KR102335574B1 - Composition, coating film, cured film, lens, solid-state image sensor, resin - Google Patents

Abstract

Provided is a composition capable of providing a cured film in which the occurrence of defects is suppressed even after repeated exposure to a high-temperature-low-temperature environment. Moreover, a coating film, a cured film, a lens, a solid-state image sensor, and novel resin are provided. The composition is selected from the group consisting of a resin comprising a repeating unit represented by the following general formula (I-1) or a repeating unit represented by the following general formula (I-2), a solvent, sodium ions, potassium ions, and calcium ions. A composition comprising a selected specific metal ion, wherein the total content of the specific metal ion is 0.01 to 30 mass ppm with respect to the total mass of the composition.

Description

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

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

High heat resistance, high transparency, high refractive index, high solubility, and low volume with respect to compounds conventionally used for optical materials (eg, microlens forming materials mounted on image sensors, refractive index modifiers of color filters, etc.) All characteristics such as 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.

Patent Document 1: Japanese Patent Application Laid-Open No. 2015-025131

The present inventors examined the cured film formed from the composition containing the triazine ring containing polymer described in patent document 1, The said cured film repeatedly exposed under high temperature environment and low temperature environment (under high temperature-low temperature environment) , made it clear that a lot of glitches occur.

Therefore, an object of this invention is to provide the composition which can provide the cured film in which defect generation|occurrence|production is suppressed even after repeated exposure in a high-temperature-low-temperature environment.

Moreover, this invention makes it a subject to provide the coating film formed of the said composition, the cured film formed by hardening|curing the said coating film, a lens, and a solid-state image sensor.

Moreover, this invention makes it a subject to provide novel resin which can be used suitably as a high refractive index material.

As a result of earnest examination of the present inventors in order to achieve the said subject, according to the composition containing resin containing a triazine ring of a specific structure, a specific metal ion of a predetermined content, and a solvent, it is that the said subject can be solved Found and completed the present invention.

That is, it discovered that the said objective could be achieved with the following structures.

(1) a resin comprising a repeating unit represented by the general formula (I-1) to be described later or a repeating unit represented by the general formula (I-2) to be described later;

solvent and

A composition comprising a specific metal ion selected from the group consisting of sodium ion, potassium ion, and calcium ion,

The composition whose total content of specific metal ion is 0.01-30 mass ppm with respect to the composition total mass.

(2) the solvent comprises toluene;

The composition as described in (1) whose content of toluene is 0.001-10 mass ppm with respect to the composition total mass.

(3) The composition according to (1) or (2), wherein in general formula (I-1), V is a group represented by 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. The composition as described in (3) which shows.

(5) The composition as described in (4), wherein group represented by general formula (II) mentioned later is group represented by general formula (IIA) mentioned later.

(6) The composition according to any one of (1) to (5), wherein in general formula (I-1), X ¹ to X ³ are all -NR ^{1 -.}

7 is a divalent connection group is W ² of the W ^1, and the general formula (I-2) in the formula (I-1), represented by the general formula (III), each as described below independently, (1) The composition according to any one of 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, ^{in W 2} of the general formula (I-2), the arylene group is a 1,4-phenylene group.

(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 of the composition according to any one of (1) to (11).

(13) A cured film formed by curing the coating film according to (12).

(14) A lens comprising the cured film according to (13).

(15) A solid-state imaging device comprising the lens according to (14).

(16) Resin containing the repeating unit represented by General formula (IV-1) mentioned later.

(17) Resin containing the repeating unit represented by General formula (IV-2) mentioned later.

ADVANTAGE OF THE INVENTION According to this invention, it can provide the composition which can provide the cured film in which defect generation|occurrence|production is suppressed even after being repeatedly exposed in a high-temperature-low-temperature environment.

Moreover, according to this invention, the coating film formed of the said composition, the cured film formed by hardening|curing the said coating film, a lens, and a solid-state image sensor can be provided.

Moreover, according to this invention, novel resin which can be used suitably as a high refractive index material can be provided.

Hereinafter, the present invention will be described in detail.

In this specification, the numerical range indicated using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In this specification, "actinic ray" or "radiation" means, for example, the bright-ray spectrum of a mercury lamp, the deep ultraviolet ray represented by an excimer laser, extreme ultraviolet ray (EUV light), X-ray, an electron beam, etc. are meant. In addition, in this invention, light means actinic light or radiation. In the present specification, "exposure" means not only exposure with a bright line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. Drawing is also included in exposure.

In this specification, "(meth)acrylate" represents acrylate and methacrylate, "(meth)acryl" represents acryl and methacryl, and "(meth)acryloyl" is acryloyl and methacryloyl.

In the present specification, the term "process" is included in this term as long as the desired action of the process is achieved even if it is not clearly distinguished from an independent process as well as other processes.

In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) use, for example, HLC-8220 (manufactured by Tosoh Corporation) as a measuring device, and TSKgel Super AWM-H (Tosoh Corporation) as a column. Note), 6.0 mmID (inner diameter) x 15.0 cm), can be obtained by using a 10 mmol/L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

In this specification, a polymeric compound means the compound which has a polymeric group, A monomer may be sufficient and a polymer may be sufficient as it. The polymerizable group refers to a group involved in the polymerization reaction.

In this specification, the total solid content means the total mass of the component except the solvent from the whole composition.

In the description of the group (atomic group) in the present specification, the description not describing substitution and unsubstituted includes those having no substituent and those having a substituent. For example, "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). As a substituent, the group chosen from the following substituent group T is mentioned, for example.

(substituent T)

Examples of the substituent T include 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, 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, Sulfamoylamino 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, aryl and an oxycarbonyl 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, and a silyl group. Below, each group is demonstrated in detail.

a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom);

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, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-chloroethyl group, 2-cyanoethyl group, and 2-ethylhexyl group);

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 a cyclohexyl group and a cyclopentyl group. In addition, as the polycyclic cycloalkyl group, for example, a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, specifically bicyclo[1,2,2]heptane) -2-yl group, bicyclo[2,2,2]octain-3-yl group, etc.), tricycloalkyl group, etc. As the cycloalkyl group, among them, a monocyclic cycloalkyl group or a bicycloalkyl group It is preferable, and a monocyclic cycloalkyl group is more preferable.

A linear or branched alkenyl group (a linear or branched, substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms. For example, a vinyl group, an allyl group, a prenyl group, zera nyl group, and oleyl group);

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- and 2-cyclohexen-1-yl group.In addition, as the polycyclic cycloalkenyl group, a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms. Specifically, is a bicyclo [2,2,1] hept-2-en-1-yl group, and a bicyclo [2,2,2] oct-2-en-4-yl group), and a tricycloalkenyl group The cycloalkenyl group is preferably a monocyclic cycloalkenyl group);

an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms. For example, an ethynyl group, a propargyl group, and a trimethylsilylethynyl group, etc.);

Aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. For example, a phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl group, pyrenyl group, bi phenyl group, and terphenyl group);

Heterocyclic group (The heterocyclic group may be either a substituted or unsubstituted alicyclic heterocyclic group or an aromatic heterocyclic group. The alicyclic heterocyclic group may be either saturated or unsaturated. In addition, the heterocyclic group may be monocyclic The heterocyclic group preferably contains at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl group, 2-thienyl group, 2-pyridyl group, 4-pyridyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.);

Cyano group, hydroxyl group, nitro group, carboxyl group,

An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms. For example, a methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, and 2-methoxy group ethoxy group, etc.),

Aryloxy group (preferably a substituted or unsubstituted aryloxy group 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, and 2-tetradecanoylaminophenoxy group);

a silyloxy group (preferably a C3-C20 silyloxy group, 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. Examples of the heterocyclic group in the heterocyclic oxy group include a divalent heterocyclic group in which one hydrogen atom is removed from the aforementioned heterocyclic group. Examples of the heterocyclic oxy group include 1-phenyltetrazole-5-oxy group and 2-tetrahydropyranyloxy group);

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, and methacryloyloxy group);

A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. For example, N,N-dimethylcarbamoyloxy group, N,N-diethylcarbamoyloxy group, morpholinocarbonyloxy group period, N,N-di-n-octylaminocarbonyloxy group, and Nn-octylcarbamoyloxy group, etc.);

Alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. For example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, and n-octyl group carbonyloxy group, etc.);

An 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 pn-hexadecyl oxyphenoxycarbonyloxy group, etc.),

An 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 heterocyclic amino group having 0 to 30 carbon atoms. For example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, and N-1,3,5-triazin-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, an acetylamino group , pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, acryloylamino group, and methacryloylamino group);

An aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. For example, a carbamoylamino group, N,N-dimethylaminocarbonylamino group, N,N-diethylaminocarbo nylamino group, and morpholinocarbonylamino group);

Alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. For example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyl group oxycarbonylamino group, and N-methyl-methoxycarbonylamino group, etc.);

An 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 mn-octyloxyphenoxy cycarbonylamino group, etc.),

A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. For example, a sulfamoylamino group, N,N-dimethylaminosulfonylamino group, and Nn-octylaminosulfonylamino 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, and p-methylphenylsulfonylamino group);

mercapto,

An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. For example, a methylthio group, an ethylthio group, and an n-hexadecylthio group, etc.);

an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms. For example, a phenylthio group, p-chlorophenylthio group, and m-methoxyphenylthio group, etc.);

Heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. Examples of the heterocyclic group in the heterocyclic thio group include a divalent heterocyclic group in which one hydrogen atom is removed from the aforementioned heterocyclic group. Examples of the heterocyclic thio group include 2-benzothiazolethio and 1-phenyltetrazol-5-ylthio);

A 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.);

tongue,

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, phenylsulfinyl 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 , a phenylsulfonyl group, and a p-methylphenylsulfonyl group);

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.);

An aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. For example, a phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, and p-tert-butylphenoxycarbonyl group, etc.),

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. For example, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, and an n-octadecyloxycarbonyl group, etc. ),

A carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. For example, a carbamoyl group, N-methylcarbamoyl group, N,N-dimethylcarbamoyl group, N,N- di-n-octylcarbamoyl group, and N-(methylsulfonyl)carbamoyl group, etc.);

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 (as the heterocyclic group in the heterocyclic azo group, the heterocyclic group and a divalent heterocyclic group excluding one hydrogen atom.) For example, a phenylazo group, a p-chlorophenylazo group, and 5-ethylthio-1,3,4-thiadiazole-2- sunrise, etc.),

an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms. For example, N-succinimide group, N-phthalimide group, etc.);

a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms. For example, a dimethylphosphino group, a diphenylphosphino group, and a methylphenoxyphosphino group, etc.);

A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms. For example, a phosphinyl group, a dioctyloxyphosphinyl group, and a diethoxyphosphinyl group, etc.);

a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. For example, a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group, etc.);

A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, a dimethoxyphosphinylamino group, and a dimethylaminophosphinylamino group, etc.), and

and 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, and a phenyldimethylsilyl group).

