JPWO2018235549A1 - Composition, film, lens, solid-state imaging device, compound - Google Patents

Abstract

The present invention provides a composition capable of forming a film having a high refractive index and having excellent step followability. The present invention also provides a film obtained by using the above composition, a lens including the film, and a solid-state imaging device including the film or the lens. Further provided are the compounds used in the above compositions. The composition of the present invention is a composition containing a compound represented by the following general formula (I) and a solvent, wherein the content of the compound represented by the above general formula (I) is the total solid content in the composition. It is 30 mass% or more with respect to the minute. (A) m-X- (B) n (I)

Description

  The present invention relates to a composition, a film, a lens, a solid-state imaging device, and a compound containing a compound having a predetermined structure.

Conventionally, a compound used for an optical material or the like has been required to have a high refractive index.
For example, Patent Literature 1 discloses a triazine ring-containing polymer as a high refractive index material. More specifically, it discloses that a polymer having a triazine ring structure as a partial structure exhibits an excellent refractive index.

International Publication No. 2012/111682

In recent years, with the demand for higher functionality or miniaturization of optical devices (solid-state imaging devices, display devices, etc.), a film having a high refractive index can be formed, and when applied to a region having unevenness, unevenness of the lower layer is reduced. There is a need for a composition that can form a film that reflects the shape. In particular, a composition capable of forming a film having a desired thickness in a concave portion in a region having irregularities is required. Hereinafter, this characteristic is also referred to as “step followability”.
The present inventors have studied the characteristics of the optical material described in Patent Literature 1, and as a result, it was not possible to achieve a balance between the above two characteristics, and further improvement was required.

In view of the above circumstances, an object of the present invention is to provide a composition that can form a film having a high refractive index and has excellent step followability.
Another object of the present invention is to provide a film obtained using the composition, a lens including the film, and a solid-state imaging device including the film or the lens. Another object is to provide a compound used in the composition.

The present inventors have conducted intensive studies on the above problems, and as a result, have found that a composition containing a compound having a predetermined structure has desired performance, and completed the present invention.
That is, the present inventors have found that the above problem can be solved by the following constitution.

(1) A composition containing a compound represented by the following general formula (I) and a solvent, wherein the content of the compound represented by the following general formula (I) is the total solid content in the composition. Is 30% by mass or more with respect to the composition.
(2) The composition according to (1), wherein at least one of A in the general formula (I) described later is a group having a monocyclic heterocyclic group.
(3) The composition according to (1) or (2), wherein in formula (I) described below, at least one of A is a group having a triazine ring group.
(4) The composition according to any one of (1) to (3), wherein in the general formula (I) described below, at least one of A is a group represented by the general formula (II) described below.
(5) The composition according to (4), wherein at least _one of C ₁ , C ₂ , and C _{3 in} the general formula (II) described below is —NH—.
(6) The composition according to (4) or (5), wherein in General Formula (II) described below, at least _{two of} C ₁ , C ₂ , and C ₃ are —NH—.
(7) The composition according to any one of (1) to (6), wherein in the general formula (I) described below, X is a group represented by the general formula (III) described below.
(8) The composition according to any one of (1) to (7), wherein the compound represented by the following general formula (I) has an acid group.
(9) The composition according to any one of (1) to (8), wherein the compound represented by the following general formula (I) has a polymerizable group.
(10) The composition according to any one of (1) to (9), further comprising a polymerizable compound.
(11) The composition according to any one of (1) to (10), further comprising a photopolymerization initiator.
(12) The composition according to (11), wherein the photopolymerization initiator contains an oxime compound.
(13) The composition according to any one of (1) to (12), further comprising a resin having a polymerizable group.
(14) A film formed using the composition according to any one of (1) to (13).
(15) A lens comprising the film according to (14).
(16) A solid-state imaging device comprising the film according to (14) or the lens according to (15).
(17) A compound represented by the following general formula (IV).

ADVANTAGE OF THE INVENTION According to this invention, while being able to form the film | membrane which has a high refractive index, the composition excellent in step followability can be provided.
Further, according to the present invention, it is possible to provide a film obtained using the composition, a lens including the film, and a solid-state imaging device including the film or the lens. Further, a compound used in the composition can be provided.

Hereinafter, the present invention will be described in detail.
In this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
The term “actinic ray” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. . In this specification, light means actinic rays or radiation. Unless otherwise specified, the term “exposure” in the present specification means not only exposure using far-ultraviolet rays such as a mercury lamp and an excimer laser, X-rays, and EUV light, but also particle beams such as electron beams and ion beams. Is also included in the exposure.
In this specification, "(meth) acrylate" represents acrylate and methacrylate, "(meth) acryl" represents acryl and methacryl, and "(meth) acryloyl" represents acryloyl and methacryloyl.
In the present specification, the term "step" is included not only in an independent step but also in the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. .
In the present specification, the weight average molecular weight and the number average molecular weight are defined as values in terms of polystyrene measured by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by Tosoh Corporation) as a measuring device and using TSKgel Super AWM-H (manufactured by Tosoh Corporation) as a column. 6.0 mmID (inner diameter) x 15.0 cm) and 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
In the present specification, the total solid content refers to a total mass of components excluding a solvent from the entire composition.

  In the notation of a group (atomic group) in this specification, the notation of not indicating substituted or unsubstituted includes a group having a substituent as well as a group having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Examples of the substituent include the following substituent T.

(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 aryloxy group. Group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfo Famoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl An acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. No. The details are described below.

Halogen atom (for example, fluorine atom, chlorine atom, bromine atom and iodine atom),
A linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms; for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert group; -Butyl group, n-octyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group, etc.),
A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms. Examples thereof include a cyclohexyl group and a cyclopentyl group, and a polycycloalkyl group (eg, a bicycloalkyl group (preferably having 5 carbon atoms) To 30 substituted or unsubstituted bicycloalkyl groups, more specifically, bicyclo [1,2,2] heptane-2-yl group and bicyclo [2,2,2] octane-3-yl group) And a polycyclic group such as a tricycloalkyl group), among which a monocyclic cycloalkyl group or a bicycloalkyl group is preferable, and a monocyclic cycloalkyl group is more preferable),

Linear or branched alkenyl group (linear or branched substituted or unsubstituted alkenyl group, preferably having 2 to 30 carbon atoms; for example, vinyl group, allyl group, prenyl group, geranyl group, and oleyl Group),
A cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms; for example, a 2-cyclopenten-1-yl group and a 2-cyclohexen-1-yl group, and a polycycloalkenyl group; Group (bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms; more specifically, bicyclo [2,2,1] hept-2-en-1-yl group and bicyclo [2,2,2] oct-2-en-4-yl group) and a polycyclic group such as a tricycloalkenyl group, etc. Among them, a monocyclic cycloalkenyl group is preferable),
An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, and a trimethylsilylethynyl group);

Aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; for example, phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl group, pyrenyl group, biphenyl Group and terphenyl group),
A heterocyclic group (a 5- to 7-membered substituted or unsubstituted heterocyclic group is preferable. The heterocyclic group is saturated or unsaturated. The heterocyclic ring is aromatic or non-aromatic. In a heterocyclic group, a ring-constituting atom is selected from a carbon atom, a nitrogen atom and a sulfur atom, and has at least one nitrogen atom, oxygen atom or sulfur atom. The group is more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyridyl, Pyrimidinyl group and 2-benzothiazolyl group),
Cyano group, hydroxyl group, nitro group, carboxyl group,

An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms; for example, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, an n-octyloxy group, and a 2-methoxyethoxy group ),
Aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms; for example, phenoxy group, 2-methylphenoxy group, 2,4-di-tert-amylphenoxy group, 4-tert-butyl Phenoxy group, 3-nitrophenoxy group, and 2-tetradecanoylaminophenoxy group),
A silyloxy group (preferably, a silyloxy group having 3 to 20 carbon atoms, such as a trimethylsilyloxy group and a tert-butyldimethylsilyloxy group);
Heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. The heterocyclic portion is preferably the heterocyclic portion described for the aforementioned heterocyclic group. For example, 1-phenyltetrazole- 5-oxy group and 2-tetrahydropyranyloxy group),

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

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms) Groups, for example, an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, and an N-1,3,5-triazin-2-ylamino group),
An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms; for example, a formylamino group; Acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, acryloylamino group, and methacryloylamino group),
An aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms; for example, a carbamoylamino group, an N, N-dimethylaminocarbonylamino group, an N, N-diethylaminocarbonylamino group, and , Morpholinocarbonylamino group),
An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms; for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, and , N-methyl-methoxycarbonylamino group),

An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms; for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, and an mn-octyloxyphenoxy group; Carbonylamino group),
Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms; for example, a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, and an Nn- Octylaminosulfonylamino group),
An alkyl or aryl sulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms; for example, a methylsulfonylamino group; Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, and p-methylphenylsulfonylamino group),
Mercapto group,

An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, and an n-hexadecylthio group);
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, and an m-methoxyphenylthio group);
Heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. The heterocyclic portion is preferably the heterocyclic portion described for the aforementioned heterocyclic group. For example, 2-benzothiazolylthio Group and 1-phenyltetrazol-5-ylthio group),
Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms; for example, N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl Group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, and N- (N'-phenylcarbamoyl) sulfamoyl group),
Sulfo group,

Alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl group, ethylsulfinyl group, phenyl Sulfinyl group and p-methylphenylsulfinyl group),
Alkyl or arylsulfonyl group (preferably, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group Phenylsulfonyl group and p-methylphenylsulfonyl group),
An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms; for example, an acetyl group, a pivaloyl group, Chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, acryloyl group, and methacryloyl group),
Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms; for example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, and a p-tert- Butylphenoxycarbonyl group),

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, and an n-octadecyloxycarbonyl group);
A carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms; for example, a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-n-octylcarbamoyl group; , And N- (methylsulfonyl) carbamoyl group),
An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (heterocyclic portion of the heterocyclic azo group) Is preferably a heterocyclic moiety described for the aforementioned heterocyclic group.) For example, a phenylazo group, a p-chlorophenylazo group, and a 5-ethylthio-1,3,4-thiadiazol-2-ylazo group),
An imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, such as an N-succinimide group and an N-phthalimido group);
A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, and a methylphenoxyphosphino group);
A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, a phosphinyl group, a dioctyloxyphosphinyl group, and a diethoxyphosphinyl group);

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);
A silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as a trimethylsilyl group, a tert-butyldimethylsilyl group, and a phenyldimethylsilyl group) is exemplified.

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

〔Composition〕
The composition of the present invention is a composition containing a compound represented by the following general formula (I) (hereinafter also referred to as a “specific compound”) and a solvent, and the content of the specific compound is a total content of the composition. It is 30% by mass or more based on the solid content.

