JP2014071306A - Curable resin composition, transfer material, cured material, method for producing the same, method for producing resin pattern, cured film, liquid crystal display device, organic el display device and touch panel display device - Google Patents

Abstract

（式（Ｌ）中、Ｘ¹及びＸ²はそれぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基又はアシル基を表し、Ｙは水素原子又は一価の置換基を表し、＊は連結位置を表し、芳香環を構成する炭素原子、複素環を構成する窒素原子又は炭素原子、あるいは、２級又は３級窒素原子と連結する。）
【選択図】なしThe present invention provides a curable resin composition having a small haze, a high refractive index, a surface tackiness suppressed, and an excellent resolution.
(Component A) an alkali-soluble resin, (Component B) a compound having a group represented by the following formula (L), (Component C) an acid generator, (Component D) metal oxide particles, and Component E) A curable resin composition containing a solvent.

(In formula (L), X ¹ and X ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an acyl group, and Y represents a hydrogen atom or a monovalent substituent. * Represents a connecting position, and is connected to a carbon atom constituting an aromatic ring, a nitrogen atom or a carbon atom constituting a heterocyclic ring, or a secondary or tertiary nitrogen atom.)
[Selection figure] None

Description

The present invention relates to a curable resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, the transfer material which has the layer of the said curable resin composition, the hardened | cured material formed by hardening | curing the said curable resin composition, its manufacturing method, the resin pattern manufacturing method using the said curable resin composition, the said sclerosis | hardenability The present invention relates to a cured film obtained by curing a resin composition, and various image display devices using the cured film.
More specifically, a curable resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, a touch panel display device, an integrated circuit element, and a solid-state imaging device. And a method for producing a cured film using the same.

With the development of solid-state imaging devices and liquid crystal display devices, it has become widely practiced to produce optical members such as microlenses, optical waveguides, and antireflection films using organic materials (resins).
In order to make these optical members have a high refractive index, it has been studied to add particles such as zirconium oxide.
Moreover, the composition of patent document 1 and 2 is known as a conventional composition.
Patent Document 1 discloses a titanium dioxide particle (A) having an average primary particle diameter of 1 nm to 100 nm and a graft copolymer (B) having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000. And a solvent (C) are disclosed.
Patent Document 2 includes the following components (A) to (C) and (E): (A) silica-coated titanium oxide particles having a primary particle size in the range of 3 to 100 nm, and (B) two or more in the molecule. (Meth) acryloyl group-containing compound, (C) a photopolymerization initiator, and (E) a solvent, and a photocurable composition containing 100 parts of the total amount of components excluding (E) solvent in the composition. When the content is mass%, the content of the component (A) is in the range of 30 to 85 mass%, and 50 mass% or more in the component (E) has a boiling point of 100 ° C. or higher and 160 ° C. or lower. A photocurable composition which is a solvent having

JP 2011-127096 A JP 2009-179678 A

  An object of the present invention is to provide a curable resin composition having a low haze, a high refractive index, a cured product having a suppressed surface tack, and an excellent resolution.

The above-described problems of the present invention have been solved by means described in the following <1>, <9>, <10> to <13>, <15> to <17>. It describes below with <2>-<8> and <14> which are preferable embodiments.
<1> (Component A) an alkali-soluble resin, (Component B) a compound having a group represented by the following formula (L), (Component C) an acid generator, (Component D) metal oxide particles, and (Component) E) a curable resin composition containing a solvent,

（式（Ｌ）中、Ｘ¹及びＸ²はそれぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基又はアシル基を表し、Ｙは水素原子又は一価の置換基を表し、＊は連結位置を表し、芳香環を構成する炭素原子、複素環を構成する窒素原子又は炭素原子、あるいは、２級又は３級窒素原子と連結する。）

(In formula (L), X ¹ and X ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an acyl group, and Y represents a hydrogen atom or a monovalent substituent. * Represents a connecting position, and is connected to a carbon atom constituting an aromatic ring, a nitrogen atom or a carbon atom constituting a heterocyclic ring, or a secondary or tertiary nitrogen atom.)

<2> The curable resin composition according to <1>, wherein the component D is metal oxide particles having a refractive index of 2.0 or more,
<3> The curable resin composition according to <1> or <2>, wherein component A is a phenolic resin,
<4> The curable resin composition according to any one of <1> to <3>, wherein Component B is a melamine compound,
<5> The curable resin composition according to any one of <1> to <4>, wherein the content of component D is 30% by mass or more based on the total solid content of the composition,
<6> The curable resin composition according to any one of <1> to <5>, wherein Component C is a photoacid generator,
<7> The curable resin composition according to any one of <1> to <6>, wherein the transmittance at a wavelength of 400 nm is 80% or more when the curable resin composition is formed to a thickness of 1 μm. object,
<8> The curable resin composition according to any one of <1> to <7>, wherein Component D is zirconium oxide particles and / or titanium oxide particles.
<9> A transfer material obtained by forming at least one layer of the curable resin composition according to any one of <1> to <8> on a support.
<10> A method for producing a cured product comprising at least steps (a) to (c) in this order,
(A) Application step of applying the curable resin composition according to any one of <1> to <8> onto a substrate (b) Solvent removal step of removing the solvent from the applied resin composition (c) ) Exposure step of irradiating the resin composition from which the solvent has been removed with actinic rays <11> A resin pattern manufacturing method including at least steps (1) to (5) in this order,
(1) Application step of applying the curable resin composition according to any one of <1> to <8> on a substrate (2) Solvent removal step of removing the solvent from the applied resin composition (3) ) An exposure step in which the resin composition from which the solvent has been removed is exposed to a pattern with actinic rays. (4) A development step in which the resin composition in the unexposed area is removed with an aqueous developer and developed. (5) The developed resin composition. Heat treatment step for heat-treating a product <12> A cured product obtained by the method for producing a cured product according to <10> or the resin pattern production method according to <11>,
<13> A cured film obtained by curing the curable resin composition according to any one of <1> to <8>,
<14> The cured film according to <13>, which is an interlayer insulating film,
<15> A liquid crystal display device having the cured film according to <13> or <14>,
<16> An organic EL display device having the cured film according to <13> or <14>,
<17> A touch panel display device having the cured film according to <13> or <14>.

  According to the present invention, a cured product having a small haze, a high refractive index, a suppressed surface tack property, and an excellent resolution can be provided.

1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. 1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. It is sectional drawing which shows the structure of an electrostatic capacitance type input device. It is explanatory drawing which shows an example of a front plate. It is explanatory drawing which shows an example of a 1st transparent electrode pattern and a 2nd transparent electrode pattern.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present invention, the description of “lower limit to upper limit” representing a numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.
In the present invention, “(component A) alkali-soluble resin” or the like is also simply referred to as “component A” or the like.
Furthermore, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.

(Curable resin composition)
The curable resin composition of the present invention (hereinafter also simply referred to as “resin composition”) includes component A) an alkali-soluble resin, (component B) a compound having a group represented by the following formula (L), (component C) an acid generator, (component D) metal oxide particles, and (component E) a solvent.

（式（Ｌ）中、Ｘ¹及びＸ²はそれぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基又はアシル基を表し、Ｙは水素原子又は一価の置換基を表し、＊は連結位置を表し、芳香環を構成する炭素原子、複素環を構成する窒素原子又は炭素原子、あるいは、２級又は３級窒素原子と連結する。）

(In formula (L), X ¹ and X ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an acyl group, and Y represents a hydrogen atom or a monovalent substituent. * Represents a connecting position, and is connected to a carbon atom constituting an aromatic ring, a nitrogen atom or a carbon atom constituting a heterocyclic ring, or a secondary or tertiary nitrogen atom.)

The curable resin composition of the present invention can be suitably used as a negative resist composition.
The curable resin composition of the present invention is preferably a resin composition having a property of being cured by light.
The curable resin composition of the present invention is preferably a negative curable resin composition, and is a chemically amplified negative curable resin composition (chemically amplified negative curable resin composition). Is more preferable.
The curable resin composition of the present invention preferably uses a photoacid generator sensitive to actinic rays as the acid generator. However, it is preferable not to include a 1,2-quinonediazide compound as a photoacid generator. A 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
In contrast, the (Component C) acid generator used in the present invention is produced by the action of one photon because the acid produced acts as a catalyst for, for example, the demethanol reaction in Component B. As a result of so-called chemical amplification, high sensitivity is obtained as a result of so-called chemical amplification. It is done.

  Furthermore, the curable resin composition of the present invention is a resin composition for optical members such as microlenses, optical waveguides, antireflection films, LED sealing materials, and LED chip coating materials, or wiring used for touch panels. A resin composition for reducing the visibility of an electrode is preferable. In addition, the composition for reducing the visibility of the wiring electrode used for the touch panel is a composition for a member that reduces the visibility of the wiring electrode used for the touch panel, that is, makes the wiring electrode difficult to see. Examples thereof include an interlayer insulating film between ITO (indium tin oxide) electrodes, and the curable resin composition of the present invention can be suitably used for the application.

In the touch panel field, the appearance of the insulating layer (photo insulator, PI) in the bridge-type ITO wiring and the wiring appearance due to indium tin oxide (ITO) were problems.
The difference in refractive index between the ITO and the insulating layer, or the refractive index difference between the ITO and the surrounding glass substrate, overcoat layer, etc. causes a difference in the reflectance of the light. Or it is a phenomenon in which the insulating layer is visible. For example, the refractive index of ITO is as large as about 1.9, and the refractive index of the glass substrate is estimated to be different from that of about 1.5.
When a cured film is formed from the compositions described in Patent Documents 1 and 2, since photoradical polymerization is used, there is a problem that curability is not sufficient due to the influence of polymerization inhibition by oxygen. In particular, (meth) acrylic monomers used as polymerizable compounds are mostly liquid or viscous materials, have an uncured film and have a surface tackiness, especially in film applications, In the case of mask contact exposure, there is a problem that components of the composition adhere to the mask and stain the mask.
In addition, the cured film using this is inhibited by polymerization due to oxygen, resulting in insufficient surface curability and surface tackiness even after the curing treatment. There was a problem such as or turning.
As a result of detailed studies, the present inventors have improved the surface curability of uncured films and cured films by using a curable resin composition containing Component A to Component E, and have excellent transparency (haze). It was found that a curable resin composition having a high refractive index, excellent resolution, and suppressed surface tack was obtained.
Hereinafter, the composition of the present invention will be described in detail.

(Component A) Alkali-soluble resin The curable resin composition of the present invention contains (Component A) an alkali-soluble resin. Component A is not particularly limited, but is preferably a phenolic resin.
The phenolic resin is a resin obtained using phenol or substituted phenol as a raw material. Specifically, (Component A-1) polyhydroxystyrenes, (Component A-2) novolak resin, and (Component A-3) are used. ) Partially alkyl etherified polyvinylphenol and partially alkyl etherified hydrogenated polyvinylphenol. Each will be described below.

(Component A-1) Polyhydroxystyrenes In the present invention, (Component A-1) polyhydroxystyrenes may be used as Component A. Polyhydroxystyrenes are hydroxystyrene homopolymers or copolymers with other monomers, and are alkali-soluble resins having a hydroxystyrene unit content of 50 mol% or more.
Component A-1 is an alkali-soluble resin in which the content of hydroxystyrene units is 30 to 100 mol%, and the content of hydroxystyrene units is preferably 50 to 100 mol%, and 70 to 100 mol% It is more preferable that it is 90-100 mol%. When the content of hydroxystyrene units is 30 mol% or more, the solubility in an alkali developer is good, and the developability and resolution are excellent.

Examples of hydroxystyrene in Component A-1 include o-hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene, and these hydroxystyrenes can be used alone or in admixture of two or more.
Moreover, you may copolymerize hydroxystyrene and another unsaturated monomer as needed, As other unsaturated monomers, aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, vinyl toluene, vinyl xylene; (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, Unsaturated carboxylic acids such as benzyl (meth) acrylate, phenyl (meth) acrylate, methyl crotonate, methyl cinnamate, dimethyl maleate, dimethyl fumarate and the like; (meth) acrylonitrile; vinylidene cyanide, α-chloro Examples are vinyl cyanide compounds such as acrylonitrile. Indicated. Among these, styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate are preferable, and styrene, methyl (meth) acrylate, n-Butyl (meth) acrylate and t-butyl (meth) acrylate are more preferable, and styrene and methyl (meth) acrylate are still more preferable. Other unsaturated monomers can be used alone or in admixture of two or more.

  Specific examples of component A-1 include poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene), p-hydroxystyrene / o-hydroxystyrene copolymer, p-hydroxy. In addition to (co) polymers of hydroxystyrenes such as styrene / m-hydroxystyrene copolymer, o-hydroxystyrene / styrene copolymer, o-hydroxystyrene / α-methylstyrene copolymer, m-hydroxystyrene / Styrene copolymer, m-hydroxystyrene / α-methylstyrene copolymer, p-hydroxystyrene / styrene copolymer, p-hydroxystyrene / α-methylstyrene copolymer, p-hydroxystyrene / methyl (meta ) Acrylate copolymer, p-hydroxystyrene / ethyl (meth) acrylate Copolymer, p-hydroxystyrene / n-propyl (meth) acrylate copolymer, p-hydroxystyrene / n-butyl (meth) acrylate copolymer, p-hydroxystyrene / t-butyl (meth) acrylate copolymer Polymer, p-hydroxystyrene / n-hexyl (meth) acrylate copolymer, p-hydroxystyrene / benzyl (meth) acrylate copolymer, p-hydroxystyrene / phenyl (meth) acrylate copolymer, p-hydroxy Styrene / methyl ethacrylate copolymer, p-hydroxystyrene / ethyl ethacrylate copolymer, p-hydroxystyrene / n-propyl ethacrylate copolymer, p-hydroxystyrene / n-butyl ethacrylate copolymer Polymer, p-hydroxystyrene / t-butyl eta Examples include a relate copolymer, a p-hydroxystyrene / n-hexyl ethacrylate copolymer, a p-hydroxystyrene / benzyl ethacrylate copolymer, and a p-hydroxystyrene / phenyl ethacrylate copolymer. it can.

