JP7008791B2 - Composition, coating film, cured film, lens, solid-state image sensor, resin - Google Patents

Description

The present invention relates to a composition, a coating film, a cured film, a lens, a solid-state image sensor, and a resin.

High heat resistance, high transparency, and high refractive index for compounds conventionally used for optical materials (for example, a microlens forming material mounted on an image sensor and a refractive index adjusting agent for a color filter). Various properties such as high solubility and low volume shrinkage are required.
For example, Patent Document 1 discloses a triazine ring-containing polymer as a material having high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage.

Japanese Unexamined Patent Publication No. 2015-025131

When the present inventors examined a cured film formed from the composition containing the triazine ring-containing polymer described in Patent Document 1, they were repeatedly exposed to a high temperature environment and a low temperature environment (high temperature-low temperature environment). It was clarified that the cured film obtained had many defects.

Therefore, it is an object of the present invention to provide a composition capable of giving a cured film in which defect generation is suppressed even after repeated exposure to a high temperature-low temperature environment.
Another object of the present invention is to provide a coating film formed by the composition, a cured film formed by curing the coating film, a lens, and a solid-state image pickup device.
Another object of the present invention is to provide a novel resin that can be suitably used as a high refractive index material.

As a result of diligent studies to achieve the above-mentioned problems, the present inventors have made the above-mentioned problems according to a composition containing a resin containing a triazine ring having a specific structure, a specific metal ion having a predetermined content, and a solvent. We found that it could be solved and completed the present invention.
That is, it was found that the above object can be achieved by the following configuration.

(1) A resin containing a repeating unit represented by the general formula (I-1) described later or a repeating unit represented by the general formula (I-2) described later.
With solvent
A composition comprising a specific metal ion selected from the group consisting of sodium ion, potassium ion, and calcium ion.
A composition having a total content of specific metal ions of 0.01 to 30 mass ppm with respect to the total mass of the composition.
(2) The solvent contains toluene and
The composition according to (1), wherein the content of toluene is 0.001 to 10 mass ppm with respect to the total mass of the composition.
(3) The composition according to (1) or (2), wherein V in the general formula (I-1) is a group represented by the general formula (II) described later.
(4) In the general formula (II), m represents 0, n represents 1, and R ⁴ represents an aryl group, a heterocyclic group, a cyano group, a nitro group, an alkyl group, an alkylthio group, or a halogen atom. , (3).
(5) The composition according to (4), wherein the group represented by the general formula (II) described later is a group represented by the general formula (IIA) described later.
(6) The composition according to any one of (1) to (5), wherein X ¹ to X ³ are all −NR ¹ − in the general formula (I-1).
(7) W ¹ in the general formula (I-1) and W ² in the general formula (I-2) are independently divalent linking groups represented by the general formula (III) described later. The composition according to any one of (1) to (6).
(8) The composition according to (7), wherein in W ² of the general formula (I-2), A ¹ to A ³ all represent an arylene group.
(9) The composition according to (7) or (8), wherein the arylene group is a 1,4-phenylene group in W2 of the general formula (I- ² ).
(10) The composition according to any one of (1) to (9), further comprising a curable compound.
(11) The composition according to any one of (1) to (10), further comprising a polymerization initiator.
(12) A coating film formed by the composition according to any one of (1) to (11).
(13) A cured film formed by curing the coating film according to (12).
(14) The lens made of the cured film according to (13).
(15) A solid-state image pickup device including the lens according to (14).
(16) A resin containing a repeating unit represented by the general formula (IV-1) described later.
(17) A resin containing a repeating unit represented by the general formula (IV-2) described later.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a composition capable of giving a cured film in which defect generation is suppressed even after repeated exposure to a high temperature-low temperature environment.
Further, according to the present invention, it is possible to provide a coating film formed by the above composition, a cured film formed by curing the coating film, a lens, and a solid-state image pickup device.
Further, according to the present invention, it is possible to provide a novel resin that can be suitably used as a high refractive index material.

Hereinafter, the present invention will be described in detail.
The numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
As used herein, the term "active light" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. .. Further, in the present invention, light means active light rays or radiation. Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, X-rays, EUV light, etc., but also electron beams, ion beams, etc. The drawing by the particle beam of is also included in the exposure.
In the present specification, "(meth) acrylate" represents acrylate and methacrylate, "(meth) acrylic" represents acrylic and methacrylic, and "(meth) acryloyl" represents acryloyl and methacryloyl.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
As used herein, weight average molecular weight and number average molecular weight are defined as polystyrene-equivalent values in gel permeation chromatography (GPC) measurements. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used as a measuring device, and TSKgel Super AWM-H (Tosoh Corporation) is used as a column. , 6.0 mm ID (inner diameter) x 15.0 cm), and obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group means a group involved in the polymerization reaction.
As used herein, the total solid content refers to the total mass of the components of the composition excluding the solvent.

In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as those having 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). Examples of the substituent include a group selected from the following substituent group T.

(Substituent T)
The substituent T includes a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group and an aryloxy group. Group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sul Famoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl Examples thereof include a group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group and the like. Each group will be described in detail below.

Halogen atoms (eg, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms),
A linear or branched alkyl group (a linear or branched, substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, n. -Propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group, etc.),
A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic. Examples of the monocyclic cycloalkyl group include , Cyclohexyl group, cyclopentyl group and the like. Further, the polycyclic cycloalkyl group is, for example, a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, and is specific. Examples thereof include a bicyclo [1,2,2] heptane-2-yl group, a bicyclo [2,2,2] octane-3-yl group, etc.), a tricycloalkyl group, and the like. Of these, a monocyclic cycloalkyl group or a bicycloalkyl group is preferable, and a monocyclic cycloalkyl group is more preferable).

A linear or branched alkenyl group (a linear or branched alkenyl group, preferably a substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, for example, a vinyl group, an allyl group, or a prenyl group. Group, geranyl group, oleyl group, etc.),
A cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms. The cycloalkenyl group may be monocyclic or polycyclic. Examples of the monocyclic cycloalkenyl group include , 2-Cyclopentene-1-yl group, and 2-cyclohexene-1-yl group. Examples of the polycyclic cycloalkenyl group include a bicycloalkenyl group (preferably substituted or unsubstituted with 5 to 30 carbon atoms). Bicycloalkenyl group, specifically, bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] octo-2-en-4-yl group, etc.) , And a tricycloalkenyl group and the like. As the cycloalkenyl group, a monocyclic cycloalkenyl group is preferable),.
An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group, a trimethylsilylethynyl group, etc.),.

Aryl groups (preferably substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, for example, phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl group, pyrenyl group, biphenyl. Group, and terphenyl group, etc.),
Heterocyclic group (The heterocyclic group may be either a substituted or unsubstituted alicyclic heterocyclic group or an aromatic heterocyclic group, and the alicyclic heterocyclic group may be saturated or unsaturated. Further, the heterocyclic group may be a monocyclic ring or a condensed ring. As the heterocyclic group, 1 heterocyclic atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom is used. It preferably contains one or more, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, a 2-furyl group, a 2-thienyl group, a 2-pyridyl group, a 4-pyridyl group, and the like. 2-pyrimidinyl group, 2-benzothiazolyl group and the like can be mentioned.),
Cyano group, hydroxyl group, nitro group, carboxyl group,

Alkoxy group (preferably substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group, etc.) ,
Aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, for example, phenoxy group, 2-methylphenoxy group, 2,4-di-tert-amylphenoxy group, 4-tert-butylphenoxy). Group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group, etc.),
A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, a trimethylsilyloxy group, a tert-butyldimethylsilyloxy group, etc.),
Heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. The heterocyclic group in the heterocyclic oxy group is a divalent group obtained by removing one hydrogen atom from the above-mentioned heterocyclic group. Examples of the heterocyclic oxy group include 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group, and the like.

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, a formyloxy group. Acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, etc.),
Carbamoyloxy group (preferably substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N- Di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group, etc.),
Alkoxycarbonyloxy group (preferably substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group, etc.) ,
Aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, and a pn-hexadecyloxyphenoxycarbonyl). Oxy group, etc.),

Amino group (preferably an unsubstituted amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocycle having 0 to 30 carbon atoms. Amino group. For example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, and N-1,3,5-triazine-2-ylamino group),.
An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, a formylamino group, acetyl. Amino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, acryloylamino group, methacryloylamino group, etc.),
Aminocarbonylamino groups (preferably substituted or unsubstituted aminocarbonylamino groups having 1 to 30 carbon atoms, such as carboxamide amino groups, N, N-dimethylaminocarbonylamino groups, N, N-diethylaminocarbonylamino groups, and morpholino. Carbonylamino group, etc.),
Alkoxycarbonylamino groups (preferably substituted or unsubstituted alkoxycarbonylamino groups having 2 to 30 carbon atoms, such as methoxycarbonylamino groups, ethoxycarbonylamino groups, tert-butoxycarbonylamino groups, n-octadecyloxycarbonylamino groups, and N-methyl-methoxycarbonylamino group, etc.),

Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, and an mn-octyloxyphenoxycarbonylamino. Basic),
Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, and an Nn-octylamino group. Sulfonylamino group, etc.),
An alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, a methylsulfonylamino group. , Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, etc.),
Mercapto group,

