TW201936788A - Composition, coating film, cured film, lens, solid-state imaging device, resin - Google Patents

Abstract

Provided is a composition capable of giving a cured film in which the occurrence of defects is suppressed even after repeated exposure to a high temperature-low temperature environment. Also provided are a coating film, a cured film, a lens, a solid-state imaging device, and a novel resin. The composition contains a resin containing a repeating unit represented by general formula (I-1) or a repeating unit represented by general formula (I-2), a solvent, and a specific metal ion selected from the group consisting of a sodium ion, potassium ion, and calcium ion, and the total content of the specific metal ion is 0.01-30 mass ppm relative to the total mass of the composition.

Description

Composition, coating film, cured film, lens, solid-state imaging device, resin

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

Conventionally, compounds for optical materials (for example, a microlens forming material mounted on an image sensor and a refractive index modifier of a color filter) are required to have high heat resistance, high transparency, high refractive index, and high solubility. Sex and low volume shrinkage and many other characteristics.
For example, Patent Document 1 discloses a tricyclic ring-containing polymer as a material having high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] JP-A-2015-025131

The inventors of the present invention have studied the cured film formed of the composition containing the triguanidine ring-containing polymer described in Patent Document 1, and are known to be in a high temperature environment and a low temperature environment (high temperature-low temperature environment). The above-mentioned cured film which is repeatedly exposed has many defects.

Accordingly, an object of the present invention is to provide a composition capable of providing a cured film which can suppress the occurrence of defects after repeated exposure in a high-temperature-low temperature environment.
Further, an object of the present invention is to provide a coating film formed of the above composition, a cured film formed by curing the coating film, a lens, and a solid-state image sensor.
Further, an object of the present invention is to provide a novel resin which can be suitably used as a high refractive index material.

As a result of intensive studies to achieve the above problems, the inventors of the present invention have found that the above problems can be solved by including a resin containing a tri-ring of a specific structure, a specific metal ion of a predetermined content, and a solvent. this invention.
That is, it was found that the above object can be achieved by the following structure.

(1) A composition comprising:
The resin includes a repeating unit represented by the following formula (I-1) or a repeating unit represented by the formula (I-2) described later;
a solvent; and a specific metal ion selected from the group consisting of sodium ions, potassium ions, and calcium ions.
The total content of the specific metal ions is 0.01 to 30 ppm by mass based on the total mass of the composition.
(2) The composition according to (1), wherein the solvent contains toluene,
The content of toluene is 0.001 to 10 ppm by mass based on the total mass of the composition.
(3) The composition according to (1) or (2), wherein, in the formula (I-1), V is a group represented by the formula (II) which will be described later.
(4) The composition according to (3), wherein, in the 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 alkyl sulfide. Base or halogen atom.
(5) The composition represented by the formula (II), wherein the group represented by the formula (II) described later is a group represented by the formula (IIA) described later.
(6) The composition according to any one of (1) to (5), wherein, in the formula (I-1), X ¹ to X ³ are each -NR ¹ -.
The composition according to any one of (1) to (6), wherein W ^{1 in the} general formula (I-1) and W ² in the general formula (I-2) are each independently A divalent linking group represented by the formula (III) which will be described later.
(8) The composition according to (7), wherein in W ² of the formula (I-2), all of A ¹ to A ³ represent an exoaryl group.
(9) The composition according to (7) or (8), wherein in the W ² of the formula (I-2), the exoaryl 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 described in (12).
(14) A lens comprising the cured film of (13).
(15) A solid-state imaging device comprising the lens described in (14).
(16) A resin comprising a repeating unit represented by the following formula (IV-1).
(17) A resin comprising a repeating unit represented by the formula (IV-2) described later.
[Effect of the invention]

According to the present invention, it is possible to provide a composition capable of providing a cured film which can suppress the occurrence of defects after repeated exposure in a high-temperature-low temperature environment.
Moreover, according to the present invention, it is possible to provide a coating film formed of the above composition, a cured film formed by curing the coating film, a lens, and a solid-state image sensor.
Moreover, according to the present invention, it is possible to provide a novel resin which can be suitably used as a high refractive index material.

Hereinafter, the present invention will be described in detail.
In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.
The "actinic ray" or "radiation" in the present specification means, for example, a far-line ultraviolet ray represented by a bright line spectrum of a mercury lamp, an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, or the like. Further, in the present invention, light means actinic rays or radiation. The "exposure" in the present specification includes not only exposures based on far-ultraviolet rays, X-rays, and EUVs, such as bright-line spectra of mercury lamps and excimer lasers, but also electron beam, ion beam, etc., unless otherwise specified. The exposure of the particle beam.
In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene fluorenyl group and nail Acryl fluorenyl.
In this specification, the term "step" includes not only independent steps, but even if it cannot be clearly distinguished from other steps, it is included in the term as long as the desired effect of the step can be achieved.
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted values measured by gel permeation chromatography (GPC). In the present specification, for example, HLC-8220 (manufactured by TOSOH CORPORATION) is used as a measuring device, and TSKgel Super AWM-H (manufactured by TOSOH CORPORATION, 6.0 mm ID (inner diameter) × 15.0 cm) is used as a column, and used as an eluent. A 10 mmol/L lithium bromide NMP (N-methylpyrrolidone) solution was used to determine a weight average molecular weight (Mw) and a number average molecular weight (Mn).
In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group related to the polymerization reaction.
In the present specification, the total solid content means the total mass of components other than the solvent from the entire composition.

In the label of the group (atomic group) in the present specification, the label which is not labeled with a substitution and an unsubstituted includes a group which has no substituent and has a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The substituent may, for example, be a group selected from the group of substituents T described below.

(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, and an aromatic group. Oxyl, decyloxy, heterocyclic oxy, decyloxy, amine methyl methoxy, amine (including alkylamino and anilino), decylamino, aminocarbonylamino, alkoxycarbonylamino , aryloxycarbonylamino, aminesulfonylamino, alkyl or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfo, alkane Or arylsulfinyl, alkyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminemethanyl, aryl or heterocyclic azo, quinone imine, phosphine A group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a formyl group, and the like. Hereinafter, each group will be described in detail.

A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom) may be mentioned.
a linear or branched alkyl group (which is a linear or branched, substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms. For example, methyl, ethyl, N-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl and 2-ethylhexyl, etc.,
a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms. The cycloalkyl group may be a single ring or a polycyclic ring. Examples of the monocyclic cycloalkyl group include a ring. Further, as the polycyclic cycloalkyl group, for example, a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms), specifically, may be mentioned. Bicyclo[1,2,2]heptan-2-yl and bicyclo[2,2,2]octane-3-yl, etc., and tricycloalkyl, etc. as a cycloalkyl group, wherein a monocyclic naphthenic group A benzyl or bicycloalkyl group is preferred, and a monocyclic cycloalkyl group is more preferred.

a linear or branched alkenyl group (which is 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 , isoprenyl, geranyl and oleyl, etc.)
a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms. The cycloalkenyl group may be a single ring or a polycyclic ring. Examples of the monocyclic cycloalkenyl group include 2 a cyclopenten-1-yl group and a 2-cyclohexen-1-yl group. Further, as a polycyclic cycloalkenyl group, a bicycloalkenyl group (preferably a substituted or unsubstituted carbon number of 5 to 30) Bicycloalkenyl. Specific examples thereof include bicyclo[2,2,1]hept-2-en-1-yl and bicyclo[2,2,2]oct-2-en-4-yl, etc., and A cycloalkenyl group or the like. As the cycloalkenyl group, a monocyclic cycloalkenyl group is preferred.)
An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, a trimethyldecyl ethynyl group, etc.),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylphenyl, fluorenyl, Biphenyl and triphenyl, etc.)
The heterocyclic group (heterocyclic group may be any of a substituted or unsubstituted alicyclic heterocyclic group and an aromatic heterocyclic group. Further, the alicyclic heterocyclic group may be either saturated or unsaturated. Further, the heterocyclic group may be a monocyclic ring or a condensed ring. As the heterocyclic group, one or more hetero atoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom are preferred, and the carbon number is 3 The aromatic heterocyclic group of 5 or 6 members of ～30 is more preferable, and examples thereof include 2-furyl group, 2-thienyl group, 2-pyridyl group, 4-pyridyl group, 2-pyrimidinyl group and 2-benzene group. And thiazolyl, etc.),
Cyano, hydroxyl, nitro, carboxyl,

Alkoxy (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy and 2 -methoxyethoxy, etc.),
An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms), for example, a phenoxy group, a 2-methylphenoxy group, a 2,4-di-tripentylphenoxy group , 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylaminophenoxy, etc.),
a decyloxy group (preferably a decyloxy group having 3 to 20 carbon atoms, such as a trimethyl decyloxy group and a tert-butyldimethyl methoxy group),
a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. As the heterocyclic group in the heterocyclic oxy group, one excluding the above heterocyclic group is mentioned a divalent heterocyclic group of a hydrogen atom. Examples of the heterocyclic oxy group include a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group.

a decyloxy group (preferably, a methyl methoxy 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, methyl methoxy, ethoxylated, trimethyl ethoxylated, stearyloxy, benzyl methoxy, p-methoxyphenylcarbonyloxy, acryloxy and propylene oxide Base, etc.)
Aminomethyloxy (preferably a substituted or unsubstituted amine methyloxy group having 1 to 30 carbon atoms. For example, N,N-dimethylaminemethyl methoxy, N,N-diethyl Aminomethyloxy, morpholinylcarbonyloxy, N,N-di-n-octylaminocarbonyloxy and N-n-octylaminemethyloxy, etc.)
Alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a third butoxycarbonyl group) Oxyl and n-octylcarbonyloxy, etc.)
An aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, and a N-hexadecyloxyphenoxycarbonyloxy, etc.),

Amino group (preferably unsubstituted amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms or carbon number 0 to a heterocyclic amino group of 30. For example, an amine group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, and an N-1,3,5-trian-2-ylamine Base, etc.)
Amidino group (preferably a formamidine 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, amidoxime, etidylamino, neopentylamino, laurylamine, benzamidine, 3,4,5-tri-n-octyloxyphenylcarbonylamino, propylene oxime Amino group and methacrylamide group, etc.)
Aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. For example, an aminomethylamino group, N,N-dimethylaminocarbonylamino group, N , N-diethylaminocarbonylamino group and morpholinylcarbonylamino group, etc.)
An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a third butoxycarbonyl group) Amino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, etc.)

