radiation-sensitive resin composition of the present invention; exposing the radiation-sensitive resin composition layer to a pattern; and developing and removing unexposed areas to form a pattern. Each step is described below.

[0435] <<Step of forming a radiation-sensitive resin composition layer>>

[0436] In the step of forming the radiation-sensitive resin composition layer, the radiation-sensitive resin composition is used to form the radiation-sensitive resin composition layer on the support.

[0437] As the support, for example, a solid-state imaging element substrate in which a solid-state imaging element (light-receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.

[0438] The pattern in the present invention may be formed on the side (front surface) of the solid-state imaging element substrate on which the solid-state imaging element is formed, or may be formed on the side (back surface) on which no solid-state imaging element is formed.

[0439] A primer layer may be provided on the support as needed to improve adhesion with an upper layer, prevent diffusion of substances, or planarize the substrate surface.

[0440] As a method for applying the radiation-sensitive resin composition to the support, various methods such as slit coating, inkjet coating, spin coating, cast coating, roll coating, and screen printing can be used.

[0441] The radiation-sensitive resin composition layer formed on the support may be dried (prebaked). However, when patterning is performed by a low-temperature process, prebaking is not required.

[0442] When prebaking, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or even 80°C or higher. By setting the prebaking temperature to 150°C or lower, these properties can be more effectively maintained, for example, when the photoelectric conversion film of an image sensor is formed using an organic material.

[0443] The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Drying can be performed using a hot plate, an oven, or the like.

[0444] Exposure Process

[0445] Next, the radiation-sensitive resin composition layer is exposed in a pattern (exposure step). For example, pattern exposure can be performed by exposing the radiation-sensitive resin composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper. This allows the exposed portion to be cured.

[0446] As radiation (light) that can be used during exposure, ultraviolet rays such as g-rays and i-rays can be preferably used (i-rays are particularly preferred). The irradiation dose (exposure dose) is preferably 0.03 to 2.5 J / cm 2 , more preferably 0.05 to 1.0 J / cm 2 .

[0447] The oxygen concentration during exposure can be appropriately selected. In addition to exposure under the atmosphere, exposure can be performed under a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or under a high oxygen atmosphere with an oxygen concentration exceeding 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). Furthermore, the exposure illuminance can be appropriately set, typically from 1000 W / m 2 ~100000W / m 2 (For example, 5000W / m 2 、15000W / m 2 、35000W / m 2The oxygen concentration and exposure illuminance can be appropriately combined, for example, the oxygen concentration can be set to 10% by volume and the illuminance can be set to 10000 W / m 2 , oxygen concentration 35% by volume and illumination 20,000 W / m 2 wait.

[0448] The thickness of the cured film is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more. By setting the film thickness to 2.0 μm or less, high resolution and high adhesion are easily achieved.

[0449] Development Process

[0450] Next, the unexposed portion is removed by development to form a pattern. The unexposed portion can be removed by development using a developer. Thus, the unexposed portion of the radiation-sensitive resin composition layer in the exposure step is dissolved in the developer, leaving only the photocured portion.

[0451] As the developer, an organic alkaline developer which does not damage the underlying solid-state imaging element, circuit, etc. is preferably used.

[0452] The temperature of the developer is preferably 20 to 30° C. The development time is preferably 20 to 180 seconds. In order to improve the residue removal performance, the following process may be repeated several times: the developer is discarded every 60 seconds and then supplied again.

[0453] As the alkaline agent used in the developer, for example, organic alkaline compounds such as ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene can be mentioned. The developer can preferably use an alkaline aqueous solution prepared by diluting these alkaline agents with pure water. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.

[0454] Furthermore, an inorganic base may be used in the developer, and preferred examples of the inorganic base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and sodium metasilicate.

[0455] Furthermore, a surfactant may be used in the developer. Examples of the surfactant include the surfactants described above for the curable composition, and nonionic surfactants are preferred.

[0456] When a developer containing such an alkaline aqueous solution is used, it is usually preferred to perform cleaning (rinsing) with pure water after development.