As described above, the feature of the composition of the present invention is that it contains a specific compound that is a high refractive index material.
As described later, the specific compound has two or more groups having a refractive index at 589 nm of 1.70 or more (hereinafter, also referred to as a “high refractive index functional group”), and the compound as a whole has a high refractive index. Is shown.
Further, the composition of the present invention is excellent in step followability.
The specific compound used in the composition of the present invention can maintain the viscosity of the composition relatively low even when the amount added is large, and such properties contribute to the excellent step followability of the composition of the present invention. Is believed to be.
The reason why the specific compound can keep the viscosity of the composition low is that the specific compound has a predetermined structure such as a radial structure, so that the molecules are less likely to be entangled as compared with the polymer described in Patent Document 1. It is believed that there is.

  When the composition further contains a polymerizable compound and a photopolymerization initiator, the composition exhibits photolithographic properties. In particular, when the specific compound has an acid group, the composition can form a pattern having excellent developability and a good shape.

<Specific compound (compound represented by general formula (I))>
The specific compound is a compound represented by the general formula (I).
Hereinafter, each group in the general formula (I) will be described.
(A) _m -X- (B) _n (I)
In the following, unless otherwise specified, the general formula (I) is preferred in terms of a better balance between the high refractive index of a film formed using the composition and the excellent step followability of the composition. A preferred embodiment of each group is selected.

In the general formula (I), m represents an integer of 2 or more.
m is preferably an integer of 2 to 20, more preferably an integer of 2 to 10, and even more preferably an integer of 2 to 6.
Note that a plurality of A's in the general formula (I) may be the same or different.

In the general formula (I), n represents an integer of 0 or more.
n is preferably an integer of 0 to 20, more preferably an integer of 0 to 10, and even more preferably an integer of 0 to 6.
When a plurality of Bs are present in the general formula (I), they may be the same or different.

(Structure of A)
A is a group having at least two groups selected from the group consisting of a benzene ring group and a monocyclic heterocyclic group, and having a refractive index of 1.70 or more at 589 nm. Hereinafter, A is also referred to as a high refractive index functional group.
In addition, in this specification, a benzene ring group included in a "condensed ring group" such as a naphthalene ring group does not correspond to a simple description "benzene ring group". That is, a group composed of only a benzene ring (for example, a phenyl group, a phenylene group, or the like) is intended.
However, the above provisions stipulate that a condensed ring group containing a benzene ring in the structure (such as a naphthalene group) or a group in which a heterocyclic group forms a condensed ring structure (such as a benzothiazole ring group or a benzimidazole ring group) is used. , A. A may or may not contain a fused ring group.

The monocyclic heterocyclic group may or may not show aromaticity, but preferably shows aromaticity.
The number of member rings of the monocyclic heterocyclic group is preferably 3 to 10, more preferably 5 to 8, and even more preferably 5 to 6.
The number of hetero atoms in the monocyclic heterocyclic group is preferably from 1 to 5, and more preferably from 2 to 4.
Specific examples of the hetero atom of the monocyclic heterocyclic group include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. Among them, a nitrogen atom, a sulfur atom, or an oxygen atom is preferable, and a nitrogen atom is more preferable.

Specific examples of the monocyclic heterocyclic group include a pyrrole ring group, a thiophene ring group, a furan ring group, a selenophene ring group, a tellurophen ring group, an imidazole ring group, a pyrazole ring group, an oxazole ring group, an isoxazole ring group, Aromatic hetero groups such as thiazole ring group, isothiazole ring group, pyridine ring group, pyridone-2-one ring group, pyrimidine ring group, pyridazine ring group, pyrazine ring group, triazine ring group, selenopyran ring group, and tellropyran ring group And a ring group, a pyrrolidine ring group, a silole ring group, a piperidine ring group, a piperazine ring group, and a morpholine ring group.
Among them, the monocyclic heterocyclic group is preferably a triazine ring group.

The total number of benzene ring groups and monocyclic heterocyclic groups in A is 2 or more, preferably 3 or more, and more preferably 4 or more. The upper limit is not particularly limited, but is often 6 or less.
In addition, at least one of A preferably has a monocyclic heterocyclic group, and more preferably has a triazine ring group.
Among them, all A preferably have a monocyclic heterocyclic group, and more preferably have a triazine ring group.

A is a group having a refractive index at 589 nm of 1.70 or more.
Here, A means that the compound (AH) in which a hydrogen atom is bonded to the group represented by A- has a refractive index of 1.89 at a wavelength of 589 nm, wherein A has a refractive index of 1.70 or more at 589 nm. It is intended to be 70 or more.
The refractive index of A at 589 nm is preferably 1.75 or more, more preferably 1.80 or more, and even more preferably 1.90 or more. The upper limit of the refractive index of A is not particularly limited, but is generally 2.50 or less.

The refractive index of the compound (AH) is typically measured according to the following steps 1 to 3.
Step 1: In a solvent containing 10% by mass of poly (allyl methacrylate / methacrylic acid) (mass ratio: 90/10, Mw: 15,000 to 20,000, dispersity: 1.5 to 2.5), The compound (AH) is dissolved, and a solution in which the content of the compound (AH) is 30% by mass, 50% by mass, or 70% by mass with respect to the total solid content is prepared. As the solvent to be used, a solvent capable of uniformly dissolving the solids in the solution is selected.
Step 2: Each of the solutions prepared in Step 1 is applied to a glass substrate, and the glass substrate is baked to remove a solvent to form a coating film. The refractive index is measured using this coating film. In the measurement of the refractive index, the refractive index at a wavelength of 300 to 1500 nm is measured using an ellipsometer, and the value of the refractive index at a wavelength of 589 nm is defined as the refractive index of each coating film.
Step 3: A plot showing the relationship between the content (content ratio) of the compound (AH) in the coating film and the refractive index of the coating film (horizontal axis: content ratio of high refractive index compound, vertical axis) : Refractive index of the coating film), the refractive index of the coating film assumed when the content of the compound (A-H) is hypothetically 100% is determined by linear approximation, and the refractive index is calculated using the compound ( A-H).

Further, from the viewpoint of excellent heat resistance of a film formed using the composition, A preferably has a polymerizable group. As the polymerizable group, a (meth) acryloyl group or a vinyl group is preferable.
The molecular weight of A is preferably from 100 to 1,000, more preferably from 200 to 800, and still more preferably from 300 to 700.

Preferred examples of A include a group represented by formula (II).
Formula (II) (QL _1- ) _p -TL ₂ -ZL _3- *
Q independently represents an aryl group or a heterocyclic group (such as a benzothiazole ring group) which may have a substituent. As the aryl group, a phenyl group is preferable.
T represents a benzene ring group or a monocyclic heterocyclic group which may have a substituent.
p represents an integer of 1 or more. p is preferably from 1 to 3, more preferably from 1 to 2, and even more preferably 2.
When p is 2 or more, a plurality of Q and L ₁ may be the same or different.
L _{1 to} L ₃ each independently represent a single bond or a divalent linking group. As the divalent linking group, for example, a divalent chain-like saturated hydrocarbon group (which may be linear or branched, preferably having 1 to 20 carbon atoms), a divalent cyclic saturated group Hydrocarbon group (preferably having 3 to 20 carbon atoms), divalent aromatic group (preferably having 5 to 20 carbon atoms, for example, phenylene group), -O-, -S-, -SO _{2 -, - NR N -,} - CO -, - NH -, - COO -, - CONR N -, - O-COO -, - SO 3 -, - NHCOO -, - SO 2 NR N -, - Examples include NH-CO-NH-, or a group obtained by combining two or more of them (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like). Here, _RN represents a hydrogen atom, an alkyl group, or an aryl group.
Among these, as _{L 1} and _{L 2, -NR N -, -} O -, - S-, or, -CONR _N - are preferred, _-NR N -, - O-, or, -S- it is more preferable. As the _{L 3, -NR N -, -} O -, - S-, or, preferably is -O- alkylene group, -NR _N -, or, more preferably -O- alkylene group.
Z represents a single bond, an arylene group, or a divalent heterocyclic group. The divalent heterocyclic group is a group formed by removing two hydrogen atoms from an arbitrary position in the above-described heterocyclic group. As the arylene group, a phenylene group is preferable. When Z is a single bond, p represents an integer of 2 or more.
* Represents a bonding position.
In the formula (II), at least one or more benzene ring groups or monocyclic heterocyclic groups are present in addition to the benzene ring group or monocyclic heterocyclic group represented by T.
Each of the phenyl group and the phenylene group is one type of a benzene ring group.

The most preferred embodiment of A is a group represented by the general formula (II).
In addition, it is preferable that at least one of A is a group represented by the general formula (II), and it is more preferable that all of A be a group represented by the general formula (II).

In General Formula (II), C ₁ , C ₂ , and C ₃ each independently represent —NR _N —, —O—, or —S—. _RN represents a hydrogen atom, an alkyl group (preferably having 1 to 7 carbon atoms), or an aryl group.
Above all, C ₁ , C ₂ , and C ₃ are each independently preferably —NH—, —N (CH ₃ ) —, —O—, or —S—, and more preferably —NH—.
Of C ₁ , C ₂ and C ₃ , one or more is preferably -NH-, more preferably two or more is -NH-, and even more preferably all are -NH-.

In the general formula (II), Ar ₁ and Ar ₂ each independently represent an aryl group or a heterocyclic group (such as a benzothiazole ring group) which may have a substituent. Among them, a phenyl group is preferable as the aryl group.
The aryl group and the heterocyclic group may have a substituent. Examples of the substituent include the substituent T described above, and include an aryl group (such as a phenyl group or a biphenyl group), a cyano group, a chlorine atom, a bromine atom, a nitro group, a heterocyclic group, and a polymerizable group described below. Or a group consisting of a combination thereof. For example, it is also preferred that Ar ₁ and / or Ar ₂ together with a substituent form a biphenyl group or a terphenyl group. It is also preferable that such a biphenyl group or terphenyl group further has a substituent (including a group having a polymerizable group described below).
The substitution position of substituents for C ₁ or C _2, preferably substituted in the para position.