An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group and a meta-n-octane group; Oxyphenoxycarbonylamino group, etc.)
Aminesulfonylamino group (preferably a substituted or unsubstituted amine sulfonylamino group having a carbon number of 0 to 30. For example, an aminesulfonylamino group, an N,N-dimethylaminosulfonyl group Amino group and N-n-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 aryl group having 6 to 30 carbon atoms Sulfhydrylamino group, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino and p-methyl Phenylsulfonylamino group, etc.)
巯基,

An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, an n-hexadecylthio group, etc.),
An arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as a phenylthio group, a p-chlorophenylthio group, a m-methoxyphenylthio group, etc.),
a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. The heterocyclic group in the heterocyclic thio group may be one removed from the above heterocyclic group. a divalent heterocyclic group of a hydrogen atom. Examples of the heterocyclic thio group include a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group.
Aminesulfonyl (preferably a substituted or unsubstituted sulfonyl group having a carbon number of 0 to 30. For example, N-ethylaminesulfonyl, N-(3-dodecyloxypropyl)amine Sulfonyl, N,N-dimethylaminesulfonyl, N-acetamimidoxime, N-benzamidesulfonyl and N-(N'-phenylaminecarbamyl)amine Sulfonyl group, etc.)
Sulfo,

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 of 6 to 30) For example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl and p-methylphenylsulfinyl, 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, methylsulfonyl, ethylsulfonyl, phenylsulfonyl and p-methylphenylsulfonyl, etc.,
Mercapto group (preferably a mercapto 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 acetamino group, a methyl ethyl fluorenyl group, a 2-chloroethyl fluorenyl group, a stearyl sulfonyl group, a benzhydryl group, a p-octyloxyphenylcarbonyl group, an acryl fluorenyl group, a methacryl fluorenyl group, etc.)
An aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, a m-nitrophenoxycarbonyl group, and a third group) Butylphenoxycarbonyl, etc.)

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group, etc.) ,
Aminomethyl thiol (preferably a substituted or unsubstituted amine carbenyl group having 1 to 30 carbon atoms), for example, an amine methyl sulfhydryl group, an N-methyl amine methyl fluorenyl group, and an N,N-dimethylamine group Anthracenyl, N,N-di-n-octylamine methyl sulfhydryl and N-(methylsulfonyl)amine methyl sulfhydryl, etc.
An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms or a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms ( Examples of the heterocyclic group in the heterocyclic azo group include a divalent heterocyclic group in which one hydrogen atom is removed from the above heterocyclic group. For example, a phenylazo group or a p-chlorophenylazo group. And 5-ethylthio-1,3,4-thiadiazol-2-ylazo, etc.),
a quinone imine group (preferably a substituted or unsubstituted quinone imine group having 2 to 30 carbon atoms, such as N-succinimide group and N-phthalimido group, etc.),
a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, etc.),
a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, etc.),

a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group) ,
a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group; And a germyl group (preferably a substituted or unsubstituted carboxyalkyl group having a carbon number of 3 to 30. For example, trimethyldecyl, tert-butyldimethylformamidin, and phenyldimethylmethyl)矽 alkyl, etc.).

In the above functional group, a portion of a hydrogen atom in a functional group having a hydrogen atom may be substituted with any of the above groups. Examples of the functional group which can be introduced as a substituent include an alkylcarbonylaminosulfonyl group (for example, an ethyl sulfonylsulfonyl group) and an arylcarbonylaminosulfonyl group (for example, benzamide). An alkylsulfonylaminocarbonyl group (for example, a methylsulfonylaminocarbonyl group) and an arylsulfonylaminocarbonyl group (for example, a p-methylphenylsulfonylaminocarbonyl group, etc.) )Wait.

[composition]
The composition of the present invention includes a resin comprising a repeating unit represented by the following formula (I-1) or a repeating unit represented by the following formula (I-2); a solvent; and a specific metal ion selected from the group consisting of In the group of sodium ions, potassium ions, and calcium ions, the total content of the specific metal ions is 0.01 to 30 ppm by mass based on the total mass of the composition.

The characteristic point of the above-mentioned composition is a resin containing a repeating unit represented by the formula (I-1) described later or a repeating unit represented by the formula (I-2) described later (hereinafter also referred to as "Specific triterpenoid resin") and a specified amount of a specific metal ion.
A material exhibiting high refractive index, represented by a triterpenoid resin, is associated by intermolecular interaction and is easy to form aggregates. The inventors of the present invention have studied the cured film containing the above aggregates, and found that if the cured film is repeatedly exposed in a high-temperature-low temperature environment, microphase separation (aggregation and non-aggregation) is likely to occur. Phase separation), due to the microphase separation, the defects of the cured film increase.
As a result of further research conducted by the present inventors based on the above findings, it is known that it is difficult to cause microphase separation by a cured film formed by blending a specific tricreide resin and a composition of a specific metal ion having a predetermined content, and as a result, The above-mentioned cured film can also suppress the occurrence of defects after repeated exposure in a high-temperature-low temperature environment.
Although the above-described mechanism of action is not clear, it is presumed that since the specific metal ion easily interacts with a nitrogen atom or the like in a specific tricreide resin, the specific triterpene resin is inhibited during formation of the coating film by the composition. Association. On the other hand, when the content of the specific metal ion in the composition is too large, the specific metal ion and the specific tricreide-based resin are easily complexed during the formation of the coating film by the composition, so that the cured film is likely to be generated. Microphase separation (phase separation of the complexed moiety from the non-complexed moiety). In particular, when the cured film is repeatedly exposed to a high-temperature-low temperature environment, the specific metal ions in the system are further complexed with the specific tricreide-based resin, and the amount of microphase separation is further increased. As a result, defects in the cured film which are repeatedly exposed in a high-temperature-low temperature environment increase.
The present inventors have known that in the composition, when the total content of the specific metal ions is 0.01 to 30 ppm by mass based on the total mass of the composition, the association of the specific triterpenoid resin and the specific triterpenoid can be suppressed. When the resin is complexed with a specific metal ion, the resulting cured film can also suppress the occurrence of defects after repeated exposure in a high-temperature environment. Further, it was confirmed that the above-mentioned cured film was repeatedly exposed to exposure in a high-temperature-low temperature environment, and the spectral variation (change in transmittance) was reduced.

In addition, when the composition contains toluene as a solvent and the content of the toluene is 0.001 to 10 ppm by mass based on the total mass of the composition, the surface of the coating film formed of the composition is excellent in appearance. Although this mechanism of action is not clear, it is presumed that toluene affects the compatibility of a specific triterpene resin.

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

<Specific triterpenoid resin>
The above composition includes a resin (specific triterpenoid resin) containing a repeating unit represented by the formula (I-1) or a repeating unit represented by the formula (I-2).
(repeating unit represented by the general formula (I-1))

[Chemical Formula 1]

In the formula (I-1), X ¹ , X ² and X ³ each independently represent -NR ¹ -, -O- or -S-.
The refractive index of the cured film after repeated exposure in a high-temperature-low temperature environment and the repeated exposure in a high-temperature-low temperature environment can also reduce the spectral variation of the cured film as X ¹ , X ² and X ^{3 .} , -NR ¹ - is preferred.

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

W ¹ represents a divalent linking group.
The divalent linking group represented by W ¹ is not particularly limited, and examples thereof include -O-, -CO-, -S-, -SO ₂ -, -NR ^A -, an extended aryl group, and an alkylene group. , heteroaryl groups and groups comprising the combinations. The alkylene group may also be substituted with a substituent such as a halogen atom (for example, a group exemplified by the substituent group T).

The carbon number of the above aryl group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10. Specific examples of the above-mentioned aryl group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,4-naphthyl group, a 1,5-anthranyl group, and a 2,7-fluorene group. The 1,4-phenylene group is preferably a group, a 3,6-fluorenyl group, a 9,9-fluorenyl group and a fluorenyl group.
The above aryl group may have a substituent (for example, a group exemplified by the substituent group T).

The above R ^A represents a hydrogen atom or a substituent, and a hydrogen atom is preferred.
The substituent represented by the above R ^A has the same meaning as the substituent represented by the above R ¹ .

The refractive index of the cured film after repeated exposure in a high-temperature-low temperature environment is more excellent, and the repeated exposure in a high-temperature-low temperature environment can also reduce the spectral variation of the cured film, and is considered to be a valence of W ¹ . The linking group is preferably a divalent linking group represented by the following formula (III).

[Chemical Formula 2]

In the formula (III), A ¹ and A ³ each independently represent a single bond or an extended aryl group, and at least one of A ¹ and A ³ represents an extended aryl group. A ² represents a single bond, -O-, CO-, -S-, -SO ₂ -, -NR ^A - or an extended aryl group. R ^A represents a hydrogen atom or a substituent. * indicates the bonding position.

Further, specific examples of the exoaryl group and R ^A represented by A ¹ , A ² and A ³ are as described above.
Among them, as the extended aryl group represented by A ¹ to A ³ , 1,4-phenylene is preferred.