[0457] After development, a heat treatment (post-baking) can also be performed after drying. Post-baking is a heat treatment after development for complete curing of the film. When post-baking is performed, the post-baking temperature is preferably, for example, 100 to 240°C. From the viewpoint of film curing, it is more preferably 200 to 230°C. Furthermore, when an organic electroluminescent (organic EL) element is used as a light source, or when a photoelectric conversion film of an image sensor is composed of organic raw materials, the post-baking temperature is preferably 150°C or less, more preferably 120°C or less, further preferably 100°C or less, and particularly preferably 90°C or less. The lower limit can be, for example, 50°C or more.

[0458] In post-baking, the developed film can be subjected to the above-mentioned conditions using a heating mechanism such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater, either continuously or intermittently. Furthermore, post-baking is not required when patterning is performed using a low-temperature process.

[0459] <Solid-state imaging device>

[0460] The solid-state imaging element of the present invention comprises the cured film of the present invention. The structure of the solid-state imaging element of the present invention is not particularly limited as long as the structure functions as a solid-state imaging element. Examples thereof include the following structures.

[0461] The structure is as follows: on a support body, there is a transfer electrode formed of multiple photodiodes and polysilicon, etc., which constitutes a light-receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.); on the above-mentioned photodiode and the above-mentioned transfer electrode, there is a light-shielding film formed of tungsten, etc., in which only the light-receiving part of the photodiode is opened; on the light-shielding film, there is a device protection film formed of silicon nitride, etc., which is formed in a manner covering the entire surface of the light-shielding film and the light-receiving part of the photodiode; and on the above-mentioned device protection film, there is a color filter of the present invention.

[0462] Furthermore, a structure having a focusing mechanism (eg, a microlens, etc., the same applies hereinafter) on the device protection film and below the color filter (on the support side) or a structure having a focusing mechanism on the color filter may also be possible.

[0463] <Image Display Device>

[0464] The cured film of the present invention can be used in image display devices such as liquid crystal displays and organic electroluminescent displays. An image display device equipped with the cured film of the present invention can display high-quality images with good color and excellent display characteristics. The definition of a display device and details of each display device are described, for example, in "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)" and "Display Devices (written by Junsho Ibuki, published by Sangyo Tosho Publishing Co., Ltd. in 1991)." Furthermore, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd. in 1994)." The liquid crystal display devices to which the present invention can be applied are not particularly limited, and for example, the present invention can be applied to liquid crystal display devices of various types described in "Next Generation Liquid Crystal Display Technology."

[0465] The cured film of the present invention can be used in color TFT (Thin Film Transistor) liquid crystal display devices. Color TFT liquid crystal display devices are described, for example, in "Color TFT Liquid Crystal Display (published by Kyoritsu Shupan Co., Ltd. in 1996)." Furthermore, the present invention can also be applied to liquid crystal display devices with expanded viewing angles, such as lateral electric field drive methods such as IPS (In Plane Switching), pixel division methods such as MVA (Multi-domain Vertical Alignment), STN (Super Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-Chip Spacer), FFS (Fringe Field Switching), and R-OCB (Reflective Optically Compensated Bend). Furthermore, the color filter of the present invention can also be used in a COA (Color-Filter On Array) format (an integrated technology in which a color filter layer is directly formed on an array substrate). These image display methods are described, for example, in "EL, PDP, and LCD Displays - Latest Trends in Technology and Markets" (published by Toray Research Center Inc. in 2001), page 43.

[0466] Example

[0467] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless otherwise specified.

[0468] <Preparation of Dispersion>

[0469] A dispersion was prepared by mixing the following composition for 2 hours using a bead mill (high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Japan BEE Co., Ltd.) using zirconia beads having a diameter of 0.3 mm. Dispersion 8 was prepared using YMS-01A-2 (manufactured by Sumitomo Metal Mini ng Co., Ltd.).

