JP2024035658A - Composition, cured product, display device, and solid-state imaging element - Google Patents

Abstract

To provide a novel composition that has superior curability and can provide a cured product demonstrating a high refractive index.SOLUTION: The present invention relates to a composition including a compound represented by formula (I), and a resin having a refractive index of at least 1.60 at a wavelength of 550 nm. In formula (I), n represents an integer from 0 to 6, L represents a single bond or a divalent group, the plurality of L's may be the same or different, R11 represents a monovalent substituent, if there are a plurality of R11's, then the plurality of R11's may be the same or different, R12 is selected from the group consisting of a hydrogen atom, formula (1a), and formula (1b), and the plurality of R12's may be the same or different.SELECTED DRAWING: None

Description

The present invention relates to compositions. The present invention also relates to a cured product of the composition, a display device including the cured product, and a solid-state imaging device including the cured product.

High refractive materials are desired in the field of optical equipment. Lenses can be obtained from highly refractive materials and can control the optical path within an optical device. Lenses are used in solid-state image sensors to improve the efficiency of light collection to each photoelectric conversion element, and lenses are used in display devices to improve the efficiency of light extraction from pixels. Conventionally, various high refractive materials have been developed (for example, Patent Document 1).

International Publication 2011/102258

One object of the present invention is to provide a new composition that can provide a cured product exhibiting a high refractive index and also has excellent curability. Another object of the present invention is to provide a cured product of the composition, a display device including the cured product, and a solid-state imaging device including the cured product.

［式（Ｉ）中、
ｎは０～６のいずれかの整数を表し、
Ｌは単結合又は２価の基を表し、複数あるＬは同一であっても異なっていてもよく、
Ｒ^１１は１価の置換基を表し、Ｒ^１１が複数ある場合、複数のＲ^１１は同一であっても異なっていてもよく、
Ｒ^１２は、水素原子、式（１ａ）、及び式（１ｂ）からなる群から選択され、複数あるＲ^１２は同一であっても異なっていてもよい。

式（１ａ）中、
ＡはＯ原子またはＳ原子を表し、式（Ｉ）においてＡが複数ある場合、複数のＡは同一であっても異なっていてもよく、
ｍ^ａは０又は１を表し、式（Ｉ）においてｍ^ａが複数ある場合、複数のｍ^ａは同一であっても異なっていてもよく、
Ｒ^２は、水素原子又は１価の置換基を表し、Ｒ^２が複数ある場合、複数のＲ^２は同一であっても異なっていてもよく、
＊はＬとの結合手を表す。
式（１ｂ）中、
Ｒ^１３は１価の置換基を表し、Ｒ^１３が複数ある場合、複数のＲ^１３は同一であっても異なっていてもよく、
＊はＬとの結合手を表す。］
〔２〕 前記樹脂は、（メタ）アクリロイル基、メルカプト基、炭素数２～４の環状エーテル基、及び炭素数２～４の環状スルフィド基からなる群より選ばれる一つの重合性基を含む、〔１〕に記載の組成物。
〔３〕 前記樹脂が式（Ａ）で表される樹脂である、〔１〕又は〔２〕に記載の組成物。

［式（Ａ）中、
Ｒは１価の炭化水素基を表し、Ｒが複数ある場合、複数のＲは同一であっても異なっていてもよく、
ｎは平均値で１以上の数を表し、
ＡはＯ原子又はＳ原子を表し、複数あるＡは同一であっても異なっていてもよい。］
〔４〕 さらに重合開始剤を含む、〔１〕～〔３〕のいずれか１項に記載の組成物。
〔５〕 式（Ｉ）で表される化合物は、式（Ｉ）中に複数あるＲ^１２が式（１ａ）で表される化合物を含む、〔１〕～〔４〕のいずれか１項に記載の組成物。
〔６〕 〔１〕～〔５〕のいずれか１項に記載の組成物の硬化物。
〔７〕 〔６〕に記載の硬化物を含む表示装置。
〔８〕 〔６〕に記載の硬化物を含む固体撮像素子。 The present invention includes the following.
[1] A composition containing a compound represented by formula (I) and a resin having a refractive index of 1.60 or more at a wavelength of 550 nm.

[In formula (I),
n represents any integer from 0 to 6,
L represents a single bond or a divalent group, and multiple Ls may be the same or different,
R ¹¹ represents a monovalent substituent, and when there are multiple R ^11s , the multiple R ^11s may be the same or different,
R ¹² is selected from the group consisting of a hydrogen atom, formula (1a), and formula (1b), and a plurality of R ^12s may be the same or different.