  In Component A-1, modified polyhydroxystyrenes obtained by modifying a part of hydroxyl groups derived from hydroxystyrene may be used. More specifically, those obtained by reacting the hydroxystyrenes with a benzenesulfonyl chloride derivative, a naphthalenesulfonyl chloride derivative, a benzenecarbonyl chloride derivative, a naphthalenecarbonyl chloride derivative or the like in a basic catalyst are exemplified. In this case, the sulfonyl chloride derivative or the carbonyl chloride derivative is preferably used in an amount of 10 to 30 parts by mass, more preferably 15 to 25 parts by mass with respect to 100 parts by mass of the polyhydroxystyrenes. Specific examples of the above sulfonyl chloride derivatives and carbonyl chloride derivatives include p-acetaminobenzenesulfonyl chloride, benzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, naphthylbenzenesulfonyl chloride, p-acetaminobenzenecarbonyl chloride, benzenecarbonyl. Examples include chloride, p-chlorobenzenecarbonyl chloride, naphthylbenzenecarbonyl chloride and the like.

  In Component A-1, a monomer unit derived from hydroxystyrene or a part of a benzene ring of a monomer unit obtained by modifying the monomer unit may be hydrogenated.

  Among these, as component A-1, poly (p-hydroxystyrene), p-hydroxystyrene / styrene copolymer, p-hydroxystyrene / methyl methacrylate copolymer, p-hydroxystyrene / n-butyl acrylate A copolymer, a p-hydroxystyrene / t-butyl methacrylate copolymer, and the like are particularly preferable, and poly (p-hydroxystyrene) is most preferable.

  In this invention, component A-1 can be used individually or in mixture of 2 or more types. The production method of component A-1 includes, for example, (i) monomers in which the hydroxyl group of hydroxystyrene is protected, such as butoxycarbonyloxystyrene, butoxystyrene, acetoxystyrene, tetrahydropyranyloxystyrene, and other unsaturated monomers. In addition, after the addition polymerization, an acid catalyst or an alkali catalyst is allowed to act to hydrolyze the protective group to obtain a hydroxyco-styrene (co) polymer. Although the method of addition polymerization can be mentioned with the unsaturated monomer, the method (i) is preferred. The above addition polymerization can be carried out by an appropriate method such as radical polymerization, anionic polymerization, cationic polymerization, thermal polymerization, etc., but the method based on anionic polymerization or cationic polymerization can reduce the degree of dispersion of the resulting resin. preferable. Examples of the acid catalyst include inorganic acids such as hydrochloric acid and sulfuric acid. Examples of the alkali catalyst include sodium hydroxide and potassium hydroxide.

(Component A-2) Novolak Resin In the present invention, (Component A-2) novolac resin can be used as Component A.
The novolak resin is obtained by condensing a phenolic compound and an aldehyde in the presence of an acid catalyst or an alkali catalyst.
The phenolic compound used for the production of the novolak resin is an aromatic compound having a phenolic hydroxyl group, for example, phenol, o-, m- or p-cresol, 2,3-, 2,5-, 3,4 -Or 3,5-xylenol, 2,3,5-trimethylphenol, 2-, 3- or 4-tert-butylphenol, 2-tert-butyl-4- or -5-methylphenol, 2-, 4- or 5-methylresorcinol, 2-, 3- or 4-methoxyphenol, 2,3-, 2,5- or 3,5-dimethoxyphenol, 2-methoxyresorcinol, 4-tert-butylcatechol, 2-, 3- Or 4-ethylphenol, 2,5- or 3,5-diethylphenol, 2,3,5-triethylphenol, 2-naphthol, 1,3-, 1 , 5- or 1,7-dihydroxynaphthalene, polyhydroxytriphenylmethane compounds obtained by condensation of xylenol and hydroxybenzaldehyde, and the like. Among these, phenol, o-cresol, m-cresol and p-cresol are preferable.
These phenolic compounds can be used alone or in combination of two or more.

  The aldehyde used for producing the novolak resin is a compound having at least one aldehyde group in the molecule or a compound that easily generates an aldehyde group in the reaction system. For example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, Aliphatic aldehydes such as isobutyraldehyde, pivalaldehyde, hexylaldehyde, acrolein and crotonaldehyde, cycloaliphatic aldehydes such as cyclohexanealdehyde, cyclopentanealdehyde, furfural and furylacrolein, benzaldehyde, o-, m- or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4- or 3,5-dimethylbenzaldehyde, o-, m- or p-hydroxybenzaldehyde 'S aldehyde, o-, aromatic aldehydes such as m- or p- anisaldehyde and vanillin, include araliphatic aldehydes such as phenylacetaldehyde and cinnamaldehyde. These aldehydes can also be used alone or in combination of two or more as desired. Among these, acetaldehyde or formaldehyde is preferable because it is easily available industrially, and formaldehyde is particularly preferable.

Examples of acid catalysts used for the condensation of phenolic compounds with aldehydes include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid and phosphoric acid, formic acid, acetic acid, oxalic acid, malonic acid, trichloroacetic acid and p-toluenesulfone Examples thereof include organic acids such as acids, divalent metal salts such as zinc acetate, zinc chloride and magnesium acetate. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia, tetramethylammonium hydroxide, triethylamine, morpholine, pyridine and the like.
Among these, it is preferable to use an acid catalyst, and it is preferable to use an organic acid such as acetic acid, oxalic acid, malonic acid, and p-toluenesulfonic acid.
The acid catalyst or alkali catalyst can be used alone or in combination of two or more. The condensation reaction can be performed according to a conventional method, for example, at a temperature in the range of 60 to 120 ° C. for about 2 to 30 hours.

Reaction solvents used for polycondensation include alcohols such as methanol, ethanol, isopropanol and t-butyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl hexyl ketone, methyl heptyl ketone and cyclohexyl ketone; propyl acetate, Esters such as butyl acetate, isobutyl acetate, methyl propionate, methyl lactate, propylene glycol acetate; ethers such as dibutyl ether, tetrahydrofuran, tetrahydropyran, dioxane, and aromatic hydrocarbons such as benzene, toluene, xylene; dichloromethane, Halogenated hydrocarbons such as chloroform, carbon tetrachloride and bromoform; hydrocarbons such as hexane, heptane, decane, and petroleum ether. These can be used alone or in combination of two or more. In addition, water may coexist in the reaction system, and in the case of a solvent that does not dissolve in water, a reaction solvent separated into two layers may be used. Water may be removed by distillation dehydration or the like.
Among these, ketones, esters, and aromatic hydrocarbons are preferably used as the reaction solvent.

  (Component A) It is preferable to contain a novolak resin having a weight average molecular weight of 900 or less as part of the alkali-soluble resin in order to improve the resolution. Such a low molecular weight novolak resin oligomer can also be produced by condensing a phenolic compound and an aldehyde as described above in the presence of an acid catalyst according to a conventional method, in which case a low molecular weight product is produced. The reaction conditions, for example, an acid catalyst may be used as small as about 0.001 to 0.01 mole times the raw material phenol compound, and the reaction time may be shortened to about 1 to 5 hours.

When the low molecular weight novolak resin oligomer is used as a part of the alkali-soluble resin, the remaining alkali-soluble resin having a higher weight average molecular weight, for example, a weight average molecular weight of 2,000 or more is suitable. In particular, it is more preferable to use a novolak resin mainly composed of a high molecular weight component in order to improve the resolution.
Specifically, when the novolak resin is analyzed by GPC, the pattern area having a molecular weight of 1,000 or less is 25% or less, further 20% with respect to the total pattern area excluding the unreacted raw material phenol compound. The following is preferable. Here, the pattern area means that measured using a 254 nm UV detector. Such a novolak resin mainly composed of a high molecular weight can be produced, for example, by subjecting the novolak resin obtained by the condensation reaction to an operation such as fractionation. In the case of fractionation, novolak resin is mixed with a good solvent such as alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, methyl isobutyl ketone, glycol ethers such as ethyl cellosolve, and ethyl cellosolve acetate. Such as glycol ether esters, ethers such as tetrahydrofuran, etc., and this solution is poured into water to precipitate the high molecular weight, or this solution is mixed with a poor solvent such as pentane, hexane, heptane Thus, a method of separating the lower layer mainly composed of high molecular weight can be employed. It is advantageous that the novolak resin mainly composed of high molecular weight has a weight average molecular weight of 5,000 or more, particularly 6,000 or more.

(Component A-3) Partially alkyl etherified polyvinyl phenol and Partially alkyl etherified hydrogenated polyvinyl phenol In the present invention, as Component A, (Component A-3) Partially alkyl ether Polyvinyl alcohol (hereinafter also referred to as component A-3-1) and partially alkyl etherified hydrogenated polyvinylphenol (hereinafter also referred to as component A-3-2). Also good.
The vinyl phenol constituting the polyvinyl phenol is not particularly limited in the positional relationship between the vinyl group and the hydroxyl group, but is preferably p-vinyl phenol. Component A-3-1 preferably has an alkyl etherification rate of 10 to 30 mol%, more preferably 15 to 22 mol%. Component A-3-2 preferably has an alkyl etherification rate of 5 to 30 mol%, more preferably 8 to 20 mol%. Component A-3-1 and Component A-3-2 may be used in combination, and the mixing ratio may be appropriately selected and is not particularly limited.

  Examples of the alkyl ether include linear or branched alkyl ethers, preferably having 1 to 4 carbon atoms, and more preferably methyl ether or ethyl ether.

Polyvinylphenol can be produced, for example, by hydrolyzing poly (t-butoxystyrene) obtained by polymerization of t-butoxystyrene. Of course, since products manufactured in this manner and having various average molecular weights and dispersities are commercially available, commercially available products can be used as they are.
Component A-3-1 includes polyvinylphenol and alkyl halides such as G.I. N. Vyas et al., Org. Syntheses Coll. Vol. IV, 836 (1963) and the like. In addition, Component A-3-2 includes, for example, hydrogenated polyvinyl phenol and an alkyl halide, the above G.I. N. It can be produced by the method of Vyas et al. Hydrogenated polyvinylphenol can be produced by hydrogenating polyvinylphenol according to a conventional method.

Other alkali-soluble resins and water-soluble resins may be used together with the components A-1 to A-3. As such an alkali-soluble resin and water-soluble resin, it is preferable to use a linear organic polymer, and any known one can be used. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxyl group alone or Copolymerized resin, acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half esterified or half amidated, epoxy resin unsaturated monocarboxylic acid and acid anhydride Examples include modified epoxy acrylate. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful. Further, vinylphenol resin, isopropenylphenol resin, a copolymer of isopropenylphenol and styrene (the proportion of isopropenylphenol in the copolymer is preferably 50 mol% or more), partially t-butoxycarbonyloxylation. Polyvinylphenol or hydrogenated polyvinylphenol.
When used in combination with Component A-1 to Component A-3, the total amount of Component A-1 to Component A-3 is preferably 50% by mass or more, and more preferably 65% by mass or more of Component A as a whole. Preferably, it is 80 mass% or more.

The weight average molecular weight of Component A-1 is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 5,000 to 30,000. .
The weight average molecular weight of Component A-2 is preferably 200 to 20,000, more preferably 300 to 10,000, and still more preferably 500 to 10,000.
The weight average molecular weight of Component A-3 is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 5,000 to 30,000. .
In the present invention, the weight average molecular weight is determined in terms of polystyrene having a known molecular weight by the GPC method.

The content of Component A in the curable resin composition of the present invention is preferably 10 to 99.9% by mass, and preferably 25 to 98% by mass with respect to the total solid content of the curable resin composition. More preferred is 35 to 95% by mass. When the content is within this range, the pattern formability during development is good, and a cured product having a higher refractive index can be obtained. The solid content of the curable resin composition represents an amount excluding volatile components such as a solvent.
Moreover, the total content of the polymer (resin) component including the component A in the curable resin composition of the present invention is 20 to 99.9% by mass with respect to the total solid content of the curable resin composition. It is preferably 50 to 98% by mass, more preferably 70 to 95% by mass. When it is in the above range, the pattern formability when developed is improved, and a cured product having a higher refractive index can be obtained.

(Component B) Compound having group represented by formula (L) The curable resin composition of the present invention contains (Component B) a compound having a group represented by the following formula (L). Component B functions as a cross-linking agent and cross-links components A together. In the following description, “(Component B) a compound having a group represented by Formula (L)” is also referred to as “(Component B) a crosslinking agent”.

（式（Ｌ）中、Ｘ¹及びＸ²はそれぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基又はアシル基を表し、Ｙは水素原子又は一価の置換基を表し、＊は連結位置を表し、芳香環を構成する炭素原子、複素環を構成する窒素原子又は炭素原子、あるいは、２級又は３級窒素原子と連結する。）

(In formula (L), X ¹ and X ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an acyl group, and Y represents a hydrogen atom or a monovalent substituent. * Represents a connecting position, and is connected to a carbon atom constituting an aromatic ring, a nitrogen atom or a carbon atom constituting a heterocyclic ring, or a secondary or tertiary nitrogen atom.)