Among the above-mentioned functional groups, in those having a hydrogen atom, a portion of the hydrogen atom in the functional group may be substituted with any of the above groups. Examples of the functional group 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 (For example, methylsulfonylaminocarbonyl group etc.), and an arylsulfonylaminocarbonyl group (For example, p-methylphenylsulfonylaminocarbonyl group etc.) etc. are mentioned.

[Composition]

The composition of the present invention comprises a resin comprising 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, potassium ions, and calcium A specific metal ion selected from the group consisting of ions is included, 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 characteristic point of the composition, a resin including a repeating unit represented by the general formula (I-1) to be described later or a repeating unit represented by the general formula (I-2) to be described later (hereinafter also referred to as “specific triazine-based resin”) And the point of using together the specific metal ion of predetermined content is mentioned.

Materials exhibiting high refractive index typified by triazine-based resins are easily associated with intermolecular interactions to form aggregates. This time, the present inventors studied a cured film containing the aggregate. When the cured film is repeatedly exposed to a high-temperature-low-temperature environment, micro-phase separation (phase separation of the agglomerated portion and the non-agglomerated portion) tends to occur, and the micro-phase separation It originates in this, and the cured film discovered that the defect increased.

Although the present inventors further advanced examination based on the said discovery, according to the composition which mix|blended the specific triazine-type resin and the specific metal ion of predetermined content, the cured film formed is hard to generate|occur|produce micro phase separation, As a result, the said Even after the cured film was repeatedly exposed in a high temperature-low temperature environment, it became clear that defect generation|occurrence|production was suppressed.

Although the mechanism of action is not clear, the specific metal ion easily interacts with a nitrogen atom in a specific triazine-based resin, etc. guessed On the other hand, when the content of the specific metal ion in the composition is too large, in the process of forming a coating film by the composition, the specific metal ion and the specific triazine-based resin are easily complexed, resulting in micro-phase separation of the cured film ( phase separation of the ignited portion and the non-ignited portion) tends to occur. In particular, when the cured film is repeatedly exposed under a high-temperature-low-temperature environment, the complexation of the specific metal ion and the specific triazine-based resin in the system further proceeds, and the amount of microphase separation is further increased. As a result, in the cured film repeatedly exposed under a high-temperature-low-temperature environment, defects increase.

The present inventors, in the composition, when the total content of the specific metal ion is 0.01 to 30 mass ppm with respect to the total mass of the composition, the association of the specific triazine-based resin and the specific triazine-based resin and the specific metal ion Even after ignition was suppressed and the cured film obtained was repeatedly exposed in high temperature - low temperature environment, it clarified that defect generation|occurrence|production was suppressed. Moreover, it is also confirmed that the said cured film has a small spectral fluctuation (change in transmittance|permeability) even after being repeatedly exposed in a high-temperature-low-temperature environment.

Moreover, when the said composition contains toluene as a solvent, and content of the said toluene is 0.001-10 mass ppm with respect to the total mass of the composition, the surface appearance of the coating film formed by the composition is excellent. Although this action mechanism is not clear, it is estimated that toluene is affecting the compatibility of a specific triazine-type resin.

Hereinafter, each component contained in the said composition is demonstrated in detail.

<Specific triazine-based resin>

The composition contains a resin (specific triazine-based resin) including 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 general formula (I-1))

[Formula 1]

In general formula (I-1), X ¹ , X ² , and X ³ each independently represent -NR ¹ -, -O-, or -S-.

As X ¹ , X ² , and X ³ , the refractive index of the cured film after repeated exposure under a high-temperature-low temperature environment is more excellent, and the spectral fluctuation of the cured film is small even when repeatedly exposed under a high-temperature-low temperature environment, -NR ¹ - is preferred.

R ¹ represents a hydrogen atom or a substituent.

Although it does not restrict|limit especially as a substituent represented by R<^1> , For example, the group illustrated by the substituent group T mentioned above is mentioned, Especially, 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, preferably an alkyl group having 1 to 6 carbon atoms, A C1-C3 alkyl group is more preferable. Moreover, although it does not restrict|limit especially as an aryl group represented by ^{R<1>, For example, a phenyl group etc. are mentioned.}

Among them, 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.

Moreover, ^{the alkyl group and aryl group represented by R<1>} may have a substituent (for example, the group illustrated by the substituent group T).

W ¹ represents a divalent linking group.

Although it does not restrict|limit especially as a divalent coupling group represented by W<^1> _{, For example, -O-, -CO-, -S-, -SO 2} -, -NR ^A -, an arylene group, an alkylene group, a heteroarylene group, and these and a group consisting of a combination of The alkylene group may be substituted with substituents, such as a halogen atom (for example, the group illustrated by the substituent group T).

Although carbon number in particular of the said arylene group is not restrict|limited, For example, 6-20 are preferable, 6-14 are more preferable, 6-10 are still more 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, 3,6 -fluorenylene group, 9,9-fluorenylene group, anthracenylene group, etc. are mentioned, The 1, 4- phenylene group is preferable.

The said arylene group may have a substituent (for example, the group illustrated by the substituent group T).

Said R ^A represents a hydrogen atom or a substituent, and a hydrogen atom is preferable.

As a substituent represented by said R ^A , it is synonymous with the substituent represented by ^{said R<1>.}

As the ^{divalent linking group represented by W 1} , the refractive index of the cured film after repeated exposure under a high-temperature-low temperature environment is more excellent, and the spectral fluctuation of the cured film is small even when repeatedly exposed under a high-temperature-low temperature environment. The divalent linking group represented by III) is preferable.

[Formula 2]

In general formula (III), A ¹ and A ³ each 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. R ^A represents a hydrogen atom or a substituent. * indicates a binding position.

With respect to a specific embodiment of the arylene group, and R ^A represented by A ^1, A ^2, and A ^3, as described above.

Among them, the aryl group represented by A ¹ ~ A ^3, preferably 1,4-phenylene group.

Although the specific example of group represented by the said General formula (III) is shown below, it is not restrict|limited to this.

[Formula 3]

[Formula 4]

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, more preferably an alkyl group having 1 to 6 carbon atoms, A C1-C3 alkyl group is more preferable.

As an aryl group represented by V, the aryl group which consists of a 6-10 membered ring or its condensed ring is mentioned, for example.

Specific examples of the ring constituting the aryl group include, but are not particularly limited to, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, and a naphthacene ring, and a benzene ring or a naphthalene ring It is preferable, and a benzene ring is more preferable. In addition, the said ring comprises an aryl group by removing one hydrogen atom on a ring.

The heterocyclic group represented by V is not particularly limited, and examples thereof include an aliphatic heterocyclic group and an aromatic heterocyclic group. Moreover, as an aliphatic heterocyclic ring, a 5-membered ring, a 6-membered ring, or a 7-membered ring, or its condensed ring is mentioned. Moreover, as an aromatic heterocyclic ring, a 5-membered ring, a 6-membered ring, or a 7-membered ring, or its condensed ring is mentioned.

Moreover, in the said condensed ring, rings other than heterocyclic groups, such as a benzene ring, may be contained.

As a hetero atom contained in the said aliphatic heterocyclic group, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned, for example. Although carbon number in particular of an aliphatic heterocyclic ring is not restrict|limited, 3-20 are preferable.

Although it does not restrict|limit especially as a specific example of the said aliphatic heterocyclic ring, For example, an oxolane ring, an oxane ring, a piperidine ring, a piperidine ring, etc. are mentioned. In addition, the aliphatic heterocyclic ring constitutes an aliphatic heterocyclic group by excluding one hydrogen atom on the ring.

As a hetero atom contained in the said aromatic heterocyclic group, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned, for example. Although carbon number in particular of an aromatic heterocyclic group is not restrict|limited, 3-20 are preferable.

Specific examples of the aromatic heterocyclic ring are not particularly limited, but a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, an oxadiazole ring, a thiazole ring, an isothiazole ring, a thiazole ring, an imidazole ring , pyrazole ring, triazole ring, furazane ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, tetrazine ring, benzofuran ring, isobenzofuran ring, benzothiophene ring, indole Ring, indoline ring, isoindole ring, benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, cinnoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, di and a benzofuran ring, a dibenzothiophene ring, a carbazole ring, an acridine ring, a phenanthridine ring, a phenanthridine ring, a phenazine ring, a naphthyridine ring, a purine ring, and a pteridine ring. In addition, the said aromatic heterocyclic ring comprises an aromatic heterocyclic group by removing one hydrogen atom on a ring.

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

As said V, the aryl group which has a substituent is preferable at the point which is more excellent in the refractive index of the cured film after repeated exposure to high temperature-low temperature environment, and especially the group represented by the following general formula (II) is more preferable.

[Formula 5]

In general formula (II), * represents a bonding position with ^{X 3 in general formula (I-1).}

R ³ represents a substituent. Especially, as R<^3> , 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, more preferably an alkyl group having 1 to 6 carbon atoms. , an alkyl group having 1 to 3 carbon atoms is more preferable.

As a halogen atom represented by R<^3> , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

Although it does not restrict|limit especially as an alkylthio group represented by R<^3> , For example, a C1-C10 alkylthio group is mentioned, A C1-C6 alkylthio group is more preferable, A C1-C3 alkylthio group is more preferable. is more preferable In addition, any of linear, branched, and cyclic|annular form may be sufficient as the alkylene group in an alkylthio group.