[0470] (Dispersion 1)

[0471] Green pigment (CI Pigment Green 58): 9.8 parts by mass

[0472] Yellow pigment (CI Pigment Yellow 185): 2.8 parts by mass

[0473] Resin 1 (structure shown below, weight average molecular weight = 24,000): 4.6 parts by mass

[0474] [Chemical Formula 26]

[0475]

[0476] Propylene glycol monomethyl ether acetate: 82.8 parts by mass

[0477] (Dispersion 2)

[0478] Titanium oxide (TiO2): 23.0 parts by mass

[0479] Resin 1: 6.2 parts by mass

[0480] Propylene glycol monomethyl ether acetate: 70.8 parts by mass

[0481] (Dispersion 3)

[0482] Alumina (Al2O3): 19.5 parts by mass

[0483] Resin (MB-517-42, manufactured by FIJIFILM Fine Chemicals Co., Ltd.): 5.3 parts by mass

[0484] Propylene glycol monomethyl ether acetate 75.2 parts by mass

[0485] (Dispersion 4)

[0486] Zirconium oxide (ZrO2): 21.1 parts by mass

[0487] Resin 1: 5.7 parts by mass

[0488] Propylene glycol monomethyl ether acetate: 73.2 parts by mass

[0489] (Dispersion 5)

[0490] Indium tin oxide (ITO): 18.0 parts by mass

[0491] Resin 1: 4.9 parts by mass

[0492] Propylene glycol monomethyl ether acetate: 77.1 parts by mass

[0493] (Dispersion 6)

[0494] Titanium black: 23.3 parts by mass

[0495] Resin 2 (structure shown below, weight average molecular weight = 38900): 7.6 parts by mass

[0496] [Chemical Formula 27]

[0497]

[0498] Propylene glycol monomethyl ether acetate: 41.5 parts by mass

[0499] Butyl acetate: 27.6 parts by mass

[0500] (Dispersion 7)

[0501] Vanadium oxynitride: 21.5 parts by mass

[0502] Resin 1: 6.4 parts by mass

[0503] Propylene glycol monomethyl ether acetate 72.1 parts by mass

[0504] (Dispersion 8)

[0505] YMS-01A-2 (manufactured by Sumitomo Metal Mining Co., Ltd., cesium tungsten oxide dispersion containing 25% by mass of cesium tungsten oxide (CsWO3) and 13.7% by mass of resin)

[0506] (Dispersion Liquid 9)

[0507] Carbon black: 19.0 parts by mass

[0508] Resin (Acrybase FFS-6824, manufactured by FUJIKURA KASEI CO., LTD.): 8.4 parts by mass

[0509] Propylene glycol monomethyl ether acetate: 38.3 parts by mass

[0510] Cyclohexanone: 16.4 parts by mass

[0511] Ethyl 3-ethoxypropionate: 17.9 parts by mass

[0512] (Dispersion 10)

[0513] Green pigment (CI Pigment Green 58): 9.77 parts by mass

[0514] Yellow pigment (CI Pigment Yellow 185): 2.8 parts by mass

[0515] Resin 1: 4.6 parts by mass

[0516] Tetrabromophthalimide: 0.03 parts by mass

[0517] Propylene glycol monomethyl ether acetate: 82.8 parts by mass

[0518] <Preparation of Radiation-Sensitive Resin Composition>

[0519] The materials listed in the following table were mixed and stirred at the ratios (mass %) shown in the table below. The water content was adjusted to the value (mass %) shown in the table below, and then filtered through a nylon filter with a pore size of 0.45 μm (DFA4201NXEY, manufactured by Nihon Pall Ltd.) to prepare radiation-sensitive resin compositions. The water content in the compositions was also measured by the Karl Fischer method.

[0520]

[0521]

[0522] The materials shown in the above table are as follows.

[0523] (resin)

[0524] A-1: ACRYCURE-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.)

[0525] A-2: Acrybase FF-426 (manufactured by FUJIKURA KASEI CO., LTD.)

[0526] A-3: The following structure (weight average molecular weight = 12,000)

[0527] A-4: The following structure (weight average molecular weight = 41,000)

[0528] A-5: The following structure (weight average molecular weight = 11,000)

[0529] [Chemical Formula 28]

[0530]

[0531] (Polymerizable compound)

[0532] B-1: NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0533] B-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[0534] B-3: The following structure

[0535] [Chemical Formula 29]

[0536]

[0537] B-4: Aronix TO-2349 (manufactured by TOAGOSEI CO., LTD.)