In addition, from the viewpoint of excellent heat resistance of a film formed using the composition, the aryl group and the heterocyclic group preferably have a polymerizable group as a substituent. As the polymerizable group, a (meth) acryloyl group or a vinyl group is preferable.
There is no limitation on the form having a polymerizable group as a substituent, and the group having such a polymerizable group may be the polymerizable group itself or may be a group partially including the polymerizable group. Good. The group having a polymerizable group may have a plurality of polymerizable groups.
Examples of the group having a polymerizable group include “-(single bond or divalent linking group)-(polymerizable group)” and “-(single bond or divalent linking group)-(trivalent linking group). )-[(Single bond or divalent linking group)-(polymerizable group)] ₂ ].
Examples of the divalent linking group each independently include, for example, a divalent chain-like saturated hydrocarbon group (which may be linear or branched, and preferably has 1 to 20 carbon atoms); A divalent cyclic saturated hydrocarbon group (preferably having 3 to 20 carbon atoms), a divalent aromatic group (preferably having 5 to 20 carbon atoms, for example, a phenylene group), -O-,- _{S -, - SO 2 -,} - NR N -, - CO -, - NH -, - COO -, - CONR N -, - O-COO -, - SO 3 -, - NHCOO -, - SO 2 Examples include NR _N- , -NH-CO-NH-, or a group obtained by combining two or more of these (e.g., an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like). Here, _RN represents a hydrogen atom, an alkyl group, or an aryl group. Above all, as the divalent linking group, independently preferred are -O-, -NH-, -divalent chain saturated hydrocarbon group -O-, or -NH-CO-NH-.
Examples of the trivalent linking group include, for example, a group represented by -CR _T <. Here, _RT represents a hydrogen atom, an alkyl group (preferably a methyl group), or an aryl group.

Ar ₃ is an arylene group or a divalent heterocyclic group which bonds to X in the general formula (I) via the L _A. Among them, a phenylene group is preferable as the arylene group.
L _A represents a single bond or a divalent linking group. The definition of the divalent linking group is as described above.
The divalent linking group represented by _{L A, -NH -, - O} -, - CO -, - CO-O-, an alkylene group (preferably 1 to 3 carbon atoms), or a combination thereof ( For example, a group consisting of -O-alkylene group-) is preferable.
The molecular weight of the _{L A} case is a divalent linking group is preferably from 14 to 300, more preferably from 16 to 200, more preferably 16 to 100.
* Represents a bonding position.
However, at least _one of Ar ₁ , Ar ₂ , and Ar ₃ represents a benzene ring group or a monocyclic heterocyclic group.
Each of the phenyl group and the phenylene group is one type of a benzene ring group.

(Structure of X)
In the general formula (I), X represents an m + n-valent linking group.
As long as X is an m + n-valent linking group, the structure thereof is not particularly limited, but may include an aromatic hydrocarbon group, a heterocyclic group, or an aliphatic hydrocarbon group which may have an oxygen atom. Is preferred. As the aromatic hydrocarbon group, a benzene ring group or a naphthalene ring group is preferable. The heterocyclic group may or may not be a fused ring group, but is preferably not a fused ring group, more preferably a triazine ring group.
When X has an aromatic hydrocarbon group or a heterocyclic group, X preferably has one aromatic hydrocarbon group or a heterocyclic group. In this case, an aromatic hydrocarbon group having a condensed ring structure is counted as one aromatic hydrocarbon group, and a heterocyclic group having a condensed ring structure is also counted as one heterocyclic group.
X is preferably a group represented by the following general formula (III).
The molecular weight of X is preferably from 50 to 2,000, more preferably from 70 to 1500, and still more preferably from 120 to 1200.

  As a preferable embodiment of X, a group represented by the following general formula (III) is preferable.

_{(* A -Z A) m -Y-} (Z B - * B) n (III)

In the general formula (III), m is the same value as m in the general formula (I) and represents an integer of 2 or more.
n is the same value as n in the general formula (I) and represents an integer of 0 or more.
* _A represents a bonding position to _A in the general formula (I).
* _B represents a bonding position with _B in the general formula (I).
m + n is preferably 2 to 6.

  In the general formula (III), Y is an m + n-valent linking group, and represents a group having an aromatic hydrocarbon group, a heterocyclic group, or an aliphatic hydrocarbon group which may have an oxygen atom.

The group having an aromatic hydrocarbon group may be a group consisting of only one or more aromatic hydrocarbon groups, or one or more (preferably two or more) aromatic hydrocarbon groups and other groups. And a group consisting of
Examples of the group consisting of an aromatic hydrocarbon group and other groups include a group represented by the following formula.
(Aromatic hydrocarbon group)-(single bond or divalent linking group)-(aromatic hydrocarbon ring group) Formula The two aromatic hydrocarbon groups in the above formula may be the same or different. .
As the divalent linking group in the above formula, for example, a divalent chain-like saturated hydrocarbon group (which may be linear or branched, preferably having 1 to 20 carbon atoms), valent cyclic saturated hydrocarbon group (preferably from 3 to 20 carbon atoms), a divalent heterocyclic _{group, -O -, - S -,} - SO 2 -, - NR N -, - CO -, - _{NH -, - COO -, -} CONR N -, - O-COO -, - SO 3 -, - NHCOO -, - SO 2 NR N -, - NH-CO-NH-, or these two above combined groups (e.g., alkyleneoxy group, an alkyleneoxy group, an alkylene carbonyl group) and the like, among them, -SO 2 _- are preferred. Here, _RN represents a hydrogen atom, an alkyl group, or an aryl group.
In the group having an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a benzene ring group or a naphthalene ring group.
When Y is a group having an aromatic hydrocarbon group, the value of m is preferably from 2 to 4.
When Y is a group having an aromatic hydrocarbon group, the value of n is preferably from 0 to 2.
When Y is a group having an aromatic hydrocarbon group, m + n is preferably 2 to 4.

When Y is a heterocyclic group, it may not be a condensed ring group or a condensed ring group, but is preferably not a condensed ring group. The preferred embodiment of the heterocyclic group which is not a fused ring group is the same as the preferred embodiment of the heterocyclic group which A in formula (I) may have.
Above all, a triazine ring group is preferable as the heterocyclic group represented by Y.
When Y is a heterocyclic group, the value of m is preferably 2 to 4, and more preferably 3.
When Y is a heterocyclic group, the value of n is preferably from 0 to 3, and more preferably 0.
When Y is an aromatic hydrocarbon group, m + n is preferably 2 to 4, and more preferably 3.

When Y is an aliphatic hydrocarbon group which may have an oxygen atom, the aliphatic hydrocarbon group may be linear or branched, and has a ring structure (preferably having 5 to 10 carbon atoms). You may have.
The oxygen atom which the aliphatic hydrocarbon group may have may be contained as -O-, -C (O)-, -COO-, -OC (O) O-, or the like. That is, the aliphatic hydrocarbon group may include the groups exemplified above.

  The carbon number of the aliphatic hydrocarbon group is not particularly limited, but is preferably 1 to 40, more preferably 2 to 30, and still more preferably 3 to 20.

One preferred embodiment of the aliphatic hydrocarbon group optionally having an oxygen atom is an alkylene group optionally having an oxygen atom. When Y is an alkylene group which may have an oxygen atom, m + n = 2.
2-15 are preferable, as for carbon number of an alkylene group, 3-12 are more preferable, 4-10 are more preferable.
Further, the aliphatic hydrocarbon group which may have an oxygen atom may be a cyclic group itself or a group partially including a cyclic group. Examples of Y in such an embodiment include those in which Y is a cyclic saturated hydrocarbon group (preferably a 5- to 7-membered ring, more preferably a 6-membered ring).

  Another preferred embodiment of the aliphatic hydrocarbon group which may have an oxygen atom includes a group represented by the formula (A). When Y is a group represented by the formula (A) and r is 1, the relationship is m + n = 6. In this case, m is preferably 2 to 6, more preferably 2 to 5, and still more preferably 3 to 5.

L _C each independently represents an alkylene group. 1-5 are preferable, as for carbon number in an alkylene group, 1-3 are more preferable, and 1 is further more preferable.
r represents 0 or 1.

In Formula (III), Z _A and Z _B each independently represent a single bond or a divalent linking group.
The definition of the divalent linking group is as described above. Among them, the divalent linking group, -O -, - S -, - CO -, - NH -, - SO 2 -, an alkylene group, or a group formed from these combinations preferred.
Examples of the group consisting of the above combinations include a -Y-alkylene group -Y- and -Y-alkylene group. Y includes -O-, -O-CO-, -S-, and -NH-. Specific examples of the group consisting of the above combinations include -O-CO-alkylene group -S-, alkylene group -S-, -alkylene group -O-, -O-CO-alkylene group, and the like.

(Structure of B)
In the general formula (I), B represents a polymer chain or a substituent. In the present specification, the “substituent” does not include a polymer chain. The “substituent” does not include the high refractive index functional group described above.

The polymer chain represented by B is a chain having a plurality of predetermined repeating units. The structure of the polymer chain is not particularly limited, and can be selected from known polymers according to the purpose and the like.
Among them, the polymer chain is a polymer or a copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, and a polymer selected from the group consisting of silicone polymers. A polymer chain composed of a polymer or a copolymer of a (meth) acrylic compound is more preferred.
The polymer chain may have a substituent. When there are a plurality of substituents, the plurality of substituents may be the same or different.
One preferred embodiment of the substituent in the polymer chain is an acid group. Examples of the type of the acid group include groups exemplified by the acid group which the specific compound described below may have.
Further, as another preferable embodiment of the substituent in the polymer chain, a polymerizable group described below is mentioned from the viewpoint of excellent heat resistance of a film formed using the composition. Among them, the polymerizable group is preferably a (meth) acryloyloxy group, and more preferably a methacryloyloxy group.
The weight average molecular weight of the polymer chain represented by B is preferably from 200 to 10,000, more preferably from 300 to 5,000.
When there are a plurality of polymer chains B, the plurality of polymer chains may be the same or different.

Examples of the substituent represented by B include the groups exemplified by the substituent T described above. The substituent represented by B may be, for example, a group obtained by combining a plurality of substituents exemplified for the substituent T.
Among them, from the viewpoint of excellent developability of the composition, as the substituent represented by B, a group having an acid group described below is preferable, a group having a thiol group or a group having a carboxy group is more preferable, and a carboxy group is preferable. Is more preferred.
However, the thiol group can form a crosslinked structure based on an ene / thiol reaction with a group having an ethylenically unsaturated bond described below. Therefore, a group having a thiol group is preferred from the viewpoint that the heat resistance of a film obtained from the composition can be improved in the presence of a polymerizable compound described below.
As the group having a thiol group, for example, a group represented by "-alkylene group (preferably having 2 to 5 carbon atoms) -SH" is preferable.
Further, as the substituent represented by B, a group having a halogen atom is also preferable.
In addition, in this specification, the group having an acid group is intended to include an embodiment in which the group is the acid group itself. A group having a thiol group and a group having a carboxy group have the same intention.
When there are a plurality of substituents represented by B, the plurality of B may be the same or different.