Specific examples of the group represented by the above formula (III) are shown below, but are not limited thereto.

[Chemical Formula 3]

[Chemical 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 and a carbon number of 1 to 6. More preferably, the alkyl group is more preferably an alkyl group having 1 to 3 carbon atoms.
The aryl group represented by V may, for example, be a 6 to 10 membered ring or an aryl group including a condensed ring thereof.
Specific examples of the ring constituting the aryl group are not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, an anthracene ring, and a naphthacene ring. A ring or a naphthalene ring is preferred, and a benzene ring is more preferred. Further, the above ring forms an aryl group by removing a hydrogen atom on one ring.
The heterocyclic group represented by V is not particularly limited, and examples thereof include an aliphatic heterocyclic group and an aromatic heterocyclic group. Further, examples of the aliphatic heterocyclic ring include a 5-membered ring, a 6-membered ring, and a 7-membered ring or a condensed ring thereof. Further, examples of the aromatic heterocyclic ring include a 5-membered ring, a 6-membered ring, and a 7-membered ring or a condensed ring thereof.
Further, the condensed ring may contain a ring other than a heterocyclic group such as a benzene ring.

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

Examples of the hetero atom contained in the aromatic heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. The carbon number of the aromatic heterocyclic group is not particularly limited, but 3 to 20 is preferred.
Specific examples of the aromatic heterocyclic ring are not particularly limited, and examples thereof include a furan ring, a thiophene ring, a pyrrole ring, an orthoazole ring, an iso-oxazole ring, a oxadiazole ring, a thiazole ring, and an isothiazole ring. , thiadiazole ring, imidazole ring, pyrazole ring, triazole ring, furazan ring, tetrazole ring, pyridine ring, anthracene ring, pyrimidine ring, pyridinium ring, triterpene ring, tetrazine ring, benzofuran Ring, isobenzofuran ring, benzothiophene ring, anthracene ring, porphyrin ring, isoindole ring, benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring , isoquinoline ring, porphyrin ring, pyridazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, indazole ring, acridine ring, pyridine ring, phenanthroline Ring, phenazine ring, naphthyridine ring, anthracene ring and pteridine ring. Further, the aromatic heterocyclic ring constitutes an aromatic heterocyclic group by removing a hydrogen atom in one ring.

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

In view of the fact that the refractive index of the cured film after the reverse exposure in the high-temperature-low temperature environment is more excellent, the aryl group having a substituent is preferable as the above-mentioned V, and the group represented by the following formula (II) is preferable. For better.

[Chemical Formula 5]

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

From the viewpoint of more excellent refractive index of the cured film after repeated exposure in a high-temperature-low temperature environment, a cyano group is preferable as R ³ .

R ⁴ represents a substituent. Among them, 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 preferred.
The aryl group and the heterocyclic group represented by R ⁴ have the same meanings as the aryl group and the heterocyclic group represented by the above V. As the aryl group represented by R ⁴ , a phenyl group is preferred.
The alkyl group, the alkylthio group and the halogen atom represented by R ⁴ have the same meanings as the alkyl group, the alkylthio group and the halogen atom represented by the above R ³ , and the preferred embodiment is also the same.
From the viewpoint of more excellent refractive index of the cured film after repeated exposure in a high-temperature-low temperature environment, as R ⁴ , an aryl group, a cyano group, a nitro group or a halogen atom is preferred.

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

In the group represented by the above formula (II), the group represented by the following formula (IIA) is considered to be more excellent in the refractive index of the cured film after the reverse exposure in a high-temperature-low temperature environment. Preferably.

[Chemical Formula 6]

In the formula (IIA), * represents a bonding position with X ³ in the formula (I-1).
In the general formula (IIA), the same as R ⁴ in the general formula (II) the meaning of R ^4, preferred aspects are also the same.
R ⁴ wherein, in the phenyl group substituted with R ⁴ , the bonding position with respect to the phenyl group adjacent to the phenyl group is preferably in the para position. That is, for example, in the case where R ⁴ represents an aryl group, the group represented by the formula (IIA) is preferably a triphenylene group.

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

[Chemical Formula 7]

In the 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 the formula (I-2), R ² has the same meaning as R ¹ in the formula (I-1), and preferred embodiments are also the same.
In the general formula (I-2), W ² has the same meaning as W ¹ in the general formula (I-1).
Moreover, the refractive index of the cured film after the reverse exposure in a high-temperature-low temperature environment is more excellent, and the repeated exposure in a high-temperature-low temperature environment can also reduce the spectral variation of the cured film, and is represented by W ² . The valent linking group is preferably a 1,4-phenylene group as an extended aryl group represented by A ¹ to A ³ .
The refractive index of the cured film after repeated exposure in a high-temperature-low temperature environment is more excellent, and the repeated exposure in a high-temperature-low temperature environment can also reduce the spectral variation of the cured film, and is considered to be a valence of W ² . The linking group, each of A ¹ to A ³ , preferably represents an extended aryl group (preferably 1,4-phenylene group).

The refractive index of the cured film after repeated exposure in a high-temperature-low temperature environment and the repeated exposure in a high-temperature-low temperature environment can also reduce the spectral variation of the cured film as X ⁴ , X ⁵ and X ^{6 .} , -NR ² - is preferred.

Examples of the compound containing the repeating unit represented by the above formula (I-2) include compounds (polycondensate and complex addition) represented by the following.

(Example 1) A polycondensate or a complex addition product of a compound represented by the following formula (V) and a compound represented by the following formula (VI).

[Chemical Formula 8]

In the above formula (V), Y ¹ to Y ³ represent a leaving group (for example, a halogen atom) or an isocyanate group.
In the above 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.
The substituent represented by the above R ² may be the same as R ² in the above formula (II-2).
The divalent linking group represented by the above W ³ may be the same as W ² in the above formula (II-2).

(Example 2) A polycondensate or a complex addition product of a compound represented by the following formula (VII) and a compound represented by the following formula (VIII).

[Chemical Formula 9]

In the above formula (VII), X ⁹ to X ¹¹ each independently represent -NR ² -, -O- or -S-. R ² represents a hydrogen atom or a substituent.
The substituent represented by the above R ² may be the same as R ² in the above formula (II-2).
In the above formula (VIII), Y ⁴ and Y ⁵ represent a leaving group (for example, a halogen atom) or an isocyanate group. W ⁴ represents a divalent linking group.
The divalent linking group represented by the above W ⁴ may be the same as W ² in the above formula (II-2).

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

[Chemical Formula 10]

[Chemical Formula 11]

In the specific triterpene resin, the repeating unit represented by the above formula (I-1) or the repeating unit represented by the above formula (I-2) is 50 to 100 with respect to the total repeating unit in the specific triterpene resin. Molar% is preferred, 80 to 100 mol% is more preferred, and 90 to 100 mol% is further preferred.

The specific triterpene resin can be synthesized by a known method (polycondensation).

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

In the above composition, the specific triterpenoid resin may be used singly or in combination of two or more.
In the above-mentioned composition, the content of the specific triterpene resin (the total amount in the case where there are a plurality of them) is generally 80.0% by mass or more based on the total solid content of the composition, and preferably 85.0% by mass or more. More than 90.0% by mass is more preferable. The upper limit is not particularly limited, but 99.9 mass% or less is preferable, and 99.5 mass% or less is more preferable.

<specific metal ion>
The above composition contains a specific metal ion selected from the group consisting of sodium ions, potassium ions, and calcium ions.
In the above-mentioned composition, the total content of the specific metal ions is 0.01 to 30 ppm by mass based on the total mass of the composition, and the defect resistance of the cured film after repeated exposure in a high-temperature-low temperature environment is more excellent, 0.03 to 10 ppm by mass is preferred.
In the above-mentioned composition, the total content of the specific metal ions is preferably 0.1 to 300 ppm by mass based on the specific tricreide resin, and the cured film after repeated exposure in a high-temperature-low temperature environment is more excellent in defect suppression property. In view of the above, 0.3 to 100 ppm by mass is preferred.
Further, the content of a specific metal ion in the above composition can be measured by an ICP (Inductively Coupled Plasma) luminescence spectrometer (for example, "Optima 7300 DV" manufactured by Perkin Elmer).

<solvent>
The above composition contains a solvent.
Examples of the solvent include ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol single. Ethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propylene glycol diacetate, diethylene Alcohol monobutyl ether acetate, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, cyclohexyl acetate and other esters; ethylene glycol monomethyl ether, ethylene glycol single Ethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, 3-methoxypropanol, 1-methoxy- 2-propanol, methoxymethoxyethanol, dipropylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and diethylene Alcohols such as alcohol diethyl ether; benzene, xylene, ethylbenzene and fennel Aromatic hydrocarbons; aliphatic hydrocarbons such as cyclohexane; nitriles such as acetonitrile; acetone, methyl ethyl ketone, ethyl ketone acetone, cyclohexanone, 2-heptanone, cyclopentanone, diacetone alcohol, etc. a ketone; a halogen compound such as dichloroethane; an ether such as cyclohexyl methyl ether and dibutyl ether; 3-methoxy-N,N-dimethylpropionamide, N-ethyl-2-pyrrole Anthranes such as anthrone and 3-butoxy-N,N-dimethylpropionamide; and the like.
Further, the details of the above-mentioned solvent can be referred to in the description of paragraph 0223 of WO 2015/166779, which is incorporated herein by reference. In particular, the aromatic hydrocarbons as the solvent may be preferably reduced for reasons such as environmental protection (for example, it may be 50 parts by mass or less per million by mass relative to the total amount of the solvent). Further, it can be 10 mass ppm or less, and can be 1 mass ppm or less.