In addition, ^{the alkyl group and alkylthio group represented by R 3} may further have a substituent (for example, the group illustrated by the substituent group T).

As R<^3> , a cyano group is preferable at the point which is more excellent in the refractive index of the cured film after repeatedly exposure in a high-temperature-low-temperature environment.

R ⁴ represents a substituent. Among them, as R ⁴ , 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 heterocyclic group represented by R 4} are synonymous with the aryl group and heterocyclic group represented by V above. As ^{the aryl group represented by R 4} , a phenyl group is preferable.

The alkyl group, alkylthio group, and halogen atom represented by ^{R 4} are synonymous with the alkyl group, alkylthio group, and halogen atom represented by ^{R 3 above, and preferred embodiments are also the same.}

As R ^4, a high temperature - in the more excellent the cured film refractive index after repeated under low temperature environment by exposure points, are preferred an aryl group, a cyano group, a nitro group, or a halogen atom.

m and n each independently represent the integer of 0-5. However, m+n is 1-5.

It is preferable that m is 0, and it is more preferable that n is 1 at the point which is more excellent in the refractive index of the cured film after repeated exposure under high temperature-low temperature environment.

As group represented by the said General formula (II), the group represented by the following general formula (IIA) from the point which is more excellent in the refractive index of the cured film after being repeatedly exposed especially in a high-temperature-low-temperature environment is preferable.

[Formula 6]

In general formula (IIA), * represents a bonding position with ^{X 3 in general formula (I-1).}

In the general formula (IIA), R ⁴ is R ⁴ is synonymous with the general formula (II), it is also the same appropriate aspect.

Examples of R ^4, in particular the phenyl group, which is substituted with R ^4, with respect to the bonding position of the phenylene groups adjacent to the phenyl group is preferably para position on. That is, for example, when R ⁴ represents an aryl group, the group represented by the general formula (IIA) is preferably p-terphenylene.

(repeating unit represented by general formula (I-2))

[Formula 7]

In general formula (I-2), X ⁴ , X ⁵ , and X ⁶ each independently represent -NR ² -, -O-, or -S-. W ² represents a divalent linking group. R ² represents a hydrogen atom or a substituent.

In general formula (I-2), as R ^{2 , it has the same meaning as R 1} in general formula (I-1), and a preferred embodiment is also the same.

In general formula (I-2), W ² is the same as ^{W 1} in general formula (I-1).

Further, ^{as the divalent linking group represented by W 2} , the refractive index of the cured film after repeated exposure under a high-temperature-low temperature environment is more excellent, and the spectral fluctuation of the cured film is small even when repeatedly exposed under a high-temperature-low temperature environment, A ¹ It is preferable that it is a 1, 4- phenylene group as an arylene group represented by -A ^{3 .}

As the ^{divalent linking group represented by W 2} , the refractive index of the cured film after repeated exposure under a high-temperature-low temperature environment is more excellent, and the spectral fluctuation of the cured film is small even when repeatedly exposed under a high-temperature-low temperature environment, A ¹ to A ^{It is more preferable that all 3} represent an arylene group (preferably a 1, 4- phenylene group).

As X ⁴ , X ⁵ , and X ⁶ , the refractive index of the cured film after repeated exposure under a high-temperature-low temperature environment is more excellent, and the spectral fluctuation of the cured film is small even when repeatedly exposed under a high-temperature-low temperature environment, -NR ^2- is preferred.

As for the compound containing the repeating unit represented by the said General formula (I-2), the compound (polycondensate and polyadduct) represented, for example by the following is mentioned.

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

[Formula 8]

In the general formula (V), Y ¹ to Y ³ represent a leaving group (eg, a halogen atom) or an isocyanate group.

In the general formula (VI), X ⁷ and X ⁸ each independently represent -NR ² -, -O-, or -S-. R ² represents a hydrogen atom or a substituent. W ³ represents a divalent linking group.

As a substituent represented by said R<^2> , the thing similar to ^R<2> in General formula (II-2) mentioned above is mentioned.

As the divalent linking group represented by the above W ^3, and W ² may be the same that of the above-described general formula (II-2).

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

[Formula 9]

In the general formula (VII), X ⁹ to X ¹¹ each independently represent -NR ² -, -O-, or -S-. R ² represents a hydrogen atom or a substituent.

As a substituent represented by said R<^2> , the thing similar to ^R<2> in General formula (II-2) mentioned above is mentioned.

In the general formula (VIII), Y ⁴ and Y ^{5 each} represent a leaving group (eg, a halogen atom) or an isocyanate group. W ⁴ represents a divalent linking group.

As the divalent linking group represented by the above W ^4, and W ² may be the same that of the above-described general formula (II-2).

Specific examples of the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2) are shown below, but the present invention is not limited thereto. In addition, in the following specific example, "Me" represents a methyl group.

[Formula 10]

[Formula 11]

Among the specific triazine-based resins, 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 moles based on all the repeating units in the specific triazine-based resin. % is preferable, 80-100 mol% is more preferable, and 90-100 mol% is still more preferable.

Specific triazine-based resin can be synthesized according to a known method (polycondensation).

2,000-100,000 are preferable, as for the weight average molecular weight of specific triazine-type resin, 2,000-50,000 are more preferable, 4,000-20,000 are still more preferable. Dispersion degree (Mw/Mn) is 1.0-3.0 normally, 1.0-2.6 are preferable, 1.0-2.0 are more preferable, 1.1-2.0 are still more preferable.

In the said composition, specific triazine-type resin may be used individually by 1 type, and may use 2 or more types together.

In the composition, the content of the specific triazine-based resin (in the case of multiple types, the total) is generally 80.0% by mass or more, preferably 85.0% by mass or more, and 90.0% by mass relative to the total solid content of the composition. % or more is more preferable. Although an upper limit in particular is not restrict|limited, 99.9 mass % or less is preferable, and 99.5 mass % or less is more preferable.

<Specific metal ions>

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 from the viewpoint of more excellent defect suppression property of the cured film after repeated exposure to a high temperature-low temperature environment, 0.03 to 10 Mass ppm is preferable.

In addition, 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 the defect suppression property of the cured film after repeated exposure to a high-temperature-low-temperature environment is more From an excellent point, 0.3-100 mass ppm is preferable.

In addition, content of the specific metal ion in the said composition can be measured with an ICP (Inductively Coupled Plasma) emission spectroscopy apparatus (for example, "Optima 7300DV" manufactured by Perkin Elmer).

<solvent>

The 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, and ethylene glycol monobutyl. Teracetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, 3-methoxybutyl acetate, 3-methoxypropionate methyl, 3-E Methyl oxypropionate, 3-ethoxypropionate ethyl, propylene glycol diacetate, diethylene glycol monobutyl ether acetate, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, cyclohexyl acetate esters such as; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol Lycol monoisopropyl ether, 3-methoxypropanol, 1-methoxy-2-propanol, methoxymethoxyethanol, dipropylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol alcohols such as ethylene 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; ketones such as acetone, methyl ethyl ketone, acetylacetone, cyclohexanone, 2-heptanone, cyclopentanone, and diacetone alcohol; halogen compounds such as ethylene dichloride; ethers such as cyclohexylmethyl ether and dibutyl ether; amides such as 3-methoxy-N,N-dimethylpropaneamide, N-ethyl-2-pyrrolidone, and 3-butoxy-N,N-dimethylpropaneamide; and the like.

Further, for details of the solvent, reference may be made to the description of paragraph No. 0223 of International Publication No. WO2015/166779, the content of which is incorporated herein by reference. However, there are cases where it is better to reduce the aromatic hydrocarbons as the solvent for reasons such as environmental reasons (for example, it may be 50 mass ppm (parts per million) or less with respect to the total amount of the solvent, It may be 10 mass ppm or less, and may be 1 mass ppm or less).

(toluene)

The composition may contain toluene as a solvent.

It is preferable that the total content of toluene in the said composition is 0.001-10 mass ppm with respect to the composition total mass. When the total content of toluene in the composition is within the above numerical range, the surface appearance of the coating film formed of the composition is excellent.

Moreover, in the said composition, it is preferable that total content of the said toluene is 0.01-100 mass ppm with respect to specific triazine-type resin.

In addition, content of toluene in the said composition can be measured by gas chromatography.

In the said composition, the said solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

In this invention, it is preferable to use a solvent with little metal content, and it is preferable that the metal content of a solvent is 10 mass ppb (parts per billion) or less, for example. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided by, for example, Toyo Kosei Corporation (Kagaku Kogyo Nippo, November 13, 2015).

As a method of removing impurities, such as a metal, from a solvent, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter is mentioned, for example. As a filter pore diameter of the filter used for filtration, 10 nm or less is preferable, 5 nm or less is more preferable, 3 nm or less is still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

The solvent may contain isomers (compounds having different structures by the same number of atoms). Moreover, only 1 type may be contained and multiple types of isomers may be contained.

In this invention, it is preferable that content of a peroxide is 0.8 mmol/L or less, and, as for a solvent, it is more preferable that a peroxide is not included substantially.

The content of the solvent is preferably an amount in which the solid content concentration of the composition is 1 to 90 mass%, more preferably an amount in which the solid content concentration of the composition is 1 to 50 mass%, and the solid content concentration of the composition is 5 to 30 mass% The amount used is more preferable, and the amount used as 5-20 mass % is especially preferable.

In addition, the solid content concentration of a composition intends the density|concentration of the total solid with respect to the composition total mass (that is, the density|concentration of the component which forms a cured film in a composition is intended). In addition, it is as above-mentioned about the definition of total solid.

<Other ingredients>

The said composition may contain other components other than the component mentioned above. Examples of other components include a curable compound (including a polymerizable compound), a polymerization initiator, an antioxidant, a silane coupling agent, a polymerization inhibitor, a surfactant, a UV absorber, a filler (eg, inorganic particles), a curing accelerator, Various additives, such as developability improvers, such as a plasticizer and low molecular-weight organic carboxylic acid, and aggregation inhibitor, are mentioned.