(Acid group)
Further, the specific compound preferably has an acid group from the viewpoint of excellent developability of the composition.
Specific examples of the acid group include a carboxy group, a thiol group, a sulfonic acid group, a monosulfate ester group, a phosphate group, a monophosphate ester group, a phosphonate group, a phosphinate group, a phenolic hydroxyl group, and a borate group. No. Among them, a carboxy group, a thiol group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate ester group, a phosphonic acid group, or a phosphinic acid group are preferable, and a carboxy group, a thiol group, a sulfonic acid group, phosphoric acid Groups, phosphonic acid groups or phosphinic acid groups are more preferred, and carboxy groups are even more preferred.
When the specific compound has an acid group, A may have an acid group, the substituent represented by B may have an acid group, and the polymer chain represented by B has an acid group. You may have.

(Polymerizable group)
The specific compound preferably has a polymerizable group from the viewpoint of excellent heat resistance of a film formed using the composition.
Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group.
As the radical polymerizable group, a known radical polymerizable group can be used, and a polymerizable group having a radically polymerizable ethylenically unsaturated bond is preferable. Among them, a (meth) acryloyl group or a vinyl group is preferable. It is also preferable that the (meth) acryloyl group be combined with -O- or -NH- to form a (meth) acryloyloxy group or a (meth) acryloylamino group.

  As the cationically polymerizable group, known cationically polymerizable groups can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and a vinyloxy group And the like.

When the specific compound has a polymerizable group, A may have a polymerizable group, the substituent represented by B may have a polymerizable group, and the polymer chain represented by B It may have a polymerizable group.
In this specification, when the specific compound has a polymerizable group, the specific compound having a polymerizable group is not included in the polymerizable compound described below.

Among them, the specific compound is preferably a compound represented by the general formula (IV).
_{(A T -Z A) m -Y-} (Z B -B) n (IV)

In the general formula (IV),
m represents an integer of 2 or more. M in the general formula (IV) has the same meaning as m in the general formula (III), and the preferred range is also the same.
n represents an integer of 0 or more. N in the general formula (IV) has the same meaning as n in the general formula (III), and the preferred range is also the same.
_AT is a group having a refractive index at 589 nm of 1.70 or more, and is a group represented by the general formula (II). The group represented by the general formula (II) in _AT in the general formula (IV) has the same meaning as the group represented by the general formula (II) described above as a preferred embodiment of A in the general formula (I). The same applies to the preferred range. The preferred range and the measuring method of the refractive index of _AT are the same as the preferred range and the measuring method of the refractive index of A.
B represents a polymer chain or a substituent. B in the general formula (IV) has the same meaning as B in the general formula (I), and the preferred range is also the same.
Y is an m + n-valent linking group, and represents a group having an aromatic hydrocarbon group, a heterocyclic group, or an aliphatic hydrocarbon group which may have an oxygen atom. Y in the general formula (IV) has the same meaning as Y in the general formula (III), and the preferred range is also the same.
Z _A and Z _B each independently represent a single bond or a divalent linking group. _{Z A} and _{Z B} in the general formula (IV), formula (III) in a respectively _{Z A} and _{Z B} synonymous, and preferred ranges are also the same.
Incidentally, A _T there are a plurality, may each be the same or different. When a plurality of Bs exist, the plurality of Bs may be the same or different. A plurality of Z _A may be the same or different. If Z _B there are a plurality, Z _B where there are a plurality, may each be the same or different.

The specific compound can be synthesized by a known method.
In addition, as the synthesis solvent, it is preferable to use amides such as 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide.
In the composition of the present invention, the content of the specific compound is 30% by mass or more based on the total solids in the composition, and from the viewpoint of excellent refractive index of the formed film, 50% by mass or more is more preferable. It is preferably at least 70% by mass.
In the composition of the present invention, the content of the specific compound is preferably 99% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less based on the total solid content in the composition.
In addition, the solid content intends a component that forms a film described later, and does not include a solvent.
The specific compounds may be used alone or in combination of two or more.

<Solvent>
The composition of the present invention contains a solvent.
The type of the solvent is not particularly limited, and includes, for example, water and an organic solvent. Examples of the organic solvent include esters, ethers, ketones, aromatic hydrocarbons, and amides. Specific examples include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide, 3-methoxy-N, N-dimethylpropanamide, and 3- Butoxy-N, N-dimethylpropanamide and the like. For details of the organic solvent, the description in paragraph No. 0223 of International Publication WO2015 / 166779 can be referred to, and the contents thereof are incorporated herein.
However, aromatic hydrocarbons (benzene, toluene, xylene, chlorobenzene, ethylbenzene, etc.) as a solvent may need to be reduced for environmental reasons. For example, the content of the aromatic solvent in the composition is preferably 0 to 10000 mass ppm (parts per million), and preferably 0 to 1000 mass ppm, for each aromatic solvent, independently of the total mass of the composition. Is more preferred. In addition, the value of "0" here is intended to be less than the detection limit by the measuring instrument.

  One organic solvent may be used alone, or two or more organic solvents may be used in combination. When using two or more organic solvents in combination, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone A mixed solution composed of two or more selected from ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferred.

  It is preferable to use a solvent having a low metal content, and it is preferable that the metal content of the solvent is, for example, 10 parts by mass ppb (parts per billion) or less. If necessary, a solvent having a level of parts per trillion (ppt) may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

  Examples of a method for removing impurities such as metals from a solvent include distillation (molecular distillation or thin film distillation or the like) 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 even more preferably 3 nm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

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

The content of the peroxide in the organic solvent is preferably 0.8 mmol / L or less, and the organic solvent is more preferably substantially free of peroxide.
When the composition contains water as a solvent, the content of water is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 5% by mass, and preferably from 0.1 to 5% by mass, based on the total mass of the composition. -3% by mass is more preferred.

  The content of the solvent in the composition of the present invention is not particularly limited, but the amount of the solid content in the composition is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and more preferably 5 to 25% by mass. The amount which becomes に な る 20% by mass is more preferable.

<Other optional ingredients>
The composition may include a compound other than the specific compound and the solvent. For example, other compounds include a resin, a curable compound (including a polymerizable compound), a polymerization initiator (preferably a photopolymerization initiator), an antioxidant, a silane coupling agent, a polymerization inhibitor, and a surfactant. , An ultraviolet absorber, a filler, and a curing accelerator.
Hereinafter, typical examples of other compounds will be described in detail.

(resin)
The composition may include a resin. The resin is a compound having a plurality of predetermined repeating units. In the present specification, when the resin has a polymerizable group, the resin having a polymerizable group is not included in the polymerizable compound described later. In this specification, when the specific compound has a polymer chain, the specific compound having a polymer chain is not included in the resin.

The resin is mixed, for example, for use as a binder.
The weight average molecular weight (Mw) of the resin is preferably from 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 5,000 or more.

  Examples of the resin include (meth) acrylic resin, (meth) acrylamide resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene Examples include ether phosphine oxide resins, polyimide resins, polyamide imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins.

  In the composition of the present invention, a resin having a refractive index to near infrared rays of 1.7 or more (hereinafter, also referred to as a high refractive index resin) may be used as the resin. The refractive index of the resin for near infrared rays is preferably 1.7 to 4.0. The lower limit is preferably 1.75 or more, more preferably 1.8 or more, and still more preferably 1.85 or more. The upper limit is preferably 3.9 or less, more preferably 3.5 or less, and still more preferably 3.0 or less. The refractive index is preferably a value for light having a wavelength of 810 nm, 850 nm, and 940 nm. Further, when a film formed from the composition of the present invention is used for an infrared sensor, it is preferable that the value of the refractive index is a value for near-infrared light having a wavelength used for detection by the infrared sensor. The high refractive index resin can be used as a binder or a dispersant.

  The refractive index of the resin can be measured in an uncured state by the following method. As a specific measuring method, a film made of only a resin to be measured is formed on a silicon wafer with a thickness of 300 nm, and the refractive index of the obtained film is measured by ellipsometry (Lambda Ace RE-3300 (trade name)). , Manufactured by Dainippon Screen Mfg. Co., Ltd.).

  From the viewpoint of excellent developability, the resin may have an acid group. These acid groups may be used alone or in combination of two or more. The resin having an acid group can be used as an alkali-soluble resin.

The acid value of the resin having an acid group is preferably from 30 to 500 mgKOH / g. The lower limit is more preferably at least 50 mgKOH / g, even more preferably at least 70 mgKOH / g. The upper limit is more preferably 400 mg KOH / g or less, further preferably 200 mg KOH / g or less,
Particularly preferred is 150 mgKOH / g or less, and most preferred is 120 mgKOH / g or less.

As the resin having an acid group, a polymer having a carboxy group in a side chain is preferable. Specific examples include methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and novolak resin. Examples thereof include an alkali-soluble phenol resin, an acidic cellulose derivative having a carboxy group in a side chain, and a resin obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds.
Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples include hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, and cyclohexyl (meth) acrylate.
Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, and polymethyl methacrylate macromonomer. .
Further, examples of other monomers include N-substituted maleimide monomers (for example, N-phenylmaleimide and N-cyclohexylmaleimide) described in JP-A-10-300922.
The other monomer copolymerizable with the (meth) acrylic acid may be only one kind or two or more kinds.

  Examples of the resin having an acid group include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, or benzyl Preference is given to multi-component copolymers consisting of (meth) acrylate / (meth) acrylic acid / other monomers. Further, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, or a copolymer of 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid described in JP-A-7-140654. Polymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, or 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer is also preferred.

  The resin having an acid group is a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimer”). It is also preferable to include a polymer obtained by polymerizing the contained monomer component.

In the general formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.

  In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description in JP-A-2010-168538 can be referred to.

  As a specific example of the ether dimer, for example, paragraph No. 0317 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated herein. The ether dimer may be only one kind or two or more kinds.

  The resin having an acid group may contain a repeating unit derived from a compound represented by the following general formula (X).

In the general formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, R ₃ is optionally carbon atoms 1 include a hydrogen atom or a benzene ring Represents 20 alkyl groups. n represents an integer of 1 to 15.

  Examples of the resin having an acid group are described in JP-A-2012-208494, paragraphs 0558 to 0571 (corresponding U.S. Patent Application Publication No. 2012/0235099, paragraphs 0689 to 0700), and JP-A-2012-208. The description in paragraphs 0076 to 999 of JP-A-198408 can be referred to, and the contents thereof are incorporated in the present specification.

The resin may have a curable group. Examples of the curable group include a group having an ethylenically unsaturated bond, an epoxy group, a methylol group, and an alkoxysilyl group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. Note that the resin having a curable group is also a curable compound.
Further, the resin may have a polymerizable group. Examples of the polymerizable group include a polymerizable group which the above-described specific compound may have.

  Examples of the resin containing a curable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, and KS resist 106 (all). Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all made by Daicel Corporation), Ebecryl3800 (made by Daicel UCB), and Acrylic RD-F8 (Nippon Shokubai) Co., Ltd.).