In the formula (L), X ¹ and X ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an acyl group, and the alkyl group has 1 to 12 carbon atoms. It is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group or an ethyl group. The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, and more preferably a cycloalkyl group having 5 to 10 carbon atoms. The alkenyl group and alkynyl group preferably have 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably a phenyl group. The acyl group preferably has 1 to 6 carbon atoms, and more preferably 1 carbon (formyl group), 2 carbon atoms (acetyl group), or 3 (propionyl group).
Among these, X ¹ and X ² are preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.

In the formula (L), Y represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is an alkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably methyl). Group or ethyl group, particularly preferably methyl group), alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms), alkynyl group (preferably having 2 carbon atoms). To 12, more preferably 2 to 6, more preferably 2 to 4 carbon atoms, a cycloalkyl group (preferably 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms), an aryl group (preferably carbon atoms). 6-20, more preferably 6-10, haloalkyl groups (preferably 1-6 carbon atoms, more preferably 1-4 carbon atoms, still more preferably 1 or 2 carbon atoms), acyl groups (preferably carbon numbers) 1-6 and more Preferably 1 to 3 carbon atoms, more preferably 1 carbon atom (acetyl group)), an alkylsulfonyl group (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, more preferably 1 or 2), arylsulfonyl Examples include a group (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), and a heterocyclic group. These groups may further have a substituent. Examples of the substituent include a hydroxyl group, a cyano group, and a thiol group.
Among these, Y is preferably a hydrogen atom, an alkyl group, or an acyl group.

The group represented by the formula (L) is a hydroxymethyl group which may have a substituent, an alkoxymethyl group which may have a substituent, or an acyloxymethyl group which may have a substituent. (For example, an acetoxymethyl group) is preferable. As the alkoxymethyl group, a methoxymethyl group is particularly preferable. It is more preferably a hydroxymethyl group or an alkoxymethyl group, and a hydroxymethyl group (—CH ₂ OH), a methoxymethyl group (—CH ₂ —O—CH ₃ ), or an ethoxymethyl group (—CH ₂ —O—CH _2). CH ₃ ) is more preferable, hydroxymethyl group or methoxymethyl group is particularly preferable, and methoxymethyl group is most preferable.

The group represented by the formula (L) is linked to a carbon atom constituting an aromatic ring, a nitrogen atom or a carbon atom constituting a heterocyclic ring, or a secondary or tertiary nitrogen atom. It is preferable to link to a carbon atom constituting an aromatic ring, a nitrogen atom or carbon atom constituting a heterocyclic ring, or a nitrogen atom bonded to the heterocyclic ring.
That is, the group represented by the formula (L) is preferably bonded to an aromatic ring or a heterocyclic ring directly or via a linking group, and when the linking group is interposed, a nitrogen atom of the linking group In the case of direct bonding, it is preferably bonded to a carbon atom or a nitrogen atom.
Component B has at least one group represented by formula (L), preferably two or more, and more preferably 3 to 6.

  Here, the heterocycle may be a heteroaromatic ring or a non-aromatic heterocycle. In addition, the aromatic ring and the heterocyclic ring may be monocyclic or polycyclic and are not particularly limited. The polycyclic structure may be a condensed ring, a bridged ring, or a spiro ring. Further, two or more single rings may be connected by a single bond.

  Among these, component B is a urea compound in which the group represented by the formula (L) is bonded to the nitrogen atom constituting the ureylene group, and the group represented by the formula (L) is a nitrogen atom on the ring of glycol lauryl. A linked glycol lauryl compound, a triazine compound in which a group represented by formula (L) is linked to a nitrogen atom bonded to a triazine ring, or a phenol in which a group represented by formula (L) is substituted on an aromatic ring It is preferable that it is a system compound. Among these, component B is preferably a glycol lauryl compound or a triazine compound, and more preferably a triazine compound. Among triazine compounds, component B is particularly preferably a melamine compound. That is, component B is particularly preferably a melamine compound in which a group represented by the formula (L) is bonded to a nitrogen atom constituting an amino group bonded to a triazine ring.

  The triazine compound is preferably a compound represented by the following formula (I) or (II), and particularly preferably a melamine compound represented by formula (II).

（式（Ｉ）中、Ｒ¹は水素原子、アルキル基、アリール基、アルコキシ基、又はアリールオキシ基を表し、Ｌは式（Ｌ）で表される基を表す。）

(In the formula (I), R ¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and L represents a group represented by the formula (L).)

（式（ＩＩ）中、Ｒ²及びＲ³はそれぞれ独立に水素原子又は式（Ｌ）で表される基を表し、Ｌは式（Ｌ）で表される基を表す。）

(In Formula (II), R ² and R ³ each independently represent a hydrogen atom or a group represented by Formula (L), and L represents a group represented by Formula (L).)

In formula (I), the alkyl group and alkoxy group as R ¹ preferably have 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 or 2. The aryl group or aryloxy group as R ¹ preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, still more preferably 6 or 10, and 6 (phenyl group or phenoxy group) Is particularly preferred. The alkyl group, aryl group, heteroaromatic group, alkoxy group, and aryloxy group may have a substituent, and examples of the substituent include an alkyl group, a hydroxyl group, and an aryl group.
Among these, in formula (I), R ¹ is preferably an aryl group, and particularly preferably a phenyl group.

  In formula (I) and formula (II), L represents a group represented by formula (L), and the preferred range is as described above.

  Specific examples of component B which is a triazine compound include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, tetramethylol benzoguanamine, tetra Examples include methoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, and tetraethoxymethyl benzoguanamine.

Furthermore, as the component B, the following compounds are also preferably exemplified.
(B-12) 2,6-bis (hydroxymethyl) -4-methylphenol,
(B-13) 4-t-butyl-2,6-bis (hydroxymethyl) phenol,
(B-14) 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or (b-15) dimethyl ether thereof ,
(B-16) dimethylol trimethylene urea or (b-17) its dimethyl ether form,
(B-18) 3,5-bis (hydroxymethyl) perhydro-1,3,5-oxadiazin-4-one (commonly known as dimethyloluron) or (b-19) its dimethyl ether form,
(B-20) Tetramethylol glyoxal diurein or (b-21) tetramethyl ether thereof.

  Furthermore, a commercially available product may be used as Component B, for example, Nicarak MW-30HM, Nicarak MW-390, Nicarac MW-100LM, Nicarax MX-750LM, Nicarac MX-270, Nicarax MX-280, Nicalac MX-290 (manufactured by Sanwa Chemical Co., Ltd.) may be mentioned.

Component B is preferably a low molecular compound, and the molecular weight (in the case of having a molecular weight distribution, the weight average molecular weight) is preferably 1,000 or less. It is more preferable that it is 100-800, and it is still more preferable that it is 200-500.
When the weight average molecular weight is within the above range, the curability is excellent.

Moreover, the component B may be used individually by 1 type and can also use 2 or more types together.
The content of Component B in the resin composition of the present invention is preferably 0.1 to 20% by mass, and 0.5 to 15% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferable, and it is still more preferable that it is 0.5-10 mass%. Within the above range, the curability is excellent and the resolution is excellent.

(Component C) Acid generator The curable resin composition of the present invention contains (Component C) an acid generator. In the present invention, the (Component C) acid generator is preferably a photoacid generator, and more preferably a compound that generates an acid in response to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm. The chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less. Most preferred is a photoacid generator that generates an acid.

  Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation and sensitivity. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP2011-221494A. It can be illustrated.

  Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following formula (C1).

（式（Ｃ１）中、Ｒ²¹は、アルキル基又はアリール基を表し、波線部分は他の基との結合箇所を表す。）

(In the formula (C1), R ²¹ represents an alkyl group or an aryl group, and a wavy line represents a bonding site with another group.)

Any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
As the alkyl group for R ^21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ²¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged type fat It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
The aryl group for R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.

  The compound containing an oxime sulfonate structure represented by the above formula (C1) is also preferably an oxime sulfonate compound represented by the following formula (C2).

（式（Ｃ２）中、Ｒ⁴²は、アルキル基又はアリール基を表し、Ｘは、アルキル基、アルコキシ基又はハロゲン原子を表し、ｍ４は、０〜３の整数を表し、ｍ４が２又は３であるとき、複数のＸは同一でも異なっていてもよい。）

(In the formula (C2), ^R42 represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and m4 is 2 or 3. In some cases, multiple Xs may be the same or different.)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1. In the above formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl. A compound which is a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

  The compound containing an oxime sulfonate structure represented by the above formula (C1) is also preferably an oxime sulfonate compound represented by the following formula (C3).

（式（Ｃ３）中、Ｒ⁴³は式（Ｃ２）におけるＲ⁴²と同義であり、Ｘ¹は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、シアノ基又はニトロ基を表し、ｎ４は０〜５の整数を表す。）

(In formula (C3), R ⁴³ has the same meaning as R ⁴² in formula (C2), and X ¹ is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano A group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the above formula (C3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As n4, the integer of 0-2 is preferable and 0 or 1 is especially preferable.

  Specific examples of the compound represented by the formula (C3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino). Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α -[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4-methoxy Phenyl] acetonitrile, α-[(4-Torr Emissions sulfonyl) -4-methoxyphenyl] can be mentioned acetonitrile.

  Specific examples of preferred oxime sulfonate compounds include the following compounds (i) to (viii) and the like, and one kind can be used alone, or two or more kinds can be used in combination. Compounds (i) to (viii) can be obtained as commercial products. It can also be used in combination with other types of (C) photoacid generators.

  The compound containing an oxime sulfonate structure represented by the above formula (C1) is also preferably a compound represented by the following formula (OS-1).

In the above formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or hetero Represents an aryl group. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ^{105 to} R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or Represents an aryl group. Two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring.
R ^{121 to} R ¹²⁴ are each independently preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R ^{121 to} R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Can be mentioned. Among these, an embodiment in which R ^{121 to} R ¹²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

  The compound represented by the formula (OS-1) is more preferably a compound represented by the following formula (OS-2).

In said formula (OS-2), R ^<101 >, R < ¹⁰² >, R < ¹²¹ > -R < ¹²⁴ > is synonymous with the thing in a formula (OS-1), respectively, A preferable example is also the same.
Among these, an embodiment in which R ¹⁰¹ in the above formula (OS-1) and the above formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the above formula (OS-2), and R ¹⁰¹ The embodiment in which is a cyano group, a phenyl group or a naphthyl group is most preferred.

  In the oxime sulfonate compound of the present invention, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

  Specific examples of the compound represented by the formula (OS-1) that can be suitably used in the present invention include compounds described in paragraphs 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b- 34), but the present invention is not limited to this.

  In the present invention, the compound containing the oxime sulfonate structure represented by the formula (B1) is represented by the following formula (OS-3), the following formula (OS-4), or the following formula (OS-5). It is preferably an oxime sulfonate compound.

（式（ＯＳ−３）〜式（ＯＳ−５）中、Ｒ²²、Ｒ²⁵及びＲ²⁸はそれぞれ独立に、アルキル基、アリール基又はヘテロアリール基を表し、Ｒ²³、Ｒ²⁶及びＲ²⁹はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、Ｒ²⁴、Ｒ²⁷及びＲ³⁰はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、Ｘ¹〜Ｘ³はそれぞれ独立に、酸素原子又は硫黄原子を表し、ｎ¹〜ｎ³はそれぞれ独立に、１又は２を表し、ｍ¹〜ｍ³はそれぞれ独立に、０〜６の整数を表す。）

(In Formula (OS-3) to Formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ are Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxy group. Represents a sulfonyl group, X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ^{1 to} m ³ each independently represents 0 Represents an integer of ~ 6)

In the above formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
Moreover, in said formula (OS-3)-(OS-5), as an aryl group in R <^22> , R <^25> and R < ²⁸ >, a C6-C30 aryl group which may have a substituent is preferable. .
Moreover, in said formula (OS-3)-(OS-5), as heteroaryl group in R <^22> , R <^25> and R < ²⁸ >, the C4-C30 heteroaryl group which may have a substituent Is preferred.
In the above formulas (OS-3) to (OS-5), at least one of the heteroaryl groups in R ²² , R ²⁵ and R ²⁸ may be a heteroaromatic ring, such as a heteroaromatic ring and a benzene ring. And may be condensed.

In the above formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. .
In the above formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in the compound may be an alkyl group, an aryl group or a halogen atom. More preferably, one is an alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group and the rest is a hydrogen atom.

The alkyl group for R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.

In the above formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represents O or S, and is preferably O.
In the above formulas (OS-3) to (OS-5), the ring containing X ^{1 to} X ³ as a ring member is a 5-membered ring or a 6-membered ring.
In the above formulas (OS-3) to (OS-5), n ^{1 to} n ³ each independently represents 1 or 2, and when X ^{1 to} X ³ are O, n ^{1 to} n ³ are each independently In addition, it is preferably 1, and when X ^{1 to} X ³ are S, n ^{1 to} n ³ are each preferably 2 independently.

In the above formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Represent. Among these, R ²⁴ , R ²⁷ and R ³⁰ are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
In the above formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. It is preferable.

Further, in the above formulas (OS-3) ~ (OS -5), m 1 ~m 3 each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, 0 or 1 More preferably, it is particularly preferably 0.
In addition, for each substituent of the above formulas (OS-3) to (OS-5), the substitution of (OS-3) to (OS-5) described in paragraphs 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.

  The compound containing an oxime sulfonate structure represented by the above formula (C1) is particularly preferably an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11).