(curable compound)

It is preferable that the said composition contains a sclerosing|hardenable compound.

As the curable compound, a known compound that can be cured by radical, acid, or heat can be used. For example, the compound which has group which has an ethylenically unsaturated bond, the compound which has an epoxy group, the compound which has reactive groups, such as a methylol group and a thiol group, etc. are mentioned. Examples of the group having an ethylenically unsaturated bond include a vinyl group, (meth)acryl group, (meth)acryloyl group, and (meth)acryloyloxy group, (meth)acryloyl group, or (meth) An acryloyloxy group is preferred. It is preferable that it is a polymeric compound, and, as for a sclerosing|hardenable compound, it is more preferable that it is a radically polymerizable compound. As a polymeric compound, the compound etc. which have group which have an ethylenically unsaturated bond are mentioned.

As for content of a sclerosing|hardenable compound, 1-80 mass % is preferable with respect to the total solid of a composition. 3 mass % or more is more preferable, and, as for a minimum, 4 mass % or more is still more preferable. The upper limit is more preferably 70 mass % or less, still more preferably 60 mass % or less, and particularly preferably 30 mass % or less.

In the said composition, 1 type may be sufficient as a sclerosing|hardenable compound, and 2 or more types may be used together. When the said composition contains 2 or more types of sclerosing|hardenable compounds, it is preferable that total content becomes the said 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. It is preferable that a polymeric compound is a monomer. As for the molecular weight of a polymeric compound, 100-3000 are preferable. 2000 or less are more preferable and, as for an upper limit, 1500 or less are still more preferable. 150 or more are more preferable, and, as for a minimum, 250 or more are still more preferable. It is preferable that it is a 3-15 functional (meth)acrylate compound, and, as for a polymeric compound, it is more preferable that it is a 3-6 functional (meth)acrylate compound.

As an example of a polymeric compound, Paragraph No. 0033 of Unexamined-Japanese-Patent No. 2013-253224 - description of 0034 can be considered into consideration, and this content is integrated in this specification. Examples of the polymerizable compound include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available, NK Ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available, KAYARAD D-330) ; Nippon Kayaku Co., Ltd. product), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; Nippon Kayaku Co., Ltd. product), dipentaerythritol penta (meth) acrylate (as a commercial item, KAYARAD D -310; Nippon Kayaku Co., Ltd. product), dipentaerythritol hexa(meth) acrylate (as a commercial item, KAYARAD DPHA; Nippon Kayaku Co., Ltd. product, A-DPH-12E; Shin-Nakamura Chemical Co., Ltd. ) agent), and a structure in which these (meth)acryloyl groups are bonded via an ethylene glycol residue and/or a propylene glycol residue is preferable. Moreover, these oligomer types can also be used. Moreover, Paragraph No. 0034 of Unexamined-Japanese-Patent No. 2013-253224 - description of 0038 can be considered into consideration, and this content is integrated in this specification. Moreover, the polymerizable monomer etc. of Paragraph No. 0477 of Unexamined-Japanese-Patent No. 2012-208494 (paragraph number 0585 of the corresponding U.S. Patent Application Publication No. 2012/0235099) are mentioned, These content is integrated in this specification. Moreover, diglycerol EO (ethylene oxide) modified (meth)acrylate (as a commercial item, M-460; Toagosei Co., Ltd. product), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd. product, A-TMMT) ) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferable. These oligomeric types can also be used. For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

A polymeric compound may have acidic radicals, 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 in which an acid group is given by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound is preferable, and more preferably, in this ester, the aliphatic polyhydroxy compound is pentaeryth ritol and/or dipentaerythritol. As a commercial item, M-305, M-510, M-520 etc. which are Aronix series as polybasic acid modified|denatured acrylic oligomer made from Toagosei Co., Ltd. product are mentioned, for example.

As for the acid value of the polymeric compound which has an acidic radical, 0.1-40 mgKOH/g is preferable. As for a minimum, 5 mgKOH/g or more is more preferable. As for an upper limit, 30 mgKOH/g or less is more preferable.

It is also a preferable aspect that a polymeric compound is a compound which has 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. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, and ditrimethylolpropane , ε-caprolactone obtained by esterifying (meth)acrylic acid and ε-caprolactone with polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine and modified polyfunctional (meth)acrylates. As a polymeric compound which has a caprolactone structure, Paragraph No. 0042 of Unexamined-Japanese-Patent No. 2013-253224 - description of 0045 can be considered into consideration, and this content is integrated in this specification. Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are marketed as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and ethylene manufactured by Sartomer Corporation. SR-494 which is a tetrafunctional acrylate which has 4 oxy chains, TPA-330 which is a trifunctional acrylate which has 3 isobutylene oxy chains, etc. are mentioned.

As a polymerizable compound, the oil described in Japanese Unexamined Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Application, Retain acrylates, and Japanese Kokai Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417 and Japanese Patent Publication No. 62-039418. Also suitable are urethane compounds having an ethylene oxide-based skeleton. Further, addition polymerization having an amino structure and/or a sulfide structure in a molecule is described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 1-105238. Acidic compounds can be used. As commercially available products, urethane oligomer UAS-10, and UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) and UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

・Compounds having an epoxy group

As a sclerosing|hardenable compound, the compound which has an epoxy group can also be used. As for the compound which has an epoxy group, the compound which has one or more epoxy groups in 1 molecule is mentioned, The compound which has two or more epoxy groups in 1 molecule is preferable. It is preferable to have 1-100 epoxy groups in 1 molecule. The upper limit may be, for example, 10 or less, or 5 or less. As for a minimum, two or more are preferable.

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 100-400 g/equivalent, and still more preferably 100-300 g/equivalent. do.

The compound having an epoxy group may be a low molecular weight compound (for example, molecular weight less than 1000), or a macromolecular compound (for example, molecular weight 1000 or more, in the case of a polymer, a weight average molecular weight of 1000 or more) do. 200-100000 are preferable and, as for the weight average molecular weight of the compound which has an epoxy group, 500-50000 are more preferable. As for the upper limit of a weight average molecular weight, 10000 or less are more preferable, 5000 or less are still more preferable, and 3000 or less are especially preferable.

A commercial item can also be used for the compound which has an epoxy group. For example, EHPE3150 (made by Daicel Corporation), EPICLON N-695 (made by DIC Corporation), etc. are mentioned. Moreover, the compound which has an epoxy group is Paragraph No. 0034 - 0036 of Unexamined-Japanese-Patent No. 2013-011869, Paragraph No. 0147-0156 of Unexamined-Japanese-Patent No. 2014-043556, Paragraph No. 0085 - 0092 of Unexamined-Japanese-Patent No. 2014-089408. It is also possible to use the compounds described in These contents are incorporated herein by reference.

(Polymerization Initiator)

The composition may contain a polymerization initiator, and it is preferable that a photoinitiator is included. There is no restriction|limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, as for a photoinitiator, the compound which has photosensitivity with respect to the light ray of an ultraviolet region to a visible region is preferable.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (eg, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbi Oxime compounds, such as imidazole and an oxime derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, hydroxyacetophenone, etc. are mentioned. A photoinitiator is a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, α-hydroxyketone compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, and a metallocene from a viewpoint of exposure sensitivity. compound, oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound, and 3-aryl substitution A compound selected from the group consisting of a coumarin compound is preferable, and a compound selected from the group consisting of an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound is more preferable. Since the film|membrane obtained is more excellent, an oxime compound is still more preferable especially. As a photoinitiator, Paragraph No. 0065 of Unexamined-Japanese-Patent No. 2014-130173 - description of 0111 can be considered into consideration, and this content is integrated in this specification.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound can also be suitably used. For example, the ?-aminoketone compound described in JP-A-10-291969 and the acylphosphine compound described in JP-A 4225898 can also be used. As a commercial item of (alpha)-hydroxy ketone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (above, the BASF company make) are mentioned. As a commercial item of (alpha)-amino ketone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (above, the BASF company make) are mentioned. As a commercial item of an acylphosphine compound, IRGACURE-819 which is a commercial item, and DAROCUR-TPO (above, the BASF company make) are mentioned. Examples of commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeca Arcles. NCI-831 (manufactured by ADEKA Corporation), ADEKA ACLZ NCI-930 (manufactured by ADEKA Corporation), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052) The described photoinitiator 2) etc. are mentioned.

In this invention, the oxime compound which has a fluorene ring can also be used as a photoinitiator. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466 is mentioned. This content is incorporated herein by reference.

In this invention, the oxime compound which has a fluorine atom can also be used as a photoinitiator. As a specific example of the oxime compound which has a fluorine atom, the compound described in Unexamined-Japanese-Patent No. 2010-262028, the compound 24 of Unexamined-Japanese-Patent No. 2014-500852, 36-40, and Unexamined-Japanese-Patent No. 2013-164471. A compound (C-3) etc. are mentioned. These contents are incorporated herein by reference.

In this invention, the oxime compound which has a nitro group can be used as a photoinitiator. It is also preferable to use the oxime compound which has a nitro group as a dimer. As a specific example of the oxime compound which has a nitro group, Paragraph Nos. 0031 to 0047 of Unexamined-Japanese-Patent No. 2013-114249, Paragraph Nos. 0008 to 0012 and 0070 to 0079 of Unexamined-Japanese-Patent No. 2014-137466, Japanese Patent Publication The compound described in Paragraph No. 0007 - 0025 of 4223071, and Adeka Arcles NCI-831 (made by ADEKA Corporation) are mentioned.

Although the specific example of the oxime compound used preferably in this invention is shown below, this invention is not restrict|limited to these.

[Formula 12]

[Formula 13]

The compound which has a maximum absorption in a wavelength range of 350-500 nm is preferable, and, as for an oxime compound, the compound which has a maximum absorption in a wavelength range of 360-480 nm is more preferable. Moreover, as for an oxime compound, the compound with high absorbance of 365 nm and 405 nm is preferable.

It is preferable that it is 1,000-300,000 from a viewpoint of a sensitivity, as for the molar extinction coefficient in 365 nm or 405 nm of an oxime compound, It is more preferable that it is 2,000-300,000, It is more preferable that it is 5,000-200,000.