  Examples of the resin include Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (NOF And ARTON F4520 (manufactured by JSR Corporation).

In the above composition, the content of the resin is preferably 0.1 to 99.9% by mass based on the total solids in the composition. The lower limit is more preferably 1% by mass or more, and still more preferably 2% by mass or more. The upper limit is more preferably 50% by mass or less, and still more preferably 30% by mass or less.
When the high refractive index resin is used as the resin, only the high refractive index resin may be used as the resin, or a resin having a refractive index of less than 1.7 with respect to near infrared rays may be used in combination with the high refractive index resin. Further, the content of the high refractive index resin in the total amount of the resin is preferably from 1 to 100% by mass, and more preferably from 10 to 100% by mass.
One type of resin may be used alone, or two or more types may be used in combination.

(Curable compound)
The composition preferably contains a curable compound.
As the curable compound, a known compound curable by a radical, an acid, or heat can be used. For example, a compound having a group having an ethylenic unsaturated bond, a compound having an epoxy group, a compound having a methylol group, and the like can be given. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group, and a (meth) acryloyl group or a (meth) An acryloyloxy group is preferred. The curable compound is preferably a polymerizable compound, and more preferably a radical polymerizable compound. Examples of the polymerizable compound include a compound having 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 in the composition. The lower limit is more preferably 3% by mass or more, and still more preferably 5% by mass or more. The upper limit is more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 30% by mass or less.
One of the curable compounds may be used alone, or two or more of them may be used in combination. When the composition contains two or more curable compounds, the total content is preferably within the above range.

.Compounds having a group having an ethylenically unsaturated bond (polymerizable compounds)
As the curable compound, a compound having a group having an ethylenically unsaturated bond (hereinafter, also referred to as a polymerizable compound) can be used. The polymerizable compound is preferably a monomer. The molecular weight of the polymerizable compound is preferably from 100 to 3000. The upper limit is more preferably 2000 or less, and still more preferably 1500 or less. The lower limit is more preferably 150 or more, and further preferably 250 or more. The polymerizable compound is preferably a 2-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound.

  As examples of the polymerizable compound, the description of paragraphs [0033] to [0034] of JP2013-253224A can be referred to, and the contents thereof are incorporated herein. Examples of the polymerizable compound include ethyleneoxy-modified pentaerythritol tetraacrylate (a commercially available product is NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and dipentaerythritol triacrylate (a commercially available product is KAYARAD D-330; Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available, KAYARAD D-320; Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available products: KAYARAD DPHA; Nippon Kayaku Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and these (Meta) acri A structure in which a royl group is bonded via an ethylene glycol residue and / or a propylene glycol residue is preferable. These oligomer types can also be used. In addition, descriptions of paragraphs 0034 to 0038 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. Moreover, the polymerizable monomer etc. of Paragraph No. 0477 of Unexamined-Japanese-Patent No. 2012-208494 (paragraph No. 0585 of corresponding US patent application publication 2012/0235099 specification) etc. are mentioned, The content of these is described in this specification. Incorporated in Further, diglycerin EO (ethylene oxide) -modified (meth) acrylate (commercially available M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT), or 1 , 6-hexanediol diacrylate (KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.) is also preferable. These oligomer types can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

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

  In a preferred embodiment, 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.For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentane Ε-caprolactone-modified polyfunctional (meth) obtained by esterifying polyhydric alcohols such as erythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. Acrylates can be mentioned. As the polymerizable compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, and the contents thereof are incorporated herein. Compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, for example, DPCA-20, DPCA-30, DPCA-60, and DPCA-120, and commercially available from Sartomer. SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

  Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also preferable. It is. Further, addition polymerizable compounds having an amino structure and / or a sulfide structure in a molecule described in JP-A-63-277563, JP-A-63-260909 and JP-A-1-105238. Compounds can be used. Commercially available products include urethane oligomers UAS-10 and UAB-140 (manufactured by Sanyo Kokusaku Pulp), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600, and light acrylate POB-A (manufactured by Kyoeisha Chemical Co., Ltd.).

  One preferred embodiment of the polymerizable compound is a polymerizable compound having two or more polymerizable groups and having a fluorene skeleton. Note that the fluorene skeleton is a skeleton containing at least a fluorene structure, and the aromatic ring group in the fluorene structure may have a so-called monocyclic structure (benzene ring) or a polycyclic structure (polycyclic aromatic ring structure).

  The content of the polymerizable compound is preferably from 1 to 80% by mass based on the total solid content in the composition. The lower limit is more preferably 3% by mass or more, and still more preferably 5% by mass or more. The upper limit is more preferably equal to or less than 70% by mass, and still more preferably equal to or less than 60% by mass.

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

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

  The compound having an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 1000) or a high molecular weight compound (a macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). . The 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 more preferably 10,000 or less, still more preferably 5,000 or less, and particularly preferably 3,000 or less.

  As the compound having an epoxy group, a commercially available product can also be used. For example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation) and the like can be mentioned. In addition, compounds having an epoxy group are described in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraph 0085 of JP-A-2014-089408. To 0092 can also be used. These contents are incorporated herein.

  The content of the compound having an epoxy group is preferably from 1 to 80% by mass based on the total solid content in the composition. The lower limit is more preferably 3% by mass or more, and still more preferably 5% by mass or more. The upper limit is more preferably equal to or less than 70% by mass, and still more preferably equal to or less than 60% by mass. As the compound having an epoxy group, one type may be used alone, or two or more types may be used in combination. When the composition contains two or more compounds having an epoxy group, the total amount is preferably within the above range.

(Photopolymerization initiator)
The composition may include a polymerization initiator.
In particular, when the composition contains a radically polymerizable compound, the composition preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, the photopolymerization initiator is preferably a compound having photosensitivity to light in the ultraviolet region to the visible region. The photopolymerization initiator is preferably a photoradical polymerization initiator.

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton and compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenone. The photopolymerization initiator is, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triarylimidazole. Compounds selected from the group consisting of dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds are preferred, and oximes Compounds selected from the group consisting of compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds are more preferred. Among them, the oxime compound is more preferable, since the obtained film has more excellent heat resistance. As the photopolymerization initiator, the description of paragraphs 0065 to 0111 of JP-A-2014-130173 can be referred to, and the contents thereof are incorporated herein.

  As the photopolymerization initiator, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound can also be suitably used. For example, an α-aminoketone compound described in JP-A-10-291969 and an acylphosphine compound described in Japanese Patent No. 4225898 can be used. Commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF). Commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF). Commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (all manufactured by BASF), which are commercially available products. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Adeka Arkles NCI-831 (manufactured by ADEKA Corporation), Adeka Arculs NCI-930 (manufactured by ADEKA Corporation), and Adeka Optomer N-1919 (manufactured by ADEKA Corporation, light disclosed in JP-A-2012-14052) And a polymerization initiator 2).

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

  An oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. And the like (C-3). These contents are incorporated herein.

  An oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is preferably a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 of JP 2014-137466 A and 0070 to 0079, Compounds described in Paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arculs NCI-831 (manufactured by ADEKA Corporation) are exemplified.

  Specific examples of the oxime compound preferably used in the composition of the present invention are shown below.

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

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

The content of the photopolymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, still more preferably from 1 to 20% by mass, based on the total solid content in the composition. 1 to 10% by weight is particularly preferred.
When the content of the photopolymerization initiator is in the above range, a pattern excellent in sensitivity and excellent in rectangularity is easily formed. In the above composition, one photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination. When the composition contains two or more photopolymerization initiators, the total content thereof is preferably within the above range.

(Antioxidant)
The composition may include 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 may be used alone or in combination of two or more. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used, and a polysubstituted phenolic compound is preferable. Polysubstituted phenolic compounds are roughly classified into three types (hindered type, semi-hindered type, and less hindered type) having different substitution positions and structures. 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. A commercially available product can be used as the antioxidant. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80 And ADK STAB AO-330 (manufactured by ADEKA Corporation). Further, as the antioxidant, the description of paragraphs [0033] to [0043] of JP-A-2014-032380 can be referred to, and the contents thereof are incorporated herein.

  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 solids in the composition. One kind of antioxidant may be used alone, or two or more kinds may be used in combination. When the composition contains two or more antioxidants, the total content thereof is preferably in the above range.

(Silane coupling agent)
The composition may include a silane coupling agent.
In this specification, the silane coupling agent means a silane compound having a hydrolyzable group and another functional group. Further, the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. The functional group other than the hydrolyzable group is preferably a group that forms an interaction or a bond with the resin and exhibits affinity. Examples include a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureide group, a sulfide group, an isocyanate group, and a phenyl group. Alternatively, an epoxy group is preferred.

  Specific examples of the silane coupling agent include, for example, 3-methacryloxypropylmethyldimethoxysilane. Examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703, and compounds described in paragraphs 0056 to 0066 of JP-A-2009-242604. These contents are incorporated herein. Commercial products can also be used as the silane coupling agent. Commercially available silane coupling agents include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, and KBM-30 manufactured by Shin-Etsu Silicone Co., Ltd. 3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, 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 silane 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 in the composition. As the silane coupling agent, one type may be used alone, or two or more types may be used in combination. When the composition contains two or more silane coupling agents, the total content is preferably in the above range.

(Polymerization inhibitor)
The composition may include a polymerization inhibitor.
Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), , 2'-methylenebis (4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxyamine salts (such as ammonium salts and cerous salts). Among them, p-methoxyphenol is preferable. Incidentally, the polymerization inhibitor sometimes functions 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, and still more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the photopolymerization initiator. . As the polymerization inhibitor, one type may be used alone, or two or more types may be used in combination. When the composition contains two or more polymerization inhibitors, the total content thereof is preferably in the above range.

(Surfactant)
The composition may 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 silicone-based surfactant can be used. The surfactant can be referred to paragraphs 0238 to 0245 of International Publication WO2015 / 166779, the contents of which are incorporated herein.

  By including a fluorine-based surfactant in the composition of the present invention, the liquid properties (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. be able to. In the case of forming a film using a coating solution to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the coated surface and the coating solution is reduced, and the wettability to the coated surface is improved, The applicability to the surface to be applied is improved. Therefore, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

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

  Specific examples of the fluorinated surfactant include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-41318 (paragraphs 0060 to 0064 of corresponding WO 2014/17669), and And surfactants described in Paragraph Nos. 0117 to 0132 of JP-A-2011-132503, the contents of which are incorporated herein. Commercially available fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (manufactured by DIC Corporation), Florado FC430, FC431, and FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, and SC-101 SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (all manufactured by Asahi Glass Co., Ltd.), and PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (OMNO A Co., Ltd.), and the like.