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

In the above-mentioned composition, one type of the above-mentioned solvents may be used alone or two or more types may be used in combination.

In the present invention, a solvent having a small metal content is preferably used, and a metal content of the solvent is, for example, 10 mass ppb (parts per billion) or less. A solvent of a mass ppt (parts per trillion) grade, which is supplied, for example, by TOYO Gosei Co., Ltd. (Chemical Industries Daily, November 13, 2015), can also be used as needed.

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

The solvent may contain isomers (compounds of the same atomic number and different structures). Further, the isomer may contain only one kind, and may also contain plural kinds.

In the present invention, the content of the peroxide in the solvent is preferably 0.8 mmol/L or less, and it is more preferable that the peroxide is not substantially contained.

In the solvent content, the solid content concentration of the composition is preferably from 1 to 90% by mass, and the solid content concentration of the composition is preferably from 1 to 50% by mass, and the solid content concentration of the composition is 5 to The amount of 30% by mass is further preferably, and the amount of 5 to 20% by mass is particularly preferable.
Further, the solid content concentration of the composition means the concentration of the total solid content relative to the total mass of the composition (that is, the concentration of the component forming the cured film in the composition). In addition, the definition of the total solid content is as described above.

<Other ingredients>
The above composition may also contain other components than the above components. Examples of the other component include a curable compound (including a polymerizable compound), a polymerization initiator, an antioxidant, a decane coupling agent, a polymerization inhibitor, a surfactant, a UV absorber, and a filler (for example, inorganic particles). Various additives such as a curing accelerator, a plasticizer, a developing property enhancer such as a low molecular weight organic carboxylic acid, and a coagulation inhibitor.

(hardening compound)
It is preferred that the above composition contains a curable compound.
As the curable compound, a known compound which can be cured by a radical, an acid or heat can be used. For example, a compound containing a group having an ethylenically unsaturated bond, a compound having an epoxy group, and a compound having a reactive group such as a methylol group and a thiol group may, for example, be mentioned. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)acryl group, a (meth)acryl fluorenyl group, a (meth) acryloxy group, and the like, and a (meth) acrylonitrile group or (Methyl) propylene fluorenyloxy group is preferred. A curable compound-based polymerizable compound is preferred, and a radical polymerizable compound is more preferred. The polymerizable compound may, for example, be a compound containing a group having an ethylenically unsaturated bond.

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

・A compound containing a group having an ethylenically unsaturated bond (polymerizable compound)
In the present invention, as the curable compound, a compound containing a group having an ethylenically unsaturated bond (hereinafter also referred to as a polymerizable compound) can be used. A polymerizable compound-based monomer is preferred. The molecular weight of the polymerizable compound is preferably from 100 to 3,000. The upper limit is preferably 2,000 or less, and more preferably 1,500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. The polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound.

As an example of the polymerizable compound, the descriptions of paragraphs 0033 to 0034 of JP-A-2013-253224 can be referred to, and the contents are incorporated in the present specification. As a polymerizable compound, ethylene oxide-modified pentaerythritol tetraacrylate (commercially available, NK ESTER ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (a commercially available product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (as a commercial product) , KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the (meth)acrylonitrile groups via ethylene glycol residues and/or The structure in which the propylene glycol residue is bonded is preferred. Also, these oligomer types can be used. Moreover, the description of paragraphs 0034 to 0038 of JP-A-2013-253224 can be referred to, and the content is incorporated in the present specification. Further, a polymerizable monomer or the like described in paragraph 0477 of the Japanese Patent Laid-Open Publication No. 2012-208494 (paragraph 0585 of the specification of the corresponding U.S. Patent Application Publication No. 2012/0235099) is incorporated herein by reference. In the manual. Further, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available, M-460; manufactured by TOAGOSEI CO., LTD.), neopentyl alcohol tetraacrylate (Shin-Nakamura Chemical) Also produced by Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) is also preferred. These oligomer types can also be used. For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) or the like can be mentioned.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfo group or 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. It is preferred to react a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to obtain an acid group-containing polymerizable compound, wherein the aliphatic polyhydroxy compound is neopentyl alcohol and/or dipentaerythritol. Alcohol is even more. As a commercially available product, for example, a polybasic acid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD., examples include M-305, M-510, and M-520 of the ARONIX series.
The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH/g. The lower limit is preferably 5 mgKOH/g or more. The upper limit is preferably 30 mgKOH/g or less.

It is also preferred that the polymerizable compound is a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include tris(hydroxymethyl)ethane, ditrimethylolethane, and trishydroxyl. Polyols such as methyl propane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentenol, glycerin, diglycerin and trimethylol melamine with (meth)acrylic acid and ε- The ε-caprolactone modified polyfunctional (meth) acrylate obtained by esterification of caprolactone. As a polymerizable compound having a caprolactone structure, the descriptions of paragraphs 0044 to 0045 of JP-A-2013-253224 can be referred to, and the contents are incorporated in the present specification. The compound having a caprolactone structure may, for example, be DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and Sartomer Company, Inc. The tetrafunctional acrylate having four ethylene oxide chains, that is, SR-494 and a trifunctional acrylate having three extended isobutoxy chains, that is, TPA-330, and the like.

The urethane described in Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. An oxirane group having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. Sho-62-039, pp. Amino ester compounds are also preferred. In addition, it is possible to have an amine group structure and/or a sulfide structure in a molecule as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Addition of polymeric compounds. A commercially available product is exemplified by an amine ester oligomer UAS-10 and UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and 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.).

・A compound having an epoxy group can be used as a curable compound, and a compound having an epoxy group can also be used. The compound having an epoxy group is preferably a compound having one or more epoxy groups in one molecule, and a compound having two or more epoxy groups in one molecule is preferred. It is preferred that the epoxy group has from 1 to 100 in one molecule. The upper limit can be, for example, 10 or less, or can be 5 or less. It is preferable that the lower limit is two or more.

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

The compound having an epoxy group may be a low molecular compound (for example, having a molecular weight of less than 1,000) or a macromolecular compound (for example, in the case of a polymer having a molecular weight of 1,000 or more, the weight average molecular weight is 1,000 or more). The weight average molecular weight of the compound having an epoxy group is preferably from 200 to 100,000, more preferably from 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and particularly preferably 3,000 or less.

A commercially available product can also be used as the compound having an epoxy group. For example, EHPE3150 (made by Daicel Chemical Industries Ltd.), EPICLON N-695 (made by DIC CORPORATION), etc. are mentioned. In addition, the compound having an epoxy group can also be used in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and 0085 to JP-A-2014-089408. The compound described in paragraph 0092. These contents are incorporated into this specification.

(polymerization initiator)
The above composition may contain a polymerization initiator, and a photopolymerization initiator is preferred. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator is preferably a compound having photosensitivity with respect to light from an ultraviolet region to a visible region.

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a compound having a triterpene skeleton and a compound having a oxindazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, or a hexaaryl double. An anthracene compound such as an imidazole or an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, and a hydroxyacetophenone. From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of a trihalo methyl triazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, and an α-aminoketone compound. , mercaptophosphine compound, phosphine oxide compound, metallocene compound, antimony compound, triaryl imidazole dimer, antimony compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene- A compound of the group of an iron complex, a halomethyl oxadiazole compound and a 3-aryl-substituted coumarin compound is preferably selected from the group consisting of a ruthenium compound, an α-hydroxyketone compound, and an α-amino ketone compound. Further, the compound in the group of the compounds in the mercaptophosphine compound is more preferred. Among them, the ruthenium compound is further preferable from the viewpoint that the obtained film is more excellent. As a photopolymerization initiator, the descriptions of paragraphs 0065 to 0111 of JP-A-2014-130173 can be referred to, and the contents are incorporated in the present specification.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-amino ketone compound, and a mercaptophosphine compound can also be preferably used. For example, the α-amino ketone compound described in Japanese Laid-Open Patent Publication No. Hei 10-291969 and the mercaptophosphine compound described in Japanese Patent No. 4,258,899 can also be used. Commercial products of the α-hydroxyketone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF Corporation). Commercial products of the α-amino ketone compound include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF Corporation). Commercially available products of the mercaptophosphine compound include IRGACURE-819 and DAROCUR-TPO (all manufactured by BASF Corporation). As a commercial product of a ruthenium compound, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (above, BASF) and TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.) are mentioned. , ADEKA ARKLSNCI-831 (made by ADEKA CORPORATION), ADEKA ARKLSNCI-930 (made by ADEKA CORPORATION), and ADEKA OPTOMER N-1919 (Photopolymerization initiators described in ADEKA CORPORATION, JP-A-2012-014052) 2) Wait.

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

In the present invention, as the photopolymerization initiator, a ruthenium compound having a fluorine atom can also be used. Specific examples of the ruthenium compound having a fluorine atom include the compounds described in JP-A-2010-262028, and the compounds 24 and 36 to 40 described in JP-A-2014-500852. Compound (C-3) or the like described in Japanese Patent Publication No. 2013-164471. These contents are incorporated into this specification.

In the present invention, a ruthenium compound having a nitro group can be used as a photopolymerization initiator. It is also preferred that the ruthenium compound having a nitro group be a dimer. Specific examples of the ruthenium compound having a nitro group include those described in paragraphs 003 to 0047 of JP-A-2013-114249, paragraphs 0008 to 0012, and paragraphs 0070 to 0079 of JP-A-2014-137466. The compound and the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4,223,071, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

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

[Chemical Formula 12]

[Chemical Formula 13]

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

It is also preferred that the photopolymerization initiator contains an anthracene compound and an α-aminoketone compound. By using both, it is easy to form a pattern which improves developability and is excellent in squareness. In the case of using an oxime compound and an α-amino ketone compound, it is preferably 50 to 600 parts by mass of the α-amino ketone compound, and more preferably 150 to 400 parts by mass, per 100 parts by mass of the ruthenium compound.