Alkylthio groups (preferably substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, for example, methylthio groups, ethylthio groups, n-hexadecylthio groups, etc.),.
An arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, a phenylthio group, a p-chlorophenylthio group, an m-methoxyphenylthio group, etc.),.
Heterocyclic thiogroup (preferably a substituted or unsubstituted heterocyclic thiogroup having 2 to 30 carbon atoms. The heterocyclic group in the heterocyclic thio group is a divalent group obtained by removing one hydrogen atom from the above-mentioned heterocyclic group. Examples of the heterocyclic thio group include 2-benzothiazolylthio group and 1-phenyltetrazole-5-ylthio group.), ,.
Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group. , N-Acetylsulfamoyl group, N-benzoylsulfamoyl group, and N- (N'-phenylcarbamoyl) sulfamoyl group, etc.),
Sulfone group,

An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, a methylsulfinyl group, an ethylsulfinyl group, or a phenylsulfinyl group. Group, and p-methylphenylsulfinyl group, etc.),
An alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, a methylsulfonyl group, an ethylsulfonyl group, etc. Phenylsulfonyl group, p-methylphenylsulfonyl group, etc.),
An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, an acetyl group, a pivaloyl group, 2-. Chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, acryloyl group, methacryloyl group, etc.),
Aryloxycarbonyl groups, preferably substituted or unsubstituted aryloxycarbonyl groups with 7-30 carbon atoms, such as phenoxycarbonyl groups, o-chlorophenoxycarbonyl groups, m-nitrophenoxycarbonyl groups, and p-tert-butylphenoxy. Carbonyl group, etc.),

Alkoxycarbonyl groups (preferably substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms, such as methoxycarbonyl groups, ethoxycarbonyl groups, tert-butoxycarbonyl groups, n-octadecyloxycarbonyl groups, etc.),
Carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-n-octylcarbamoyl group, And N- (methylsulfonyl) carbamoyl group, etc.),
An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (heterocyclic group in the heterocyclic azo group). Examples thereof include a divalent heterocyclic group obtained by removing one hydrogen atom from the above-mentioned heterocyclic group). For example, a phenylazo group, a p-chlorophenylazo group, and 5-ethylthio-1,3,4-thiadiazole. -2-Ilazo group, etc.),
An imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, for example, an N-succinimide group and an N-phthalimide group),
A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, etc.),.
Phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms, for example, phosphinyl groups, dioctyloxyphosphinyl groups, diethoxyphosphinyl groups, etc.),.

Phosphinyloxy groups (preferably substituted or unsubstituted phosphinyloxy groups having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy groups, dioctyloxyphosphinyloxy groups, etc.),.
A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group), and
Examples thereof include a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, a trimethylsilyl group, a tert-butyldimethylsilyl group, a phenyldimethylsilyl group, etc.).

Among the above functional groups, those having a hydrogen atom may have a hydrogen atom portion in the functional group substituted with any of the above groups. Examples of functional groups that can be introduced as a substituent include an alkylcarbonylaminosulfonyl group (eg, acetylaminosulfonyl group, etc.), an arylcarbonylaminosulfonyl group (eg, benzoylaminosulfonyl group, etc.), an alkylsulfonylaminocarbonyl group (eg, etc.). , Methylsulfonylaminocarbonyl group, etc.), arylsulfonylaminocarbonyl group (eg, p-methylphenylsulfonylaminocarbonyl group, etc.) and the like.

〔Composition〕
The composition of the present invention contains a resin containing a repeating unit represented by the general formula (I-1) described later or a repeating unit represented by the general formula (I-2) described later, a solvent, sodium ions, and potassium. It contains a specific metal ion selected from the group consisting of ions and calcium ions, and the total content of the specific metal ion is 0.01 to 30 mass ppm with respect to the total mass of the composition.

As a feature of the above composition, a resin containing a repeating unit represented by the general formula (I-1) described later or a repeating unit represented by the general formula (I-2) described later (hereinafter, “specific triazine type”). (Also referred to as "resin") and a specific metal ion having a predetermined content are used in combination.
Materials exhibiting high refractive index, such as triazine-based resins, tend to associate with each other due to their intramolecular interaction to form aggregates. Now, when the present inventors have investigated a cured film containing the aggregate, the cured film undergoes microphase separation (phase separation between the aggregated portion and the non-aggregated portion) when repeatedly exposed to a high temperature-low temperature environment. It has been found that defects are increased in the cured film due to this microphase separation, which is likely to occur.
As a result of further studies based on the above findings, the present inventors have found that, according to the composition in which the specific triazine-based resin and the specific metal ion having a predetermined content are blended, the cured film formed is microphase-separated. As a result, it was clarified that the cured film was suppressed from causing defects even after being repeatedly exposed to a high temperature-low temperature environment.
Although the mechanism of action is not clear, the specific metal ion easily interacts with nitrogen atoms and the like in the specific triazine-based resin, and therefore, the association of the specific triazine-based resin in the process of forming the coating film with the composition. Is presumed to be suppressed. On the other hand, if the content of the specific metal ion in the composition is too large, the specific metal ion and the specific triazine resin are likely to be complicated in the process of forming the coating film by the composition, which is caused by this. , Micro-phase separation of the cured film (phase separation between the complexed portion and the non-complexed portion) is likely to occur. In particular, when the cured film is repeatedly exposed to a high temperature-low temperature environment, the complexation of the specific metal ion and the specific triazine resin in the system further progresses, and the amount of microphase separation generated further increases. As a result, the cured film repeatedly exposed to the high temperature-low temperature environment has an increased number of defects.
When the total content of the specific metal ion in the composition is 0.01 to 30 mass ppm with respect to the total mass of the composition, the present inventors associate the specific triazine-based resin and the specific triazine. It has been clarified that the complexation between the triazine resin and the specific metal ion is suppressed, and that the obtained cured film suppresses the generation of defects even after repeated exposure to a high temperature-low temperature environment. It has also been confirmed that the cured film has a small spectral fluctuation (change in transmittance) even after being repeatedly exposed to a high temperature-low temperature environment.

When the composition contains toluene as a solvent and the content of the toluene is 0.001 to 10 mass ppm with respect to the total mass of the composition, the surface appearance of the coating film formed by the composition Excellent. Although the mechanism of action is not clear, it is speculated that toluene affects the compatibility of specific triazine-based resins.

Hereinafter, each component contained in the above composition will be described in detail.

<Specific triazine resin>
The composition contains a resin (specific triazine-based resin) containing a repeating unit represented by the general formula (I-1) or a repeating unit represented by the general formula (I-2).
(Repeating unit represented by the general formula (I-1))

In the general formula (I-1), X ¹ , X ² , and X ³ independently represent −NR ¹ −, — O—, or —S—, respectively.
As X ¹ , X ² and X ³ , the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is superior, and the spectroscopy of the cured film even after repeated exposure to a high temperature-low temperature environment. -NR ^1- is preferable because the fluctuation is small.

R ¹ represents a hydrogen atom or a substituent.
The substituent represented by R ¹ is not particularly limited, and examples thereof include the groups exemplified in the above-mentioned substituent group T, and among them, an alkyl group or an aryl group is preferable.
The alkyl group represented by R ¹ (which may be linear, branched, or cyclic) is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms and 1 to 6 carbon atoms. Alkyl groups of 1 to 3 are preferable, and alkyl groups having 1 to 3 carbon atoms are more preferable. The aryl group represented by R ¹ is not particularly limited, and examples thereof include a phenyl group and the like.
As R ¹ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.
Further, the alkyl group and the aryl group represented by R ¹ may have a substituent (for example, a group exemplified in the substituent group T).

W ¹ represents a divalent linking group.
The divalent linking group represented by W ¹ is not particularly limited, and is, for example, -O-, -CO-, -S-, -SO _2- , ^-NRA- , arylene group, alkylene group, heteroarylene. Examples include a group and a group consisting of a combination thereof. The alkylene group may be substituted with a substituent such as a halogen atom (for example, the group exemplified in the substituent group T).

The carbon number of the arylene group is not particularly limited, but for example, 6 to 20 is preferable, 6 to 14 is more preferable, and 6 to 10 is further preferable. Specific examples of the arylene group include 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,7-fluorenylene group, and 3,6-. Examples thereof include a fluorenylene group, a 9,9-fluorenylene group, an anthrasenylene group and the like, and a 1,4-phenylene group is preferable.
The arylene group may have a substituent (for example, a group exemplified in the substituent group T).

The above ^RA represents a hydrogen atom or a substituent, and a hydrogen atom is preferable.
The substituent represented by ^RA is synonymous with the substituent represented by ^R1 .

The divalent linking group represented by W ¹ is that the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is more excellent, and that the cured film is repeatedly exposed to a high temperature-low temperature environment. A divalent linking group represented by the following general formula (III) is preferable because the spectral variation of the above is small.

In the general formula (III), A ¹ and A ³ independently represent a single bond or an arylene group, and at least one of A ¹ and A ³ represents an arylene group. A ² represents a single bond, -O-, CO-, -S-, -SO _2- , -NR ^A- , or an arylene group. ^RA represents a hydrogen atom or a substituent. * Represents the bond position.

The specific embodiments of the arylene group represented by ^{A 1} , A ² and A ³ and RA are as described above.
Among them, the arylene group represented by A1 to A3 is preferably ^a 1,4 ^- phenylene group.

Hereinafter, specific examples of the group represented by the above general formula (III) will be shown, but the present invention is not limited thereto.