[0538] B-5: The following structure

[0539] [Chemical formula 30]

[0540]

[0541] (Photopolymerization initiator)

[0542] [Oxime ester compound having at least one group selected from branched alkyl groups and cyclic alkyl groups]

[0543] C-1: Compound having the following structure (oxime ester compound having a branched alkyl group)

[0544] C-2: Compound having the following structure (oxime ester compound having a cyclic alkyl group)

[0545] C-3: Compound having the following structure (oxime ester compound having a branched alkyl group)

[0546] [Chemical Formula 31]

[0547]

[0548] [Other photopolymerization initiators]

[0549] C-4: IRGACURE-OXE02 (manufactured by BASF)

[0550] C-5: IRGACURE-OXE01 (manufactured by BASF)

[0551] C-6: IRGACURE-369 (manufactured by BASF)

[0552] C-7: IRGACURE-379 (manufactured by BASF)

[0553] C-8: IRGACURE-819 (manufactured by BASF)

[0554] C-9: the following compound

[0555] [Chemical Formula 32]

[0556]

[0557] (Solvent)

[0558] D-1: Propylene glycol monomethyl ether acetate

[0559] D-2: Cyclohexanone

[0560] (UV absorber)

[0561] E-1: UV-503 (manufactured by DAITO CHEMICAL CO., LTD.)

[0562] E-2: TINUVIN 477 (manufactured by BASF)

[0563] (Thermosetting compounds)

[0564] F-1: EHPE3150 (manufactured by Daicel Corporation)

[0565] (Polymerization Inhibitor)

[0566] G-1: p-Methoxyphenol (manufactured by Sanritsu Chemie)

[0567] (Surfactant)

[0568] H-1: KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone surfactant)

[0569] H-2: The following mixture (Mw = 14000)

[0570] [Chemical Formula 33]

[0571]

[0572] (Silane coupling agent)

[0573] I-1: The following structure (in the following structural formula, Et represents an ethyl group)

[0574] [Chemical Formula 34]

[0575]

[0576] (color colorant)

[0577] J-1: The following structure

[0578] [Chemical Formula 35]

[0579]

[0580] <Evaluation Method>

[0581] (Evaluation of initial sensitivity)

[0582] <Preparation of Silicon Wafer Substrate with Primer Coat>

[0583] An 8-inch (1 inch = 25.4 mm) diameter silicon wafer was heat-treated in an oven at 200°C for 30 minutes. A primer resist solution (CT-4000, manufactured by FUJIFILM Flectronic Materials Co., Ltd.) was then applied to the silicon wafer to a dry film thickness of 0.1 μm. The wafer was then heat-dried in an oven at 220°C for 1 hour to form a primer layer, thereby obtaining a silicon wafer substrate with a primer layer.

[0584] The radiation-sensitive resin composition obtained above (radiation-sensitive resin composition immediately after production) was applied to the primer layer of the primer-coated silicon wafer substrate prepared above to form a coating film. The coating film was then heated (prebaked) for 120 seconds using a 100°C hot plate to achieve the dry film thickness listed in the table below.

[0585] Next, an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used to expose at a wavelength of 365 nm through a mask having a pattern and with the exposure amount described in Table 3. In addition, in Examples 1 to 4, Example 17, and Comparative Examples 1 to 7, a mask having a Bayer pattern of 0.9 μm × 0.9 μm was used. Furthermore, in Examples 5 to 8, a mask having a Bayer pattern of 1.1 μm × 1.1 μm was used. Furthermore, in Examples 9 to 10 and 12, a mask having a hole pattern with a diameter of 100 μm was used. Furthermore, in Examples 11 and 13, a mask having a Bayer pattern of 10 μm × 10 μm was used. Furthermore, in Example 14, a mask having a Bayer pattern of 0.8 μm × 0.8 μm was used. Furthermore, in Examples 15 and 16, a mask having an island pattern of 1.0 μm×1.0 μm was used.