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

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

  The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating 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. As specific examples, compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation, And RS-72-K. As the fluorinated surfactant, compounds described in Paragraph Nos. 0015 to 0158 of JP-A-2015-117327 can also be used.

  Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate and glycerol ethoxylate). Also, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10 , L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Corporation) ), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, Beauty, (manufactured by Takemoto Oil & Fat Co., Ltd.) D-6315, as well as Olfine E1010, Surfynol 104,400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like can be mentioned.

  Further, as the fluorine-based surfactant, a vinyl ether polymerization-type fluorine-based surfactant can also be used. Examples of the vinyl ether polymerizable fluorine-based surfactant include those described in the Examples section of JP-A-2006-216602 (for example, fluorine-based surfactant (1)).

  The content of the surfactant is preferably from 0.001 to 5.0% by mass, more preferably from 0.005 to 3.0% by mass, based on the total solid content in the composition. One type of surfactant may be used alone, or two or more types may be used in combination. When the composition contains two or more surfactants, the total content thereof is preferably within the above range.

(UV absorber)
The composition may include 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 hydroxyphenyltriazine compound. For details thereof, paragraphs 0052 to 0072 of JP-A-2012-208374 and paragraphs 0317 to 0334 of JP-A-2013-68814 can be referred to, and the contents thereof are incorporated herein. It is. Commercially available conjugated diene compounds include, for example, UV-503 (manufactured by Daito Chemical Co., Ltd.). As the benzotriazole compound, MYUA series (manufactured by Chemical Industry Daily, February 1, 2016) manufactured by Miyoshi Oil & Fats may 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 in the composition. . Further, one kind of the ultraviolet absorber may be used alone, or two or more kinds may be used in combination. When the composition contains two or more ultraviolet absorbers, the total content thereof is preferably within the above range.

(Filling material)
Examples of the filler include inorganic particles. As the inorganic particles, a high refractive index, colorless, white, or transparent inorganic particles are preferable, and titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), zinc (Zn), or Oxide particles such as magnesium (Mg) are preferable, and titanium dioxide (TiO ₂ ) particles, zirconium oxide (ZrO ₂ ) particles, or silicon dioxide (SiO ₂ ) particles are more preferable.
The primary particle diameter 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 is preferably 1.75 to 2.70, more preferably 1.90 to 2.70, from the viewpoint of obtaining a high refractive index.
Is not particularly limited specific surface area of the inorganic particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, more preferably 30 to 150 m ² / g.
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 irregular shape.
The inorganic particles may be surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include a polyol, an alkanolamine, stearic acid, a silane coupling agent, and a titanate coupling agent. Among them, stearic acid or a silane coupling agent is preferable.
In addition, the surface of the inorganic particles is preferably covered with an oxide such as aluminum, silicon, and zirconia from the viewpoint of further improving weather resistance.
As the inorganic particles, commercially available inorganic particles can be preferably used.
One kind of the inorganic particles may be used alone, or two or more kinds may be used in combination.

(Curing 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.
Curing accelerators that improve the curing speed include acid anhydrides, bases (such as aliphatic amines, aromatic amines, and modified amines), acids (such as sulfonic acid, phosphoric acid, and carboxylic acid), and poly (polycarboxylic acids). Mercaptan and the like. Among them, an acid anhydride is preferable, and an aliphatic acid anhydride is more preferable.

The composition may further include components other than those described above.
It is also conceivable that the composition contains impurities. Examples of the impurities include halide ions and metal components.
Examples of the halide ion include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion. The content of halide ions in the composition is preferably 0 to 10000 ppm by mass, more preferably 0 to 1000 ppm by mass, more preferably 0 to 1000 ppm by mass, with respect to the total mass of the composition. Mass ppm is more preferred.
The metal component is present in the composition, for example, as a metal ion, and specific metals include, for example, sodium, potassium, and iron. The content of the metal component in the composition is preferably 0 to 10000 ppm by mass, more preferably 0 to 1000 ppm by mass, for each metal independently of the total mass of the composition.
In addition, the value of "0" described about the preferable range of the content of these impurities is intended to be less than the detection limit by a measuring instrument.

<Method for preparing composition>
The above composition can be prepared by mixing the above-mentioned components. In preparing the composition, the components may be blended together, or the components may be dissolved or dispersed in a solvent and then blended sequentially. For example, the composition may be prepared by simultaneously dissolving or dispersing all components in a solvent.

  When the composition contains particles, the method for preparing the composition preferably includes a process for dispersing the particles. In the process of dispersing particles, examples of mechanical force used for dispersing particles include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, a sand grinder, a flow jet mixer, a high-pressure wet atomization, and an ultrasonic dispersion. In the pulverization of particles in a sand mill (beads mill), it is preferable to use beads having a small diameter or to increase the packing ratio of the beads, for example, to increase the pulverization efficiency. Further, it is preferable to remove coarse particles by filtration or centrifugation after the pulverization. Further, as a process and a disperser for dispersing particles, "Dispersion Technology Taizen, published by Information Technology Co., Ltd., July 15, 2005" and "Dispersion technology and industrial technology centering on suspension (solid / liquid dispersion system)" Practical Application The process and the dispersing machine described in Paragraph No. 0022 of Japanese Unexamined Patent Application Publication No. 2015-157893, “General Materials Collection, Published by Management Development Center Publishing Division, Oct. 10, 1978” can be preferably used. In the process of dispersing the particles, the particles may be refined in a salt milling step. For the materials, equipment, processing conditions, and the like used in the salt milling step, for example, descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.

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

  When using filters, different filters (for example, a first filter and a second filter) may be combined. At that time, the filtration by each filter may be performed only once or may be performed twice or more. Further, filters having different hole diameters may be combined within the above-described range. The pore diameter here can refer to the nominal value of the filter manufacturer. Examples of commercially available filters include various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), and Kitz Microfilter Co., Ltd. You can choose from. As the second filter, a filter formed of the same material or the like as the first filter can be used. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after the other components are mixed, the filtration with the second filter may be performed.

[Application]
Although the use of the composition of the present invention is not particularly limited, for example, a high refraction member of a solid-state imaging device (a microlens, a base layer of a color filter, a transparent film such as an adjacent layer, a white pixel of a color filter, and the like). , Lenses (eyeglass lenses, digital camera lenses, Fresnel lenses, prism lenses, etc.), optical overcoating agents, hard coating agents, anti-reflection films, optical fibers, optical waveguides, sealing materials for LEDs (Light Emitting Diodes) It is useful as a planarizing material for LEDs and a coating material for solar cells.

<Membrane>
The film of the present invention is a film obtained from the composition of the present invention. When a curable compound (for example, a polymerizable compound) is contained in the composition, a cured film can be obtained by subjecting the composition to a curing treatment.
Although the refractive index of the film is not particularly limited, it is preferably 1.55 or more, more preferably 1.6 to 2.0.
The light transmittance of the film is not particularly limited, but is preferably 90% or more, more preferably 95% or more, even more preferably 100% over the entire wavelength range of 400 to 700 nm.
The thickness of the film is not particularly limited, but is preferably from 0.1 to 20 μm, more preferably from 0.1 to 10 μm, even more preferably from 0.5 to 4 μm.

  The method for curing the composition of the present invention is not particularly limited, and examples thereof include heating and exposure. The apparatus used for heating is not particularly limited, and a blow dryer, an oven, an infrared dryer, a heating drum, 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, and the like can be used.

(Method of manufacturing a patterned cured film)
Hereinafter, a method for producing 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 a step of applying the composition on a substrate to form a composition layer (coating film) (hereinafter, abbreviated as “composition layer forming step” as appropriate). A step of exposing the composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and a step of developing the composition layer after exposure to form a patterned cured film (hereinafter, referred to as “exposure step”). Abbreviated as “development step” as appropriate).
The composition used above usually contains a polymerizable compound and a photopolymerization initiator.

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

-Composition layer forming step In the composition layer forming step, the composition of the present invention is applied on a substrate to form a composition layer (coating film).

  The substrate is not particularly limited, and includes, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for a liquid crystal display device and the like, and a transparent conductive film adhered thereto, a solid-state imaging device For example, a photoelectric conversion element substrate (for example, a silicon substrate or the like), a CCD (Charge Coupled Device) substrate, a CMOS (Complementary Metal Oxide Semiconductor) substrate, or the like is used.

  As a method for applying the composition of the present invention onto a substrate, various application methods such as slit coating, ink jetting, spin coating, casting coating, roll coating, and screen printing can be applied.

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

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

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

Development Step Following the exposure step, an alkali development treatment (development step) is performed to elute the unirradiated portion in the exposure step into an aqueous alkali solution. As a result, only the photocured portion (the portion of the coating film irradiated with light) remains.
As the developing solution, an organic alkali developing solution which does not cause damage to the underlying circuit and the like is desirable. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.

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

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

<Lens>
The film (preferably a cured film) of the present invention can also be used as a lens. As the lens, among others, a microlens of a solid-state imaging device can be suitably used.

<Solid-state imaging device>
The film (preferably a cured film) of the present invention and the lens of the present invention can be suitably applied to a solid-state imaging device.
As a configuration of the solid-state imaging device of the present invention, for example, a plurality of photodiodes constituting a light-receiving area of a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and a light-receiving element made of polysilicon or the like are provided on a substrate. In addition, a configuration in which an undercoat film, which is the film of the present invention, is provided below the color filter can be given.

<Compound>
The invention also includes the invention of compounds. The compound of the present invention is a compound represented by the above general formula (IV).
The compound of the present invention can be suitably used in the composition of the present invention.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

(Synthesis of Compound)
Compounds (A-1) to (A-28) and comparative compound (H-1) were synthesized by the following method.

<Synthesis Example 1: Compound (A-1)>
Compound (A-1) was synthesized according to the following synthesis scheme.

Pyromellitic anhydride (2.8 g) and the high refractive index compound (r-1) (10.0 g) were added to N, N-dimethylacetamide (50 g) and stirred at room temperature. Diisopropylethylamine (4.0 g) was added dropwise to this mixed solution, and the mixture was stirred at room temperature for 5 hours. Further, 1N hydrochloric acid (100 mL) was added dropwise to this mixed solution to precipitate a solid. Next, the precipitated solid was recovered by filtration. The collected solid was washed twice with water (100 mL), and dried by blowing at 40 ° C. to obtain Compound (A-1) (12.0 g).
The compound (A-1) includes isomers of the compound (r-1) having different substitution positions.

<Synthesis Examples 2 to 16, 20 to 24: Compounds (A-2) to (A-16), (A-20) to (A-24)>
In the same manner as in Synthesis Example 1 except that pyromellitic anhydride and high refractive index compound (r-1) in Synthesis Example 1 were replaced with compounds corresponding to the structures of the following compounds, compound (A- 2) to (A-16) and (A-20) to (A-24) were obtained.