The content of the polymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, even more preferably from 1 to 20% by mass, even more preferably from 1 to 10% by mass, based on the total solid content of the composition. good.
When the content of the polymerization initiator is in the above range, it is easy to form a pattern having more excellent sensitivity and excellent squareness. The above composition may contain only one type of polymerization initiator, or may contain two or more types of polymerization initiators. When the composition contains two or more kinds of polymerization initiators, the total content thereof is preferably within the above range.

(Antioxidants)
The above composition may also contain an antioxidant.
Examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. As the antioxidant, a phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is preferable. These can be used by mixing two or more types. As the phenol compound, any phenol compound known as a phenol antioxidant can be used, and a polysubstituted phenol compound is preferable. The polysubstituted phenol-based compound is roughly classified into three types (blocked type, semi-blocked type, and low-blocked type) having different substitution positions and structures. Further, as the antioxidant, a compound having a phenol group and a phosphite group in the same molecule is preferably used. Further, as the antioxidant, a phosphorus-based antioxidant is also preferably used. Commercially available products can also be used as the antioxidant. As a commercial product of the antioxidant, for example, ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO- 80 and ADKSTAB AO-330 (made by ADEKA CORPORATION). Moreover, as an antioxidant, the description of paragraphs 0033 to 0043 of JP-A-2014-032380 can be referred to, and the contents are incorporated in the present specification.

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

(decane coupling agent)
The above composition also contains a decane coupling agent.
In the present invention, the coupling agent means a decane compound having a hydrolyzable group and a functional group other than the same. Further, the hydrolyzable group means a substituent which is directly bonded to a ruthenium atom and which is capable of generating a siloxane chain bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and a decyloxy group, and an alkoxy group is preferred. That is, a decane coupling agent is preferably a compound having an alkoxyfluorenyl group. Further, a functional group other than the hydrolyzable group is preferably a group which exhibits an affinity or bond with the resin to exhibit affinity. Examples thereof include a vinyl group, a styryl group, a (meth)acryl fluorenyl group, a fluorenyl group, an epoxy group, an oxetanyl group, an amine group, a ureido group, a thioether group, an isocyanate group, and a phenyl group. Acryl fluorenyl or epoxy groups are preferred.

Specific examples of the decane coupling agent include 3-methacryloxypropylmethyldimethoxydecane. In addition, examples of the decane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703, and the compounds described in paragraphs 0056 to 0066 of JP-A-2009-242604. The content is incorporated into this specification. Commercially available products can also be used as the decane coupling agent. As a commercial item of a decane coupling agent, KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033 by Shin-Etsu Chemical Co., Ltd. , 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.

The content of the decane coupling agent is preferably from 0.01 to 15.0% by mass, more preferably from 0.05 to 10.0% by mass, based on the total solid content of the composition. The decane coupling agent may be used alone or in combination of two or more. When the composition contains two or more kinds of decane coupling agents, the total content thereof is preferably within the above range.

(polymerization inhibitor)
The above composition may also contain a polymerization inhibitor.
The polymerization inhibitor may, for example, be hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thio Bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and N-nitrosophenylhydroxylamine salt (ammonium salts and sulfonium salts, etc.). Among them, p-methoxyphenol is preferred. Further, the polymerization inhibitor may also function as an antioxidant.

The content of the polymerization inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, even more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the polymerization initiator.

(surfactant)
The above composition may also contain various surfactants from the viewpoint of further improving coatability.
As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a polyfluorene-based surfactant can be used. The surfactant can be referred to paragraphs 0238 to 0245 of International Publication WO2015/166779, which is incorporated herein by reference.

When the composition contains a fluorine-based surfactant, the liquid properties (especially fluidity) at the time of preparation of the coating liquid are further improved, and the uniformity of the coating thickness and the liquid-saving property can be further improved. When the film formation is carried out using a coating liquid using a composition containing a fluorine-based surfactant, the interfacial tension between the coated surface and the coating liquid is lowered, and the wettability to the coated surface is improved, and the film is improved. The coatability of the coated surface. Therefore, film formation of a uniform thickness having a small thickness unevenness can be more preferably performed.

The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, even more preferably from 7 to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective from the viewpoint of the uniformity of the thickness of the coating film and the liquid-saving property, and the solubility in the composition is also good.

Specific examples of the fluorine-based surfactants include the interfacial activity described in paragraphs 0060 to 0064 of JP-A-2014-041318 (corresponding to paragraphs 0060 to 0064 of International Publication No. 2014/017669). The surfactants described in paragraphs 0117 to 0132 of JP-A-2011-132503, the contents of which are incorporated herein by reference. Examples of commercially available fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, and MEGAFACE F475. MEGAFACE F479, MEGAFACE F482, MEGAFACE F554 and MEGAFACE F780 (above DIC CORPORATION), FLUORAD FC430, FLUORAD FC431 and FLUORAD FC171 (above is Sumitomo 3M Limited), SURFLON S-382, SURFLON SC-101, SURFLON SC- 103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-1068, SURFLON SC-381, SURFLON SC-383, SURFLON S-393, and SURFLON KH-40 (above, manufactured by ASAHI GLASS CO., LTD.) and PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (above, OMNOVA SOLUTIONS INC. SOLUTIONS INC.).

Further, the fluorine-based surfactant can also preferably use an acrylic compound having a molecular structure containing a functional group of a fluorine atom and a portion containing a functional group containing a fluorine atom when heat is applied, and the fluorine atom is volatilized. As such a fluorine-based surfactant, MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Industry News, February 23, 2016), for example, MEGAFACE DS-21 .

As the fluorine-based surfactant, a block polymer can also be used. For example, the compound described in JP-A-2011-089090 can be mentioned. The fluorine-based surfactant can also preferably be a fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound having a fluorine atom and having two or more sources (preferably). It is a repeating unit of a (meth) acrylate compound which is an alkoxy group (preferably an ethoxy group or a propoxy group) of 5 or more. The following compounds can also be exemplified as the fluorine-based surfactant used in the present invention.

[Chemical Formula 14]

The weight average molecular weight of the above compound is preferably, for example, 3,000 to 50,000, and specifically, 14,000. In the above compound, % of the ratio of the repeating unit is % by mass.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, for example, MEGAFACE RS-101, RS-102, RS-718K, and RS manufactured by DIC Corporation. -72-K and so on. As the fluorine-based surfactant, the compound described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and the like, and ethoxylates and propoxylates (for example, glycerol propoxylate and glycerol ethoxylate). and many more. Further, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl 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 Corporation), TETRONIC 304, 701, 704, 901 904 and 150R1 (manufactured by BASF Corporation), SOLSPERSE 20000 (manufactured by Lubrizol Japan Limited), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112 -W and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.) and OLFINE E1010, SURFYNOL 104, 400 and 440 (manufactured by Issin Chemical Co., Ltd.) and the like.

Further, as the fluorine-based surfactant, a vinyl ether polymerizable fluorine-based surfactant can also be used. For example, as described in the column of the examples of JP-A-2016-216602 (for example, a fluorine-based surfactant (1)), etc. are mentioned as a vinyl ether type-type fluorine-type surfactant.

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

(UV absorber)
The above composition may also contain an 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 hydroxyphenyl triazine compound. For the details, the descriptions of paragraphs 0053 to 0823 of JP-A-2012-208374 and paragraphs 0317 to 0334 of JP-A-2013-068814 can be referred to in the present specification. The commercially available product of the conjugated diene compound is, for example, UV-503 (manufactured by DAITO CHEMICAL CO., LTD.). Further, as the benzotriazole compound, MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by MIYOSHI OIL & FAT CO., LTD. can be used.
The content of the ultraviolet absorber is preferably from 0.1 to 10% by mass, more preferably from 0.1 to 5% by mass, even more preferably from 0.1 to 3% by mass, based on the total solid content of the composition. Further, the ultraviolet absorber may be used alone or in combination of two or more. When the composition contains two or more kinds of ultraviolet absorbers, the total content thereof is preferably within the above range.

(Filler)
Examples of the filler include inorganic particles. As the inorganic particles, inorganic particles having a high refractive index and being colorless, white or transparent are preferable, and titanium (Ti), zirconium (Zr), aluminum (Al), cerium (Si), zinc (Zn) or magnesium (Mg), etc. The oxide particles are preferably titanium dichloride (TiO ₂ ) particles, zirconium oxide (ZrO ₂ ) particles or cerium disilicate (SiO ₂ ) particles.
The primary particle diameter of the inorganic particles is not particularly limited, and is preferably 1 to 100 nm, more preferably 1 to 80 nm, and still more preferably 1 to 50 nm. When the primary particle diameter of the inorganic particles is within the above range, the dispersibility is more excellent and the refractive index and the transmittance are further improved.
The refractive index of the inorganic particles is not particularly limited, but from the viewpoint of obtaining a high refractive index, 1.75 to 2.70 is preferable, and 1.90 to 2.70 is more preferable.
The specific surface area of the inorganic particles is not particularly limited, but 10 ~ 400m ² / g is preferred, 20 ~ 200m ² / g is more preferably, 30 ~ 150m ² / g is further preferred.
Further, the shape of the inorganic particles is not particularly limited, and examples thereof include a rice grain shape, a spherical shape, a cubic shape, a spindle shape, and an indefinite shape.
The inorganic particles may also be surface treated by an organic compound. Examples of the organic compound used for the surface treatment include a polyhydric alcohol, an alkanolamine, a stearic acid, a decane coupling agent, and a titanate coupling agent. Among them, stearic acid or a decane coupling agent is preferred.
Further, from the viewpoint of further improving the weather resistance, the surface of the inorganic particles is preferably coated with an oxide such as aluminum, lanthanum or zirconia.
As the inorganic particles, a commercially available one can be preferably used.
In the above composition, the inorganic particles may be used alone or in combination of two or more.