[0586] Thereafter, the silicon wafer substrate having the irradiated coating film formed thereon was placed on a horizontal rotary table of a spin / shower developer (DW-30 model, manufactured by Chemitronics Co., Ltd.), and a developer at 23° C. (CD-1030, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was supplied from a nozzle in a shower state four times (15 seconds) and maintained in a paddle state for 30 seconds to perform paddle development, thereby forming a pattern.

[0587] Next, the patterned substrate was fixed on a horizontal rotating workbench using a vacuum suction cup, the silicon wafer substrate was rotated at a rotation speed of 50 rpm by a rotating device, and pure water was supplied from a spray nozzle in a shower-like manner above its rotation center for rinsing (23 seconds × 2 times), followed by spin drying, and then post-drying using a hot plate at 200°C for 300 seconds to obtain a pattern.

[0588] The width of each pattern portion was evaluated at a magnification of 20,000 times using a scanning electron microscope (SEM), and the initial sensitivity was evaluated based on the following criteria.

[0589] A: The width of the pattern portion is in the range of 95% to 105% of the pattern size of the mask used.

[0590] B: The width of the pattern portion is 90% or more and less than 95% of the pattern size of the mask used, or exceeds 105% and less than 110% of the pattern size of the mask used.

[0591] C: The width of the pattern portion is less than 90% of the pattern size of the mask used, or exceeds 110% of the pattern size of the mask used.

[0592] (Evaluation of temporal stability)

[0593] The radiation-sensitive resin composition was placed in a sealed container and stored for 3 to 9 months at 10° C. The radiation-sensitive resin composition after storage was used to form a pattern under the same conditions as those for the initial sensitivity evaluation.

[0594] The obtained patterns were examined using a scanning electron microscope (SEM) at a magnification of 20,000x to evaluate the width of the patterned portion. Initial sensitivity was also evaluated based on the following criteria: If the pattern width increased compared to the initial state, the sensitivity was considered to have increased; if the pattern width decreased compared to the initial state, the sensitivity was considered to have decreased.

[0595] In addition, in Comparative Examples 2 to 6, since the initial sensitivity was poor, the evaluation of stability over time was not performed.

[0596] A: The pattern width of the pattern produced using the radiation-sensitive resin composition after storage for 9 months is within a range of 90% to 110% of the pattern width of the pattern produced using the radiation-sensitive resin composition immediately after production.

[0597] B: The pattern width of the pattern using the radiation-sensitive resin composition after storage for 9 months is less than 90% of the pattern width of the pattern produced using the radiation-sensitive resin composition immediately after production, or exceeds 110%, but the rate of change in the pattern width of the pattern using the radiation-sensitive resin composition after storage for 6 months is in the range of -10% to +10% of the pattern width of the pattern produced using the radiation-sensitive resin composition immediately after production.

[0598] C: The pattern width of the pattern produced using the radiation-sensitive resin composition stored for 6 months is less than 90% or exceeds 110% of the pattern width of the pattern produced using the radiation-sensitive resin composition immediately after production.

[0599] The evaluation results are described in the following table.

[0600] (Spectral Evaluation)

[0601] The radiation-sensitive resin composition was applied on a glass substrate and pre-baked (100°C, 120 seconds) and heated to 500 mJ / cm 2A flat film (a film without a pattern) was produced by exposure (maskless full-surface exposure) and post-baking (200°C for 300 seconds). The spectral transmittance of the obtained flat film was measured in 5 nm steps from 350 nm to 800 nm using a multi-channel spectrometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the transmittance at a wavelength of 365 nm was also measured.

[0602] [Table 3]

[0603]

[0604] As shown in the above table, the examples exhibited good initial sensitivity and excellent sensitivity stability over time. Furthermore, the development speed was good, and post-development residue was minimal. Furthermore, compared to Example 17, which used only an oxime ester compound having at least one group selected from branched alkyl groups and cyclic alkyl groups as a photopolymerization initiator, Examples 1 to 16, which used both an oxime ester compound having at least one group selected from branched alkyl groups and cyclic alkyl groups and other photopolymerization initiators as photopolymerization initiators, exhibited good developability and excellent pattern shape.