In formula (1a),
A represents an O atom or an S atom, and when there are multiple A's in formula (I), the multiple A's may be the same or different,
m ^a represents 0 or 1, and when there is a plurality of m ^a in formula (I), the plural m ^a may be the same or different,
R ² represents a hydrogen atom or a monovalent substituent, and when there is a plurality of R ² , the plurality of R ² may be the same or different,
* represents a bond with L.
In formula (1b),
R ¹³ represents a monovalent substituent, and when there are multiple R ^13s , the multiple R ^13s may be the same or different,
* represents a bond with L. ]
[2] The resin contains one polymerizable group selected from the group consisting of a (meth)acryloyl group, a mercapto group, a cyclic ether group having 2 to 4 carbon atoms, and a cyclic sulfide group having 2 to 4 carbon atoms. The composition according to [1].
[3] The composition according to [1] or [2], wherein the resin is a resin represented by formula (A).

[In formula (A),
R represents a monovalent hydrocarbon group, and when there are multiple R's, the multiple R's may be the same or different,
n represents an average value of 1 or more,
A represents an O atom or an S atom, and multiple A's may be the same or different. ]
[4] The composition according to any one of [1] to [3], further comprising a polymerization initiator.
[5] The compound represented by formula (I) is a compound represented by any one of [1] to [4], including a compound in which multiple R ^12s in formula (I) are represented by formula (1a). Compositions as described.
[6] A cured product of the composition according to any one of [1] to [5].
[7] A display device comprising the cured product according to [6].
[8] A solid-state imaging device comprising the cured product according to [6].

It is possible to provide a new composition that can provide a cured product that exhibits a high refractive index and also has excellent curability. Further, it is possible to provide a cured product of the composition, a display device including the cured product, and a solid-state imaging device including the cured product.

<Composition>
The composition according to the present invention (hereinafter also referred to as "composition (I)") has a refractive index of 1 at a wavelength of 550 nm with a compound represented by formula (I) (hereinafter also referred to as "compound (I)"). .60 or higher (hereinafter also referred to as "resin (I)"). By containing the compound (I) and the resin (I), the composition (I) can provide a cured product exhibiting a high refractive index, and can also exhibit excellent curability. Composition (I) may contain two or more types of compound (I). Composition (I) may contain two or more types of resin (I). Composition (I) may contain compound (I), resin (I), and other components other than these. By curing composition (I), a molded article containing a cured product of composition (I) can be formed. The molded product containing the cured product is a product containing the cured product and molded into a desired shape.

［式（Ｉ）中、
ｎは０～６のいずれかの整数を表し、
Ｌは単結合又は２価の基を表し、複数あるＬは同一であっても異なっていてもよく、
Ｒ^１１は１価の置換基を表し、Ｒ^１１が複数ある場合、複数のＲ^１１は同一であっても異なっていてもよく、
Ｒ^１２は、水素原子、式（１ａ）、及び式（１ｂ）からなる群から選択され、複数あるＲ^１２は同一であっても異なっていてもよい。

式（１ａ）中、
ＡはＯ原子またはＳ原子を表し、式（Ｉ）においてＡが複数ある場合、複数のＡは同一であっても異なっていてもよく、
ｍ^ａは０又は１を表し、式（Ｉ）においてｍ^ａが複数ある場合、複数のｍ^ａは同一であっても異なっていてもよく、
Ｒ^２は、水素原子又は１価の置換基を表し、Ｒ^２が複数ある場合、複数のＲ^２は同一であっても異なっていてもよく、
＊はＬとの結合手を表す。
式（１ｂ）中、
Ｒ^１３は１価の置換基を表し、Ｒ^１３が複数ある場合、複数のＲ^１３は同一であっても異なっていてもよく、
＊はＬとの結合手を表す。］ <Compound (I)>
Compound (I) is a compound represented by formula (I).

[In formula (I),
n represents any integer from 0 to 6,
L represents a single bond or a divalent group, and multiple Ls may be the same or different,
R ¹¹ represents a monovalent substituent, and when there are multiple R ^11s , the multiple R ^11s may be the same or different,
R ¹² is selected from the group consisting of a hydrogen atom, formula (1a), and formula (1b), and a plurality of R ^12s may be the same or different.