The molar extinction coefficient of a compound can be measured using a well-known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g/L using an ethyl acetate solvent.

It is also preferable that a photoinitiator contains an oxime compound and (alpha)-amino ketone compound. By using both together, developability improves and it is easy to form the pattern excellent in rectangular property. When using together an oxime compound and (alpha)-amino ketone compound, it is preferable to contain 50-600 mass parts of (alpha)-amino ketone compounds with respect to 100 mass parts of oxime compounds, and 150-400 mass parts is more preferable.

As for content of a polymerization initiator, 0.1-50 mass % is preferable with respect to total solid of a composition, 0.5-30 mass % is more preferable, 1-20 mass % is still more preferable, 1-10 mass % is especially preferable do.

When content of a polymerization initiator is the said range, it is excellent in a sensitivity more and it is easy to form the pattern excellent in rectangular property. The said composition may contain only 1 type of polymerization initiator, and may contain it 2 or more types. When the said composition contains 2 or more types of polymerization initiators, it is preferable that the total content becomes the said range.

(Antioxidant)

The said composition may also contain antioxidant.

As antioxidant, a phenol compound, a phosphorous acid ester compound, a thioether compound, etc. are mentioned. As the antioxidant, a phenol compound having a molecular weight of 500 or more, a phosphorous acid ester compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is preferable. You may use these in mixture of 2 or more types. As the phenolic compound, any phenolic compounds known as phenolic antioxidants can be used, and polysubstituted phenolic compounds are preferred. There are three types of polysubstituted phenolic compounds (hindered type, semi-hindered type, and less hindered type) which are broadly divided into different substitution positions and structures. Moreover, as antioxidant, the compound which has a phenol group and a phosphite group in the same molecule|numerator is used preferably. Moreover, as antioxidant, a phosphorus antioxidant is also used preferably. A commercial item can also be used for antioxidant. As a commercial item of antioxidant, For example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-50F, and ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (ADEKA Corporation). Moreover, as antioxidant, Paragraph No. 0033 of Unexamined-Japanese-Patent No. 2014-032380 - description of 0043 can be considered into consideration, and this content is integrated in this specification.

0.01-20 mass % is preferable with respect to the total solid of a composition, and, as for content of antioxidant, 0.3-15 mass % is more preferable. The number of antioxidants may be one, and two or more types may be sufficient as them. When the said composition contains 2 or more types of antioxidant, it is preferable that the total content becomes the said range.

(Silane coupling agent)

The said composition may also contain a silane coupling agent.

In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than that. Moreover, a hydrolysable group refers to the substituent which is directly connected to a silicon atom, and can generate|occur|produce a siloxane bond by at least any one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group, etc. are mentioned, for example, An alkoxy group is preferable. That is, as for a silane coupling agent, the compound which has an alkoxysilyl group is preferable. Moreover, the functional group other than a hydrolysable group forms interaction or bond with resin, and the group which shows affinity is preferable. For example, 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, etc. are mentioned, (meth) ) An acryloyl group or an epoxy group is preferable.

Specific examples of the silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane. Moreover, as a silane coupling agent, the compound of Paragraph Nos. 0018 - 0036 of Unexamined-Japanese-Patent No. 2009-288703, and the compound of Paragraph No. 0056 - 0066 of Unexamined-Japanese-Patent No. 2009-242604 are mentioned, These contents are It is incorporated herein by reference. A commercial item can also be used for a silane coupling agent. As a commercial item of a silane coupling agent, Shin-Etsu Silicone Co., Ltd. product KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM- 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-9659, 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.

0.01-15.0 mass % is preferable with respect to the total solid of a composition, and, as for content of a silane coupling agent, 0.05-10.0 mass % is more preferable. The number of silane coupling agents may be one, and two or more types may be sufficient as them. When the said composition contains 2 or more types of silane coupling agents, it is preferable that the total content becomes the said 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 salt (ammonium salt, cerium salt, etc.) are mentioned. can Especially, p-methoxyphenol is preferable. Moreover, a polymerization inhibitor may function as antioxidant.

0.01-10 mass parts is preferable with respect to 100 mass parts of polymerization initiators, as for content of a polymerization inhibitor, 0.01-8 mass parts is more preferable, 0.01-5 mass parts is still more preferable.

(Surfactants)

The said composition may also contain various surfactant from a viewpoint of improving applicability|paintability more.

As surfactant, various surfactants, such as a fluorine type surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone type surfactant, can be used. For surfactant, reference may be made to paragraphs 0238 to 0245 of International Publication No. WO2015/166779, the contents of which are incorporated herein by reference.

When the composition contains a fluorine-based surfactant, liquid properties (especially fluidity) when prepared as a coating liquid are further improved, and uniformity and liquid stability after application can be further improved. In the case of film formation using a coating solution to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the coated surface and the coating liquid is lowered, the wettability to the coated surface is improved, and the applicability to the coated surface is improved. . For this reason, film formation of a uniform thickness with small thickness nonuniformity can be performed more suitably.

As for the fluorine content rate in a fluorochemical surfactant, 3-40 mass % is suitable, More preferably, it is 5-30 mass %, Especially preferably, it is 7-25 mass %. The fluorine-containing surfactant having a fluorine content in this range is effective from the viewpoints of the uniformity of the thickness of the coating film and the liquid-forming properties, and the solubility in the composition is also good.

Specifically as a fluorochemical surfactant, Paragraph No. 0060-0064 of Unexamined-Japanese-Patent No. 2014-041318 (paragraph No. 0060-0064 of International Publication No. 2014/17669 corresponding), etc., Surfactant, and Unexamined-Japanese-Patent No. 2011-132503 specifically, and surfactants described in paragraphs 0117 to 0132 of the heading, the contents of which are incorporated herein by reference. Examples of commercially available fluorine-based surfactants include Megapac F171, Copper F172, Copper F173, Copper F176, Copper F177, Copper F141, Copper F142, Copper F143, Copper F144, Copper R30, Copper F437, Copper F475, Copper F479, Copper F482, copper F554, and copper F780 (above, manufactured by DIC Corporation), Fluorad FC430, copper FC431, and copper FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Sufflon S-382, copper SC-101 , SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.) ), and PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (above, manufactured by OMNOVA).

In addition, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, a portion of the functional group containing a fluorine atom is cut and an acrylic compound in which the fluorine atom is volatilized can also be suitably used. As such a fluorine-based surfactant, Megapac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo, February 22, 2016) (Nikkei Sangyo Shinbun, February 23, 2016), for example, Megapac DS- 21 can be cited.

A block polymer can also be used as a fluorochemical surfactant. For example, the compound of Unexamined-Japanese-Patent No. 2011-089090 is mentioned. The fluorine-based surfactant has 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) ( A fluorine-containing high molecular compound containing a repeating unit derived from a meth)acrylate compound can also be preferably used. The following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 14]

As for the weight average molecular weight of said compound, 3,000-50,000 are preferable, for example, and 14,000 are mentioned specifically,. Among the above compounds, % indicating the proportion of the repeating unit is mass %.

Further, as the fluorine-containing surfactant, a fluorinated polymer having an ethylenically unsaturated group in the side chain may be used. As a specific example, Paragraph Nos. 0050 - 0090 and Paragraph Nos. 0289 - 0295 of Unexamined-Japanese-Patent No. 2010-164965, for example, DIC Corporation Megapac RS-101, RS-102, RS-718K, and RS-72-K etc. are mentioned. Paragraph Nos. 0015 to 0158 of Unexamined-Japanese-Patent No. 2015-117327 can also be used for a fluorine-type surfactant.

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (eg, 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 ( BASF Corporation), Solsperse 20000 (Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Junyaku Kogyo Co., Ltd.), Pionein D-6112, D-6112 -W and D-6315 (made by Takemoto Yushi Co., Ltd.), Olphin E1010, Surfinol 104, 400 and 440 (made by Nisshin Chemical Industry Co., Ltd.), etc. are mentioned.

Moreover, as a fluorine-type surfactant, a vinyl ether polymerization type|mold fluorine-type surfactant can also be used. Examples of the vinyl ether polymerization type fluorine-based surfactant include those described in the Examples column of Japanese Patent Application Laid-Open No. 2016-216602 (eg, fluorine-based surfactant (1)).

0.0001-5.0 mass % is preferable with respect to the total solid of a composition, and, as for content of surfactant, 0.0005-3.0 mass % is more preferable. One type may be sufficient as surfactant, and two or more types may be sufficient as it. When the said composition contains 2 or more types of surfactant, it is preferable that the total content becomes the said range.

(Ultraviolet absorber)

The said composition may also contain a ultraviolet absorber.

Examples of the ultraviolet absorber include a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, and a hydroxyphenyltriazine compound. About these details, Paragraph Nos. 0052 to 0072 of Unexamined-Japanese-Patent No. 2012-208374, and description of Paragraph Nos. 0317 to 0334 of Unexamined-Japanese-Patent No. 2013-068814 can be considered into consideration, and these content is integrated in this specification. . As a commercial item of a conjugated diene compound, UV-503 (made by Daito Chemical Co., Ltd.) etc. is mentioned, for example. Moreover, as a benzotriazole compound, you may use the MYUA series (Kagaku Kogyo Nippo, February 1, 2016) manufactured by Miyoshi Yushi.

0.1-10 mass % is preferable with respect to total solid of a composition, as for content of a ultraviolet absorber, 0.1-5 mass % is more preferable, 0.1-3 mass % is still more preferable. Moreover, only one type may be sufficient as a ultraviolet absorber, and two or more types may be sufficient as it. When the said composition contains 2 or more types of ultraviolet absorbers, it is preferable that the total content becomes the said range.

(filling)

As a filler, an inorganic particle is mentioned, for example. The inorganic particles have a high refractive index and are preferably colorless, white or transparent inorganic particles, such as titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), zinc (Zn), or magnesium (Mg). of oxide particles are preferable, and titanium dioxide (TiO ₂ ) particles, zirconium oxide (ZrO ₂ ) particles, or silicon dioxide (SiO ₂ ) particles are more preferable.