V represents an alkyl group, an aryl group, or a heterocyclic group.
The alkyl group represented by V (which may be linear, branched, or cyclic) is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms and having 1 to 6 carbon atoms. Alkyl groups are more preferable, and alkyl groups having 1 to 3 carbon atoms are even more preferable.
Examples of the aryl group represented by V include an aryl group composed of a 6 to 10-membered ring or a fused ring thereof.
Specific examples of the ring constituting the aryl group are not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a naphthalene ring, and the like, and a benzene ring or a naphthalene ring. Is preferable, and a benzene ring is more preferable. The ring constitutes an aryl group by removing one hydrogen atom on the ring.
The heterocyclic group represented by V is not particularly limited, and examples thereof include an aliphatic heterocyclic group and an aromatic heterocyclic group. Examples of the aliphatic heterocycle include a 5-membered ring, a 6-membered ring, a 7-membered ring, or a fused ring thereof. Examples of the aromatic heterocycle include a 5-membered ring, a 6-membered ring, a 7-membered ring, or a fused ring thereof.
The condensed ring may contain a ring other than the heterocyclic group such as a benzene ring.

Examples of the hetero atom contained in the aliphatic heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom. The number of carbon atoms in the aliphatic heterocycle is not particularly limited, but is preferably 3 to 20.
Specific examples of the aliphatic heterocycle are not particularly limited, and examples thereof include an oxoran ring, an oxane ring, a piperidine ring, and a piperazine ring. The aliphatic heterocycle constitutes an aliphatic heterocyclic group by removing one hydrogen atom on the ring.

Examples of the hetero atom contained in the aromatic heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom. The number of carbon atoms of the aromatic heterocyclic group is not particularly limited, but is preferably 3 to 20.
Specific examples of the aromatic heterocycle are not particularly limited, but are furan ring, thiophene ring, pyrrole ring, oxazole ring, isooxazole ring, oxazole ring, thiazole ring, isothiazole ring, thiadiazol ring, imidazole ring, and pyrazole. Ring, Triazole ring, Frazan ring, Tetrazole ring, pyridine ring, Pyridazine ring, Pyrimidine ring, Pyrazine ring, Triazine ring, Tetradin ring, Benzofuran ring, Isobenzofuran ring, Benzothiophene ring, Indol ring, Indolin ring, Isoindole ring, Benzoxazole ring, benzothiazole ring, indazole ring, benzoimidazole ring, quinoline ring, isoquinoline ring, cinnoline ring, phthalazine ring, quinazoline ring, quinoxalin ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, aclysine ring, phenanthridine ring. , Phenantroline ring, phenazine ring, naphthylidine ring, purine ring, pteridine ring and the like. The aromatic heterocycle constitutes an aromatic heterocyclic group by removing one hydrogen atom on the ring.

The alkyl group, aryl group, and heterocyclic group represented by V may have a substituent (for example, a group exemplified in the substituent group T).

As the above V, an aryl group having a substituent is preferable in that the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is more excellent, and among them, it is represented by the following general formula (II). Groups are more preferred.

In the general formula (II), * represents the bonding position with X ³ in the general formula (I-1).
R ³ represents a substituent. Among them, as R3 ^, a cyano group, a nitro group, an alkyl group, an alkylthio group, or a halogen atom is preferable.
The alkyl group represented by R ³ (which may be linear, branched, or cyclic) is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms and 1 to 6 carbon atoms. Alkyl groups of 1 to 3 are more preferable, and alkyl groups having 1 to 3 carbon atoms are further preferable.
Examples of the halogen atom represented by R ³ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
The alkylthio group represented by R ³ is not particularly limited, and examples thereof include an alkylthio group having 1 to 10 carbon atoms, more preferably an alkylthio group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 3 carbon atoms. More preferred. The alkylene group in the alkylthio group may be linear, branched or cyclic.
The alkyl group and the alkylthio group represented by R ³ may further have a substituent (for example, a group exemplified in the substituent group T).

As R3 ^, a cyano group is preferable because the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is more excellent.

^R4 represents a substituent. Of these, as ^R4 , an aryl group, a heterocyclic group, a cyano group, a nitro group, an alkyl group, an alkylthio group, or a halogen atom is preferable.
The aryl group and the heterocyclic group represented by ^R4 have the same meaning as the aryl group and the heterocyclic group represented by V. As the aryl group represented by R ⁴ , a phenyl group is preferable.
The alkyl group, alkylthio group, and halogen atom represented by ^R4 have the same meanings as the alkyl group, alkylthio group, and halogen atom represented by R3 ^, and the preferred embodiments are also the same.
As ^R4 , an aryl group, a cyano group, a nitro group, or a halogen atom is preferable because the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is more excellent.

m and n each independently represent an integer of 0 to 5. However, m + n is 1 to 5.
M is preferably 0 and n is more preferably 1 in that the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is more excellent.

The group represented by the above general formula (II) is represented by the following general formula (IIA) in that the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is particularly excellent. Groups are preferred.

In the general formula (IIA), * represents the bonding position with X3 in the general formula (I ^- 1).
In the general formula (IIA), R ⁴ has the same meaning as R ⁴ in the general formula (II), and the preferred embodiment is also the same.
Among the R ^4s , the phenyl group substituted with R ⁴ is preferably located at the para position with respect to the bonding position with the phenylene group adjacent to the phenyl group. That is, for example, when R ⁴ represents an aryl group, the group represented by the general formula (IIA) is preferably a p-terphenylene group.

(Repeating unit represented by the general formula (I-2))

^In the general formula (I- ² ), X4, ^X5 , and X6 independently represent -NR ^2- , -O-, or -S-, respectively. W ² represents a divalent linking group. R ² represents a hydrogen atom or a substituent.

In the general formula (I-2), R ² has the same meaning as R ¹ in the general formula (I-1), and the preferred embodiment is also the same.
In the general formula (I-2), W ² is synonymous with W ¹ in the general formula (I-1).
Further, as the divalent linking group represented by W ² , the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is more excellent, and even if it is repeatedly exposed to a high temperature-low temperature environment. The arylene group represented by A ¹ to A ³ is preferably a 1,4-phenylene group because the spectral variation of the cured film is small.
The divalent linking group represented by W ² is that the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is more excellent, and that the cured film is repeatedly exposed to a high temperature-low temperature environment. It is more preferable that all of A 1 to A 3 represent an arylene group (preferably a 1,4-phenylene group) in that the spectral variation of A ¹ to A ³ is small.

As X ⁴ , X ⁵ and X ⁶ , the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is superior, and the spectroscopy of the cured film even after repeated exposure to a high temperature-low temperature environment. -NR ² -is preferable because the fluctuation is small.

Examples of the compound containing the repeating unit represented by the general formula (I-2) include compounds represented by the following (hypercondensate and heavy adduct).

(Example 1) A polycondensate or a heavy adduct of a compound represented by the following general formula (V) and a compound represented by the following general formula (VI).

In the above general formula (V), Y ¹ to Y ³ represent a leaving group (for example, a halogen atom) or an isocyanate group.
In the above general formula (VI), X ⁷ and X ⁸ independently represent -NR ^2- , -O-, or -S-, respectively. R ² represents a hydrogen atom or a substituent. W ³ represents a divalent linking group.
Examples of the substituent represented by the above-mentioned R ² include the same as those of the above-mentioned R ² in the general formula (II-2).
Examples of the divalent linking group represented by W ³ include the same groups as W ² in the general formula (II-2) described above.

(Example 2) A polycondensate or a heavy adduct of a compound represented by the following general formula (VII) and a compound represented by the following general formula (VIII).

In the above general formula (VII), X ⁹ to X ¹¹ independently represent -NR ^2- , -O-, or -S-. R ² represents a hydrogen atom or a substituent.
Examples of the substituent represented by the above-mentioned R ² include the same as those of the above-mentioned R ² in the general formula (II-2).
In the above general formula (VIII), Y ⁴ and Y ⁵ represent a leaving group (for example, a halogen atom) or an isocyanate group. W ⁴ represents a divalent linking group.
Examples of the divalent linking group represented by W ⁴ include the same groups as W ² in the general formula (II-2) described above.

Hereinafter, specific examples of the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2) will be shown, but the present invention is not limited thereto. In the following specific examples, "Me" represents a methyl group.

In the specific triazine-based resin, the repeating unit represented by the general formula (I-1) or the repeating unit represented by the general formula (I-2) is used with respect to all the repeating units in the specific triazine-based resin. It is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%.

The specific triazine resin can be synthesized according to a known method (polycondensation).

The weight average molecular weight of the specific triazine resin is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 20,000. The degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further preferably 1.1 to 2.0. preferable.

In the above composition, the specific triazine-based resin may be used alone or in combination of two or more.
In the above composition, the content of the specific triazine-based resin (in the case where a plurality of types are present, the total thereof) is generally 80.0% by mass or more with respect to the total solid content of the composition, and 85. 0% by mass or more is preferable, and 90.0% by mass or more is more preferable. The upper limit is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.5% by mass or less.

<Specific metal ion>
The composition contains a specific metal ion selected from the group consisting of sodium ion, potassium ion, and calcium ion.
In the composition, the total content of the specific metal ion is 0.01 to 30 mass ppm with respect to the total mass of the composition, and defect suppression of the cured film after repeated exposure to a high temperature-low temperature environment is suppressed. 0.03 to 10 mass ppm is preferable because it is more excellent in properties.
Further, in the composition, the total content of the specific metal ion is preferably 0.1 to 300 mass ppm with respect to the specific triazine-based resin, and after repeated exposure to a high temperature-low temperature environment. 0.3 to 100 mass ppm is preferable because it is more excellent in defect suppressing property of the cured film.
The content of the specific metal ion in the composition can be measured by an ICP (Inductively Coupled Plasma) emission spectrophotometer (for example, "Optima 7300DV" manufactured by PerkinElmer).