[0605] In contrast, in Comparative Example 1, which does not contain water, the pattern width increases with time, and sensitivity increases with time, indicating poor temporal stability of sensitivity. Furthermore, the development speed of Comparative Example 1 is also slower than that of the Examples.

[0606] Furthermore, in Comparative Examples 2 to 7 using photopolymerization initiators not containing an oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group, the initial sensitivity of Comparative Examples 2 to 6 was poor.

[0607] Furthermore, in Comparative Example 7, although the initial sensitivity was good, the pattern width became smaller with the passage of time, and a decrease in sensitivity was observed with the passage of time, indicating poor stability of sensitivity over time.

Claims

1. A radiation-sensitive resin composition comprising a resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, an organic solvent, and water. In the radiation-sensitive resin composition, The photopolymerization initiator comprises an oxime ester compound having a cyclic alkyl group represented by formula (1), The content of water is 0.1 to 2% by mass relative to the mass of the radiation-sensitive resin composition. In formula (1), Ar 1 and Ar 2 Each independently represents a benzene ring or a naphthalene ring, R 1 ~R 3 Each independently represents an alkyl group or an aryl group; wherein, R 1 ~R 3 At least one of them is a cyclic alkyl group having 3 to 30 carbon atoms, or R 1 ~R 3 At least one of them has a cyclic alkyl group having 3 to 30 carbon atoms.

2. The radiation-sensitive resin composition according to claim 1, wherein The resin includes an alkali-soluble resin.

3. The radiation-sensitive resin composition according to claim 1 or 2, wherein The polymerizable compound is a multifunctional (meth)acrylate compound having an ethylenically unsaturated bond equivalent of 3.0 to 12.0 mmol / g.

4. The radiation-sensitive resin composition according to claim 1 or 2, wherein The oxime ester compound has at least one group selected from a branched alkyl group having 7 or more carbon atoms and a cyclic alkyl group having 7 or more carbon atoms.

5. The radiation-sensitive resin composition according to claim 1 or 2, wherein The oxime ester compound has a carbazole structure.

6. The radiation-sensitive resin composition according to claim 5, wherein The carbazole structure further has a structure in which a ring is fused on the benzene ring of the carbazole portion.

7. The radiation-sensitive resin composition according to claim 1 or 2, wherein The oxime ester compound is an oxime ester compound containing a fluorine atom.

8. The radiation-sensitive resin composition according to claim 1 or 2, wherein The organic solvent is at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, butyl acetate, ethyl 3-ethoxypropionate, propylene glycol monoethyl ether acetate, xylene, ethylbenzene, methyl isobutyl ketone, 2-butanol, and dipropylene glycol monomethyl ether. 9 . The radiation-sensitive resin composition according to claim 1 , further comprising at least one selected from the group consisting of a colorant and inorganic particles. 10 . The radiation-sensitive resin composition according to claim 1 , further comprising a phthalimide compound. 11 . The radiation-sensitive resin composition according to claim 1 , further comprising an ultraviolet absorber. 12 . The radiation-sensitive resin composition according to claim 1 , further comprising a thermosetting compound.

13. The radiation-sensitive resin composition according to claim 1 or 2, wherein The photopolymerization initiator further includes a compound other than the oxime ester compound.

14. The radiation-sensitive resin composition according to claim 13, wherein The compound other than the oxime ester compound is at least one selected from the group consisting of an oxime ester compound having no branched alkyl group and no cyclic alkyl group, an alkylphenone compound, and an acylphosphine compound. 15 . A cured film formed using the radiation-sensitive resin composition according to claim 1 .

16. The cured film according to claim 15, wherein The transmittance of light with a wavelength of 365nm is less than 15%.

17. A pattern forming method comprising: a step of forming a radiation-sensitive resin composition layer on a support using the radiation-sensitive resin composition according to any one of claims 1 to 14; a step of exposing the radiation-sensitive resin composition layer in a pattern; and a step of developing and removing the unexposed portion to form a pattern. 18 . A solid-state imaging element comprising the cured film according to claim 15 . 19 . An image display device comprising the cured film according to claim 15 .

Images