The primary particle diameter in particular of an inorganic particle is not restrict|limited, 1-100 nm is preferable, 1-80 nm is more preferable, 1-50 nm is still more preferable. While the dispersibility is more excellent that the primary particle diameter of an inorganic particle is in the said range, a refractive index and a transmittance|permeability improve more.

Although the refractive index in particular of an inorganic particle is not restrict|limited, From a viewpoint of obtaining a high refractive index, 1.75-2.70 are preferable, and 1.90-2.70 are more preferable.

A specific surface area of the inorganic particles is not particularly limited, but, 10 ~ 400m ² / g are preferred, and 20 to 200m ² / g more preferably, 30 ~ 150m ² / g is more preferable.

Moreover, there is no restriction|limiting in particular in the shape of an inorganic particle, For example, a fine particle, spherical shape, a cube shape, a spindle shape, an irregular shape, etc. are mentioned.

The inorganic particle may be surface-treated with an organic compound. As an organic compound used for surface treatment, a polyol, an alkanolamine, a stearic acid, a silane coupling agent, and a titanate coupling agent are mentioned, for example. Especially, a stearic acid or a silane coupling agent is preferable.

Moreover, it is also preferable that the surface of an inorganic particle is covered with oxides, such as aluminum, a silicon, and a zirconia, at the point which weather resistance improves more.

As an inorganic particle, a commercially available thing can be used preferably.

In the said composition, an inorganic particle may be used individually by 1 type, or may be used in combination of 2 or more type.

(curing accelerator)

When the said composition contains the compound (for example, the compound which has an epoxy group) containing a cationically polymerizable group as a sclerosing|hardenable compound, it is preferable that a composition contains a hardening accelerator.

Examples of the curing accelerator for improving the curing rate include acid anhydrides, bases (aliphatic amines, aromatic amines, and modified amines), acids (sulfonic acid, phosphoric acid, carboxylic acid, etc.), and polymercaptan. Especially, an acid anhydride is preferable and an aliphatic acid anhydride is more preferable.

<Method for preparing the composition>

The composition can be prepared by mixing the above-mentioned components. At the time of preparation of a composition, you may mix|blend each component collectively, and after melt|dissolving or disperse|distributing each component in a solvent, you may mix|blend sequentially. For example, all components may be simultaneously dissolved or dispersed in a solvent to prepare a composition. Moreover, you may mix the composition which disperse|distributes the component which shows particle property in a solvent and resin, and the obtained composition and other components (for example, a specific triazine type resin, curable compound, etc.).

When the composition contains a component exhibiting particulate properties, it is preferable to include a process for dispersing the particles in the method for preparing the composition. In the process of dispersing particles, examples of the mechanical force used to disperse the particles include compression, compression, impact, shear, and cavitation. 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, and ultrasonic dispersion. Moreover, in the grinding|pulverization of the particle|grains in a sand mill (bead mill), it is preferable to process under the conditions which improved grinding|pulverization efficiency by using small diameter beads, increasing the filling rate of beads, etc. After the pulverization treatment, it is preferable to remove the coarse particles by filtration, centrifugation, or the like. In addition, as a process and disperser for dispersing particles, "Dispersion Technology Exhibition, Published by Johokiko Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid/liquid dispersion system) and practical synthesis of industrial applications" The process and disperser described in Paragraph No. 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. Moreover, in the process of dispersing the particle|grains, you may perform the refinement|miniaturization process of particle|grains by a salt milling process. As for the raw material used in the salt milling process, the apparatus, the processing conditions, etc., for example, description of Unexamined-Japanese-Patent No. 2015-194521 and Unexamined-Japanese-Patent No. 2012-046629 can be considered into consideration.

In the preparation of the composition, it is preferable to filter the composition through a filter for the purpose of removing foreign substances and reducing defects. As a filter, if it is a filter conventionally used for a filtration use etc., it can use without restrict|limiting in particular. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6 and nylon-6,6), and polyethylene and polypropylene (PP) A filter using a material such as a polyolefin resin (including a high-density and/or ultra-high molecular weight polyolefin resin) may be mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore diameter of the filter is preferably about 0.01 to 7.0 μm, more preferably about 0.01 to 3.0 μm, and still 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. As a fibrous filter medium, a polypropylene fiber, a nylon fiber, a glass fiber, etc. are mentioned, for example. Specifically, filter cartridges, such as SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) manufactured by Rocky Techno, and SHPX type series (SHPX003 etc.) are mentioned.

When using a filter, you may combine other filters (for example, a 1st filter, a 2nd filter, etc.). In that case, the filtration in each filter may be performed only once, and may be performed 2 times or more. Moreover, you may combine filters of different pore diameters within the above-mentioned range. The hole diameter here can refer to the nominal value of a filter maker. As a commercially available filter, for example, Nippon Pole Co., Ltd. (DFA4201NIEY etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microliss Co., Ltd.), and Kits Microfilter Co., Ltd. can select from various filters provided. The second filter may be formed of the same material as the first filter or the like. Moreover, after performing filtration with a 1st filter with respect to the liquid mixture which mixed only resin and the solvent, and mixing another component, you may filter with a 2nd filter.

<Use>

The use of the composition and the resin of the present invention described later is not particularly limited, and for example, a high refractive member of a solid-state image pickup device (a micro lens, a transparent film such as an underlying layer and an adjacent layer of a color filter, and a color filter) of white pixels), lenses (spectacle lenses, digital camera lenses, Fresnel lenses, and prism lenses, etc.), optical overcoat agents, hard coat agents, anti-reflection films, optical fibers, optical waveguides, LEDs (Light Emitting Diodes) It is useful as a sealing material for use, a planarization material for LEDs, and a coating material for solar cells.

〔membrane〕

The film of the present invention is a film obtained from the composition of the present invention.

Here, the above-mentioned "film" intends both a coating film (an uncured film) formed of the composition of the present invention and a cured film formed by curing the coating film.

In addition, a cured film is obtained by hardening-processing with respect to the coating film formed with the said composition, when a sclerosing|hardenable compound is contained in a composition.

Although the refractive index in particular (wavelength 589 nm) of the said film|membrane is not restrict|limited, It is preferable that it is 1.55 or more, and it is more preferable that it is 1.6-2.0.

Although the light transmittance of the film is not particularly limited, it is preferably 90% or more over the entire wavelength region of 400 to 700 nm, more preferably 95% or more, and still more preferably 100%.

Although the thickness in particular of the said film|membrane is not restrict|limited, It is preferable that it is 0.1-20 micrometers, It is more preferable that it is 0.1-10 micrometers, It is more preferable that it is 0.5-4 micrometers.

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

<The manufacturing method of a patterned cured film>

Hereinafter, as an example of the manufacturing method of a cured film, the method of manufacturing a pattern-shaped cured film is demonstrated in detail.

The method for producing a patterned cured film includes a step of forming a composition layer (coating film) by applying the composition on a substrate (hereinafter, appropriately abbreviated as “composition layer forming step”), and applying the composition layer to a mask. It includes a process of exposing through exposure (hereinafter, appropriately abbreviated as "exposure process"), and a process of forming a pattern-shaped cured film by developing the composition layer after exposure (hereinafter, suitably abbreviated as "development process").

In addition, a curable compound and a photoinitiator are normally contained in the composition used above.

Specifically, the composition is applied on a substrate directly or through another layer to form a composition layer (composition layer formation process), exposed through a predetermined mask pattern, and cured only the portion of the composition layer irradiated with light (Exposure process) By developing with a developing solution (development process), the pattern-shaped cured film which consists of a pixel can be formed.

Hereinafter, each process is demonstrated.

·Composition layer forming process

In a composition layer formation process, the said composition is apply|coated on a board|substrate, and a composition layer (coating film) is formed.

The substrate is not particularly limited, and for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used in liquid crystal display devices, etc. A conversion element substrate (eg, a silicon substrate, etc.), a CCD (Charge Coupled Device) substrate, a CMOS (Complementary Metal Oxide Semiconductor) substrate, etc. are mentioned.

As a coating method of the said composition to a board|substrate, various coating methods, such as a slit coating, an inkjet method, a rotation coating, a cast coating, roll coating, or the screen printing method, are applicable.

As a coating film thickness of a composition, although it can select suitably according to a use, For example, it is 0.1-20 micrometers, 0.1-10 micrometers is more preferable, 0.5-4 micrometers is still more preferable.

The composition applied on the substrate is usually dried at 70 to 110° C. for about 2 to 4 minutes. Thereby, a composition layer can be formed.

・Exposure process

In an exposure process, the composition layer (coating film) formed in the composition layer formation process is exposed through a mask, and only the light-irradiated coating film part is hardened.

It is preferable to perform exposure by irradiation of actinic ray or radiation, and, especially, ultraviolet-rays, such as g line|wire, h line|wire, or i line|wire, are more preferable. ^{5-1500 mJ/cm<2>} is preferable and, as for irradiation intensity|strength, 10-1000mJ ^/cm<2> is more preferable.

・Development process

Following the exposure step, an alkali developing treatment (development step) is performed, and the light unirradiated portion in the exposure step is eluted in an aqueous alkali solution. Thereby, only the photocured part (light-irradiated coating film part) remains.

As the developer, an organic alkali developer that does not cause damage to the underlying circuit or the like is preferable. As image development temperature, it is 20-30 degreeC normally, and image development time is 20-90 second.

As an alkaline aqueous solution, an inorganic type developing solution and an organic type developing solution are mentioned, for example. Examples of the inorganic developer include an alkaline aqueous solution in which sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, or sodium metasilicate has a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. have. Examples of the organic developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabi. An alkaline aqueous solution in which an alkaline compound such as cyclo-[5.4.0]-7-undecene is dissolved so as to have a concentration of 0.001 to 10 mass%, preferably 0.01 to 1 mass% is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant may be added to the alkaline aqueous solution, for example. In addition, when a developing solution composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

As a developing method, the puddle developing method, the shower developing method, etc. can be used, for example.

〔lens〕

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

[Solid-State Imaging Device]

The film (preferably cured film) of the present invention is suitably applicable to a solid-state imaging device.