<Solvent>
The above composition contains a solvent.
Examples of the solvent include ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene. Glycol monoethyl ether acetate, 3-methoxypropyl acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propylene glycol diacetate, diethylene glycol monobutyl ether acetate, Esters such as γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, cyclohexyl acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl Alcohols such as ether, ethylene glycol monoisopropyl ether, 3-methoxypropanol, 1-methoxy-2-propanol, methoxymethoxyethanol, dipropylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether. Aromatic hydrocarbons such as benzene, xylene, ethylbenzene, and anisole; aliphatic hydrocarbons such as cyclohexane; nitriles such as acetonitrile; acetone, methyl ethyl ketone, acetylacetone, cyclohexanone, 2-heptanone, cyclopentanone, and di Ketones such as acetone alcohol; halogen compounds such as ethylene dichloride; ethers such as cyclohexylmethyl ether and dibutyl ether; 3-methoxy-N, N-dimethylpropanamide, N-ethyl-2-pyrrolidone, and 3-butoxy. Amides such as -N, N-dimethylpropanamide; and the like.
The details of the solvent can be referred to in paragraph No. 0223 of WO2015 / 166779, and the contents thereof are incorporated in the present specification. However, it may be better to reduce the amount of aromatic hydrocarbons as the solvent for environmental reasons (for example, the amount may be 50 mass ppm (parts per million) or less with respect to the total amount of the solvent. It can be 10 mass ppm or less, or 1 mass ppm or less).

(toluene)
The above composition may contain toluene as a solvent.
In the above composition, the total content of toluene is preferably 0.001 to 10 mass ppm with respect to the total mass of the composition. When the total content of toluene in the composition is within the above numerical range, the surface appearance of the coating film formed by the composition is excellent.
Further, the total content of the toluene in the composition is preferably 0.01 to 100 mass ppm with respect to the specific triazine resin.
The toluene content in the composition can be measured by gas chromatography.

In the composition, the solvent may be used alone or in combination of two or more.

In the present invention, it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, a solvent at the mass ppt (parts ppt) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).

Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.

In the present invention, the solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

The content of the solvent is preferably such that the solid content concentration of the composition is 1 to 90% by mass, more preferably the solid content concentration of the composition is 1 to 50% by mass, and the solid content concentration of the composition is 1 to 50% by mass. An amount of 5 to 30% by mass is more preferable, and an amount of 5 to 20% by mass is particularly preferable.
The solid content concentration of the composition is intended to be the concentration of the total solid content with respect to the total mass of the composition (that is, the concentration of the component forming the cured film in the composition). The definition of total solid content is as described above.

<Other ingredients>
The above composition may contain other components other than the above-mentioned components. Other components include curable compounds (including polymerizable compounds), polymerization initiators, antioxidants, silane coupling agents, polymerization inhibitors, surfactants, UV absorbers, fillers (eg, inorganic particles). ), Curing accelerator, plasticizer, developable improver such as low molecular weight organic carboxylic acid, and various additives such as anti-aggregation agent.

(Curable compound)
The composition preferably contains a curable compound.
As the curable compound, a known compound that can be cured by a radical, an acid, or heat can be used. For example, a compound having a group having an ethylenically unsaturated bond, a compound having an epoxy group, a compound having a reactive group such as a methylol group and a thiol group, and the like can be mentioned. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) acrylic group, a (meth) acryloyl group, a (meth) acryloyloxy group and the like, and a (meth) acryloyl group or a (meth) acryloyloxy group. Groups are preferred. The curable compound is preferably a polymerizable compound, more preferably a radically polymerizable compound. Examples of the polymerizable compound include compounds having a group having an ethylenically unsaturated bond.

The content of the curable compound is preferably 1 to 80% by mass with respect to the total solid content of the composition. The lower limit is more preferably 3% by mass or more, further preferably 4% by mass or more. The upper limit is more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 30% by mass or less.
In the above composition, the curable compound may be used alone or in combination of two or more. When the composition contains two or more curable compounds, the total content is preferably in the above range.

-A compound having a group having an ethylenically unsaturated bond (polymerizable compound)
In the present invention, as the curable compound, a compound having a group having an ethylenically unsaturated bond (hereinafter, also referred to as a polymerizable compound) can be used. The polymerizable compound is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more. The polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.

As an example of the polymerizable compound, the description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. Examples of the polymerizable compound include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and dipentaerythritol triacrylate (commercially available product KAYARAD D-330). ; Nippon Kayaku Co., Ltd.), Dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D) -310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available: KAYARAD DPHA; Nihon Kayaku Co., Ltd., A-DPH-12E; ), And a structure in which these (meth) acryloyl groups are bonded via an ethylene glycol residue and / or a propylene glycol residue is preferable. Also, these oligomer types can be used. Further, the description in paragraphs 0034 to 0038 of JP2013-253224A can be referred to, and this content is incorporated in the present specification. In addition, the polymerizable monomers described in paragraph No. 0477 of JP2012-208494A (paragraph No. 0585 of the corresponding US Patent Application Publication No. 2012/0235099) are mentioned, and the contents thereof are described in the present specification. Will be incorporated into. In addition, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., A-TMMT), 1 , 6-Hexanediol diacrylate (KAYARAD HDDA manufactured by Nippon Kayaku Co., Ltd.) is also preferable. These oligomer types can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

The polymerizable compound may have an acid group such as a carboxy group, a sulfo group, and a phosphoric acid group. Examples of the polymerizable compound having an acid group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A polymerizable compound obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group is preferable, and more preferably, in this ester, the aliphatic polyhydroxy compound is penta. It is erythritol and / or dipentaerythritol. Examples of commercially available products include M-305, M-510, and M-520 of the Aronix series as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g. The lower limit is more preferably 5 mgKOH / g or more. The upper limit is more preferably 30 mgKOH / g or less.

It is also a preferred embodiment that the polymerizable compound is a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and is, for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta. Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohols such as erythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelan with (meth) acrylic acid and ε-caprolactone. Can be mentioned. As the polymerizable compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc. commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and ethylene manufactured by Sartmer. Examples thereof include SR-494, which is a tetrafunctional acrylate having four oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutylene oxy chains.

Examples of the polymerizable compound include urethane acrylates described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Laid-Open No. 2-16765, and Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. .. Further, an addition-polymerizable compound having an amino structure and / or a sulfide structure in the molecule, which is described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can be used. Commercially available products include urethane oligomer UAs-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

-Compound having an epoxy group As the curable compound, a compound having an epoxy group can also be used. Examples of the compound having an epoxy group include a compound having one or more epoxy groups in one molecule, and a compound having two or more epoxy groups in one molecule is preferable. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit may be, for example, 10 or less, or 5 or less. The lower limit is preferably two or more.

The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g. / Equivalent is more preferred.

The compound having an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 1000) or a polymer compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). .. The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, further preferably 5000 or less, and particularly preferably 3000 or less.

As the compound having an epoxy group, a commercially available product can also be used. For example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation) and the like can be mentioned. Further, the compounds having an epoxy group include paragraph numbers 0034 to 0036 of JP2013-011869, paragraph numbers 0147 to 0156 of JP-A-2014-0435556, and paragraph numbers 805 to JP-A-2014-089408. The compounds described in 0092 can also be used. These contents are incorporated in the present specification.

(Polymer initiator)
The composition may contain a polymerization initiator, and preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, the photopolymerization initiator is preferably a compound having photosensitivity to light rays in the ultraviolet region to the visible region.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton and compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, and oxime derivatives. Oxime compounds such as, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like can be mentioned. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole. A compound selected from the group consisting of a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-aryl substituted coumarin compound is preferable, and an oxime compound is preferable. , Α-Hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds are more preferred. Among them, the oxime compound is more preferable in that the obtained film is more excellent. As the photopolymerization initiator, the description in paragraphs 0065 to 0111 of JP-A-2014-130173 can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound can also be preferably used. For example, the α-aminoketone compound described in JP-A No. 10-291969 and the acylphosphine compound described in Japanese Patent No. 4225898 can also be used. Examples of commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF). Examples of commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF). Examples of commercially available acylphosphine compounds include commercially available IRGACURE-819 and DAROCUR-TPO (all manufactured by BASF). Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), and ADEKA ARC. Described in Luz NCI-831 (manufactured by ADEKA Co., Ltd.), ADEKA Arklus NCI-930 (manufactured by ADEKA Co., Ltd.), and ADEKA PTOMER N-1919 (manufactured by ADEKA Co., Ltd., Japanese Patent Application Laid-Open No. 2012-14052). The photopolymerization initiator 2) and the like can be mentioned.

In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466. This content is incorporated herein.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. The compound (C-3) and the like described in the above can be mentioned. These contents are incorporated in the present specification.

In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples thereof include the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and ADEKA ARCULDS NCI-831 (manufactured by ADEKA Corporation).

Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

The oxime compound is preferably a compound having a maximum absorption in the wavelength region of 350 to 500 nm, and more preferably a compound having a maximum absorption in the wavelength region of 360 to 480 nm. Further, the oxime compound is preferably a compound having a high absorbance at 365 nm and 405 nm.
From the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, It is more preferably 000.
The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

The photopolymerization initiator also preferably contains an oxime compound and an α-aminoketone compound. By using both in combination, the developability is improved and it is easy to form a pattern having excellent rectangularity. When the oxime compound and the α-aminoketone compound are used in combination, it is preferable that the α-aminoketone compound is contained in an amount of 50 to 600 parts by mass, more preferably 150 to 400 parts by mass, based on 100 parts by mass of the oxime compound.

The content of the polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass, and 1 to 20% by mass with respect to the total solid content of the composition. 10% by mass is particularly preferable.
When the content of the polymerization initiator is in the above range, it is easy to form a pattern having excellent sensitivity and rectangularity. The above composition may contain only one kind of polymerization initiator, or may contain two or more kinds of polymerization initiators. When the composition contains two or more kinds of polymerization initiators, the total content thereof is preferably in the above range.

(Antioxidant)
The composition may contain an antioxidant.
Examples of the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like. As the antioxidant, a phenol compound having a molecular weight of 500 or more, a phosphite ester compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is preferable. These may be used by mixing two or more kinds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used, and a polysubstituted phenol-based compound is preferable. Polysubstituted phenolic compounds are roughly classified into three types (hindered type, semi-hindered type, and less hindered type) having different substitution positions and structures. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is preferably used. Further, as the antioxidant, a phosphorus-based antioxidant is also preferably used. Commercially available products can also be used as the antioxidant. Commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , And ADEKA STAB AO-330 (ADEKA Corporation) and the like. Further, as the antioxidant, the description in paragraphs 0033 to 0043 of JP-A-2014-032380 can be referred to, and the content thereof is incorporated in the present specification.

The content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total solid content of the composition. Only one type of antioxidant may be used, or two or more types may be used. When the composition contains two or more kinds of antioxidants, the total content thereof is preferably in the above range.

(Silane coupling agent)
The composition may contain a silane coupling agent.
In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Further, as the functional group other than the hydrolyzable group, a group that exhibits an affinity by forming an interaction or a bond with the resin is preferable. Examples thereof include a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, a phenyl group and the like, and the (meth) acryloyl group or An epoxy group is preferred.

Specific examples of the silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane and the like. Examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. The contents of are incorporated herein by reference. Commercially available products can also be used as the silane coupling agent. Commercially available silane coupling agents include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM manufactured by Shinetsu Silicone Co., Ltd. -3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402 , KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE -903, KBE-9103, KBM-573, KBM-575, KBM-9569, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053, X-41-1059A , X-41-1056, X-41-1805, X-41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, KR -516, KR-517, X-40-9296, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510 , KR-9218, KR-213, X-40-2308, and X-40-9238 and the like.

The content of the silane coupling agent is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, based on the total solid content of the composition. The silane coupling agent may be only one kind or two or more kinds. When the composition contains two or more kinds of silane coupling agents, the total content thereof is preferably in the above range.

(Polymerization inhibitor)
The composition may contain a polymerization inhibitor.
Polymerization inhibitors are hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2 , 2'-Methylenebis (4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, etc.). Of these, p-methoxyphenol is preferable. The polymerization inhibitor may also function as an antioxidant.

The content of the polymerization inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, still more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerization initiator.

(Surfactant)
The composition may contain various surfactants from the viewpoint of further improving the coatability.
As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Surfactants can be referred to in paragraphs 0238-0245 of WO2015 / 166779, the contents of which are incorporated herein.

When the composition contains a fluorine-based surfactant, the liquid characteristics (particularly, fluidity) when prepared as a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. When a film is formed using a coating liquid to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. The applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the composition.

Specific examples of the fluorine-based surfactant include the surfactants described in paragraphs Nos. 0060 to 0064 of JP-A-2014-41318 (paragraphs Nos. 0060-0064 of the corresponding International Publication No. 2014/17669) and the like. The surfactants described in paragraphs 0117 to 0132 of JP-A-2011-132503 are mentioned, and their contents are incorporated in the present specification. Examples of commercially available fluorosurfactants include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, and F475. F479, F482, F554, and F780 (all manufactured by DIC Co., Ltd.), Florard FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC- 101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by Asahi Glass Co., Ltd.) ), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA) and the like.

Further, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied can also be preferably used. .. Examples of such a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafuck DS. -21 can be mentioned.

A block polymer can also be used as the fluorine-based surfactant. For example, the compounds described in JP-A-2011-89090 can be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups) (meth). ) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compounds is preferably, for example, 3,000 to 50,000, and specific examples thereof include 14,000. In the above compounds,% indicating the ratio of the repeating unit is mass%.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, for example, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. , And RS-72-K and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate and glycerol ethoxylate). In addition, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10. , L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.) , NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), and Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like can also be mentioned.

Further, as the fluorine-based surfactant, a vinyl ether polymerized fluorine-based surfactant can also be used. Examples of the vinyl ether polymerized fluorine-based surfactant include those described in the Example column of JP-A-2016-216602 (for example, the fluorine-based surfactant (1)).

The content of the surfactant is preferably 0.0001 to 5.0% by mass, more preferably 0.0005 to 3.0% by mass, based on the total solid content of the composition. The surfactant may be only one kind or two or more kinds. When the composition contains two or more types of surfactants, the total content thereof is preferably in the above range.

(UV absorber)
The composition may contain an ultraviolet absorber.
Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds and the like. For details thereof, the description of paragraph numbers 0052 to 0072 of JP2012-208374A and paragraph numbers 0317 to 0334 of JP2013-68814A can be referred to, and these contents are incorporated in the present specification. .. Examples of commercially available conjugated diene compounds include UV-503 (manufactured by Daito Kagaku Co., Ltd.) and the like. Further, as the benzotriazole compound, the MYUA series (The Chemical Daily, February 1, 2016) manufactured by Miyoshi Oil & Fat may be used.
The content of the ultraviolet absorber is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.1 to 3% by mass, based on the total solid content of the composition. Further, the ultraviolet absorber may be of only one type or may be two or more types. When the composition contains two or more types of ultraviolet absorbers, the total content thereof is preferably in the above range.

(Filler)
Examples of the filler include inorganic particles. The inorganic particles preferably have a high refractive index and are colorless, white or transparent, and are preferably titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), zinc (Zn), or magnesium (Mg). ) And the like, and titanium dioxide (TiO ₂ ) particles, zirconium oxide (ZrO ₂ ) particles, or silicon dioxide (SiO ₂ ) particles are more preferable.
The primary particle diameter of the inorganic particles is not particularly limited, and is preferably 1 to 100 nm, more preferably 1 to 80 nm, still more preferably 1 to 50 nm. When the primary particle diameter of the inorganic particles is within the above range, the dispersibility is further improved, and the refractive index and the transmittance are further improved.
The refractive index of the inorganic particles is not particularly limited, but is preferably 1.75 to 2.70, more preferably 1.90 to 2.70, from the viewpoint of obtaining a high refractive index.
The specific surface area of the inorganic particles is not particularly limited, but is preferably 10 to 400 m ² / g, more preferably 20 to 200 m ² / g, and even more preferably 30 to 150 m ² / g.
The shape of the inorganic particles is not particularly limited, and examples thereof include rice granules, spherical shapes, cube shapes, spindle shapes, and indefinite shapes.
The inorganic particles may be 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 or a silane coupling agent is preferable.
It is also preferable that the surface of the inorganic particles is covered with an oxide such as aluminum, silicon, and zirconia from the viewpoint of further improving the weather resistance.
As the inorganic particles, commercially available particles can be preferably used.
In the above composition, the inorganic particles may be used alone or in combination of two or more.

(Curing accelerator)
When the composition contains a compound containing a cationically polymerizable group (for example, a compound having an epoxy group) as the curable compound, the composition preferably contains a curing accelerator.
Examples of the curing accelerator for improving the curing rate include acid anhydrides, bases (aliphatic amines, aromatic amines, modified amines, etc.), acids (sulfonic acid, phosphoric acid, carboxylic acid, etc.), polypeptide, and the like. Can be mentioned. Of these, acid anhydrides are preferable, and aliphatic acid anhydrides are even more preferable.

<Preparation method of composition>
The above composition can be prepared by mixing the above-mentioned components. In preparing the composition, each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then sequentially blended. For example, the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time. Further, even if a composition exhibiting particle properties is dispersed in a solvent and a resin to prepare a composition, and the obtained composition is mixed with other components (for example, a specific triazine-based resin and a curable compound). good.

When the composition contains a component exhibiting particle properties, it is preferable to include a process of dispersing the particles in the method for preparing the composition. In the process of dispersing particles, the mechanical force used for dispersing the particles includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like. Further, in the pulverization of particles in a sand mill (bead mill), it is preferable to use beads having a small diameter and to process the particles under conditions in which the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. In addition, as the process and disperser for dispersing particles, "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial Practical application The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used. Further, in the process of dispersing the particles, the particles may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.

In preparing the above composition, it is preferable to filter the composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6 and nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density and / Or a filter using a material such as (including an ultra-high molecular weight polyolefin resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
The pore size of the filter is preferably about 0.01 to 7.0 μm, more preferably about 0.01 to 3.0 μm, and even more preferably about 0.05 to 0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be reliably removed. It is also preferable to use a fibrous filter medium. Examples of the fiber-like filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specific examples thereof include filter cartridges such as SBP type series (SBP008 etc.), TPR type series (TPR002 and TPR005 etc.), and SHPX type series (SHPX003 etc.) manufactured by Loki Techno Co., Ltd.