（式（ＯＳ−６）〜（ＯＳ−１１）中、Ｒ³⁰¹〜Ｒ³⁰⁶はアルキル基、アリール基又はヘテロアリール基を表し、Ｒ³⁰⁷は、水素原子又は臭素原子を表し、Ｒ³⁰⁸〜Ｒ³¹⁰、Ｒ³¹³、Ｒ³¹⁶及びＲ³¹⁸はそれぞれ独立に、水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、Ｒ³¹¹及びＲ³¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Ｒ³¹²、Ｒ³¹⁵、Ｒ³¹⁷及びＲ³¹⁹はそれぞれ独立には、水素原子又はメチル基を表す。）

(In the formulas (OS-6) to (OS-11), R ^{301 to} R ³⁰⁶ represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ^{308 to} R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group. , R ³¹¹ and R ³¹⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group. )

  Preferred ranges in the above formulas (OS-6) to (OS-11) are the same as the preferred ranges of (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of JP2011-221494A. It is.

  Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to the above formula (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP2011-221494A. The invention is not limited to these.

In the curable resin composition of the present invention, the (component C) acid generator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (resin) component containing the component A in the curable resin composition. It is preferable to use it, and it is more preferable to use 0.5-10 mass parts.
Component C is preferably 0.1 to 10% by mass, and preferably 0.5 to 10% by mass, based on the solid content of the curable resin composition (excluding metal oxide particles). More preferred.
Moreover, the component C may be used individually by 1 type and can also use 2 or more types together.

(Component D) Metal Oxide Particles The curable resin composition of the present invention contains metal oxide particles for the purpose of adjusting the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a negative curable resin composition having a high refractive index and excellent transparency can be obtained.
Component D preferably has a refractive index higher than that of the resin composition made of the material excluding the particles. Specifically, the refractive index in light having a wavelength of 400 to 750 nm is 1.50. The above particles are more preferable, particles having a refractive index of 1.70 or more are more preferable, particles of 1.90 or more are particularly preferable, and most preferably 2.00 or more.
Here, that the refractive index in light having a wavelength of 400 to 750 nm is 1.50 or more means that the average refractive index in light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more. The average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.

Note that the metal of the metal oxide particles in the present invention includes semimetals such as B, Si, Ge, As, Sb, and Te.
The light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide, and zirconium oxide are more preferable, titanium oxide and zirconium oxide (refractive index 2.4) are particularly preferable, and titanium dioxide is most preferable. As titanium dioxide, a rutile type (refractive index of 2.7) having a particularly high refractive index is preferable. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.

The average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, more preferably 1 to 100 nm, still more preferably 1 to 80 nm, and particularly preferably 1 to 50 nm. Within the above range, a cured product having excellent particle dispersibility, a high refractive index, and excellent transparency can be obtained.
The average primary particle diameter of the metal oxide particles can be obtained from a photograph obtained by observing the dispersed metal oxide particles with a transmission electron microscope. Specifically, the projected area of the metal oxide particles is obtained, and the corresponding equivalent circle diameter is defined as the average primary particle diameter of the metal oxide particles. In addition, let the average primary particle diameter in this invention be the arithmetic mean value of the equivalent circle diameter calculated | required about 300 metal oxide particles.
In the present invention, the number average particle diameter can also be used as an index of the average primary particle diameter. The number average particle diameter of the metal oxide particles in the present invention is obtained by diluting a mixed solution or dispersion containing the metal oxide particles 80 times with propylene glycol monomethyl ether acetate, and using the obtained diluted solution, a dynamic light scattering method. It means the value obtained by measuring using. This measurement is preferably the number average particle diameter obtained by using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.

The refractive index of the metal oxide particles is not particularly limited, but is preferably 1.70 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index. More preferably, it is 2.00-2.70.
The specific surface area of the metal oxide particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.
There is no restriction | limiting in particular in the shape of a metal oxide particle. For example, it can be a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.

The metal oxide particles may have been surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, stearic acid is preferred.
The surface treatment may be carried out by using a single surface treatment agent or a combination of two or more surface treatment agents.
Moreover, it is also preferable that the surface of the metal oxide particles is covered with an oxide such as aluminum, silicon, or zirconia. Thereby, a weather resistance improves more.

  As a metal oxide particle in this invention, what is marketed can be used preferably. Specifically, for example, as titanium oxide particles, TTO series (TTO-51 (A), TTO-51 (C), etc.) manufactured by Ishihara Sangyo Co., Ltd., TTO-S, V series (TTO-S-1, TTO) -S-2, TTO-V-3, etc.), MT series (MT-01, MT-05, etc.) manufactured by Teika Co., Ltd., Optolake TR-502, Optolake TR-504 as tin oxide-titanium oxide composite particles. , Op-tlake TR-503, Op-tlake TR-513, Op-tlake TR-520, Op-tlake TR-521, Op-tlake TR-527, Zirconium oxide particles (Co) ), Tin oxide-zirconium oxide composite particles (manufactured by JGC Catalysts & Chemicals Co., Ltd.), and niobium oxide particles such as viral Nb-X10 (many Chemical Co., Ltd.), and the like.

Moreover, the component D may be used individually by 1 type, and can also use 2 or more types together.
The content of the metal oxide particles in the resin composition of the present invention may be appropriately determined in consideration of the refractive index required for the optical member obtained from the resin composition, light transmittance, etc. The total solid content of the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. Moreover, it is preferable that it is 80 mass% or less, and it is more preferable that it is 70 mass% or less.

In the present invention, the particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill. The dispersant will be described later.
Examples of the solvent used for the preparation of the dispersion include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, in addition to the (Component E) solvent described below. -Alcohols such as pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol, etc. Can be mentioned.
These solvent can be used individually by 1 type or in mixture of 2 or more types.

(Component E) Solvent The curable resin composition of the present invention contains (Component E) a solvent. The curable resin composition of the present invention is prepared as a solution obtained by dissolving or dispersing Component A to Component D and further optional components described below in (Component E) solvent.
As the solvent used in the curable resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like. Specific examples of the solvent used in the curable resin composition of the present invention also include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents. Solvents such as benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate can also be added.
These solvents can be used alone or in combination of two or more. It is preferable that the solvent which can be used for this invention is single 1 type, or uses 2 types together.

Component E is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.
Among these, as the solvent, propylene glycol monoalkyl ether acetates are preferable, and propylene glycol monomethyl ether acetate is particularly preferable.

  The content of the (component E) solvent in the curable resin composition of the present invention is preferably 50 to 95 parts by mass per 100 parts by mass of the resin component including the component A in the curable resin composition, and is preferably 60 to More preferably, it is 90 mass parts.

(Component F) Antioxidant The curable resin composition of the present invention may contain (Component F) an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Among these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used individually by 1 type and may mix 2 or more types.
Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 , ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS 90, ADK STAB ZS 90 -91 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Company, Ltd.), Tinuvin 405 (manufactured by BASF), and the like. Among them, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035, Irganox 1098, and Tinuvin 405 can be preferably used.

The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the curable resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
Further, as additives other than antioxidants, various UV absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators and the like are used in the curability of the present invention. You may add to a resin composition.

(Component G) Dispersant The curable resin composition of the present invention preferably contains (Component G) a dispersant. By containing a dispersing agent, the dispersibility in the composition of the component D can be improved more.
As the (Component G) dispersant, for example, a known pigment dispersant can be appropriately selected and used. (Component S) A dispersion represented by the formula (S) described later and having at least one acid group Agents are particularly preferred.
(Component G) As the dispersant, a polymer dispersant can be preferably used. The polymer dispersant is a dispersant having a molecular weight (weight average molecular weight) of 1,000 or more.

  (Component G) Many types of compounds can be used as the dispersant. Specifically, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl Nonionic surfactants such as ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), DE Polymer dispersing agents such as Sparse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000 , 26000, 28000, etc. (AstraZeneca Co., Ltd.); 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 Isonet S-20 (manufactured by Sanyo Chemical Industries), DISPERBYK 101, 103, 106, 108, 109, 111, 112, 116, 130, 140 142 , 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

  The resin composition of the present invention preferably contains (Component S) a dispersant represented by the following formula (S) and having at least one acid group as the (Component G) dispersant. Since the resin composition of the present invention contains the component S, there are few coarse particles when the metal oxide particles are dispersed, and there is no aggregation when the dispersion and the polymer component are mixed. A cured product having excellent transparency can be formed.

（式（Ｓ）中、Ｒ³は（ｍ＋ｎ）価の連結基を表し、Ｒ⁴及びＲ⁵はそれぞれ独立に、単結合又は２価の連結基を表し、Ａ²は有機色素構造、複素環構造、酸基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基及び水酸基よりなる群から選択された部分構造を少なくとも１種含む１価の有機基を表し、ｎ個のＡ²、Ｒ⁴は、同一であっても、異なっていてもよく、ｍは０〜８を表し、ｎは２〜９を表し、ｍ＋ｎは３〜１０であり、Ｐ²は高分子骨格を表し、ｍ個のＰ²、Ｒ⁵は、同一であっても、異なっていてもよい。）

(In formula (S), R ³ represents an (m + n) -valent linking group, R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group, and A ² represents an organic dye structure or a heterocyclic ring. Structure, acid group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, alkoxysilyl group, epoxy group, isocyanate group and hydroxyl group Represents a monovalent organic group containing at least one partial structure selected from the group, n A ² and R ⁴ may be the same or different, m represents 0 to 8, n represents 2 to 9, m + n is 3 to 10, P ² represents a polymer skeleton, and m P ² and R ⁵ may be the same or different.)

Component S is a dispersant having at least one acid group. By having an acid group, it is presumed to act as an adsorbing group for the metal oxide particles, and the dispersibility of the metal oxide particles is excellent.
Examples of the acid group include a carboxylic acid group (carboxy group), a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like. From the viewpoint of adsorbing power and dispersibility on metal oxide particles, a carboxylic acid group, a sulfone group, and the like. It is preferably at least one selected from the group consisting of an acid group and a phosphate group, and a carboxylic acid group is particularly preferable. The acid groups in the dispersant may have one of these alone or in combination of two or more.
The acid group in component S may have any structure of formula (S). Specifically, for example, acid groups, both of the above formulas may be included in the A ² in (S), also it may be included in the polymer backbone represented by P ^2, A ² and P ² it may be included in, from the viewpoint of effect, it is preferably included in a ^2.

In the above formula (S), A ² represents an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a group having 4 or more carbon atoms. A monovalent organic group containing at least one partial structure selected from the group consisting of a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. Further, n A ² present in the formula (S) may be the same or different.

That is, the above A ² is a structure having an adsorption ability for metal oxide particles such as an organic dye structure or a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, or a coordinating oxygen. A monovalent group containing at least one functional group capable of adsorbing to metal oxide particles, such as a group having an atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. Represents an organic group.
Hereinafter, the partial structure having the ability to adsorb to the metal oxide particles (the above structure and functional group) will be collectively referred to as “adsorption site” as appropriate.

The adsorption sites are in one A ^2, it may be contained at least one, may contain two or more kinds.
Further, in the present invention, the “monovalent organic group containing at least one kind of adsorption site” means the aforementioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 To 100 oxygen atoms, 1 to 400 hydrogen atoms, and a linking group consisting of 0 to 40 sulfur atoms are monovalent organic groups. In the case where adsorption sites themselves may constitute a monovalent organic group, adsorption sites itself may be an organic monovalent group represented by A ^2.
First, the adsorption site constituting A ² will be described below.

  Examples of the “organic dye structure” include, for example, phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavan. Examples of preferable dye structures of throne, perinone, perylene, and thioindigo are phthalocyanine, azo lake, anthraquinone, dioxazine, and diketopyrrolopyrrole, and phthalocyanine and anthraquinone. A diketopyrrolopyrrole dye structure is particularly preferred.

  The “heterocyclic structure” may be a group having at least one heterocyclic ring. Examples of the heterocyclic ring in the “heterocyclic structure” include, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, Pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone And a heterocyclic ring selected from the group consisting of anthraquinone is a preferred example, pyrroline, pyrrolidine, pyrazole Pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carbazole, acridine, acridone And a heterocyclic ring selected from the group consisting of anthraquinone is more preferable.

  The “organic dye structure” or “heterocyclic structure” may further have a substituent. Examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group. An acyloxy group having 1 to 6 carbon atoms, such as an aryl group having 6 to 16 carbon atoms such as a group, phenyl group or naphthyl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamide group, an N-sulfonylamide group, or an acetoxy group. Alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine atom and bromine atom, alkoxy having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group And carbonic acid ester groups such as a carbonyl group, a cyano group, and a t-butyl carbonate group. Here, these substituents may be bonded to the organic dye structure or the heterocyclic structure through the following structural unit or a linking group constituted by combining the structural units.

  Examples of the “acid group” include carboxylic acid group, sulfonic acid group, monosulfate group, phosphoric acid group, monophosphate group, and boric acid group. Preferred examples include carboxylic acid group, sulfonic acid group, A monosulfate group, a phosphate group, and a monophosphate group are more preferable, a carboxylic acid group, a sulfonic acid group, and a phosphate group are more preferable, and a carboxylic acid group is particularly preferable.

Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ and R ¹⁰ Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), the following formula ( Preferred examples include the amidinyl group represented by a2).

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl having 1 to 10 carbon atoms. Group, a phenyl group, a benzyl group), a guanidyl group represented by the above formula (a1) (in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, Phenyl group and benzyl group), an amidinyl group represented by the above formula (a2) (in the formula (a2), R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, And represents a benzyl group).
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms, A phenyl group and a benzyl group), a guanidyl group represented by the above formula (a1) (in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group; Amidinyl group represented by the above formula (a2) (in the formula (a2), R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 5 carbon atoms, phenyl group, benzyl group, Represents a group) and the like are preferably used.