As a configuration of the solid-state imaging device of the present invention, for example, a plurality of photodiodes constituting a light-receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) In addition, the structure provided with the undercoat layer film which is the film|membrane of this invention under a color filter, etc. are mentioned.

〔profit〕

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). In addition, 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 aspect of the specific triazine-type resin mentioned above.

EMBODIMENT OF THE INVENTION Hereinafter, resin of this invention is demonstrated in detail.

<Repeating unit represented by general formula (IV-1)>

[Formula 15]

In general formula (IV-1), X ¹ , X ² , and X ³ each independently represent -NR ¹ -, -O-, or -S-. 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.

General formula (IV-1) of, X ^1, X ^2, X ^3, and W ¹ is the above-described general formula (I-1) and X ^1, X ^2, X ^3, and W ¹ of the agreement, suitable The aspect is also the same.

In 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.

Preferred embodiments of the heterocyclic group, alkyl group, alkylthio group, and halogen atom represented by R ⁵ include a heterocyclic group, an alkyl group, an alkylthio group, and a halogen atom represented by R ⁴ in the above-mentioned general formula (II). are identical to each

As said general formula (IV-1), it is preferable that the refractive index of the cured film after exposure repeatedly in a high-temperature-low-temperature environment is more excellent, Especially, it is group represented by the following general formula (IV-1A).

[Formula 16]

Among them, with respect to the coupling position of the phenylene groups adjacent to the phenyl group, and R ⁵ it is optionally substituted, R ⁵ is preferably located above para.

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

[Formula 17]

In general formula (IV-2), X ⁴ , X ⁵ , and X ⁶ each independently represent -NR ² -, -O-, or -S-. R ² represents a hydrogen atom or a substituent.

In the general formula ^{(IV-2), X 4} , X 5, and X ⁶ are the above-described general formula (I-2) and X ^4, X ^5, and X ⁶ and consent of, it is also suitable for the same embodiment.

As said general formula (IV-2), it is preferable that the refractive index of the cured film after repeated exposure in a high-temperature-low-temperature environment is more excellent, and it is group represented by the following general formula (IV-2A) especially.

[Formula 18]

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 preferably 50 to 100 mol% based on all the repeating units in the resin, and 80 to 100 mol% is more preferable, and 90-100 mol% is still more preferable.

2,000-100,000 are preferable, as for the weight average molecular weight of the said resin, 2,000-50,000 are more preferable, 4,000-20,000 are still more preferable. Dispersion degree (Mw/Mn) is 1.0-3.0 normally, 1.0-2.6 are preferable, 1.0-2.0 are more preferable, 1.1-2.0 are still more preferable.

Example

The present invention will be described in more detail below based on examples. Materials, usage amounts, ratios, treatment details, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the Examples shown below.

[1] Synthesis of a resin comprising 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)>

[Formula 19]

In the container, 9.0 g of cyanuric acid chloride and 13.2 g of tetrahydrofuran were weighed, and the resulting solution was ice-cooled while stirring under a nitrogen stream. Next, a solution obtained by dissolving 10.0 g of 4-amino-4'-cyanobiphenyl in 76.8 g of tetrahydrofuran was added dropwise to the ice-cooled solution, followed by stirring for another 2 hours. 380 g of 0.2 mass % hydrochloric acid water was added to the reaction solution after stirring, and the obtained solid was filtered. Next, 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).

[Formula 20]

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

<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 reacted with the same molar equivalent Except for that, the same operation as in Synthesis 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 replaced with 4-amino-4'-chlorobiphenyl and 4,4'-diaminobenzanilide, respectively, and the same mole The same operation as in Synthesis Example 1 was carried out except that the reaction was carried out in equivalents, to obtain compound (A-3).

<Synthesis Example 4: Resin (A-4)>

4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine were changed to 4-amino-4'-methylbiphenyl and 4,4'-diaminodiphenyl ether, respectively, and the same The same operation as in Synthesis Example 1 was carried out except for reacting in a molar equivalent to obtain compound (A-4).

<Synthesis Example 5: Resin (A-5)>

4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine were replaced with 4-amino-4'-nitrobiphenyl and bis(4-aminophenyl)sulfide, respectively, and the same molar equivalent Compound (A-5) was obtained in the same manner as in Synthesis Example 1 except that it was reacted with

<Synthesis Example 6: Resin (A-6)>

4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine were replaced with 4-amino-4'-methylthiobiphenyl and bis(4-aminophenyl)sulfone, respectively, and the same molar equivalent Compound (A-6) was obtained in the same manner as in Synthesis Example 1 except that it was reacted with

<Synthesis Example 7: Resin (A-7)>

4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine were changed to p-cyanoaniline and 4,4'-diamino-p-terphenyl, respectively, and the same molar equivalent Except for reacting, 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 the same The same operation as in Synthesis Example 1 was carried out except for reacting in a molar equivalent to obtain compound (A-8).

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

[Formula 21]

In a container, 9.2 g of cyanuric acid chloride, 8.7 g of 4,4''-diamino-p-terphenyl, and 56.7 g of N,N-dimethylacetamide were weighed, and the resulting mixture was heated to 100° C. under a nitrogen stream. It heated and stirred for 1 hour. Next, 3.0 mL of aniline was added to the reaction solution after stirring, and it stirred for 10 minutes again. After cooling the obtained reaction solution to room temperature, it added to the aqueous solution of 14.0 g of triethylamine and 760 g of ion-exchange water. After filtering the precipitated solid, the filtered solid was washed three times with 200 g of ion-exchanged water, and then washed once with 200 g of ethanol. 15.1 g of compound (A-9) was obtained by vacuum-drying the obtained solid at 60 degreeC.

<Synthesis Example 10: Resin (A-10)>

4,4''-diamino-p-terphenyl was changed to 1,3-phenylenediamine, and the same operation as in Synthesis Example 9 was carried out except that the reaction was carried out in the same molar equivalent to compound (A-10) ) was obtained.

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

[Formula 22]

In a 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]-7- 14.0 g of undecene and 32.7 g of N,N-dimethylacetamide were weighed, and the resulting mixture was heated to 100° C. under a nitrogen stream and stirred for 1 hour. Then, 2.0 mL of aniline was added to the reaction solution after stirring, and it stirred for further 10 minutes. After cooling the obtained reaction solution to room temperature, it added to the aqueous solution of 760 g of ion-exchange water. After filtering the precipitated solid, the filtered solid was washed three times with 200 g of ion-exchanged water, and then washed once with 200 g of ethanol. 10.7 g of compound (A-11) was obtained by vacuum-drying the obtained solid at 60 degreeC.

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

[Formula 23]

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

Moreover, although content of the sodium ion, potassium ion, and calcium ion contained in resin (A-1) - (A-11) was quantified, it confirmed that it was less than 0.01 mass ppm, respectively. In addition, ICP emission spectroscopy apparatus ("Optima 7300DV" manufactured by PerkinElmer) was used for quantification of sodium ion, potassium ion, and calcium ion.

Moreover, although content of toluene contained in resin (A-1) - (A-11) was quantified, it confirmed that it was less than 0.001 mass ppm.

In addition, the toluene concentration in resin was quantified after creating a calibration curve by gas chromatography according to a well-known method.

[Table 1]

[2] Various ingredients

Below, the various components contained in a composition are shown.

<Specific triazine-based resin>

Regarding 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>

Curable compounds M-1 to M-7 shown below were used.

[Formula 24]

<Photoinitiator>

The photoinitiators I-1 to I-12 shown below were used.

In the structural formula, "Me" represents a methyl group, and "Ph" represents a phenyl group.

[Formula 25]

<Solvents other than toluene>

As solvents other than toluene, the solvents shown below were used.

NEP: N-ethyl-2-pyrrolidone

MFG: 1-methoxy-2-propanol

CPN: cyclopentanone

<Surfactant>

The surfactant shown below was used.

Megapac R-40 (manufactured by DIC Corporation)

<Content of specific metal ion in each component>

About each component mentioned above, it refine|purified, respectively, and used after confirming that content of the sodium ion in each component, potassium ion, and calcium ion was less than 0.01 mass ppm, respectively. In addition, it is as above-mentioned about the quantitative method of a sodium ion, a potassium ion, and a calcium ion.

<Content of toluene in each component>

About each component mentioned above, it used after confirming that content of toluene in each component was less than 0.001 mass ppm by vacuum drying. In addition, about the quantitative method of content of toluene in each component, it is as above-mentioned.

[3] Preparation of composition

After mixing the above-mentioned various components (resin, solvent other than toluene, curable compound, polymerization initiator, and surfactant) at the mixing ratio shown in Table 2, the obtained mixture is vacuum dried, sodium ions, potassium ions, and calcium in the dried product It confirmed that content of ion was less than 0.01 mass ppm, respectively. Moreover, it confirmed that content of toluene was less than 0.001 mass ppm.

Next, a resin, a curable compound, a polymerization initiator, a surfactant, a solvent other than toluene, and toluene shown below, sodium ions (as a sodium source, sodium bromide solution), potassium ions (as a potassium source, potassium methanol bromide) solution) and calcium ions (as a calcium ion source, calcium methanol solution of bromide) were added so that it might become content of Table 2, and various compositions were prepared, respectively. In addition, in the column of "solvent other than toluene" in Table 2, methanol in the said ion source is also contained in a trace amount. In addition, content of each component in Table 2 shows the content rate (%) with respect to the composition total mass.

About content of sodium ion, potassium ion, and calcium ion in the obtained composition, it quantified using the ICP emission spectroscopy apparatus ("Agilent 7800 ICP-MS" manufactured by Agilent Technologies).

Moreover, about content of toluene in the obtained composition, according to a well-known method, after creating a calibration curve by gas chromatography, it quantified.

[4] Evaluation

Using the obtained composition, evaluation of the refractive index of the cured film after the thermocycle, the spectral fluctuation of the cured film after the thermocycle, evaluation of the defect suppression property of the cured film after the thermocycle, and the surface appearance of the coating film were evaluated.