When using filters, different filters (eg, first filter and second filter, etc.) may be combined. At that time, the filtration with each filter may be performed only once or twice or more. Further, filters having different pore diameters may be combined within the above-mentioned range. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. Examples of commercially available filters include various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), and KITZ Microfilter Co., Ltd. You can choose. As the second filter, one formed of the same material as the first filter can be used. Further, the filtration with the first filter may be performed on the mixed liquid in which only the resin and the solvent are mixed, and after mixing the other components, the filtration may be performed with the second filter.

<Use>
The use of the above composition and the resin of the present invention described later is not particularly limited. White pixels, etc.), lenses (eyeglass lenses, digital camera lenses, Fresnel lenses, prism lenses, etc.), optical overcoat agents, hard coat agents, antireflection films, optical fibers, optical waveguides, LEDs (Light Emitting Diodes) It is useful as a sealing material for lenses, a flattening material for LEDs, and a coating material for solar cells.

〔film〕
The film of the present invention is a film obtained from the composition of the present invention.
Here, the above-mentioned "film" is intended to be both a coating film (uncured film) formed by the composition of the present invention and a cured film formed by curing the coating film.
When the curable compound is contained in the composition, the cured film can be obtained by subjecting the coating film formed of the above composition to a curing treatment.
The refractive index (wavelength 589 nm) of the film is not particularly limited, but is preferably 1.55 or more, and more preferably 1.6 to 2.0.
The light transmittance of the film is not particularly limited, but is preferably 90% or more, more preferably 95% or more, still more preferably 100% over the entire wavelength region of 400 to 700 nm.
The thickness of the film is not particularly limited, but is preferably 0.1 to 20 μm, more preferably 0.1 to 10 μm, and even more preferably 0.5 to 4 μm.

The method for curing the composition is not particularly limited, and examples thereof include heating and exposure. The device used for heating is not particularly limited, and a blower dryer, an oven, an infrared dryer, a heating drum, and the like can be used. The apparatus used for exposure is not particularly limited, and a mercury lamp, a metal halide lamp, a xenon (Xe) lamp, a chemical lamp, a carbon arc lamp, or the like can be used.

<Manufacturing method of patterned cured film>
Hereinafter, as an example of a method for producing a cured film, a method for producing a patterned cured film will be described in detail.

The method for producing a patterned cured film includes a step of applying the above composition on a substrate to form a composition layer (coating film) (hereinafter, appropriately abbreviated as "composition layer forming step"). A step of exposing the composition layer via a mask (hereinafter, appropriately abbreviated as "exposure step") and a step of developing the exposed composition layer to form a patterned cured film (hereinafter, referred to as "exposure step"). As appropriate, abbreviated as "development step").
The composition used above usually contains a curable compound and a photopolymerization initiator.

Specifically, the above composition is applied onto a substrate directly or via another layer to form a composition layer (composition layer forming step), exposed through a predetermined mask pattern, and subjected to light. By curing only the irradiated composition layer portion (exposure step) and developing with a developing solution (development step), a patterned cured film composed of pixels can be formed.
Hereinafter, each step will be described.

-Composition layer forming step In the composition layer forming step, the above composition is applied onto a substrate to form a composition layer (coating film).

The substrate is not particularly limited, and for example, non-alkali glass, soda glass, Pylex (registered trademark) glass, quartz glass used for liquid crystal display devices, etc., those to which a transparent conductive film is attached, a solid-state image sensor, etc. Examples thereof include a photoelectric conversion element substrate (for example, a silicon substrate), a CCD (Charge Coupled Device) substrate, and a CMOS (Complementary Metal Oxide Semiconductor) substrate used in the above.

As a method for applying the composition onto a substrate, various coating methods such as slit coating, inkjet method, rotary coating, cast coating, roll coating, and screen printing method can be applied.

The coating film thickness of the composition can be appropriately selected depending on the intended use, but is, for example, 0.1 to 20 μm, more preferably 0.1 to 10 μm, still more preferably 0.5 to 4 μm.

The composition applied on the substrate is usually dried at 70 to 110 ° C. under the condition of about 2 to 4 minutes. This makes it possible to form a composition layer.

-Exposure step In the exposure step, the composition layer (coating film) formed in the composition layer forming step is exposed through a mask, and only the light-irradiated coating film portion is cured.
The exposure is preferably performed by irradiation with active light rays or radiation, and in particular, ultraviolet rays such as g-line, h-line, or i-line are more preferable. The irradiation intensity is preferably 5 to 1500 mJ / cm ² , more preferably 10 to 1000 mJ / cm ² .

-Development process Following the exposure process, an alkaline development process (development process) is performed to elute the unirradiated portion of the light in the exposure process into an alkaline aqueous solution. As a result, only the photo-cured portion (light-irradiated coating film portion) remains.
As the developer, an organic alkaline developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. As the inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, or sodium metasilicate is used at a concentration of 0.001 to 10% by mass, preferably 0.01 to. Examples thereof include an alkaline aqueous solution dissolved in an amount of 1% by mass. Examples of the organic developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5.4. .0] Examples thereof include an alkaline aqueous solution in which an alkaline compound such as -7-undecene is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the alkaline aqueous solution. When a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

As the developing method, for example, a paddle developing method, a shower developing method, or the like can be used.

〔lens〕
The film of the present invention (preferably a cured film) can also be used as a lens. As the lens, among them, it can be suitably used for the microlens of the above-mentioned solid-state image sensor.

[Solid image sensor]
The film of the present invention (preferably a cured film) can be suitably applied to a solid-state image sensor.
The configuration of the solid-state image sensor of the present invention includes, for example, a light-receiving element composed of a plurality of photodiodes and polysilicon that constitute a light-receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a substrate. In addition, a configuration in which an undercoat film, which is the film of the present invention, is provided under the color filter can be mentioned.

〔resin〕
The present invention also relates to a novel resin that can be suitably used as a high refractive index material. The resin of the present invention is a resin containing a repeating unit represented by the following general formula (IV-1) or a repeating unit represented by the following general formula (IV-2). The resin containing the repeating unit represented by the following general formula (IV-1) or the repeating unit represented by the following general formula (IV-2) corresponds to one form of the above-mentioned specific triazine-based resin.
The resin of the present invention will be described in detail below.
<Repeating unit represented by the general formula (IV-1)>

In the general formula (IV-1), X ¹ , X ² , and X ³ independently represent -NR ^1- , -O-, or -S-, respectively. W ¹ represents a divalent linking group. R ¹ represents a hydrogen atom or a substituent. R ⁵ represents a heterocyclic group, a cyano group, a nitro group, an alkyl group, an alkylthio group, or a halogen atom.

In the general formula (IV-1), X ¹ , X ² , X ³ , and W ¹ are synonymous with X ¹ , X ² , X ³ , and W ¹ in the general formula (I-1) described above. , The preferred embodiment is also the same.

In the general formula (IV-1), R ⁵ represents a heterocyclic group, a cyano group, a nitro group, an alkyl group, an alkylthio group, or a halogen atom.
As a preferred embodiment of the heterocyclic group, alkyl group, alkylthio group and halogen atom represented by R5, the heterocyclic group and alkyl group represented by ^R4 in the general formula ⁽ II) described above are used. The same applies to the alkylthio group and the halogen atom.

As the above general formula (IV-1), the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is more excellent, and in particular, the group represented by the following general formula (IV-1A). It is preferable to have.

Above all, it is preferable that R ⁵ is located at the para position with respect to the bonding position with the phenylene group adjacent to the phenyl group substituted by R ⁵ .

<Repeating unit represented by the following general formula (IV-2)>

^In the general formula ( ^IV -2), X4, ^X5 , and X6 independently represent -NR ^2- , -O-, or -S-, respectively. R ² represents a hydrogen atom or a substituent.

In the general formula ( ^IV - ² ), X4, ^X5 , and X6 are synonymous with ^X4 , ^X5 , and X6 in the above ^- mentioned general formula (I-2), and the preferred embodiments are also the same. be.

As the above general formula (IV-2), the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is more excellent, and in particular, the group represented by the following general formula (IV-2A). It is preferable to have.

In the resin, the repeating unit represented by the general formula (I-1) or the repeating unit represented by the general formula (I-2) is 50 to 100 mol% with respect to all the repeating units in the resin. Is preferable, 80 to 100 mol% is more preferable, and 90 to 100 mol% is further preferable.

The weight average molecular weight of the resin is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 20,000. The degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further preferably 1.1 to 2.0. preferable.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

[1] Synthesis of a resin containing a repeating unit represented by the general formula (I-1) or a repeating unit represented by the following general formula (I-2) <Synthesis Example 1: Resin (A-1)>

9.0 g of cyanuric chloride and 13.2 g of tetrahydrofuran were weighed in a container, and the obtained solution was ice-cooled with stirring under a nitrogen stream. Then, a solution prepared by dissolving 10.0 g of 4-amino-4'-cyanobiphenyl in 76.8 g of tetrahydrofuran was added dropwise to this ice-cooled solution, and the mixture was further stirred for 2 hours. 380 g of 0.2% by mass hydrochloric acid water was added to the reaction solution after stirring, and the obtained solid was filtered. Then, the filtered solid was washed with 1000 g of ion-exchanged water and vacuum dried at 60 ° C. to obtain 16.0 g of compound (i-1).