Examples of the “urea group” include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon number of 6 The above aryl group or an aralkyl group having 7 or more carbon atoms may be mentioned as a preferred example, and —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom, carbon number 1). To an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms is more preferable, and —NHCONHR ¹⁷ (where R ¹⁷ is a hydrogen atom, 1 to 10 carbon atoms). Or an alkyl group having 6 or more carbon atoms or an aralkyl group having 7 or more carbon atoms) is particularly preferable.

Examples of the “urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (here, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ^23). Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.), Etc., and —NHCOOR ¹⁸ , —OCONHR ²¹ (wherein R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms). , -NHCOOR ^18, -OCONHR ²¹ (wherein each R ¹⁸ and R ²¹ are independently an alkyl group having from 1 to 10 carbon atoms, having 6 or more aryl group having a carbon or a carbon number of 7 or more It represents an aralkyl group.) And the like are particularly preferred.

  Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a group having a crown ether structure.

  Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferably, an alkyl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and 6 to 15 carbon atoms. Particularly preferred are aryl groups (for example, phenyl group, naphthyl group and the like), aralkyl groups having 7 to 15 carbon atoms (for example, benzyl group and the like), and the like.

  Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.

  The linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. A linking group comprising up to 0 hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this linking group may be unsubstituted or may further have a substituent. Specific examples of this linking group include the following structural units or groups formed by combining the structural units.

  When the linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Group, hydroxyl group, amino group, carboxy group, sulfonamido group, N-sulfonylamido group, acetoxy group and other C1-C6 acyloxy groups, methoxy group, ethoxy group and other C1-C6 alkoxy groups , Halogen atoms such as chlorine atom and bromine atom, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate ester groups such as cyano group and t-butyl carbonate group, etc. Is mentioned.

In the above, as A ² , a portion selected from the group consisting of an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms A monovalent organic group containing at least one structure is preferable, and a monovalent organic group containing at least one acid group is particularly preferable.

A ² is more preferably a monovalent organic group represented by the following formula (4).

In the above formula (4), B ¹ represents the adsorption site (that is, an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, A partial structure selected from the group consisting of a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group), and R ²⁴ represents a single bond or a (a + 1) -valent linking group. . a represents an integer of 1 to 10, and a ¹ B ¹ existing in the formula (4) may be the same or different.

Examples of the adsorption site represented by B ¹ include those similar to the adsorption site constituting A ² of the above formula (S), and preferred examples are also the same.
Among these, a partial structure selected from the group consisting of an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is preferable, and an acid group is particularly preferable preferable.

R ²⁴ represents a single bond or a (a + 1) -valent linking group, a represents an integer of 1 to 10, preferably an integer of 1 to 7, more preferably an integer of 1 to 5, An integer of 1 to 3 is particularly preferable.
(A + 1) valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, In addition, a group composed of 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.

  Specific examples of the (a + 1) -valent linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

R ²⁴ may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, And a (a + 1) -valent linking group consisting of 0 to 10 sulfur atoms, preferably a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 More preferred are (a + 1) -valent linking groups consisting of from 1 to 15 oxygen atoms, from 1 to 50 hydrogen atoms, and from 0 to 7 sulfur atoms, a single bond or from 1 to 10 Consisting of up to 5 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms ( The a + 1) -valent linking group is particularly preferable.

  Among the above, when the (a + 1) -valent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Carbons having 1 to 6 carbon atoms, such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc. having 6 to 16 carbon atoms, methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine atoms and bromine atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl And carbonate ester groups such as carbonate groups.

In the above formula (S), R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. n R ^{4 s} may be the same or different. Further, m R ^{5 s} may be the same or different.
Examples of the divalent linking group in R ⁴ and R ⁵ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. And a group consisting of 0 to 20 sulfur atoms, may be unsubstituted or may further have a substituent.

  Specific examples of the divalent linking group include the following structural units or groups formed by combining the structural units.

R ⁴ and R ⁵ are each independently a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 Divalent linking groups consisting of up to 10 hydrogen atoms and 0 to 10 sulfur atoms are preferred, single bonds or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms More preferred are divalent linking groups consisting of atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond or 1 From 0 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms. Particularly preferred are divalent linking groups.

  Among the above, when the divalent linking group has a substituent, examples of the substituent include carbon numbers such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxy group, sulfonamido group, N-sulfonylamido group, acetoxy group and the like having 6 to 16 carbon atoms, methoxy group, ethoxy group and the like To 6 alkoxy groups, halogen atoms such as chlorine atom and bromine atom, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate group And the like, and the like.

In the above formula (S), R ³ represents a (m + n) -valent linking group. m + n satisfies 3-10.
The (m + n) -valent linking group represented by R ³ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups comprising up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.

  Specific examples of the (m + n) -valent linking group include the following structural units or a group formed by combining the structural units (which may form a ring structure).

  (M + n) -valent linking group includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And preferred are groups consisting of 0 to 10 sulfur atoms, preferably 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to More preferred are groups consisting of up to 100 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 atoms. Particularly preferred are groups consisting of up to oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms.

  Among the above, when the (m + n) -valent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Carbons having 1 to 6 carbon atoms, such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc. having 6 to 16 carbon atoms, methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine atoms and bromine atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl Examples thereof include carbonate groups such as carbonate groups.

Specific examples [specific examples (1) to (17)] of the (m + n) -valent linking group represented by R ³ are shown below. However, the present invention is not limited to these.

  Among the above specific examples, the most preferable (m + n) -valent linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.

In the above formula (S), m represents 0-8. As m, 0.5-5 are preferable, 0.5-4 are more preferable, and 0.5-3 are especially preferable.
Moreover, in said formula (S), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

P ² in the formula (S) represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. M P ² present in the formula (S) may be the same or different.
Among polymers, in order to constitute a polymer skeleton, a polymer or copolymer of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and these Modified products or copolymers of [for example, polyether / polyurethane copolymers, copolymers of polyether / vinyl monomers, etc. (any of random copolymers, block copolymers, and graft copolymers). May be included). And at least one selected from the group consisting of vinyl monomers, polymers or copolymers, ester polymers, ether polymers, urethane polymers, and their modified products or copolymers. At least one selected is more preferable, a polymer or copolymer of a vinyl monomer is further preferable, and an acrylic resin (a polymer or copolymer of a (meth) acryl monomer) is particularly preferable.
Furthermore, the polymer is preferably soluble in an organic solvent. Component S is preferably soluble in an organic solvent. When the affinity with the organic solvent is low, for example, the affinity with the dispersion medium is weakened, and it may be impossible to secure an adsorption layer formed by the component S on the surface of the metal oxide particles, which is sufficient for stabilizing the dispersion.

In the present invention, the polymer skeleton in P ² preferably has at least one acid group. Moreover, it is preferable that the polymer skeleton in P ² does not have an acid group.
Examples of the polymer having an acid group constituting the polymer skeleton include, for example, a polyamidoamine and salt thereof, a polycarboxylic acid and salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, and a modified polymer having an acid group. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like. Among these, a (meth) acrylic acid copolymer is preferable.

The means for introducing an acid group into the polymer skeleton is not particularly limited. For example, a means for introducing an acid group with a vinyl monomer, a means for introducing an acid group using a crosslinkable side chain, and the like are adopted. However, as will be described later, the mode in which the acid group is introduced by the constitution of the polymer skeleton including a structural unit derived from a vinyl monomer having an acid group makes it easy to control the amount of acid group introduced. From the viewpoint of synthesis cost.
Here, the “acid group” may be the same as those mentioned as the “acid group” in the description of A ² above, and is preferably a carboxy group.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acid group, and the like are preferable.
Hereinafter, preferable examples of these vinyl monomers will be described.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) (meth) acrylate Ethyl, 3-methoxy-2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) acrylic acid Vinyl, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, (meth) acrylic Benzyl acid, (meth) acrylic acid diethylene glycol monomethyl ether (Meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol Monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acrylic acid Trifluoroethyl, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) a Acrylic acid tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid γ- butyrolactone-2-yl.

Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-butoxycarbonyl group (t-Boc) and the like), methyl vinylbenzoate, and α-methylstyrene.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

  (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. are also used. it can.

  In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or urea group can be appropriately synthesized by utilizing an addition reaction between an isocyanate group and a hydroxyl group or an amino group, for example. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group, or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer, primary or It can be appropriately synthesized by an addition reaction between a secondary amino group-containing monomer and monoisocyanate.

Next, a vinyl monomer having an acid group used for introducing an acid group into the polymer skeleton P ² will be described.
Examples of the vinyl monomer having an acid group include a vinyl monomer having a carboxy group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxy group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxypolycaprolactone mono (Meth) acrylate and the like can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

Furthermore, as the vinyl monomer having an acid group, a vinyl monomer containing a phenolic hydroxy group or a vinyl monomer containing a sulfonamide group can be used.
When the polymer skeleton P ² includes a monomer unit derived from a vinyl monomer containing an acid group, the content of the monomer unit derived from a vinyl monomer having an acid group in the polymer skeleton is expressed in terms of mass in the entire polymer skeleton. On the other hand, it is preferable that it is 3 mass%-40 mass%, and it is more preferable that it is the range of 5 mass%-20 mass%.

Of the dispersants represented by the above formula (S) and having at least one acid group, those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m and n shown below are most preferable.
R ³ : Specific example (1), (2), (10), (11), (16) or (17) above
R ⁴ : a single bond, or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10” A divalent linking group comprising an oxygen atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, For example, an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamide group, N- C1-C6 acyloxy groups such as sulfonylamide groups and acetoxy groups, C1-C6 alkoxy groups such as methoxy groups and ethoxy groups, halogen atoms such as chlorine atoms and bromine atoms, methoxycarbonyl , An ethoxycarbonyl group, an alkoxycarbonyl group having from 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, and a carbonate group such as t- butyl carbonate group.)

R ⁵ : single bond, ethylene group, propylene group, the following group (a) or the following group (b)
In the following groups, R ¹² represents a hydrogen atom or a methyl group, and L represents 1 or 2.

P ² : a copolymer of a vinyl monomer having a carboxy group and another vinyl monomer; a polymer or copolymer of a vinyl monomer having no acid group; an ester-based polymer, an ether-based polymer, and a urethane-based polymer; and , A polymer m selected from the group consisting of these modified products and optionally containing at least one acid group: 0.5 to 3
n: 3-6

  The content of acid groups in the component S is appropriately determined depending on the acid value of the component S. The acid value of component S is preferably 20 to 300 mgKOH / g, more preferably 50 to 250 mgKOH / g, and particularly preferably 50 to 210 mgKOH / g. When the acid value is 20 mgKOH / g or more, sufficient alkali developability of the curable resin composition is obtained, and when the acid value is 300 mgKOH / g or less, the dispersibility and dispersion stability of the metal oxide particles are improved. Excellent.

  The molecular weight of component S is preferably 2,000 to 200,000, more preferably 2,000 to 15,000, and particularly preferably 2,500 to 10,000 in terms of weight average molecular weight. When the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exhibited, and the adsorptivity to the solid surface is exhibited. The component S contained in the resin composition of the present invention may be only one type or two or more types. In the case of two or more types, the total is preferably in the above range.

  Although the exemplary compound of the component S is mentioned below, this invention is not limited to this, As long as it is included by Formula (S), it can take arbitrary structures. Moreover, in the following exemplary compounds, P1 and P2 can take arbitrary values in terms of mass.

In the exemplary compound of component S, the content ratio (P1: P2) of the monomer unit having a carboxylic acid ester and the monomer unit having a carboxy group in the polymer skeleton is in the range of 100: 0 to 80:20 in terms of mass. It is preferable that
Component S can be synthesized, for example, with reference to the method described in JP-A-2006-278118.

A dispersing agent may be used individually by 1 type, or may be used together 2 or more types.
The content of the dispersant in the curable resin composition of the present invention is preferably in the range of 5 to 70% by mass and more preferably in the range of 10 to 50% by mass with respect to the total solid content of the curable resin composition.

<Other ingredients>
In addition to the above components, the curable resin composition of the present invention includes (Component H) sensitizer, (Component I) adhesion improver, (Component J) basic compound, and (Component K) as necessary. A surfactant can be preferably added. Further, the curable resin composition of the present invention includes (Component L) an acid proliferating agent, (Component M) a development accelerator, (Component N) a plasticizer, an ultraviolet absorber, a metal deactivator, and a thermal radical generator. , Known additives such as thermal acid generators, thickeners, and organic or inorganic suspending agents can be added.

(Component H) Sensitizer The curable resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (Component C) an acid generator. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squariums (eg, squalium), styryls, base styryls ( For example, 2- {2- [4- (dimethylamino) phenyl] ethenyl} benzoxazole), coumarins (eg, 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.

The addition amount of the sensitizer in the curable resin composition of the present invention is preferably 0 to 1,000 parts by mass, and 10 to 500 parts by mass with respect to 100 parts by mass of the acid generator of the curable resin composition. It is more preferable that it is a part, and it is still more preferable that it is 50-200 mass parts.
Moreover, a sensitizer may be used individually by 1 type and can also use 2 or more types together.

(Component I) Adhesion improving agent The curable resin composition of the present invention may contain (Component I) an adhesion improving agent.
The (component I) adhesion improver that can be used in the curable resin composition of the present invention is an inorganic substance that serves as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, or aluminum. It is a compound that improves the adhesion between the insulating film and the insulating film. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the (component I) adhesion improver used in the present invention is intended to modify the interface, and any known silane coupling agent can be used without any particular limitation.

Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.
The following compounds can also be preferably employed. Ph represents a phenyl group.

These can be used alone or in combination of two or more. These are effective for improving the adhesion to the substrate and also for adjusting the taper angle with the substrate.
0.1-20 mass parts is preferable with respect to 100 mass parts of component A, and, as for content of the (component I) contact | adherence improving agent in curable resin composition of this invention, 0.5-10 mass parts is more preferable.

(Component J) Basic compound The curable resin composition of the present invention may contain (Component J) a basic compound. (Component J) The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraphs 0204 to 0207 of JP2011-221494A.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more.
The content of the basic compound in the curable resin composition of the present invention is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid content in the curable resin composition. More preferably, it is ˜1 part by mass.

(Component K) Surfactant The curable resin composition of the present invention may contain (Component K) a surfactant.
As (Component K) surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . Specific examples of fluorine surfactants and silicone surfactants include JP-A Nos. 62-36663, 61-226746, 61-226745, and 62-170950. , JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2001-330953, etc. An activator can be mentioned and a commercially available surfactant can also be used. In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (manufactured by Toray Dow Corning Co., Ltd.), and the like.
In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula (K-1), and is a polystyrene equivalent weight measured by gel permeation chromatography when tetrahydrofuran (THF) is used as a solvent. Preferred examples include copolymers having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

（式（Ｋ−１）中、Ｒ⁴⁰¹及びＲ⁴⁰³はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ⁴⁰²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴⁰⁴は水素原子又は炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐ及びｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。）

(In Formula (K-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. A numerical value is represented, q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 to 18 and s represents an integer of 1 to 10)

L is preferably a branched alkylene group represented by the following formula (K-2). R ⁴⁰⁵ in formula (K-2) represents an alkyl group having 1 to 3 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

  The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the curable resin composition of the present invention is preferably 10 parts by mass or less, and 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the curable resin composition. Part is more preferable, and 0.01 to 3 parts by mass is still more preferable.

(Component L) Acid Proliferating Agent The curable resin composition of the present invention can use an acid proliferating agent for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The strength of the acid is preferably 3 or less, particularly preferably 2 or less, as the acid dissociation constant, pKa.
Specific examples of the acid proliferating agent include paragraphs 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39, line 12 of JP-T 9-512498. Examples of the compounds described in the first to page 47, line 2 are listed.
Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
Specific examples include the following compounds.

  The content of the acid multiplication agent in the curable resin composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator, in view of the dissolution contrast between the exposed part and the unexposed part. To 20 to 500 parts by mass.

(Component M) Development accelerator The curable resin composition of the present invention may contain a development accelerator.
As the development accelerator, any compound having a development acceleration effect can be used, but a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group is preferable. A compound having a carboxyl group or a phenolic hydroxyl group is more preferred, and a compound having a phenolic hydroxyl group is most preferred.
As the development accelerator, the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.

A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the curable resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition, from the viewpoints of sensitivity and residual film ratio. 0.1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.

(Component N) Plasticizer The resin composition of the present invention may contain (Component N) a plasticizer.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The plasticizer content in the resin composition of the present invention is preferably 0.1 to 30 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of component A. .

  Further, as other additives, a thermal radical generator described in paragraphs 0120 to 0121 of JP2012-8223A, and a nitrogen-containing compound and a thermal acid generator described in International Publication No. 2011-136704 are also used. it can.

(Physical properties)
<Transmissivity>
When the curable resin composition of the present invention is formed to a thickness of 1 μm, the transmittance at a wavelength of 400 nm is preferably 80% or more. When the transmittance is 80% or more, the transparency is excellent.
In addition, forming into a film thickness of 1 micrometer means that the film thickness after forming the layer of curable resin composition, heating this, removing a solvent, and carrying out exposure hardening after that is 1 micrometer. Further, when there is a baking process after exposure curing, the film thickness after the baking process is 1 μm.
The transmittance is more preferably 85% or more, and more preferably 90% or more.

<Haze>
The haze when the curable resin composition of the present invention is formed to a film thickness of 1 μm is preferably 2% or less. When the haze is 2% or less, the transparency is excellent.
In addition, forming into a film thickness of 1 micrometer means that the film thickness after forming the layer of curable resin composition, heating this, removing a solvent, and carrying out exposure hardening after that is 1 micrometer. Further, when there is a baking process after exposure curing, the film thickness after the baking process is 1 μm.
The haze is more preferably 1% or less, and more preferably 0.5% or less.

<Refractive index>
The curable resin composition of the present invention preferably has a refractive index of 1.65 or more at a wavelength of 589 nm. When the refractive index is 1.65 or more, for example, when used for a touch panel material, an effect of improving the ITO pattern appearance can be seen. In addition, a refractive index means the refractive index of what formed the layer of the curable resin composition, heated this, removed the solvent, and was exposed and hardened after that. Further, when there is a baking process, it means the refractive index after the baking process.
The refractive index is more preferably 1.70 or more, and more preferably 1.75 or more.

(Method for producing cured film)
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) A coating process for coating the curable resin composition of the present invention on a substrate;
(2) a solvent removal step of removing the solvent from the applied resin composition;
(3) An exposure step of exposing the resin composition from which the solvent has been removed to a pattern with actinic rays;
(4) A developing step in which the unexposed portion of the resin composition is removed with an aqueous developer and developed;
(5) A heat treatment step of heat-treating the developed resin composition.
Each step will be described below in order.

In the application step (1), the curable resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the curable resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesion of the curable resin composition to the substrate is improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, resin composite materials, ITO, Cu substrates, polyethylene terephthalate, and plastic substrates such as cellulose triacetate (TAC).
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester resin, cyclic polyolefin, Is it a synthetic resin such as aromatic ether resin, maleimide-olefin resin, cellulose, episulfide resin, etc. These substrates include a substrate made of the is less if used while the above embodiment, depending on the form of the final product, for example, when the multi-layered structure such as a TFT element is formed is usually.
The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
The coating film thickness is not particularly limited and can be applied with a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 μm.

  In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are within the above ranges, the pattern adhesion is good and the residue can be reduced.

In the exposure step (3), the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used, and g-line (436 nm), i-line (365 nm), h-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In the region where the acid catalyst is generated, post exposure bake (hereinafter also referred to as “PEB”) can be performed in order to accelerate the crosslinking reaction. PEB can further promote the crosslinking reaction. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, a negative image can be formed by exposure without necessarily performing PEB.

In the developing step (4), development is performed by removing an unexposed portion using an alkaline developer. A negative image is formed by removing the unexposed area including the resin composition containing the alkali-soluble resin.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
Preferred examples of the developer include a 0.4% by mass aqueous solution, a 0.5% by mass aqueous solution, a 0.7% by mass aqueous solution, or a 2.38% by mass aqueous solution of tetraethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be either a liquid piling method or a dipping method. After the development, washing with running water can be performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.

In the heat treatment step (post bake) of (5), by heating the obtained negative image, an acid group, for example, a carboxyl group or a phenolic hydroxyl group is generated and crosslinked with a crosslinkable group, a crosslinking agent or the like. Further, a hardened cured film can be formed. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 ° C. to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. By proceeding with a crosslinking reaction that is preferably treated, a protective film and an interlayer insulating film having excellent heat resistance, hardness, and the like can be formed. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere. When using a plastic substrate, it is preferable to heat-process at 80 to 140 degreeC for 5 to 120 minutes.
Prior to the heat treatment step (post-bake), the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Further, middle baking and post baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the pattern-formed substrate is re-exposed with actinic rays (post-exposure) and then post-baked to generate acid from the photoacid generator present in the exposed portion, thereby further performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

  Furthermore, the cured film obtained from the curable resin composition of the present invention can also be used as a dry etching resist. When the cured film is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

(Cured film)
The cured film of the present invention is a cured film obtained by curing the curable resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
With the curable resin composition of the present invention, an interlayer insulating film having excellent transparency and high transparency even when baked at a high temperature can be obtained. Since the interlayer insulating film using the curable resin composition of the present invention has high transparency and excellent cured film properties, it is useful for organic EL display devices and liquid crystal display devices.

(Hardened product and manufacturing method thereof)
The cured product of the present invention is a cured product obtained by curing the curable resin composition of the present invention. As described above, the shape does not have to be a film, and may be any shape.
Although the manufacturing method of the hardened | cured material of this invention does not have a restriction | limiting in particular, It is preferable that the following process (a)-(c) is included at least in this order.
(A) a coating step of coating the curable resin composition of the present invention on a substrate;
(B) a solvent removal step of removing the solvent from the applied resin composition;
(C) An exposure step of irradiating the resin composition from which the solvent has been removed with actinic rays.

Process (a) and process (b) are synonymous with the said application | coating process and the said solvent removal process, respectively, A preferable aspect is also the same.
Step (c) is the same step as the above exposure step, and the preferred embodiment is also the same.

The cured product or cured film of the present invention is for reducing the visibility of wiring members used for optical members such as microlenses, optical waveguides, antireflection films, LED sealing materials and LED chip coating materials, or touch panels. It can be suitably used as a cured product.
The cured product or cured film of the present invention is, for example, a flattening film or interlayer insulating film in a liquid crystal display device or an organic EL device as described later, a protective film for a color filter, and a thickness of a liquid crystal layer in a liquid crystal display device Can be suitably used for spacers for holding the substrate constant, structural members of MEMS (Micro Electro Mechanical Systems) devices, and the like.

(Liquid crystal display device)
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the curable resin composition of the present invention, and known liquid crystal display devices having various structures. Can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, liquid crystal driving methods that the liquid crystal display device of the present invention can take are TN (Twisted Nematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (OCB). Optical Compensated Bend) method.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Allay) type liquid crystal display device. For example, the organic insulating film (115) described in JP-A-2005-284291, It can be used as the organic insulating film (212) described in Japanese Unexamined Patent Application Publication No. 2005-346054.
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer alignment may be supported by the PSA (Polymer Sustained Alignment) technique described in JP2003-149647A or JP2011-257734A.
Moreover, the curable resin composition of this invention and the cured film of this invention are not limited to the said use, but can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interphase insulating film (48) described in JP2011-145686A or the interphase insulating film (520) described in JP2009-258758A. Can do.

(Organic EL display device)
The organic EL display device of the present invention comprises the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the curable resin composition of the present invention, and various known organic materials having various structures. An EL display device and a liquid crystal display device can be given.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

  Since the curable resin composition of the present invention is excellent in curability and cured film properties, a resist pattern formed by using the curable resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part. Examples of such MEMS devices include SAW (surface acoustic wave) filters, BAW (bulk acoustic wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, biochips, and sealants. And the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

  Since the curable resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP2011-107476A, JP2010-2010A. Partition wall (12) and planarization film (102) described in FIG. 4A of JP-A-9793, and bank layer (221) and third interlayer insulating film (FIG. 10 of JP 2010-27591A). 216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4 (a) of Japanese Patent Laid-Open No. 2009-128577, and FIG. 3 of Japanese Patent Laid-Open No. 2010-182638. It can also be used to form a planarization film (12) and a pixel isolation insulating film (14).

  Moreover, since the curable resin composition of this invention is excellent in transparency and a refractive index, it is used suitably as a member for microlenses or prisms, and a member for light extraction. For example, it can be used as a prism member or a member for joining a prism and a light guide plate used in a backlight unit of a flat panel for display. For example, it can be used as a member for improving the light extraction efficiency of an organic EL display.

(Touch panel display)
The touch panel display device of the present invention includes a capacitive input device having the cured film of the present invention. Moreover, the capacitance-type input device of the present invention has the cured film of the present invention.
The capacitance-type input device of the present invention has at least the following elements (1) to (5) on the non-contact side of the front plate and the front plate, and the above (4) is the cured product of the present invention. Preferably there is.
(1) Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) The first transparent electrode pattern and the electric A plurality of second transparent electrode patterns comprising a plurality of pad portions which are insulated and extend in a direction intersecting the first direction. (4) The first transparent electrode pattern and the second An insulating layer that electrically insulates the transparent electrode pattern of (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and the first transparent electrode pattern and the above Conductive element different from the second transparent electrode pattern In the capacitive input device of the present invention, a transparent protective layer is further provided so as to cover all or part of the elements (1) to (5). The transparent protective layer is preferably And more preferably the cured film.

  First, the configuration of the capacitive input device will be described. FIG. 3 is a cross-sectional view showing the configuration of the capacitive input device. In FIG. 3, the capacitive input device 30 includes a front plate 31, a mask layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, and a conductive element 36. And a transparent protective layer 37.

  The front plate 31 is made of a light-transmitting substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Moreover, in FIG. 3, the side in which each element of the front plate 31 is provided is called a non-contact surface. In the capacitive input device 30 of the present invention, input is performed by bringing a finger or the like into contact with the contact surface (the surface opposite to the non-contact surface) of the front plate 31. Hereinafter, the front plate may be referred to as a “base material”.

A mask layer 32 is provided on the non-contact surface of the front plate 31. The mask layer 32 is a frame-like pattern around the display area formed on the non-contact side of the touch panel front plate, and is formed so as not to show the lead wiring and the like.
In the capacitive input device of the present invention, as shown in FIG. 4, a mask layer 32 is provided so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 4). . Further, the front plate 31 can be provided with an opening 38 in part as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.