(hardening accelerator)
When the composition contains a compound having a cationically polymerizable group (for example, a compound having an epoxy group) as the curable compound, the composition preferably contains a curing accelerator.
Examples of the curing accelerator for increasing the curing rate include an acid anhydride, a base (such as an aliphatic amine, an aromatic amine, and a modified amine), an acid (such as a sulfonic acid, a phosphoric acid, and a carboxylic acid), and a polythiol. Among them, an acid anhydride is preferred, and an aliphatic acid anhydride is further preferred.

<Preparation method of composition>
The above composition can be prepared by mixing the above components. When the composition is prepared, the components may be blended together, or the components may be gradually mixed after dissolving or dispersing the components in a solvent. For example, it is also possible to prepare a composition by simultaneously dissolving or dispersing all the components in a solvent. Further, a component which exhibits particle properties may be dispersed in a solvent or a resin to prepare a composition, and the obtained composition and other components (for example, a specific triterpenoid resin and a curable compound) may be mixed.

In the case where the above composition contains a component exhibiting particle properties, the method for preparing the composition includes a process of dispersing the particles. In the process of dispersing the particles, as the mechanical force for dispersing the particles, compression, pressing, impact, shearing, cavitation, and the like are exemplified. Specific examples of such processes include bead milling, sanding, roll milling, ball milling, paint agitator, microjet, high speed impeller, sand mixing, jet mixing, high pressure wet micronization, and ultrasonic dispersion. Further, in the pulverization of the particles in the sanding (bead grinding), it is preferred to treat the pulverization efficiency by using microbeads having a small diameter and increasing the filling ratio of the microbeads. Further, it is preferred to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. Further, as a process for dispersing particles and a dispersing machine, it is possible to preferably use "dispersion technology, JOHOKIKO CO., LTD., issued July 15, 2005" and "surrounding suspension (solid/liquid dispersion system)" The process and disperser described in paragraph 0022 of the Japanese Patent Laid-Open Publication No. 2015-157893, issued on October 10, 1978. Further, in the process of dispersing the particles, the particles may be subjected to a refining treatment in the salt milling step. For the raw materials, the equipment, the processing conditions, and the like, which are used in the salt milling step, for example, the descriptions of JP-A-2015-194521 and JP-A-2012-046629 can be referred to.

When the above composition is prepared, it is preferred to filter the composition by a filter for the purpose of removing foreign matter and reducing defects. The filter can be used without any particular limitation as long as it is a filter that has been conventionally used for filtration applications. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6 and nylon-6,6), and a polyolefin resin such as polyethylene or polypropylene (PP) may be used. A filter containing raw materials such as high density and/or ultra high molecular weight polyolefin resin). Among these raw materials, polypropylene (including high density polypropylene) and nylon are preferred.
The pore size of the filter is preferably about 0.01 to 7.0 μm, more preferably about 0.01 to 3.0 μm, and still more preferably about 0.05 to 0.5 μm. When the pore diameter of the filter is in the above range, fine foreign matter can be reliably removed. It is also preferred to use a fibrous filter material. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Specifically, a filter core such as an SBP type series (SBP008 or the like), a TPR type series (such as TPR002 and TPR005), and a SHPX type series (SHPX003 or the like) manufactured by ROKI TECHNO CO., LTD.

When a filter is used, different filters (for example, a first filter, a second filter, etc.) can be combined. At this time, the filtration in each filter may be performed only once or twice or more. Further, it is also possible to combine filters of different apertures within the above range. The aperture can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters supplied by NIHON PALL Corporation (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (Formerly Nippon Mykrolis Corporation), and KITZ MICROFILTER CORPORATION. The second filter can be formed using the same material or the like as the first filter. Further, the filtration in the first filter is performed only on the mixed liquid in which the resin and the solvent are mixed, and after mixing the other components, the filtration may be carried out by the second filter.

<Use>
The composition of the present invention and the resin of the present invention to be described later are not particularly limited, but are, for example, a high refractive member (a microlens, a base layer of a color filter, a transparent film such as an adjacent layer, and a color filter). White pixels, etc., lenses (glass lenses, digital camera lenses, Fresnel lenses, prism lenses, etc.), optical external coating agents, hard coating agents, antireflection films, optical fibers, optical waveguides, LEDs (Light Emitting Diodes) Light-emitting diodes are useful for sealing materials, planarizing materials for LEDs, and coating materials 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" means a cured film formed by curing a coating film (unhardened film) formed by the composition of the present invention and a coating film.
Further, when the composition contains a curable compound, the cured film is obtained by subjecting the coating film formed of the above composition to a curing treatment.
The refractive index (wavelength: 589 nm) of the film is not particularly limited, but is preferably 1.55 or more, and more preferably 1.6 to 2.0.
The light transmittance of the film is not particularly limited, but 90% or more of all regions in the wavelength region of 400 to 700 nm are preferable, 95% or more is more preferable, and 100% is further preferable.
The thickness of the film is not particularly limited, but is preferably 0.1 to 20 μm, more preferably 0.1 to 10 μm, and still more preferably 0.5 to 4 μm.

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

<Method for Producing Patterned Cured Film>
Hereinafter, a patterned cured film will be described in detail as an example of a method for producing a cured film.

The method for producing a patterned cured film includes the step of forming the composition layer (coating film) by coating the above composition on a substrate (hereinafter, simply referred to as "the composition layer forming step"); The step of exposing the composition layer (hereinafter, simply referred to as "exposure step" as appropriate) and the step of developing the patterned composition layer after exposure to form a patterned cured film (hereinafter, simply referred to as "development step" as appropriate). ).
Further, the composition generally used in the above contains a curable compound and a photopolymerization initiator.

Specifically, the composition is applied onto a substrate directly or via another layer to form a composition layer (formation layer forming step), and exposure is performed via a predetermined mask pattern, and only the portion of the composition layer that is irradiated with light is hardened. (Exposure step), development is carried out by a developing solution (developing step), whereby a cured film including a pattern of pixels can be formed.
Hereinafter, each step will be described.

- Composition Layer Formation Step In the composition layer formation step, the composition is applied onto a substrate to form a composition layer (coating film).

The substrate is not particularly limited, and examples thereof include alkali-free glass for liquid crystal display devices, soda glass, PYREX (registered trademark) glass, quartz glass, and those having a transparent conductive film attached thereto, and are used for a solid-state image sensor. A photoelectric conversion element substrate (for example, a germanium substrate), a CCD (Charge Coupled Device) substrate, a CMOS (Complementary Metal Oxide Semiconductor) substrate, or the like.

As a method of applying the above composition to the substrate, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, or screen printing can be employed.

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

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

In the exposure step exposure step, the composition layer (coating film) formed in the composition layer forming step is exposed through the mask, and only the portion of the coating film irradiated with light is hardened.
The exposure is preferably carried out by irradiation with actinic rays or radiation, and in particular, ultraviolet rays such as g-rays, h-rays or i-rays are more preferable. The irradiation intensity is preferably 5 to 1,500 mJ/cm ^{2 , more} preferably 10 to 1000 mJ/cm ² .

- Development Step The exposure step is followed by an alkali development treatment (development step) in which the light is not irradiated in the alkali aqueous solution elution step. Thereby, only the portion which is photohardened (the portion of the coating film which is irradiated with light) remains.
As the developer, an organic alkaline developer which does not cause damage to the circuit of the substrate or the like is desired. The development temperature is usually 20 to 30 ° C, and the development time is 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. The inorganic developing solution is dissolved in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate or aluminum so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution of sodium citrate. The organic developing solution is dissolved in ammonia, ethylamine, diethylamine, dimethylethanolamine or tetramethylammonium hydroxide so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution of a basic compound such as (TMAH), tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-dioxabicyclo-[5.4.0]-7-undecene. A water-soluble organic solvent such as methanol or ethanol and/or a surfactant may be added to the alkaline aqueous solution in an appropriate amount. Further, in the case where a developer containing the alkaline aqueous solution is used, it is usually washed (rinsed) with pure water after development.

As the developing method, for example, a spin-on immersion developing method, a shower developing method, or the like can be used.

〔lens〕
The film of the present invention (preferably a cured film) can also be used as a lens. As the lens, a microlens of the above solid-state imaging element can be preferably used.

[solid-state imaging device]
The film of the present invention (preferably a cured film) can be preferably applied to a solid-state image sensor.
The structure of the solid-state imaging device of the present invention includes, for example, a plurality of photodiodes and polycrystalline silicon including a light receiving region constituting a solid-state imaging device (a CCD image sensor, a CMOS image sensor, etc.) on a substrate. The light-receiving element and the structure of the film of the present invention, that is, the undercoat film, are provided under the color filter.

[resin]
The present invention also relates to a novel resin which 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 formula (IV-1) or a repeating unit represented by the following formula (IV-2). Further, a resin containing a repeating unit represented by the following formula (IV-1) or a repeating unit represented by the following formula (IV-2) corresponds to one form of the above specific triterpenoid resin.
Hereinafter, the resin of the present invention will be described in detail.
<Repeating unit represented by the general formula (IV-1)>

[Chemical Formula 15]

In the 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.

Formula (IV-1) ^{In, X 1, X 2, X} 3 , and W ¹ of the aforementioned general formula X ^{1 (I-1)} is, X ^2, X ³ and W ¹ have the same meaning and preferred The same is true.