2.0 g of 1,4-phenylenediamine and 40.6 g of N, N-dimethylacetamide were weighed in a container, and the obtained mixture was heated to 100 ° C. under a nitrogen stream. Then, a solution prepared by dissolving 6.4 g of compound (i-1) in 25.7 g of N, N-dimethylacetamide was added to the heated solution, and the mixture was stirred for 1 hour. Next, 0.9 mL of aniline was added to the reaction solution after stirring, and the mixture was further stirred for 10 minutes. The obtained reaction solution was cooled to room temperature and then added to an aqueous solution of 7.0 g of triethylamine and 380 g of ion-exchanged water. After filtering the precipitated solid, the filtered solid was washed 3 times with 100 g of ion-exchanged water and then once with 100 g of ethanol. The obtained solid was vacuum dried at 60 ° C. to obtain 7.2 g of compound (A-1).

<Synthesis Example 2: Resin (A-2)>
4-Amino-4'-cyanobiphenyl and 1,4-phenylenediamine were changed to 4-amino-p-terphenyl and 1,3-phenylenediamine, respectively, and synthesized except that they were reacted at the same molar equivalent. The same operation as in Example 1 was carried out to obtain compound (A-2).

<Synthesis Example 3: Resin (A-3)>
4-Amino-4'-cyanobiphenyl and 1,4-phenylenediamine were changed to 4-amino-4'-chlorobiphenyl and 4,4'-diaminobenzanilide, respectively, and reacted at the same molar equivalent. The same operation as in Synthesis Example 1 was carried out except for the compound (A-3).

<Synthesis Example 4: Resin (A-4)>
Except that 4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine were changed to 4-amino-4'-methylbiphenyl and 4,4'-diaminodiphenyl ether, respectively, and reacted at the same molar equivalent. The same operation as in Synthesis Example 1 was carried out to obtain compound (A-4).

<Synthesis Example 5: Resin (A-5)>
4-Amino-4'-cyanobiphenyl and 1,4-phenylenediamine were converted to 4-amino-4'-nitrobiphenyl and bis (4-aminophenyl) sulfide, respectively, and reacted at the same molar equivalent. The same operation as in Synthesis Example 1 was carried out except for the above, to obtain compound (A-5).

<Synthesis Example 6: Resin (A-6)>
4-Amino-4'-cyanobiphenyl and 1,4-phenylenediamine were changed to 4-amino-4'-methylthiobiphenyl and bis (4-aminophenyl) sulfone, respectively, and reacted at the same molar equivalent. The same operation as in Synthesis Example 1 was carried out except for the compound (A-6).

<Synthesis Example 7: Resin (A-7)>
Except that 4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine were changed to p-cyanoaniline and 4,4 "-diamino-p-terphenyl, respectively, and reacted at the same molar equivalent. The same operation as in Synthesis Example 1 was carried out to obtain compound (A-7).

<Synthesis Example 8: Resin (A-8)>
4-Amino-4'-cyanobiphenyl and 1,4-phenylenediamine were changed to 4-amino-p-terphenyl and 4,4 "-diamino-p-terphenyl, respectively, and reacted at the same molar equivalent. The same operation as in Synthesis Example 1 was carried out except that the compound (A-8) was obtained.

<Synthesis Example 9: Resin (A-9)>

Weigh 9.2 g of cyanuric chloride, 8.7 g of 4,4 "-diamino-p-terphenyl, and 56.7 g of N, N-dimethylacetamide in a container, and weigh the resulting mixture at 100 ° C. under a nitrogen stream. Then, 3.0 mL of aniline was added to the reaction solution after stirring, and the mixture was further stirred for 10 minutes. After cooling the obtained reaction solution to room temperature, 14.0 g of triethylamine and 14.0 g of triethylamine and It was added to an aqueous solution of 760 g of ion-exchanged water. After filtering the precipitated solid, the filtered solid was washed 3 times with 200 g of ion-exchanged water and then once with 200 g of ethanol. The obtained solid was washed 60 times. By vacuum drying at ° C., 15.1 g of the compound (A-9) was obtained.

<Synthesis Example 10: Resin (A-10)>
The same operation as in Synthesis Example 9 was carried out except that 4,4 "-diamino-p-terphenyl was changed to 1,3-phenylenediamine and reacted at the same molar equivalent, and the compound (A-10) was obtained. Obtained.

<Synthesis Example 11: Resin (A-11)>

In the container, 9.6 g of compound (i-2), 4.4 g of 4-aminophenol, 1,8-diazabicyclo [5.4.0] -7-undecene 1,8-diazabicyclo [5.4.0]- 14.0 g of 7-undecene and 32.7 g of N, N-dimethylacetamide were weighed, and the obtained mixture was heated to 100 ° C. under a nitrogen stream and stirred for 1 hour. Next, 2.0 mL of aniline was added to the reaction solution after stirring, and the mixture was further stirred for 10 minutes. The obtained reaction solution was cooled to room temperature and then added to an aqueous solution of 760 g of ion-exchanged water. After filtering the precipitated solid, the filtered solid was washed 3 times with 200 g of ion-exchanged water and then once with 200 g of ethanol. The obtained solid was vacuum dried at 60 ° C. to obtain 10.7 g of compound (A-11).

The structures of the resins (A-1) to (A-11) are shown below.

Table 1 shows the weight average molecular weight (polystyrene conversion value) measured by GPC (Gel Permeation Chromatography) of the resins (A-1) to (A-11).

Moreover, when the contents of sodium ion, potassium ion, and calcium ion contained in the resin (A-1) to (A-11) were quantified, it was confirmed that each was less than 0.01 mass ppm. An ICP emission spectrophotometer (“Optima7300DV” manufactured by PerkinElmer) was used for the quantification of sodium ion, potassium ion, and calcium ion.

Further, when the content of toluene contained in the resins (A-1) to (A-11) was quantified, it was confirmed that the content was less than 0.001 mass ppm.
The toluene concentration in the resin was quantified after preparing a calibration curve by gas chromatography according to a known method.

[2] Various components The following shows various components contained in the composition.
<Specific triazine resin>
For the specific triazine-based resin (resin containing the repeating unit represented by the general formula (I-1) or the repeating unit represented by the following general formula (I-2)), the above-mentioned resins (A-1) to ( A-11) was used.

<Curable compound>
The curable compounds M-1 to M-7 shown below were used.

<Photopolymerization initiator>
The photopolymerization initiators I-1 to I-12 shown below were used.
In the structural formula, "Me" indicates a methyl group and "Ph" indicates a phenyl group.

<Solvents other than toluene>
As the solvent other than toluene, the following solvents were used.
NEP: N-ethyl-2-pyrrolidone MFG: 1-methoxy-2-propanol CPN: cyclopentanone

<Surfactant>
The following surfactants were used.
Mega Fuck R-40 (manufactured by DIC Corporation)

<Contents of specific metal ions in each component>
Each of the above-mentioned components is purified and used after confirming that the content of sodium ion, potassium ion, and calcium ion in each component is less than 0.01 mass ppm. .. The method for quantifying sodium ion, potassium ion, and calcium ion is as described above.

<Content of toluene in each component>
Each of the above-mentioned components is used after confirming that the content of toluene in each component is less than 0.001 mass ppm by vacuum drying. The method for quantifying the toluene content in each component is as described above.

[3] Preparation of composition After mixing the above-mentioned various components (resin, solvent other than toluene, curable compound, polymerization initiator, and surfactant) at the blending ratios shown in Table 2, the obtained mixture is vacuumed. After drying, it was confirmed that the contents of sodium ion, potassium ion, and calcium ion in the dried product were less than 0.01% by mass, respectively. It was also confirmed that the toluene content was less than 0.001 mass ppm.

Next, resins, curable compounds, polymerization initiators, surfactants, solvents other than toluene, and the following toluene, sodium ions (sodium bromide methanol solution as a sodium source), potassium ions (as a potassium source) Various compositions were prepared by adding potassium bromide methanol solution) and calcium ions (calcium bromide methanol solution as a calcium ion source) so as to have the contents shown in Table 2. In addition, in the column of "solvent other than toluene" in Table 2, methanol in the above ion source is also contained in a trace amount. The content of each component in Table 2 represents the content ratio (%) with respect to the total mass of the composition.

The contents of sodium ion, potassium ion, and calcium ion in the obtained composition were quantified using an ICP emission spectrophotometer (“Agilent 7800 ICP-MS” manufactured by Agilent Technologies).
The toluene content in the obtained composition was quantified after preparing a calibration curve by gas chromatography according to a known method.

[4] Evaluation Using the obtained composition, evaluation of the refractive index of the cured film after the thermocycle, spectral variation of the cured film after the thermocycle, evaluation of defect suppression of the cured film after the thermocycle, and evaluation. The surface appearance of the coating film was evaluated.

<Evaluation of the refractive index of the cured film after the thermocycle>
The compositions shown in Table 2 are spin-coated on a 5 cm × 5 cm glass substrate on which an epoxy resin layer is formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resin), and baked at 100 ° C. for 3 minutes. (Heating). Next, the obtained coating film was exposed using a high-pressure mercury lamp so that the integrated exposure amount was 200 mJ / cm ² . Then, the glass substrate was baked at 200 ° C. for 3 minutes to obtain a cured film having a film thickness of 1 μm. The obtained cured film was placed in a thermal shock test device (ESPEC THERMAL Shock CHAMBER TSA-70L (manufactured by TABAI ESPEC)), and a cooling cycle of −65 ° C./30 minutes → 125 ° C./30 minutes was performed for 300 cycles. J. A. The refractive index at a wavelength of 300 to 1500 nm was measured using VASE manufactured by Woollam, and the value of the refractive index at a wavelength of 589 nm was taken as the refractive index of each film.