  The structures of Compounds (A-1) to (A-16) and (A-20) to (A-24) obtained by Synthesis Examples 1 to 16 are shown below.

The structures of the high refractive index functional groups of the compounds (A-1) to (A-16) and (A-20) to (A-24) are shown below. * Indicates a bonding position.
Compounds in which a hydrogen atom is bonded to a bonding position of the following high refractive index functional groups R _{1 to} R ₉ and R _{11 to} R ₁₅ are high refractive index compounds (r-1) to (r-9) and (r-11) to (R-15).
The structures of the high refractive index functional groups R ₁₀ and R _{16 to} R _{19 of} the compounds (A-17) to (A-19) and (A-25) to (A-28) described below are also shown in the same manner. Compounds having a hydrogen atom bonded to the coupling position of the high refractive index functional groups _{R 10} and _R 16 _{to R 19} are described later high refractive index compound (r-10') and (r-16') ~ (r -19' ).

<Synthesis Example 17: Synthesis of compound (A-17)>
Compound (A-17) was synthesized according to the synthesis scheme shown below.

  Dipentaerythritol hexakis (3-mercaptopropionate) (3.0 g), high refractive index compound (r-10) (10.0 g), triethylamine (1.0 g), and N, N-dimethylacetamide ( 100 g) was prepared and stirred at 50 ° C. for 6 hours. Further, 1N hydrochloric acid (500 g) was added to this mixed solution to precipitate a solid. Next, the precipitated solid was recovered by filtration. The collected solid was washed twice with water (100 mL), and dried by blowing at 40 ° C. to obtain a compound (A-17) (12.1 g).

<Synthesis Example 18: Synthesis of compound (A-18)>
Compound (A-18) was synthesized according to the synthesis scheme shown below.

Dipentaerythritol hexakis (3-mercaptopropionate) (6.0 g), high refractive index compound (r-10) (10.0 g), triethylamine (1.0 g), and N, N-dimethylacetamide ( 100 g) was prepared and stirred at 50 ° C. for 6 hours. Further, 1N hydrochloric acid (500 g) was added to this mixed solution to precipitate a solid. Next, the precipitated solid was recovered by filtration. The collected solid was washed twice with water (100 mL), and dried by blowing air at 40 ° C. to obtain a compound (A-18) (14.9 g).
In addition, the compound (A-18) includes isomers of the compound (r-10) in which the substitution positions are different.

<Synthesis Example 19: Compound (A-19)>
Compound (A-19) was synthesized according to the synthesis scheme shown below.

A mixed solution composed of compound (A-18) (5.0 g), methacrylic acid (3.1 g), and N, N-dimethylacetamide (50 g) was heated to 80 ° C. under a nitrogen stream. Next, azobis (isobutyronitrile) (0.1 g) was added to the mixed solution, and the temperature condition at 80 ° C. was maintained for 2 hours. Further, azobis (isobutyronitrile) (0.1 g) was added to the mixed solution, the temperature was maintained at 80 ° C. for 4 hours, and the mixture was heated at 95 ° C. for 2 hours. Glycidyl methacrylate (1.7 g) and tetrabutylammonium bromide (0.1 g) were added to the mixed solution, and the temperature was maintained at 95 ° C. for 12 hours. After cooling the mixed solution to room temperature, 1N hydrochloric acid (200 mL) was added to precipitate a solid. Next, the precipitated solid was recovered by filtration. The collected solid was washed twice with water (100 mL), and dried by blowing at 40 ° C. to obtain Compound (A-19) (6.6 g).
In addition, the compound (A-19) includes isomers having different substitution positions of the compound (r-10) and the polymer chain P.

<Synthesis Examples 25 to 28: Compounds (A-25) to (A-28)>
Compounds (A-25) to (A-28) having the following structures were synthesized such that the high refractive index functional groups in compound (A-19) were R _{16 to} R ₁₉ , respectively.
In the synthesis, instead of the high refractive index compound (r-10), the high refractive index compounds (r-16) to (r-) corresponding to the structures of the high refractive index functional groups R _{16 to} R ₁₉ , respectively. Synthesis was performed with reference to Synthesis Examples 18 and 19 except that 19) was used.

_{[P] 3 -X- [R 16} ] 3 (A-25)
_{[P] 3 -X- [R 17} ] 3 (A-26)
_{[P] 3 -X- [R 18} ] 3 (A-27)
_{[P] 3 -X- [R 19} ] 3 (A-28)
In the above structural formula, X and P are the same groups as X and P shown in the synthesis scheme of Synthesis Example 19, respectively.

<Measurement of refractive index of high refractive index functional group>
Compound (A-1) ~ as a refractive index measurements (A-28) high refractive index functional group having the _R 1 _{to R 19,} corresponding to a high refractive index functional groups _R 1 _{to R 19,} a high refractive index compound (r -1) to (r-9), (r-10 '), (r-11) to (r-15), and (r-16') to (r-19 ') Measured according to the process. Here, the high-refractive-index compound (r-10') and (r-16') ~ (r -19'), a hydrogen atom bonded to a coupling position of the high refractive index functional groups _{R 10} and _R 16 _{to R 19} This is a compound. Other high refractive index compounds (r-1) to (r-9) and (r-11) to (r-15) also have bonding positions of the high refractive index functional groups R _{1 to} R ₉ and R _{11 to} R ₁₅ . Is a compound in which a hydrogen atom is bonded.

Step 1: An N, N-dimethylacetamide solution containing 10% by mass of poly (allyl methacrylate / methacrylic acid) (mass ratio: 90/10, Mw: 15,000, dispersity: 2.0) Refractive index compounds (r-1) to (r-9), (r-10 '), (r-11) to (r-15), and (r-16') to (r-19 ') Each was dissolved to prepare a solution in which the content of the high refractive index compound with respect to the total solid content was 30% by mass, 50% by mass, or 70% by mass, respectively.
Step 2: The solution prepared in Step 1 was applied to a glass substrate, and the glass substrate was baked at 100 ° C. for 3 minutes, and further baked at 200 ° C. for 3 minutes to obtain a coating film having a thickness of 1 μm. . The refractive index was measured using the obtained coating film.
In the measurement of the refractive index, J. Org. A. The refractive index at a wavelength of 300 to 1500 nm was measured using Woollam VASE, and the value of the refractive index at a wavelength of 589 nm was taken as the refractive index of each coating film.
Step 3: A plot showing the relationship between the content (content ratio) of the high refractive index compound in the coating film and the refractive index of the coating film (horizontal axis: content ratio of high refractive index compound, vertical axis: coating) The refractive index of the film is calculated, and the refractive index of the coating film assumed when the content of the high refractive index compound is assumed to be 100% is obtained by linear approximation, and the refractive index is calculated for each high refractive index compound. And the refractive index of the high refractive index functional group corresponding to.

The following table shows the measurement results of the refractive index of the high refractive index functional groups R _{1 to} R ₁₉ .

<Comparative Synthesis Example 1: Compound (H-1)>
Compound (H-1) was synthesized according to the synthesis scheme shown below.

Cyanuric chloride (15.0 g) and tetrahydrofuran (200 mL) were added to a three-necked flask to prepare a mixed solution. The mixed solution was stirred under a nitrogen stream while the three-necked flask containing the mixed solution was placed in an ice bath obtained by adding ice to methanol. With the ice bath maintained, a solution of aniline (8.2 g) dissolved in tetrahydrofuran (60 mL) was added dropwise to the mixed solution over 1.5 hours, and the mixture was further stirred for 2 hours. 1N hydrochloric acid (200 g) was added to the mixed solution, and the mixture was stirred for 1 hour while maintaining the internal temperature of the mixed solution at 0 to 5 ° C., and then the solid precipitated in the mixed solution was filtered. The obtained solid was washed with water (100 g), and further dried at 60 ° C. for 24 hours using a vacuum drier to obtain Intermediate (h-1) (17.1 g).
A mixture obtained by adding 1,4-diaminobenzene (3.6 g) and N, N-dimethylacetamide (66 mL) to a three-necked flask was stirred at 100 ° C. for 10 minutes. To this mixture, a solution of the intermediate (h-1) (8.8 g) dissolved in N, N-dimethylacetamide (33 mL) was added, and the mixture was stirred at 100 ° C. for 30 minutes. Thereafter, aniline (1.6 mL) was added to the mixture.
Water (660 mL) in which potassium carbonate (12 g) was dissolved was added to the mixture after cooling to precipitate a solid. The precipitated solid was filtered. The obtained solid was washed with water (100 mL), and further washed with ethanol (100 mL). Further, the washed solid was dried using a vacuum dryer at 60 ° C. for 24 hours to obtain a compound (H-1) (8.2 g). The molecular weight of the obtained compound (H-1) was 5,600.

(Preparation of composition)
Using the obtained compounds (A-1) to (A-28) and (H-1), compositions 1 to 33 and a comparative composition were prepared.
The compositions of the obtained compositions 1 to 33 and the comparative composition are shown in Table 2 below.
In addition, in the table, the numerical values described in the column of “addition amount” indicate parts by mass.

  Details of components other than the compounds (A-1) to (A-28) and (H-1) in Table 2 are shown below.

<Polymerizable compound>

<Binder (resin)>

<Photopolymerization initiator>

<Solvent>
DMAc: N, N-dimethylacetamide NEP: N-ethyl-2-pyrrolidone DMF: dimethylformamide

<Surfactant>
Megafac R-40 (manufactured by DIC Corporation)

[Evaluation]
Using the obtained composition, the spectral characteristics, the refractive index, the step followability, the heat resistance, the developability, and the pattern shape were evaluated.

<Evaluation of spectral characteristics>
Compositions 1 to 24 and a comparative composition were spin-coated on a 5 cm × 5 cm glass substrate on which an epoxy resin layer was formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resin Co.), and heated at 100 ° C. Baking (heating) for 3 minutes. Next, the obtained coating film was exposed using a high-pressure mercury lamp so that the integrated exposure amount became 200 mJ / cm ^2, and a film having a film thickness of 1 μm was obtained.
The absorbance at a wavelength of 300 to 800 nm of the glass substrate having the above film was measured using U-4150 (manufactured by Hitachi High-Technologies Corporation). Note that a glass substrate having an epoxy resin layer under the same conditions was used as a reference except that no film was formed.

The criteria for evaluating the spectral characteristics are as follows.
A: The maximum absorption wavelength is less than 450 nm.
B: The maximum absorption wavelength is 450 nm or more.

<Measurement of refractive index>
The film obtained in the evaluation of the above-mentioned spectral characteristics is referred to A. The refractive index at a wavelength of 300 to 1500 nm was measured using Woollam VASE, and the value of the refractive index at a wavelength of 589 nm was determined.