As shown in FIG. 5, on the contact surface of the front plate 31, a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns 34 each including a plurality of pad portions that are electrically insulated from one transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the electrode pattern 33 and the second transparent electrode pattern 34 is formed. The first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 to be described later are translucent conductive materials such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide). It can be made of a conductive metal oxide film. Examples of such metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO ₂ . At this time, the film thickness of each element can be 10 to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced. In addition, the first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 described later use a photosensitive transfer material having a curable resin composition using the conductive fibers. Can also be manufactured. In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs [0014] to [0016] of Japanese Patent No. 4506785 can be referred to.

  In addition, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 extends over both the non-contact surface of the front plate 31 and the region opposite to the front plate 31 of the mask layer 32. Can be installed. In FIG. 3, a diagram is shown in which the second transparent electrode pattern is installed across both areas of the non-contact surface of the front plate 31 and the surface opposite to the front plate 31 of the mask layer 32. Yes.

  The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. FIG. 5 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention. As shown in FIG. 5, the first transparent electrode pattern 33 is formed such that a pad portion 33a extends in a first direction via a connection portion 33b. The second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35 and extends in a direction intersecting the first direction (second direction in FIG. 5). It is constituted by a plurality of pad portions that are formed. Here, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be manufactured as one body, or only the connection portion 33b is manufactured, and the pad portion 33a and the second portion 33b are formed. The transparent electrode pattern 34 may be integrally formed (patterned). When the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 5, a part of the connection part 33b and a part of the pad part 33a are connected, and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by 35.

  In FIG. 3, a conductive element 36 is provided on the side of the mask layer 32 opposite to the front plate 31. The conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34, and is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34. Is another element. In FIG. 3, a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.

  Moreover, in FIG. 3, the transparent protective layer 37 is installed so that all of each component may be covered. The transparent protective layer 37 may be configured to cover only a part of each component. The insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.

<Capacitance type input device and touch panel display device provided with capacitance type input device>
The capacitive input device obtained by the manufacturing method of the present invention and the touch panel display device including the capacitive input device as a constituent element are “latest touch panel technology” (issued July 6, 2009). Techno Times), supervised by Yuji Mitani, "Touch Panel Technology and Development", CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. Can be applied.

(Transfer material)
Next, the transfer material of the present invention will be described. For the transfer material, a curable resin layer provided on a support (temporary support) is pasted on the final substrate, the support (temporary support) is peeled off, the curable resin layer is exposed with an image, and developed. To do.
The transfer material of the present invention is preferably formed using a transfer material described in JP-A-5-72724, that is, an integral film. Examples of the structure of the integrated film include a structure in which a support (temporary support) / thermoplastic resin layer / intermediate layer / curable resin layer / protective film are laminated in this order, but is not limited thereto. It is sufficient that at least one layer of the curable resin composition of the present invention is formed on the support. That is, it is essential for the transfer material of the present invention to provide a curable resin layer by using the curable resin composition of the present invention described above.

<Support (temporary support)>
In the present invention, the temporary support is required to be flexible and not to cause significant deformation, shrinkage or elongation even under pressure or pressure and heating. Examples of such a support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

<Thermoplastic resin layer>
As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferred that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer United nylon, copolymer nylon, - alkoxymethyl nylon, and organic polymers of the polyamide resin such as N- dimethylamino nylon. In addition, 2-30 micrometers is preferable, as for the dry thickness of a thermoplastic resin layer, 5-20 micrometers is more preferable, and 7-16 micrometers is still more preferable.

<Intermediate layer>
In the photosensitive resin transfer material of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable. The dry thickness of the intermediate layer is preferably 0.2 to 5 μm, more preferably 0.5 to 3 μm, and still more preferably 1 to 2.5 μm.

<Protective film>
It is preferable to provide a thin protective film on the curable resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the curable resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material. In addition, 4-40 micrometers is preferable, as for the thickness of a protective film, 5-30 micrometers is more preferable, and 10-25 micrometers is still more preferable.

<Method for producing transfer material>
The transfer material of the present invention is provided with a thermoplastic resin layer by applying a coating solution (a coating solution for a thermoplastic resin layer) in which a thermoplastic resin layer additive is dissolved on a temporary support, followed by drying. An intermediate layer material solution composed of a solvent that does not dissolve the thermoplastic resin layer is applied on the plastic resin layer, dried, and then the curable resin layer is applied by applying a solvent that does not dissolve the intermediate layer and then dried. be able to.
In addition, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the curable resin layer on the protective film are prepared, and the intermediate layer and the curable resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a curable resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. Can also be produced by bonding them so that the intermediate layer is in contact with each other.
Note that the coating in the above production method can be performed by a known coating apparatus or the like.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

In the following examples, the following symbols represent the following compounds, respectively.
(Component A) Alkali-soluble resin Polymer (P-1): 40 wt% PGMEA solution of Marcalinker M (polyhydroxystyrene, weight average molecular weight 18,000, manufactured by Maruzen Chemical Co., Ltd.) Polymer (P-2): Sumilite Resin PR54046 (Novolac resin, m-cresol / p-cresol = 60/40, manufactured by Sumitomo Bakelite Co., Ltd.) 40 wt% PGMEA solution Polymer (P-3): PGMEA 30 wt% of the following polymer (weight average molecular weight 30,000) Solution (The following polymerization ratio means a molar ratio.)

(Component B) Crosslinking agent B-1: Nicarak MW-100LM, manufactured by Sanwa Chemical Co., Ltd. B-2: Nicarak-750LM, manufactured by Sanwa Chemical Co., Ltd. B-3: Nicarak MX-270, Co., Ltd. B-4: Nikalac MX-280, Sanwa Chemical Co., Ltd. B-5: Nicalak MX-290, Sanwa Chemical Co., Ltd. B-6: Tetramethylol benzoguanamine B-7: Trimethoxymethyl benzoguanamine B-8: 2,6-bis (hydroxymethyl) -4-methylphenol B-9: 5-ethyl-1,3-bis (methoxymethyl) perhydro-1,3,5-triazin-2-one B- 10: Di (methoxymethyl) trimethylene urea B-11 (for comparative example): JER-1001 (Bisphenol A epoxy resin, manufactured by Mitsubishi Chemical Corporation)
B-12 (for comparative example): EPICLON-680 (phenol / novolak type epoxy resin, manufactured by Dainippon Ink Co., Ltd.)

(monomer)
M1: Kayalad DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
M2: Light acrylate PE-4A (pentaerythritol tetraacrylate, manufactured by Kyoeisha Chemical Co., Ltd.)
M3: Kayarad DPCA-30 (Caprolactone-modified dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

(Oxime-based photopolymerization initiator)
I-1: Irgacure OXE 01 (the following structure, manufactured by BASF)

(Component E) Solvent PGMEA: Propylene glycol monomethyl ether acetate

<Preparation of dispersion D1>
A dispersion having the following composition was prepared, mixed with 17,000 parts of zirconia beads (0.3 mmφ), and dispersed for 12 hours using a paint shaker. Zirconia beads (0.3 mmφ) were filtered off to obtain dispersion D1.
-Titanium dioxide (Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C), average primary particle size: 10-30 nm) 1,875 parts-Dispersant (DISPERBYK-111: manufactured by Big Chemie Japan Co., Ltd.) 30% PGMEA solution) 2,200 parts, solvent PGMEA 3,425 parts

<Preparation of dispersion D2>
Dispersion D2 was prepared in the same manner as Dispersion D1, except that the dispersant was changed to a 30% PGMEA solution of Compound 1 below.

<Dispersion D3>
A commercially available ZrO ₂ particle dispersion (Nanouse OX-S30K, manufactured by Nissan Chemical Industries, Ltd.) was used as it was.

Example 1
<Preparation of curable resin composition>
Using the titanium dioxide dispersion (dispersion D1) obtained above, the components were mixed so as to have the following composition, and a curable resin composition of Example 1 was obtained.
Propylene glycol monomethyl ether acetate 321.4 parts Polymer (P-1) 162.1 parts Crosslinking agent (B-1) 10.5 parts Photoacid generator C-1 (the following compound) 5.1 parts Perfluoroalkyl group-containing nonionic surfactant (2.0% PGMEA solution manufactured by F-554 (DIC Corporation)) 0.25 parts, dispersion D1 500 parts

<Synthesis of C-1>
The above C-1 was synthesized according to the following method.
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated. The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature (25 ° C.). The reaction was allowed to warm for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, then reslurried with methanol (20 mL), filtered, and dried to obtain 2.3 g of C-1.
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of C-1 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

(Example 2)
A curable resin composition of Example 2 was obtained in the same manner as in Example 1 except that the polymer (P-1) was changed to the polymer (P-2).

(Examples 3 to 13)
A curable resin composition was obtained in the same manner as in Example 1 except that the dispersion, polymer, and crosslinking agent were changed as shown in Table 1.

(Example 14)
Each material was mixed with the composition ratio shown below, and the curable resin composition of Example 14 was obtained.
Propylene glycol monomethyl ether acetate 321.4 parts Polymer (P-1) 162.1 parts Crosslinking agent (B-1) 10.5 parts Photoacid generator (C-1) 5.67 parts Perfluoro Alkyl-containing nonionic surfactant (F-554, 2.0% PGMEA solution manufactured by DIC Corporation) 0.25 part, dispersion D3 416.7 parts

(Example 15)
A curable resin composition of Example 14 was obtained in the same manner as Example 14 except that the polymer (P-1) was changed to the polymer (P-2).

(Comparative Example 1)
Using the titanium dioxide dispersion obtained above (dispersion D1), the components were mixed so as to have the following composition, to obtain a curable resin composition of Comparative Example 1.
Propylene glycol monomethyl ether acetate 362.3 parts Polymer (P-3) 94.2 parts Dipentaerythritol hexaacrylate (M1) 37.7 parts Oxime-based photopolymerization initiator (I-1) 5.67 parts -Perfluoroalkyl-containing nonionic surfactant (F-554, 2.0% PGMEA solution manufactured by DIC Corporation) 0.25 parts-Dispersion D1 500.0 parts

(Comparative Examples 2 and 3)
A curable resin composition was obtained by curing in the same manner as in Comparative Example 1 except that the monomers used were changed to the compounds shown in Table 1.

(Comparative Examples 4 and 5)
A curable resin composition was obtained in the same manner as in Example 1 except that the used crosslinking agent and dispersion were changed to the compounds shown in Table 1.

(Evaluation method)
<Evaluation of surface tackiness>
The obtained curable resin composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) with a spin coater so as to have a film thickness of 1.0 μm, and on a hot plate at 90 ° C. And dried for 120 seconds (pre-baked). Next, the entire surface was exposed with an energy intensity of 20 mW / cm ² and 50 mJ / cm ² using a ghi-line high-pressure mercury lamp exposure machine. The surface tackiness of this sample was evaluated by sensory evaluation. The evaluation criteria are as shown below.
1: No tack 2: Slightly tack 3: Tack

<Evaluation of haze (transparency)>
The obtained curable resin composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) with a spin coater, and dried (prebaked) for 120 seconds on a hot plate at 80 ° C. Next, the entire surface was exposed with an energy intensity of 20 mW / cm ² and 200 mJ / cm ² using a ghi-line high pressure mercury lamp exposure machine. Furthermore, the coating film was subjected to heat treatment (post-bake) for 45 minutes in an oven at 220 ° C. The initial coating film thickness was adjusted so that the film thickness would be 1 μm after post baking. The haze of the post-baked sample is NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd., and the haze (haze) is determined according to the plastic product test method (JIS K7136, JIS K7361, ASTM D1003). Value).
In addition, a haze value refers to the value represented by the ratio (%) of the diffuse transmitted light with respect to all the light transmitted light. The smaller the haze value, the higher the transparency.
1: The haze value was less than 0.5%.
2: The haze value was 0.5% or more and less than 0.7%.
3: The haze value was 0.7% or more and less than 1.0%.
4: The haze value was 1.0% or more and less than 2.0%.
5: Haze value was 2.0% or more.

<Evaluation of transmittance>
The obtained curable resin composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) with a spin coater, and dried (prebaked) for 120 seconds on a hot plate at 80 ° C. Next, the entire surface was exposed with an energy intensity of 20 mW / cm ² and 200 mJ / cm ² using a ghi-line high pressure mercury lamp exposure machine. Furthermore, the coating film was subjected to heat treatment (post-bake) for 45 minutes in an oven at 220 ° C. The initial coating film thickness was adjusted so that the film thickness would be 1 μm after post baking. The spectrum of the post-baked sample was measured with MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the transmittance at 400 nm was evaluated according to the following evaluation criteria.
The transmittance at 1: 400 nm was 90% or more.
2: The transmittance at 400 nm was 80% or more and less than 90%.
3: The transmittance at 400 nm was less than 80%.

<Evaluation of sensitivity>
The obtained curable resin composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) with a spin coater so as to have a film thickness of 2.0 μm, and then on an 80 ° C. hot plate. And dried for 120 seconds (pre-baked).
Next, using a ghi-line high-pressure mercury lamp exposure machine, exposure was performed through a mask with a gradation of 1% to 90% transmittance at an energy intensity of 20 mW / cm ² and 200 mJ / cm ² . Thereafter, heat treatment was performed at 110 ° C. for 90 seconds.
Next, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 30 seconds by immersion and further rinsed with ultrapure water for 10 seconds. The film thickness of each gradient portion was measured, and the exposure amount at which 95% or more of the original film thickness remained was defined as sensitivity.
1: 30 mJ / cm ² or less 2: exceed ^{30mJ / cm 2, 100mJ / cm} 2 or less 3: more than 100 mJ / cm ²

<Evaluation of refractive index>
The obtained curable resin composition was applied onto a silicon wafer substrate using a spinner and dried at 80 ° C. for 120 seconds to form a film having a thickness of 0.5 μm. This substrate was exposed at 200 mJ / cm ² (measured by i-line) using an ultrahigh pressure mercury lamp, and then heated in an oven at 220 ° C. for 45 minutes.
The refractive index of the cured film at 589 nm was measured using an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.). A higher refractive index is preferable, and 1.70 or more is more preferable.