In formula (1a),
A represents an O atom or an S atom, and when there are multiple A's in formula (I), the multiple A's may be the same or different,
m ^a represents 0 or 1, and when there is a plurality of m ^a in formula (I), the plural m ^a may be the same or different,
R ² represents a hydrogen atom or a monovalent substituent, and when there is a plurality of R ² , the plurality of R ² may be the same or different,
* represents a bond with L.
In formula (1b),
R ¹³ represents a monovalent substituent, and when there are multiple R ^13s , the multiple R ^13s may be the same or different,
* represents a bond with L. ]

がいずれもナフタレン環の１～４位の任意の位置、もしくは５～８位の任意の位置に結合していてもよく、また、一方の基がナフタレン環の１～４位の任意の位置に結合して、かつ他方の基がナフタレン環の５～８位の任意の位置に結合していてもよいことを表す。２つのＲ^１１についても同様である。 Formula (I) is a group represented by the two following formulas

may be bonded to any of the 1st to 4th positions of the naphthalene ring, or any of the 5th to 8th positions, and one group may be bonded to any of the 1st to 4th positions of the naphthalene ring. represents that the other group may be bonded to any position from the 5th to 8th positions of the naphthalene ring. The same applies to the two R ^11s .

L represents a single bond or a divalent group. The two L's representing a divalent group each independently include, for example, a divalent aliphatic chain hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, A divalent hydrocarbon group such as an alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group which may have a substituent, and a divalent group consisting of a combination thereof (aralkylene group, etc.) Can be mentioned. -CH ₂ - contained in the divalent hydrocarbon group is -O-, -S-, -NR ^1A - (R ^1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, It may be substituted with -SO ₂ -.

Examples of the divalent aliphatic chain hydrocarbon group include saturated or unsaturated aliphatic chain hydrocarbon groups, and specifically, methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, etc. group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, decanediyl group, undecanediyl group, dodecanediyl group, tridecanediyl group, tetradecanediyl group, pentadecanediyl group, hexadecanediyl group, heptadecanediyl group, octadecanediyl group group, alkanediyl groups such as nonadecanediyl group, eicosandiyl group, and the like. The divalent aliphatic chain hydrocarbon group may be linear or branched. The number of carbon atoms in the divalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, even more preferably 1 or 2. be.

Examples of substituents that the divalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, hydroxy group, amino group, acetyl group, and cyano group. Examples include groups.

Examples of the divalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups, specifically cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group. monocyclic alicyclic hydrocarbon groups such as group, cyclooctanediyl group, cyclononanediyl group, cyclodecanediyl group; bicyclo[1.1.0]butanediyl group, tricyclo[2.2.1.0]heptanediyl group group, bicyclo[3.2.1]octanediyl group, bicyclo[2.2.2. ] Polycyclic alicyclic hydrocarbon groups such as an octanediyl group, an adamantanediyl group, a bicyclo[4.3.2]undecanediyl group, and a tricyclo[5.3.1.1]dodecanediyl group. The divalent alicyclic hydrocarbon group usually has 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and still more preferably 5 or 6 carbon atoms.

Examples of substituents that the divalent alicyclic hydrocarbon group may have include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as decyl groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, hydroxy groups, amino groups, acetyl groups, cyano Examples include groups.

The divalent aromatic hydrocarbon group may be monocyclic or polycyclic, and includes, for example, a phenylene group, a naphthylene group, an anthracenediyl group, a fluorenediyl group, and the like. The divalent aromatic hydrocarbon group usually has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms.

Examples of substituents that the divalent aromatic hydrocarbon group may have include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. Alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, hydroxy groups, amino groups, acetyl groups, cyano groups etc.

For example, at least one of the two L's is a single bond or an alkanediyl group, and more preferably both are a single bond or an alkanediyl group. In this case, the alkanediyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms.

The two n's are each independently an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1. More preferably, both n's are 0.

As R ¹¹ representing a monovalent substituent, when there is a plurality of R ¹¹ , each independently represents, for example, a monovalent aliphatic chain hydrocarbon group which may have a substituent, a monovalent aliphatic chain hydrocarbon group which may have a substituent, monovalent alicyclic hydrocarbon groups which may have substituents, monovalent aromatic hydrocarbon groups which may have substituents, monovalent groups consisting of combinations thereof (aralkyl groups, etc.), etc. Monovalent hydrocarbon group; hydroxy group; substituted with one or two alkyl groups having 1 to 6 carbon atoms such as amino group, monomethylamino group, monoethylamino group, dimethylamino group, diethylamino group, methylethylamino group, etc. Amino groups that may be substituted; pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, oxazolinyl group, thiazolyl group, piperidinyl group, morpholinyl group, piperazinyl group, indolyl group, isoindolyl group, quinolyl group, thienyl group, pyrrolyl group, and heterocyclic groups such as aliphatic heterocyclic groups having 4 to 20 carbon atoms such as furyl group or aromatic heterocyclic groups having 3 to 20 carbon atoms; halogen atom; nitro group; cyano group; carboxy group; sulfo group; thiol group; formyl group; -SF ₃ group; -SF ₅ group. -CH ₂ - contained in the monovalent hydrocarbon group is -O-, -S-, -NR ^1B - (R ^1B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, It may be substituted with -SO ₂ -. In addition, examples of groups in which -CH ₂ - contained in the monovalent hydrocarbon group are substituted with -O- include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group. and alkoxy groups having 1 to 12 carbon atoms such as octyloxy groups; alkoxyalkyl groups such as methoxymethyl groups, ethoxymethyl groups, and methoxyethyl groups.