In the 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 examples of the heterocyclic group, the alkyl group, the alkylthio group and the halogen atom represented by the above R ⁵ are the same as the heterocyclic group, alkyl group or alkyl sulfide represented by R ⁴ in the above formula (II). The base is the same as the halogen atom.

In the above formula (IV-1), the refractive index of the cured film after the reverse exposure in a high-temperature-low temperature environment is more excellent, wherein the group represented by the following general formula (IV-1A) is good.

[Chemical Formula 16]

Among them, R ⁵ is preferably in the para position with respect to the bonding position of the phenyl group adjacent to the phenyl group substituted with R ⁵ .

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

[Chemical Formula 17]

In the 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 of the aforementioned general formula X (I-2) ^4, and X ⁵ have the same meaning of X ^6, preferred aspects are also the same.

The above formula (IV-2) is considered to be more excellent in the refractive index of the cured film after the reverse exposure in a high-temperature-low temperature environment, wherein the group represented by the following formula (IV-2A) is comparatively preferable. good.

[Chemical Formula 18]

In the above resin, the repeating unit represented by the above formula (I-1) or the repeating unit represented by the above formula (I-2) is preferably 50 to 100 mol% based on the total repeating unit in the resin. More preferably, 80 to 100 mol%, and still more preferably 90 to 100 mol%.

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

Hereinafter, the present invention will be described in detail based on examples. The materials, the amounts, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. However, the scope of the invention is not to be construed as being limited by the embodiments shown below.

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

[Chemical Formula 19]

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

[Chemical Formula 20]

In 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 ° C under a nitrogen gas stream. Next, a solution of 6.4 g of the compound (i-1) dissolved in 25.7 g of N,N-dimethylacetamide was added to the heated solution, and the mixture was stirred for 1 hour. Next, 0.9 mL of aniline was added to the stirred reaction solution, and the mixture was further stirred for 10 minutes. After the obtained reaction solution was cooled to room temperature, an aqueous solution of 7.0 g of triethylamine and 380 g of ion-exchanged water was added. After the precipitated solid was filtered, the filtered solid was washed three times with 100 g of ion-exchanged water, and then washed once with 100 g of ethanol. The obtained solid was vacuum dried at 60 ° C, whereby 7.2 g of the compound (A-1) was obtained.

<Synthesis Example 2: Resin (A-2)>
Change 4-amino-4'-cyanobiphenyl and 1,4-phenylene diamine to 4-amino-p-terphenyl and 1,3-phenylene diamine, respectively, to the same molar The same operation as in Synthesis Example 1 was carried out except that the reaction was carried out to give Compound (A-2).

<Synthesis Example 3: Resin (A-3)>
4-Amino-4'-cyanobiphenyl and 1,4-phenylenediamine were changed to 4-amino-4'-chlorobiphenyl and 4,4'-diaminophenyl anilide, respectively. The same operation as in Synthesis Example 1 was carried out, except that the reaction was carried out in the same molar ratio to give Compound (A-3).

<Synthesis Example 4: Resin (A-4)>
Change 4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine to 4-amino-4'-methylbiphenyl and 4,4'-diaminodiphenyl The same procedure as in Synthesis Example 1 was carried out except that the ether was reacted in the same molar ratio to obtain Compound (A-4).

<Synthesis Example 5: Resin (A-5)>
Change 4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine to 4-amino-4'-nitrobiphenyl and bis(4-aminophenyl) sulfide, respectively The same procedure as in Synthesis Example 1 was carried out, except that the reaction was carried out in the same molar ratio to give Compound (A-5).

<Synthesis Example 6: Resin (A-6)>
Change 4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine to 4-amino-4'-methylthiobiphenyl and bis(4-aminophenyl)anthracene The compound (A-6) was obtained by the same operation as in Synthesis Example 1 except that the reaction was carried out in the same molar ratio.

<Synthesis Example 7: Resin (A-7)>
Change 4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine to p-cyanoaniline and 4,4"-diamino-p-terphenyl, respectively, with the same molar equivalent The same operation as in Synthesis Example 1 was carried out, and the compound (A-7) was obtained.

<Synthesis Example 8: Resin (A-8)>
Change 4-amino-4'-cyanobiphenyl and 1,4-phenylenediamine to 4-amino-p-terphenyl and 4,4"-diamino-p-terphenyl, respectively. The same operation as in Synthesis Example 1 was carried out, and the compound (A-8) was obtained.

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

[Chemical Formula 21]

9.2 g of guanidine cyanurate chloride, 8.7 g of 4,4"-diamino-p-terphenyl and 56.7 g of N,N-dimethylacetamide were weighed in a container, and the obtained mixture was obtained under a nitrogen stream. The mixture was heated to 100 ° C and stirred for 1 hour. Then, 3.0 mL of aniline was added to the stirred reaction solution, and the mixture was further stirred for 10 minutes. After the obtained reaction solution was cooled to room temperature, it was added to 14.0 g of triethylamine and An aqueous solution of 760 g of ion-exchanged water was filtered. After the precipitated solid was filtered, the filtered solid was washed three times with 200 g of ion-exchanged water, and then washed once with 200 g of ethanol. The obtained solid was subjected to 60 ° C. It was dried under vacuum, whereby 15.1 g of the compound (A-9) was obtained.

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

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

[Chemical Formula 22]

The compound (i-2) 9.6 g, 4-aminophenol 4.4 g, 1,8-dioxabicyclo[5.4.0]-7-undecene 1,8-diindole bicyclo[5.4. 0]-7-undecene 14.0 g and N,N-dimethylacetamide 32.7 g, the resulting mixture was heated to 100 ° C under a nitrogen stream, and stirred for 1 hour. Next, 2.0 mL of aniline was added to the stirred reaction solution, and the mixture was further stirred for 10 minutes. After the obtained reaction solution was cooled to room temperature, it was added to an aqueous solution of 760 g of ion-exchanged water. After the precipitated solid was filtered, the filtered solid was washed three times with 200 g of ion-exchanged water, and then washed once with 200 g of ethanol. The obtained solid was vacuum dried at 60 ° C, whereby 10.7 g of the compound (A-11) was obtained.

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

[Chemical Formula 23]

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

Further, as a result of quantifying the contents of sodium ions, potassium ions, and calcium ions contained in the resins (A-1) to (A-11), it was confirmed that they were each less than 0.01 ppm by mass. Further, an ICP emission spectroscopic analyzer ("Optima 7300 DV" manufactured by Perkin Elmer) was used for the quantification of sodium ions, potassium ions, and calcium ions.

In addition, as a result of quantifying the content of toluene contained in the resins (A-1) to (A-11), it was confirmed that the content was less than 0.001 ppm by mass.
Further, the toluene concentration in the resin was quantified based on a calibration curve prepared by gas chromatography in accordance with a known method.

[Table 1]

[2] Various Components The various components included in the composition are shown below.
<Specific triterpenoid resin>
With respect to a specific triterpene resin (a resin comprising a repeating unit represented by the formula (I-1) or a repeating unit represented by the following formula (I-2)), the above-mentioned resin (A-1) is used. (A-11).

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

[Chemical Formula 24]

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

[Chemical Formula 25]

<Solvent other than toluene>
As a solvent other than toluene, the solvent shown below was used.
NEP: N-ethyl-2-pyrrolidone
MFG: 1-methoxy-2-propanol
CPN: cyclopentanone

<Surfactant>
The surfactants shown below were used.
MEGAFACE R-40 (made by DIC CORPORATION)

<Content of specific metal ions in each component>
Each of the above components was purified, and it was confirmed that the content of sodium ions, potassium ions, and calcium ions in each component was less than 0.01 mass ppm, respectively. Further, the quantitative methods for sodium ions, potassium ions, and calcium ions are as described above.

<Content of toluene in each component>
Each of the above components was used by vacuum drying to confirm that the content of toluene in each component was less than 0.001 ppm by mass. Further, the method for quantifying the content of toluene in each component is as described above.

[3] Preparation of Composition The above various components (resin, solvent other than toluene, curable compound, polymerization initiator, and surfactant) were mixed at the blending ratio shown in Table 2, and the obtained mixture was obtained. Vacuum drying was performed to confirm that the content of sodium ions, potassium ions, and calcium ions in the dried product was less than 0.01 ppm by mass, respectively. Further, it was confirmed that the content of toluene was less than 0.001 ppm by mass.

Then, a resin, a curable compound, a polymerization initiator, a surfactant, a solvent other than toluene, and toluene and sodium ions (to be used as a sodium source, bromine) are added so as to have a content as shown in Table 2 Various compositions were prepared by separately dissolving sodium chloride solution, potassium ion (as potassium source, potassium bromide methanol solution) and calcium ion (as calcium ion source, calcium bromide methanol solution). Further, in the column of "solvent other than toluene" in Table 2, a trace amount of methanol in the above ion source is also included. Further, the content of each component in Table 2 indicates the content ratio (%) with respect to the total mass of the composition.

The content of sodium ions, potassium ions, and calcium ions in the obtained composition was quantified using an ICP emission spectroscopic analyzer ("Agilent 7800 ICP-MS" manufactured by Agilent Technologies Japan Co., Ltd.).
Further, the content of toluene in the obtained composition was quantified based on a calibration curve prepared by gas chromatography in accordance with a known method.

[4] Evaluation of the composition obtained by using the obtained composition, evaluation of the refractive index of the cured film after thermal cycling, spectroscopic fluctuation of the cured film after the thermal cycle, evaluation of the defect suppressing property of the cured film after the thermal cycle, and coating Evaluation of the surface appearance of the film.