<Evaluation of refractive index of cured film after thermocycle>

On a 5 cm x 5 cm glass substrate on which an epoxy resin layer was formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resin Co., Ltd.), the compositions described in Table 2 were respectively spin-coated and baked (heated) at 100°C for 3 minutes. did. Next, with respect to the obtained coating film, it exposed using a high-pressure mercury-vapor lamp so that an accumulated exposure amount might be set to 200 mJ/cm<^2>. Then, the glass substrate was baked at 200 degreeC for 3 minutes, and the cured film whose film thickness is 1 micrometer was obtained. The obtained cured film was put into a cold and thermal shock test apparatus (ESPEC THERMAL Shock CHAMBER TSA-70L (manufactured by TABAI ESPEC)), and 300 cycles of cooling and heating cycles from -65°C/30 minutes to 125°C/30 minutes were applied. The refractive index of wavelength 300-1500 nm was measured using VASE by JA Woollam, and the value of the refractive index in wavelength 589 nm was made into the refractive index of each film|membrane.

The refractive index of the cured film after a thermocycle was evaluated with reference to the following reference|standard for the value of the measured refractive index.

"A": refractive index of 1.85 or more

"B": refractive index of 1.70 or more and less than 1.85

"C": refractive index less than 1.70

<Spectral fluctuation (change in transmittance) of cured film after thermocycle>

Evaluation of the said refractive index WHEREIN: The change amount of the transmittance|permeability of wavelength 450nm of the cured film before and after a cold-and-heat shock test (|transmittance after a cold-and-heat shock test-transmittance|transmittance before a cold-and-heat shock test|(absolute value)) was measured.

The spectral fluctuation (change in transmittance) of the cured film after a thermocycle was evaluated with reference to the following reference|standard for the measured change amount of transmittance|permeability.

"A": The rate of change of transmittance is less than 1%.

"B": The rate of change of transmittance is 1% or more and less than 5%.

"C": The rate of change of transmittance is 5% or more, and it is a level which poses a problem practically.

In addition, the change rate (%) of the said transmittance|permeability is a value computed by {(transmittance change amount)/(transmittance before cold-heat shock test)} x 100.

<Evaluation of defect suppression property of cured film after thermocycle>

On a silicon wafer on which an epoxy resin layer was formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resin Co., Ltd.), the compositions shown in Table 2 were respectively spin-coated, and further baked (heated) at 100° C. for 3 minutes to form a film A coating film having a thickness of 1 µm was formed. Next, with respect to the obtained coating film, it exposed using a high-pressure mercury-vapor lamp so that an accumulated exposure amount might be set to 200 mJ/cm<^2>. Then, the glass substrate was baked at 200 degreeC for 3 minutes, and the cured film whose film thickness is 1 micrometer was obtained. The obtained cured film was put in a cold and thermal shock test apparatus (ESPEC THERMAL Shock CHAMBER TSA-70L (manufactured by TABAI ESPEC)), and after 300 cycles of cooling and heating cycles of -65 ° C./30 min → 125 ° C./30 min., a defect inspection device ( The number of defects (piece/cm ² ) of the cured film was measured using ComPlus manufactured by Applied Materials).

The number of measured defects was divided into the following reference|standards, and the defect suppression property of the cured film in after a thermocycle was evaluated.

"A": 0 defects/cm ² or more and less ^{than 10 defects/cm 2}

"B": the number of defects to 10 / cm ² or more to 20 / cm ² under

"C": The number of defects is 20 pieces/cm ² or more, and is a level that is problematic in practice.

<Evaluation of the surface appearance of the coated film (PCD (Post Coating Delay) of the coated film)>

On a silicon wafer on which an epoxy resin layer was formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resin Co., Ltd.), the compositions shown in Table 2 were respectively spin-coated, and further baked (heated) at 100° C. for 3 minutes, followed by a film The coating film A with a thickness of 1 micrometer was formed, and it observed that there was no abnormality with the optical microscope. This coating film A was left to stand at 25 degreeC for 100 hours, and the coating film B was observed with the optical microscope.

The following criteria were used to classify, the observed coating film B was evaluated, and the surface appearance of the coating film was evaluated.

"A": Surface roughness or foreign matter of the film is not observed

"B": The surface roughness or foreign matter of the film is partially observed, but it is a level that does not pose a problem in practice.

"C": The surface roughness or foreign matter of the film is partially observed, and is a level that is problematic in practice

Table 2 is shown below.

In addition, in Table 2, "0" in the "specific metal ion" column intends that content of the specific metal ion in a composition was less than 0.01 mass ppm. In addition, "0" in the "toluene" column intends that content of toluene in a composition was less than 0.001 mass ppm.

In addition, the "residual amount" in the "solvent other than toluene" column in Table 2 means an amount obtained by subtracting the total mass ratio of constituents other than the "solvent other than toluene" in the composition from the total ratio (100%) of the composition .

[Table 2]

From the results in Table 2, according to the compositions of Examples, the resulting cured film suppressed the occurrence of defects even after repeated exposure to a high-temperature-low-temperature environment, and spectral fluctuations (transmittance of change) is clear.

Moreover, from the comparison of Examples 1-21, when the total content of a specific metal ion in the said composition is 0.03-10 mass ppm with respect to the total mass of a composition, the defect suppression of the cured film after repeated exposure under high temperature-low temperature environment. It was confirmed that the performance was more excellent.

Moreover, from the comparison with Examples 1-21, when content of toluene in the said composition was 0.001-10 mass ppm with respect to the composition total mass, it was confirmed that the surface appearance characteristic was more excellent.

Moreover, from the comparison of Example 9, Example 15, and Example 19, when the composition contains the triazine resin represented by the above-mentioned general formula (I-2), W ² is the above-mentioned general formula ( As a divalent linking group represented by III), when the ^{arylene group included in A 1} to A ³ is a 1,4-phenylene group, or when ^{all of A 1} to A ³ represent an arylene group, it is repeated under a high-temperature-low-temperature environment. It was confirmed that the refractive index of the cured film after exposure was more excellent, and the spectral fluctuation (change in transmittance) of the cured film was small even after repeated exposure under a high-temperature-low-temperature environment.

Moreover, from the comparison of Examples 1-3, Examples 7 and 8, Examples 10-14, Examples 17-18, and Example 16, the said composition is X in the above-mentioned general formula (I-1) ^{When 1} to X ³ all contain -NR ¹ -, a specific triazine-based resin, the refractive index of the cured film after repeated exposure under high-temperature-low temperature environment is superior, and even after repeated exposure under high-temperature-low temperature environment It was confirmed that the spectral fluctuation|variation (change of transmittance|permeability) of a cured film was small.

Claims (19)

A resin comprising a repeating unit represented by the general formula (I-1) or a repeating unit represented by the general formula (I-2);
solvent and
A composition comprising a specific metal ion selected from the group consisting of sodium ion, potassium ion, and calcium ion,
The total content of the said specific metal ion is 0.01-30 mass ppm with respect to the composition total mass, The composition.
[Formula 1]

In general formula (I-1), X ¹ , X ² , and X ³ each independently represent -NR ¹ -, -O-, or -S-. 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.
[Formula 2]

In general formula (I-2), X ⁴ , X ⁵ , and X ⁶ each independently represent -NR ² -, -O-, or -S-. W ² represents a divalent linking group. R ² represents a hydrogen atom or a substituent. The method according to claim 1,
The solvent comprises toluene,
The composition, wherein the content of the toluene is 0.001 to 10 mass ppm with respect to the total mass of the composition. The method according to claim 1 or 2,
The composition in which said V in general formula (I-1) is group represented by general formula (II).
[Formula 3]

In general formula (II), * represents a bonding position with ^{X 3 in general formula (I-1).} R ³ and R ⁴ each independently represent a substituent. m and n each independently represent the integer of 0-5. However, m+n is 1-5. 4. The method according to claim 3,
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. representing the composition. 5. The method according to claim 4,
The composition in which group represented by the said general formula (II) is group represented by general formula (IIA).
[Formula 4]

In general formula (IIA), * represents a bonding position with ^{X 3 in general formula (I-1).} 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. The method according to claim 1 or 2,
In the general formula (I-1), X ¹ to X ³ are all -NR ¹ -, the composition. The method according to claim 1 or 2,
Wherein W ¹ and W ² are wherein in the formula (I-2), each independently represent a divalent connecting group represented by the general formula (III) in the formula (I-1), compositions.
[Formula 5]

In general formula (III), A ¹ and A ³ each 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. R ^A represents a hydrogen atom or a substituent. * indicates a binding position. 8. The method of claim 7,
The composition in which all of A ¹ to A ^{3 represent an arylene group in W 2} of the general formula (I-2). 8. The method of claim 7,
^{The composition according to W 2} of the general formula (I-2), wherein the arylene group is a 1,4-phenylene group. The method according to claim 1 or 2,
A composition further comprising a curable compound. The method according to claim 1 or 2,
A composition further comprising a polymerization initiator. A coating film formed of the composition according to claim 1 or 2. A cured film formed by curing the coating film according to claim 12 . The lens which consists of the cured film of Claim 13. A solid-state imaging device comprising the lens according to claim 14 . A resin comprising a repeating unit represented by the general formula (IV-1A).

In general formula (IV-1A), X ¹ , X ² , and X ³ each independently represent -NR ¹ -, -O-, or -S-. W ¹ represents a divalent linking group. R ¹ represents a hydrogen atom or a substituent. R ⁵ represents a cyano group, a nitro group, an alkyl group, an alkylthio group, or a halogen atom. However, with respect to the bonding position of the phenylene groups adjacent to the phenyl group, and R ⁵ it is optionally substituted, R ⁵ is located on para. A resin comprising a repeating unit represented by the general formula (IV-2A).

In general formula (IV-2A), X ⁴ , X ⁵ , and X ⁶ each independently represent -NR ² -, -O-, or -S-. R ² represents a hydrogen atom or a substituent. 17. The method of claim 16,
The resin, wherein ^{X 1 , X 2} , and X ³ each ^{represent —NR 1} —, and R ¹ represents a hydrogen atom. 18. The method of claim 17,
X ⁴ , X ⁵ , and X ⁶ each ^{represent —NR 2} —, and R ² represents a hydrogen atom.