Examples of the monovalent aliphatic chain hydrocarbon group include saturated or unsaturated aliphatic chain hydrocarbon groups, and specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group. , alkyl groups such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. can be mentioned. The monovalent aliphatic chain hydrocarbon group may be linear or branched. The number of carbon atoms in the monovalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, even more preferably 1 or 2. be.

Examples of substituents that the monovalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, hydroxy group, amino group, acetyl group, and cyano group. Examples include groups.

Examples of the monovalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups, specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group. , cyclononyl group, monocyclic alicyclic hydrocarbon group such as cyclodecyl group; bicyclo[1.1.0]butyl group, tricyclo[2.2.1.0]heptyl group, bicyclo[3.2.1] Octyl group, bicyclo [2.2.2. ] Polycyclic alicyclic hydrocarbon groups such as an octyl group, an adamantyl group, a bicyclo[4.3.2]undecyl group, and a tricyclo[5.3.1.1]dodecyl group. The monovalent alicyclic hydrocarbon group usually has 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 5 or 6 carbon atoms.

Examples of substituents that the monovalent alicyclic hydrocarbon group may have include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as decyl groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, hydroxy groups, amino groups, acetyl groups, cyano Examples include groups.

The monovalent aromatic hydrocarbon group may be monocyclic or polycyclic, and includes, for example, a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and the like. The monovalent aromatic hydrocarbon group usually has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms.

Examples of the substituents that the monovalent aromatic hydrocarbon group may have include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as decyl groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, hydroxy groups, amino groups, acetyl groups, cyano Examples include groups.

R ¹² is selected from the group consisting of a hydrogen atom, formula (1a), and formula (1b), and a plurality of R ^12s may be the same or different. Preferably, compound (I) includes a curable compound (I).

Examples of compounds in which multiple R ^12s in formula (I) are represented by hydrogen atoms include compounds represented by formula (IB).

Examples of compounds in which multiple R ^12s in formula (I) are represented by formula (1b) include compounds represented by formula (IC).

In the case of a compound in which a plurality of R ¹² in formula (I) are represented by formula (1a), L to which R ¹² is connected is preferably an alkanediyl group. Compound (I) preferably includes a compound in which multiple R ^12s in formula (I) are represented by formula (1a).

In formula (1a), two m ^a are each independently 0 or 1, preferably 0. More preferably, both m ^a are 0.

In formula (1a), R ² represents a hydrogen atom or a monovalent substituent, and a plurality of R ² may be the same or different, preferably the same. Specific examples of the monovalent substituent include the same as R ¹¹ . The two R ² 's are each independently preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group, more preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms. It is a hydrocarbon group, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group. .

式（ＩＡ）中、Ｌ、Ｒ^１１、Ｒ^２、Ａ、ｎ、ｍ^ａは、前記と同じ意味である。式（ＩＡ）で表される化合物として、以下の化合物が例示される。

A compound in which multiple R ^12s in formula (I) are represented by formula (1a) is represented by formula (IA) below.

In formula (IA), L, R ¹¹ , R ² , A, n, and m ^a have the same meanings as above. The following compounds are exemplified as the compound represented by formula (IA).

Formula (Ia-1), Formula (Ia-2), Formula (Ib-1), Formula (Ib-2), Formula (Ic-1), Formula (Ic-2), Formula (Id-1), Formula (Id-2), formula (Ie-1), and formula (Ie-2), preferably at least one of the two L is an alkanediyl group, more preferably both are an alkanediyl group. It is. In this case, the alkanediyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms.

Formula (Ia-1), Formula (Ia-2), Formula (Ib-1), Formula (Ib-2), Formula (Ic-1), Formula (Ic-2), Formula (Id-1), Formula (Id-2), formula (Ie-1), and formula (Ie-2), the two m ^a 's are each independently 0 or 1, preferably 0. More preferably, both m ^a are 0.
The two n's are each independently an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1. More preferably, both n's are 0.