The refractive index of the cured film after the thermocycle was evaluated by comparing the measured refractive index values with the following criteria.
"A": Refractive index is 1.85 or more "B": Refractive index is 1.70 or more and less than 1.85 "C": Refractive index is less than 1.70

<Spectroscopic fluctuation of cured film after thermocycle (change in transmittance)>
In the evaluation of the refractive index, the amount of change in the transmittance of the cured film at a wavelength of 450 nm before and after the cold shock test (| transmittance before the cold shock test-transmittance before the cold shock test | (absolute value)) was measured.
The measured change in transmittance was compared with the following criteria to evaluate the spectral variation (change in transmittance) of the cured film after the thermocycle.
"A": The fluctuation rate of the transmittance is less than 1%.
"B": The fluctuation rate of the transmittance is 1% or more and less than 5%.
"C": The fluctuation rate of the transmittance is 5% or more, which is a practically problematic level.
The change rate (%) of the transmittance is a value calculated by {(change amount of transmittance) / (transmittance before thermal impact test)} × 100.

<Evaluation of defect suppression of cured film after thermocycle>
The compositions shown in Table 2 are spin-coated on a silicon wafer on which an epoxy resin layer is formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resin), and further baked (heated) at 100 ° C. for 3 minutes. Then, a coating film having a thickness of 1 μm was formed. Next, the obtained coating film was exposed using a high-pressure mercury lamp so that the integrated exposure amount was 200 mJ / cm ² . Then, the glass substrate was baked at 200 ° C. for 3 minutes to obtain a cured film having a film thickness of 1 μm. The obtained cured film was placed in a thermal shock tester (ESPEC THERMAL Shock CHAMBER TSA-70L (manufactured by TABAI ESPEC)), and after applying a cold heat cycle of -65 ° C./30 minutes → 125 ° C./30 minutes for 300 cycles. , The number of defects (pieces / cm ² ) of the cured film was measured using a defect inspection device (ComPlus manufactured by Applied Materials).

The measured number of defects was classified into the following criteria, and the defect suppression property of the cured film after the thermocycle was evaluated.
"A": Number of defects is 0 / cm ² or more and less than 10 / cm ² "B": Number of defects is 10 / cm ² or more and less than 20 / cm ² "C": Number of defects is 20 / cm ² The above is a level that poses a practical problem.

<Evaluation of surface appearance of coating film (PCD (Post Coating Delay) evaluation of coating film>
The compositions shown in Table 2 are spin-coated on a silicon wafer on which an epoxy resin layer is formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resin), and further baked (heated) at 100 ° C. for 3 minutes. Then, a coating film A having a thickness of 1 μm was formed, and it was observed with an optical microscope that there was no abnormality. The coating film A was left at 25 ° C. for 100 hours, and the coating film B was observed with an optical microscope.

The coating film B observed was evaluated according to the following criteria, and the surface appearance of the coating film was evaluated.
"A": No surface roughness or foreign matter is observed on the film.
"B": Rough surface of the film or some foreign matter is observed, but it is a level that does not pose a problem in practical use.
"C": Rough surface of the film or some foreign matter is observed, which is a practically problematic level.

Table 2 is shown below.
In Table 2, "0" in the "Specified metal ion" column means that the content of the specific metal ion in the composition was less than 0.01 mass ppm. Further, "0" in the "toluene" column means that the content of toluene in the composition was less than 0.001 mass ppm.
Further, the "remaining amount" in the "solvent other than toluene" column in Table 2 is the total mass ratio of the constituent components other than the "solvent other than toluene" in the composition from the total ratio (100%) of the composition. Intended for quantities excluding.

From the results in Table 2, according to the composition of the example, the obtained cured film was repeatedly exposed to the high temperature-low temperature environment, and the defect generation was suppressed even after the cured film was repeatedly exposed to the high temperature-low temperature environment. It is clear that the spectral fluctuation (change in transmittance) is small even after this.
Further, from the comparison of Examples 1 to 21, when the total content of the specific metal ion in the above composition is 0.03 to 10 mass ppm with respect to the total mass of the composition, it is repeated under a high temperature-low temperature environment. It was confirmed that the cured film was more excellent in suppressing defects after being exposed.
Further, from the comparison of Examples 1 to 21, it was confirmed that when the content of toluene in the above composition is 0.001 to 10 mass ppm with respect to the total mass of the composition, the surface appearance characteristics are superior. ..
Further, from the comparison of Examples 9, 15 and 19, when the above composition contains the triazine resin represented by the above-mentioned general formula (I-2), W ² is the above-mentioned general formula (the above-mentioned general formula ( It is a divalent linking group represented by III), and when the arylene group contained in A ¹ to A ³ is a 1,4-phenylene group, or A ¹ to A ³ all represent an arylene group. In some cases, the refractive index of the cured film after repeated exposure to the high temperature-low temperature environment is better, and the spectral fluctuation (change in transmittance) of the cured film even after repeated exposure to the high temperature-low temperature environment. It was confirmed that it was small.
Further, from the comparison between Examples 1 to 3, Examples 7 and 8, Examples 10 to 14, and Examples 17 to 18 and Example 16, the above composition is found in the above-mentioned general formula (I-1). When each of X ¹ to X ³ contains a specific triazine-based resin having -NR ^1- , the refractive index of the cured film after repeated exposure to a high temperature-low temperature environment is better, and the high temperature-low temperature environment is obtained. It was confirmed that the spectral fluctuation (change in transmittance) of the cured film was small even after repeated exposure to the bottom.

Claims (15)

A resin containing a repeating unit represented by the general formula (I-1) or a repeating unit represented by the general formula (I-2).
With solvent
Specific metal ions selected from the group consisting of sodium ions, potassium ions, and calcium ions ,
Curable compounds and
A composition comprising a polymerization initiator .
A composition having a total content of the specific metal ion of 0.01 to 30 mass ppm with respect to the total mass of the composition.

In the general formula (I-1), X ¹ , X ² , and X ³ independently represent −NR ¹ −, — O—, or —S—, respectively. W ¹ represents a divalent linking group. V represents an alkyl group, an aryl group, or a heterocyclic group. R ¹ represents a hydrogen atom or a substituent.

^In the general formula (I- ² ), X4, ^X5 , and X6 independently represent -NR ^2- , -O-, or -S-, respectively. W ² represents a divalent linking group. R ² represents a hydrogen atom or a substituent. The solvent contains toluene and
The composition according to claim 1, wherein the content of toluene is 0.001 to 10 mass ppm with respect to the total mass of the composition. The composition according to claim 1 or 2, wherein V in the general formula (I-1) is a group represented by the general formula (II).

In the general formula (II), * represents the bonding position with X ³ in the general formula (I-1). R ³ and R ⁴ each independently represent a substituent. m and n each independently represent an integer of 0 to 5. However, m + n is 1 to 5. In the general formula (II), the m represents 0, the n represents 1, and the ^R4 represents an aryl group, a heterocyclic group, a cyano group, a nitro group, an alkyl group, an alkylthio group, or a halogen atom. , The composition according to claim 3. The composition according to claim 4, wherein the group represented by the general formula (II) is a group represented by the general formula (IIA).

In the general formula (IIA), * represents the bonding position with X3 in the general formula (I ^- 1). ^R4 represents an aryl group, a heterocyclic group, a cyano group, a nitro group, an alkyl group, an alkylthio group, or a halogen atom. The composition according to any one of claims 1 to 5, wherein in the general formula (I-1), X ¹ to X ³ are all −NR ¹ −. Claim 1 in which the W ¹ in the general formula (I-1) and the W ² in the general formula (I-2) are each independently a divalent linking group represented by the general formula (III). The composition according to any one of 6 to 6.

In the general formula (III), A ¹ and A ³ independently represent a single bond or an arylene group, and at least one of A ¹ and A ³ represents an arylene group. A ² represents a single bond, -O-, CO-, -S-, -SO _2- , -NR ^A- , or an arylene group. ^RA represents a hydrogen atom or a substituent. * Represents the bond position. The composition according to claim 7, wherein in the W ² of the general formula (I-2), all of the A ¹ to A ³ represent an arylene group. The composition according to claim 7 or 8, wherein in the W2 of the general formula (I- ² ), the arylene group is a 1,4-phenylene group. A coating film formed by the composition according to any one of claims 1 to 9 . A cured film formed by curing the coating film according to claim 10 . The lens made of the cured film according to claim 11 . A solid-state image sensor comprising the lens according to claim 12 . A resin containing a repeating unit represented by the general formula (IV-1).

In the general formula (IV-1), X ¹ , X ² , and X ³ independently represent -NR ^1- , -O-, or -S-, respectively. W ¹ represents a divalent linking group. R ¹ represents a hydrogen atom or a substituent. R ⁵ represents a heterocyclic group, a cyano group, a nitro group, an alkyl group, an alkylthio group, or a halogen atom. A resin containing a repeating unit represented by the general formula (IV-2).

^In the general formula ( ^IV -2), X4, ^X5 , and X6 independently represent -NR ^2- , -O-, or -S-, respectively. R ² represents a hydrogen atom or a substituent.