<Resolution evaluation>
The obtained curable resin composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) with a spin coater so as to have a film thickness of 2.0 μm, and then on an 80 ° C. hot plate. And dried for 120 seconds (pre-baked).
Next, using a ghi-line high pressure mercury lamp exposure machine, exposure was performed through a 1% to 60% gradation mask with a line-and-space ratio of 1: 1 at an energy intensity of 20 mW / cm ² and 200 mJ / cm ² . Thereafter, heat treatment was performed at 110 ° C. for 90 seconds.
Next, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds by immersion and further rinsed with ultrapure water for 10 seconds. Subsequently, a pattern was obtained by heating at 220 ° C. for 45 minutes. This pattern was observed with an optical microscope.
This operation was started from the width of the mask line and space of 50 μm, the width was narrowed by 5 μm up to 10 μm by 1 μm, and the minimum width at which the optimum exposure amount portion could be finely formed was defined as the resolution. 1 or 2 is a practical range.
1: The resolution was 5 μm or less.
2: The resolution was more than 5 μm and 10 μm or less.
3: The resolution was more than 10 μm and 50 μm or less.
4: A pattern could not be formed with a mask line and space width of 50 μm.

<Evaluation of ITO visibility>
An ITO pattern is formed in advance on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning), and the obtained curable resin composition is applied to a spin coater so as to have a film thickness of 1.0 μm. And then dried (prebaked) for 120 seconds on a hot plate at 80 ° C.
Next, the entire surface of the substrate was exposed with an energy intensity of 20 mW / cm ² and 200 mJ / cm ² using a ghi-line high pressure mercury lamp exposure machine.
Subsequently, the film was heated at 220 ° C. for 45 minutes to provide a dry film of the curable resin composition on the ITO pattern. The obtained substrate was observed with the naked eye in the bright room while tilting, and the visibility was evaluated as compared with the case where the photosensitive resin composition was not provided on the ITO pattern. Note that the evaluation standard is so good that the ITO pattern is difficult to see. 1 or 2 is a practical range.
1: The ITO pattern is almost invisible.
2: The ITO pattern appears faint.
3: The ITO pattern is clearly visible.

(Example 16)
In the active matrix liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 16 was obtained. That is, the curable resin composition of Example 13 was spin-coated on a substrate, pre-baked on a hot plate (90 ° C./120 seconds), and then i-line (365 nm) was 45 mJ / mm from the mask using a high-pressure mercury lamp. After irradiation with cm ² (energy intensity 20 mW / cm ² ), development was performed with an alkaline aqueous solution to form a pattern, and heat treatment was performed at 230 ° C./30 minutes to form a cured film 17 as an interlayer insulating film.

  When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

(Example 17)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the curable resin composition of Example 13 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm ² (energy intensity 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C./30 minutes.
The applicability when applying the curable resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the curable resin composition of Example 13 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 18)
A touch panel display device was prepared by using the high refractive index curable resin material of the present invention by the method described below.
<Formation of first transparent electrode pattern>
[Formation of transparent electrode layer]
A front plate of tempered glass (300 mm × 400 mm × 0.7 mm) with a mask layer formed in advance is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5) with a SnO ₂ content of 10% by mass. (Molar ratio)) was used to form an ITO thin film having a thickness of 40 nm by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer was formed. A formed front plate was obtained. The surface resistance of the ITO thin film was 80Ω / □.

Next, a commercially available etching resist was applied onto ITO and dried to form an etching resist layer. The distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 μm, pattern exposure is performed at an exposure amount of 50 mJ / cm ² (i-line), and then a dedicated developer And a post-bake treatment at 130 ° C. for 30 minutes to obtain a front plate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.

The front plate on which the transparent electrode layer and the photocurable resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched resist. The exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
Next, the front plate with the transparent electrode layer pattern with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the photocurable resin layer for etching is removed, and the mask layer and the first transparent electrode pattern A front plate formed was obtained.

[Formation of insulating layer]
On the front plate on which the mask layer and the first transparent electrode pattern are formed, the curable resin composition of Example 1 is applied and dried (film thickness: 1 μm, 90 ° C., 120 seconds), and the curable resin composition layer is formed. Got. The distance between the exposure mask (quartz exposure mask having the insulating layer pattern) surface and the curable resin composition layer was set to 30 μm, and pattern exposure was performed at an exposure amount of 50 mJ / cm ² (i-line).
Next, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds by immersion and further rinsed with ultrapure water for 10 seconds. Subsequently, a post-bake treatment at 220 ° C. for 45 minutes was performed to obtain a front plate on which a mask layer, a first transparent electrode pattern, and an insulating layer pattern were formed.

<Formation of second transparent electrode pattern>
[Formation of transparent electrode layer]
In the same manner as the formation of the first transparent electrode pattern, the front plate formed up to the insulating layer pattern was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa). An ITO thin film having a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.
Similar to the formation of the first transparent electrode pattern, the first transparent electrode pattern, the insulating layer pattern formed using the curable resin composition of Example 1, a transparent electrode, using a commercially available etching resist A front plate on which a layer and an etching resist pattern were formed was obtained (post-bake treatment; 130 ° C. for 30 minutes).
Further, by etching and removing the etching resist layer in the same manner as the formation of the first transparent electrode pattern, the mask layer, the first transparent electrode pattern, and the curable resin composition of Example 1 were used. A front plate on which the formed insulating layer pattern and second transparent electrode pattern were formed was obtained.

<Formation of Conductive Element Different from First and Second Transparent Electrode Pattern>
Similar to the formation of the first and second transparent electrode patterns, the first transparent electrode pattern, the insulating layer pattern formed using the curable resin composition of Example 1, and the second transparent electrode pattern The front plate on which was formed was subjected to DC magnetron sputtering to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.
Insulating layer formed using the first transparent electrode pattern, the curable resin composition of Example 1, using a commercially available etching resist in the same manner as the first and second transparent electrode patterns. A front plate on which a pattern, a second transparent electrode pattern, and an etching resist pattern were formed was obtained. (Post-bake treatment; 130 ° C. for 30 minutes).
Further, in the same manner as in the formation of the first transparent electrode pattern, etching (30 ° C. for 50 seconds) is performed, and the etching resist layer is removed (45 ° C. for 200 seconds), whereby the mask layer and the first transparent electrode pattern are removed. In addition, an insulating layer pattern formed using the curable resin composition of Example 1, a second transparent electrode pattern, and a front plate on which conductive elements different from the first and second transparent electrode patterns were formed were obtained. .

<Formation of transparent protective layer>
In the same manner as the formation of the insulating layer, the curable resin composition of Example 1 was applied and dried (film thickness: 1 μm) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a curable resin composition film. Furthermore, the front exposure is performed with an exposure amount of 50 mJ / cm ² (i-line) without using an exposure mask, development, post-exposure (1,000 mJ / cm ² ), and post-bake treatment are performed to obtain a mask layer and a first transparent The electrode pattern, the insulating layer pattern formed using the curable resin composition of Example 1, the second transparent electrode pattern, and all the conductive elements different from the first and second transparent electrode patterns are covered. The front board which laminated | stacked the insulating layer (transparent protective layer) formed using the curable resin composition of Example 1 was obtained.

<Production of image display device (touch panel)>
The liquid crystal display element manufactured by the method described in Japanese Patent Application Laid-Open No. 2009-47936 was bonded to the previously manufactured front plate, and an image display device including a capacitive input device as a constituent element was manufactured by a known method. .

<Evaluation of front plate and image display device>
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and other conductive elements, while the first transparent electrode pattern and the second transparent electrode pattern Between the electrode patterns, there was insulation, and good display characteristics as a touch panel were obtained. Furthermore, the first and second transparent electrode patterns were hardly visible and an image display device having excellent display characteristics was obtained.

(Example 19)
-Production of transfer material-
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, the curable resin composition of Example 1 was applied and dried, a thermoplastic resin layer having a dry film thickness of 14.6 μm on the temporary support, an intermediate layer having a dry film thickness of 1.6 μm, A curable resin layer having a dry film thickness of 1 μm was provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
Thus, a transfer material T1 in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the curable resin layer were integrated was produced.

<Coating liquid for thermoplastic resin layer: Formulation H1>
Methanol: 11.1 parts Propylene glycol monomethyl ether: 6.36 parts Methyl ethyl ketone: 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio)) = 55/30/10/5, molecular weight = 100,000, Tg≈70 ° C.): 5.83 parts Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35, molecular weight = 10,000 , Tg≈100 ° C.): 13.6 parts. Compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (BPE-500, Shin-Nakamura Chemical Co., Ltd.): 9.1 parts. Fluoropolymer ( and _{C 6 F 13 CH 2 CH 2} OCOCH = CH 2 40 _{parts, H (O (CH 3)} CHCH 2) and ₇ OCOCH = CH ₂ 55 parts H (OCHCH _{2) 7} copolymer of OCOCH = CH ₂ 5 parts, molecular weight 30,000, 30% methyl isobutyl ketone solution, DIC (trade name) manufactured by: Megafac F780F): 0.54 parts

<Intermediate layer coating solution: Formulation P1>
PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550): 32.2 parts Polyvinylpyrrolidone (manufactured by BASF, K-30): 14.9 parts Distilled water: 524 parts・ Methanol: 429 parts

<Transfer and image formation>
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device and sent to the next laminator.
After peeling off the protective film of the transfer material T1, a substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Techno Engineering Co., Ltd.), rubber roller temperature 130 ° C., linear pressure 100 N / cm, conveyance speed 2.2 m Laminated at / min.
When the temporary support was peeled off, the sample was peeled cleanly between the temporary support and the thermoplastic resin layer, and a sample in which the curable resin layer / intermediate layer / thermoplastic resin layer was transferred to glass was obtained.

This transfer sample was exposed through a 1% to 60% gradation mask with a line and space ratio of 1 and ² at an energy intensity of 20 mW / cm ² and 200 mJ / cm ² using a ghi line high pressure mercury lamp exposure machine. Thereafter, heat treatment was performed at 110 ° C. for 90 seconds.
Next, a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoaming agent, trade name: T-PD1, Fuji Photo Film Co., Ltd.) 30 Shower development was performed at 50 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier film.
Next, the mask pattern is obtained by developing the curable resin layer with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds and rinsing with ultrapure water for 10 seconds. A line and space pattern corresponding to the pattern was obtained. The resolution of the obtained pattern was equivalent to that of Example 1 evaluated as a liquid material, and it was confirmed that this material was also effective as a transfer material.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: planarization film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12: Backlight unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter, 30: Capacitive input device 31: front plate, 32: mask layer, 33: first transparent electrode pattern, 33a: pad portion, 33b: connection portion, 34: second transparent electrode pattern, 35: insulating layer, 36: conductive element, 37: Transparent protective layer, 38: Opening

Claims (17)

(Component A) alkali-soluble resin,
(Component B) a compound having a group represented by the following formula (L),
(Component C) acid generator,
(Component D) metal oxide particles, and
(Component E) A curable resin composition containing a solvent.

(In formula (L), X ¹ and X ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an acyl group, and Y represents a hydrogen atom or a monovalent substituent. * Represents a connecting position, and is connected to a carbon atom constituting an aromatic ring, a nitrogen atom or a carbon atom constituting a heterocyclic ring, or a secondary or tertiary nitrogen atom.)   The curable resin composition according to claim 1, wherein Component D is metal oxide particles having a refractive index of 2.0 or more.   The curable resin composition according to claim 1 or 2, wherein Component A is a phenolic resin.   The curable resin composition of any one of Claims 1-3 whose component B is a melamine type compound.   The curable resin composition of any one of Claims 1-4 whose content of the component D is 30 mass% or more with respect to the total solid of a composition.   The curable resin composition according to any one of claims 1 to 5, wherein Component C is a photoacid generator.   The curable resin composition according to any one of claims 1 to 6, wherein the transmittance at a wavelength of 400 nm is 80% or more when the curable resin composition is formed to a thickness of 1 µm.   The curable resin composition of any one of Claims 1-7 whose component D is a zirconium oxide particle and / or a titanium oxide particle.   A transfer material obtained by forming at least one layer of the curable resin composition according to any one of claims 1 to 8 on a support. A method for producing a cured product comprising at least steps (a) to (c) in this order.
(A) Application step of applying the curable resin composition according to any one of claims 1 to 8 on a substrate (b) Solvent removal step of removing the solvent from the applied resin composition (c) Solvent Exposure step of irradiating the resin composition from which actinides are removed with actinic rays A resin pattern manufacturing method comprising at least steps (1) to (5) in this order.
(1) Application step of applying the curable resin composition according to any one of claims 1 to 8 on a substrate (2) Solvent removal step of removing the solvent from the applied resin composition (3) Solvent (4) Development step of removing the unexposed resin composition with an aqueous developer and developing (5) Developing the resin composition Heat treatment process for heat treatment   The hardened | cured material obtained by the manufacturing method of the hardened | cured material of Claim 10, or the resin pattern manufacturing method of Claim 11.   The cured film formed by hardening | curing the curable resin composition of any one of Claims 1-8.   The cured film of Claim 13 which is an interlayer insulation film.   The liquid crystal display device which has a cured film of Claim 13 or 14.   An organic EL display device having the cured film according to claim 13 or 14.   A touch panel display device comprising the cured film according to claim 13.

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