The criteria for the evaluation of the refractive index are as follows.
A: The refractive index is 1.70 or more.
B: The refractive index is 1.60 or more and less than 1.70.
C: The refractive index is less than 1.60.

<Evaluation of step followability>
A plurality of grooves having a depth of 2 μm and a width of 5 μm were provided on the silicon wafer so that the intermediate interval between the grooves was 20 μm. The obtained plurality of grooves is referred to as a simulated uneven pattern. In the subsequent stage, the groove corresponds to the concave portion, and the space between the grooves corresponds to the convex portion.
Each composition was spin-coated on a silicon wafer having the above-described simulated uneven pattern under an application condition under which the film thickness was 1 μm when the film was formed on a silicon wafer having no simulated uneven pattern. The obtained coating film was pre-baked at 100 ° C. for 3 minutes, and further cured by performing an ultraviolet curing treatment (exposure with a high-pressure mercury lamp so that the integrated exposure amount becomes 200 mJ / cm ² ). The cross section of the concavo-convex portion of the obtained silicon wafer with a film was observed by SEM (Scanning Electron Microscope), the film thickness of the thinnest portion of the concave portion was measured, and the step followability was evaluated.
The step followability was evaluated by evaluating the ratio of the difference between the target value of 1 μm and the film thickness X μm of the thinnest portion of the concave portion to the target value of 1 μm. The ratio (%) of the difference corresponds to “| 1−X | × 100”.
The smaller the ratio is, the better the step followability of the composition is.
In the above description, the film thickness at the thinnest portion of the concave portion means the film thickness of the thinnest portion of the film formed in the concave portion.

The criteria for the evaluation of step followability are as follows.
A: The ratio of the difference is less than 5%.
B: The difference ratio is 5% or more and less than 10%.
C: The difference ratio is 10% or more.

<Evaluation of heat resistance>
The sample obtained in the evaluation of the step followability was heated at 260 ° C. for 10 minutes, the change in the film thickness at the convex portion of the film before and after the heat treatment was measured, and the rate of change was calculated. The smaller the rate of change, the better the heat resistance.

The criteria for evaluation of heat resistance are as follows.
A: The rate of change of the film thickness of the projections is less than 1%.
B: The rate of change of the film thickness of the projections is 1% or more and less than 3%.
C: The change rate of the film thickness of the projections is 3% or more and less than 5%.
D: The change rate of the film thickness of the projection is 5% or more.

The results of the evaluation of spectral characteristics, refractive index, step followability, and heat resistance are shown below.
In addition, the column of "R" in the following table shows the type number of the high refractive index functional group which the compounds (A-1) to (A-28) used have. For example, the compounds described as "1" in the column "R", having a high refractive index functional group R _1.
The column of “general formula (II)” indicates the presence or absence of the high refractive index functional group represented by the general formula (II) in the compounds (A-1) to (A-28) used.
The column of “Number of —NH—” indicates that each of the compounds (A-1) to (A-28) used has a high refractive index functional group represented by the general formula (II). group corresponding to _C 1 -C ₃ in the group indicates the number is -NH-.
The column of "polymerizable group of specific compound / thiol group" indicates the presence or absence of a polymerizable group or a thiol group in compounds (A-1) to (A-28) used. If each compound has a polymerizable group, it is described as "C = C", if it has a thiol group, it is described as "SH", and if it does not have any, it is described as "absent" Described.
The column of “polymerizable group of binder” indicates the presence or absence of a polymerizable group in the binder used.
The column of "oxime compound" indicates the presence or absence of a photopolymerization initiator which is an oxime compound in the composition.

As shown in Table 3, it was confirmed that the composition of the present invention was able to form a film having a high refractive index and was excellent in step followability.
In addition, it was confirmed that the film obtained using the composition of the present invention had excellent heat resistance.
Above all, from the comparison between Examples 6 and 10, and the other examples, when the high refractive index functional group is a group represented by the general formula (II), the composition has a film having a higher refractive index. It could be formed and showed better step followability.
Also, from the comparison between Examples 4, 7, and 8, and other Examples, when two or more of C ₁ , C ₂ , and C ₃ in General Formula (II) are —NH—, The composition was able to form a film having a higher refractive index, and showed better step followability.
From the results of Examples 5, 11, 13, 14, 18, 19, and 25 to 33, when the specific compound has a polymerizable group or a thiol group, the formed film has more excellent heat resistance. Was.
From the results of Examples 21 to 24, when the photopolymerization initiator used for the composition was an oxime compound, the heat resistance of the formed film was more excellent.
When the binder had a polymerizable group, the heat resistance of the formed film was more excellent.

<Evaluation of developability and pattern shape>
Compositions 1 and 24 and a comparative composition were spin-coated on a 5 cm × 5 cm glass substrate on which an epoxy resin layer was formed using an epoxy resin (JER-827, manufactured by Japan Epoxy Resin Co.), and heated at 100 ° C. For 3 minutes. Using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the obtained coating film was passed through a mask having an island pattern of 1 μm at a wavelength of 365 nm and a wavelength of 50 to 1200 mJ / cm ² . Exposure amount. Thereafter, the glass substrate having the exposed coating film is placed on a horizontal rotary table of a spin shower developing machine (DW-30, manufactured by Chemitronics), and a developing solution (CD-2000, Fujifilm Electronics Materials) Paddle development at 23 ° C. for 60 seconds.

  After the paddle development, the glass substrate having the pattern formed on the surface is fixed to the horizontal rotary table by a vacuum chuck method, and then rotated at 50 rpm while pure water is supplied from above the rotation center. Rinsing treatment was performed by supplying the mixture in the form of a shower, followed by spray drying.

For the dried pattern, the pattern shape was evaluated using a critical dimension scanning electron microscope (CD-SEM: S-9260A, manufactured by Hitachi High-Technologies Corporation) (SEM: CD-SEM: Critical Dimension Scanning Electron Microscope).
As a result, it was confirmed that when the composition 1 and the composition 24 were used, the unexposed portion was developed better and the pattern was formed more clearly than when the comparative composition was used.
As described above, it was confirmed that a pattern having a good shape can be formed by using the composition of the present invention. Such a composition of the present invention can be suitably used for manufacturing a lens, and the manufactured lens is also preferably used for a solid-state imaging device.

Claims (17)

A composition comprising a compound represented by the general formula (I) and a solvent,
A composition wherein the content of the compound represented by the general formula (I) is 30% by mass or more based on the total solid content in the composition.
(A) _m -X- (B) _n (I)
In the general formula (I),
m represents an integer of 2 or more.
n represents an integer of 0 or more.
A is a group having at least two groups selected from the group consisting of a benzene ring group and a monocyclic heterocyclic group, and having a refractive index at 589 nm of 1.70 or more.
X represents an m + n-valent linking group.
B represents a polymer chain or a substituent.
Note that a plurality of A may be the same or different. When a plurality of Bs exist, the plurality of Bs may be the same or different.   The composition according to claim 1, wherein at least one of A is a group having the monocyclic heterocyclic group.   The composition according to claim 1, wherein at least one of A is a group having a triazine ring group. The composition according to any one of claims 1 to 3, wherein at least one of A is a group represented by the general formula (II).

In General Formula (II), C ₁ , C ₂ , and C ₃ each independently represent —NR _N —, —O—, or —S—. _RN represents a hydrogen atom, an alkyl group, or an aryl group. Ar ₁ and Ar ₂ each independently represent an aryl group or a heterocyclic group which may have a substituent. Ar ₃ represents an arylene group or a divalent heterocyclic group. L _A represents a single bond or a divalent linking group. * Represents a bonding position.
However, at least _one of Ar ₁ , Ar ₂ , and Ar ₃ represents a benzene ring group or a monocyclic heterocyclic group. C _{1, C 2,} and one or more of _{C 3,} is -NH-, A composition according to claim 4. The composition according to claim 4, wherein two or more of C ₁ , C ₂ , and C ₃ are —NH—. The composition according to any one of claims 1 to 6, wherein X is a group represented by the general formula (III).
_{(* A -Z A) m -Y-} (Z B - * B) n Formula (III)
m represents an integer having the same value as m in the general formula (I).
n represents an integer having the same value as n in the general formula (I).
Y represents a group having an aromatic hydrocarbon group, a heterocyclic group, or an aliphatic hydrocarbon group which may have an oxygen atom.
Z _A and Z _B each independently represent a single bond or a divalent linking group. The plurality of Z _A may be the same or different. If Z _B there are a plurality, Z _B where there are a plurality, may each be the same or different.
* _A represents a bonding position with A in the general formula (I).
* _B represents a bonding position with B in the general formula (I).   The composition according to any one of claims 1 to 7, wherein the compound represented by the general formula (I) has an acid group.   The composition according to any one of claims 1 to 8, wherein the compound represented by the general formula (I) has a polymerizable group.   The composition according to any one of claims 1 to 9, further comprising a polymerizable compound.   The composition according to any one of claims 1 to 10, further comprising a photopolymerization initiator.   The composition according to claim 11, wherein the photopolymerization initiator comprises an oxime compound.   The composition according to any one of claims 1 to 12, further comprising a resin having a polymerizable group.   A film formed using the composition according to claim 1.   A lens comprising the film according to claim 14.   A solid-state imaging device comprising the film according to claim 14 or the lens according to claim 15. A compound represented by the general formula (IV).
_{(A T -Z A) m -Y-} (Z B -B) n (IV)
In the general formula (IV),
m represents an integer of 2 or more.
n represents an integer of 0 or more.
_AT is a group having a refractive index at 589 nm of 1.70 or more, and is a group represented by the general formula (II).
B represents a polymer chain or a substituent.
Y is an m + n-valent linking group, and represents a group having an aromatic hydrocarbon group, a heterocyclic group, or an aliphatic hydrocarbon group which may have an oxygen atom.
Z _A and Z _B each independently represent a single bond or a divalent linking group.
Incidentally, A _T there are a plurality, may each be the same or different. When a plurality of Bs exist, the plurality of Bs may be the same or different. A plurality of Z _A may be the same or different. If Z _B there are a plurality, Z _B where there are a plurality, may each be the same or different.

In General Formula (II), C ₁ , C ₂ , and C ₃ each independently represent —NR _N —, —O—, or —S—. _RN represents a hydrogen atom, an alkyl group, or an aryl group. Ar ₁ and Ar ₂ each independently represent an aryl group or a heterocyclic group which may have a substituent. Ar ₃ represents an arylene group or a divalent heterocyclic group. L _A represents a single bond or a divalent linking group. * Represents a bonding position.
However, at least _one of Ar ₁ , Ar ₂ , and Ar ₃ represents a benzene ring group or a monocyclic heterocyclic group.