<Evaluation of refractive index of cured film after thermal cycle>
The composition described in Table 2 was spin-coated on a glass substrate of 5 cm × 5 cm in which an epoxy resin layer was formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resins Co., Ltd.) at 100 ° C. Bake (heated) for 3 minutes. Next, the obtained coating film was subjected to exposure with an integrated exposure amount of 200 mJ/cm ² using a high pressure mercury lamp. Thereafter, the glass substrate was baked at 200 ° C for 3 minutes to obtain a cured film having a film thickness of 1 μm. The obtained cured film was placed in a thermal shock test apparatus (ESPEC THERMAL Shock CHAMBER TSA-70L (manufactured by TABAI ESPEC)), and 300 cycles of -65 ° C / 30 minutes → 125 ° C / 30 minutes of hot and cold cycles were applied. The refractive index of the wavelength of 300 to 1500 nm was measured using VASE manufactured by JA Woollam Co., Inc., and the value of the refractive index at a wavelength of 589 nm was defined as the refractive index of each film.

Regarding the value of the measured refractive index, the refractive index of the cured film after the thermal cycle was evaluated in accordance with the following criteria.
"A": refractive index is 1.85 or more "B": refractive index is 1.70 or more and less than 1.85
"C": refractive index less than 1.70

<Spectral variation of the cured film after thermal cycling (change in transmittance)>
In the evaluation of the refractive index, the amount of change in transmittance at a wavelength of 450 nm of the cured film before and after the thermal shock test (the transmittance after the thermal shock test - the transmittance before the thermal shock test | (absolute value)) was measured.
Regarding the amount of change in the measured transmittance, the spectral variation (change in transmittance) of the cured film after the heat cycle was evaluated based on the following criteria.
"A": The rate of change of transmittance is less than 1%.
"B": The rate of change of the transmittance is 1% or more and less than 5%.
"C": The rate of change in transmittance is 5% or more, and is practically problematic.
In addition, the rate of change (%) of the transmittance is a value calculated by {(amount of change in transmittance)/(transmittance before cold shock test)}×100.

<Evaluation of defect inhibition property of cured film after thermal cycle>
The composition described in Table 2 was spin-coated on a tantalum wafer in which an epoxy resin layer was formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resins Co., Ltd.), and further baked at 100 ° C. (heating) for 3 minutes, a coating film having a film thickness of 1 μm was formed. Next, the obtained coating film was subjected to exposure with an integrated exposure amount of 200 mJ/cm ² using a high pressure mercury lamp. Thereafter, the glass substrate was baked at 200 ° C for 3 minutes to obtain a cured film having a film thickness of 1 μm. The obtained cured film was placed in a thermal shock test apparatus (ESPEC THERMAL Shock CHAMBER TSA-70L (manufactured by TABAI ESPEC)), and after 300 cycles of -65 ° C / 30 minutes → 125 ° C / 30 minutes of hot and cold cycles were applied. The number of defects (number/cm ² ) of the cured film was measured using a defect inspection device (ComPlus manufactured by Applied Materials, Inc.).

Regarding the number of defects measured, the defect suppressing property of the cured film after the heat cycle was evaluated based on the following criteria.
"A": the number of defects is 0 / cm ² or more and less than 10 / cm ²
"B": the number of defects is 10 / cm ² or more and less than 20 / cm ²
"C": The number of defects is 20 pieces/cm ² or more, and there is a problem level in practical use.

<Evaluation of Surface Appearance of Coating Film (PCD (Post Coating Delay) of Coating Film) Evaluation>
The composition described in Table 2 was spin-coated on a silicon wafer on which an epoxy resin layer was formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resins Co., Ltd.), and further baked at 100 ° C ( The coating film A having a film thickness of 1 μm was formed by heating for 3 minutes, and no abnormality was observed by an optical microscope. This coating film A was allowed to stand at 25 ° C for 100 hours, and the coating film B was observed by an optical microscope.

The coating film B observed was evaluated in accordance with the following criteria, and the surface appearance of the coating film was evaluated.
"A": No surface roughness or foreign matter of the film was observed.
"B": Although the surface roughness or foreign matter of the film was partially observed, there was no problem in practical use.
"C": The surface roughness or foreign matter of the film was observed locally, and the level of the problem was practically problematic.

Table 2 is shown below.
Further, in Table 2, "0" in the column of "specific metal ions" means that the content of the specific metal ions in the composition is less than 0.01 mass ppm. Further, "0" in the "toluene" column means that the content of toluene in the composition is less than 0.001 ppm by mass.
In addition, the "residual amount" in the column of "solvent other than toluene" in Table 2 means the total of the components other than the solvent other than toluene removed from the composition in all ratios (100%) of the composition. The amount of mass ratio.

[Table 2]

From the results of Table 2, it is understood that the cured film obtained by the composition of the examples can also suppress the occurrence of defects after repeated exposure in a high-temperature-low temperature environment, and can also suppress the spectral change after repeated exposure in a high-temperature-low temperature environment. (change in transmittance) is reduced.
Further, from the comparison of Examples 1 to 21, it was confirmed that the total content of the specific metal ions in the above composition was from 0.03 to 10 ppm by mass based on the total mass of the composition, and hardening after repeated exposure in a high-temperature-low temperature environment. The film has more excellent defect suppressing properties.
Moreover, it was confirmed from the comparison of Examples 1 to 21 that when the content of the toluene in the above composition is 0.001 to 10 ppm by mass based on the total mass of the composition, the surface appearance characteristics are more excellent.
Further, from the comparison of Example 9, Example 15, and Example 19, it was confirmed that the above composition contains the triterpene resin represented by the above formula (I-2), and the W ² system has the above formula. (III) indicates a divalent linking group and the exoaryl group contained in A ¹ to A ³ is a 1,4-phenylene group or when both of A ¹ to A ³ represent an exoaryl group, in a high-temperature environment The cured film after the reverse exposure is more excellent in refractive index, and the spectral variation (change in transmittance) of the cured film after repeated exposure in a high-temperature-low temperature environment is also reduced.
Further, from the comparison of Examples 1 to 3, Examples 7 and 8, Examples 10 to 14, and Examples 17 to 18 and Example 16, it was confirmed that the above composition contained the above formula (I-1). In the case where the specific triterpene resin of X ¹ to X ³ is -NR ¹ -, the refractive index of the cured film after repeated exposure in a high-temperature-low temperature environment is more excellent, and is formed after repeated exposure in a high-temperature-low temperature environment. The spectral variation (change in transmittance) of the cured film is also reduced.

no

Claims (17)

A composition comprising: a resin comprising a repeating unit represented by the formula (I-1) or a repeating unit represented by the formula (I-2); a solvent; and a specific metal ion selected from the group consisting of sodium ions and potassium The group of ions and calcium ions, the total content of the specific metal ions is 0.01 mass ppm to 30 mass ppm, relative to the total mass of the composition. In the 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, and V represents an alkyl group or an aryl group. Or a heterocyclic group, R ¹ represents a hydrogen atom or a substituent, Formula (I-2) in, X ^4, X ⁵ and X ⁶ each independently represents a -NR ² -, - O- or -S-, W ² represents a divalent linking group, R ² represents a hydrogen atom or a substituted base. Such as the composition described in claim 1, wherein The solvent contains toluene, The content of the toluene is from 0.001 ppm by mass to 10 ppm by mass based on the total mass of the composition. The composition according to claim 1 or 2, wherein in the formula (I-1), the V is a group represented by the formula (II), In the formula (II), * represents a bonding position with X ³ in the formula (I-1), and R ³ and R ⁴ each independently represent a substituent, and m and n each independently represent an integer of 0 to 5 Where m+n is 1 to 5. The composition according to claim 3, wherein in the formula (II), the m represents 0, and the n represents 1, and the R ⁴ represents an aryl group, a heterocyclic group, a cyano group, a nitro group, an alkyl group. , alkylthio or halogen atom. The composition according to claim 4, wherein the group represented by the formula (II) is a group represented by the formula (IIA). In the formula (IIA), * represents a bonding position with X ³ in the formula (I-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 according to claim 1 or 2, wherein in the formula (I-1), the X ¹ to X ³ are -NR ¹ -. The composition according to claim 1 or 2, wherein the W ^{1 in the} formula (I-1) and the W ² in the formula (I-2) are each independently a formula (III) indicates a divalent linking group, In the formula (III), A ¹ and A ³ each independently represent a single bond or an extended aryl group, and at least one of A ¹ and A ³ represents an extended aryl group, and A ² represents a single bond, -O-, CO-. , -S-, -SO ₂ -, -NR ^A - or an extended aryl group, R ^A represents a hydrogen atom or a substituent, and * represents a bonding position. The composition according to claim 7, wherein in the W ² of the formula (I-2), the A ¹ to A ³ each represent an extended aryl group. The composition according to claim 7, wherein in the W ² of the formula (I-2), the extended aryl group is a 1,4-phenylene group. The composition of claim 1 or 2, further comprising a curable compound. The composition of claim 1 or 2, further comprising a polymerization initiator. A coating film which is formed from the composition according to any one of claims 1 to 11. A cured film formed by curing the composition described in claim 12 of the patent application. A lens comprising the cured film of claim 13 of the patent application. A solid-state imaging device comprising the lens of claim 14 of the patent application. a resin comprising a repeating unit represented by the formula (IV-1), In the 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, and R ¹ represents a hydrogen atom or a substitution. And R ⁵ represents a heterocyclic group, a cyano group, a nitro group, an alkyl group, an alkylthio group or a halogen atom. a resin comprising a repeating unit represented by the formula (IV-2), In the formula (IV-2), X ⁴ , X ⁵ and X ⁶ each independently represent -NR ² -, -O- or -S-, and R ² represents a hydrogen atom or a substituent.