Formula (Ia-1), Formula (Ia-2), Formula (Ib-1), Formula (Ib-2), Formula (Ic-1), Formula (Ic-2), Formula (Id-1), Formula (Id-2), formula (Ie-1), and formula (Ie-2), the two R ² are each independently preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group. More preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms, still more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably, A hydrogen atom, a methyl group or an ethyl group. Two R ² are preferably the same.

Specific examples of the compound represented by formula (IA) are illustrated below, but the invention is not limited thereto.

From the viewpoint of synthesis, the molecular weight of compound (I) is preferably 2000 or less, more preferably 1000 or less, even more preferably 500 or less. Further, from the viewpoint of volatility, the molecular weight is preferably 50 or more, more preferably 100 or more, and still more preferably 150 or more.

The content of compound (I) in composition (I) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 5% by mass, based on the total solid content of composition (I). The content is preferably 99% by mass or less, more preferably 95% by mass or less, and may be 90% by mass or less or 80% by mass or less.

The total solid content of composition (I) means the total of the components contained in composition (I) excluding the solvent. The content of each component in the solid content of the composition can be measured by known analytical means such as liquid chromatography or gas chromatography. The content of each component in the solid content of composition (I) may be calculated from the formulation at the time of preparing the composition.

［式（ＩＩ）中、ｎ及びＲ^１１は前記と同じ意味を表す。］
で表される化合物と、式（ＩＩＩ）

［式（ＩＩＩ）中、Ｒ^２、Ｌ及びｍ^ａは前記と同じ意味を表し、Ｘは脱離基を表す。］
で表される化合物とを反応させることにより、式（１ａ）中のＡがＯ原子である式（Ｉ）で表される化合物を得る工程；
第２工程：式（１ａ）中のＡがＯ原子である式（Ｉ）で表される化合物と硫化剤との反応により、式（１ａ）中のＡがＳ原子である式（Ｉ）で表される化合物を得る工程 <Method for producing compound (I)>
Compound (I) in which R ¹² is a group represented by formula (1a) can be produced by a method including the first step or the first step and the second step shown below.
First step: Formula (II)

[In formula (II), n and R ¹¹ represent the same meanings as above. ]
A compound represented by and formula (III)

[In formula (III), R ² , L and m ^a have the same meanings as above, and X represents a leaving group. ]
A step of obtaining a compound represented by formula (I) in which A in formula (1a) is an O atom by reacting with a compound represented by;
2nd step: By the reaction of the compound represented by formula (I) in which A in formula (1a) is an O atom and a sulfiding agent, the compound represented by formula (I) in which A in formula (1a) is an S atom is formed. Steps for obtaining the represented compound

Reaction of the compound represented by formula (II) (hereinafter also referred to as "compound (II)") and the compound represented by formula (III) (hereinafter also referred to as "compound (III)") in the first step can be carried out, for example, in the presence of a base. Two or more types of bases may be used in combination. As the base, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium hydride, lithium aluminum hydride, sodium borohydride, sodium hydrogen carbonate, Inorganic bases such as potassium bicarbonate, lithium bicarbonate, cesium bicarbonate; sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium t-butoxide , metal alkoxides such as potassium t-butoxide; ammonia, methylamine, dimethylamine, trimethylamine, triethylamine, diisopropylethylamine, triisopropylamine, DBU, DABCO, pyridine, 2,6-dimethylpyridine, 2,6-di-t-butyl Examples include organic bases such as pyridine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and tetramethylammonium chloride. The amount of the base used is, for example, 0.01 to 10 mol, preferably 0.5 to 5 mol, per 1 mol of compound (II).

In formula (III), the leaving group represented by X includes halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; Alkylsulfonyl groups such as fluoromethylsulfonyl group, perfluoroethylsulfonyl group, perfluoropropylsulfonyl group, perfluorobutylsulfonyl group; phenylsulfonyl group, p-toluenesulfonyl group, p-fluorophenylsulfonyl group, pentafluorophenylsulfonyl group Examples include arylsulfonyl groups such as. An example of compound (III) is an epihalohydrin compound (a compound in which X is a halogen atom, L is a methylene group, and m ^a is 0). The amount of compound (III) used is, for example, 0.01 to 20 mol, preferably 0.5 to 15 mol, per 1 mol of compound (II). The first step may be carried out using two or more types of compound (III).

The reaction between compound (II) and compound (III) is preferably carried out in a solvent. In addition to water, solvents include ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glymes, and esters. , aliphatic nitriles, sulfoxides, amides, and other organic solvents. Two or more types of solvents may be used in combination. Specific examples of the organic solvent include the following solvents.

Ketones: acetone, methyl ethyl ketone, diethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, etc. Aromatic hydrocarbons: benzene, toluene, xylene , mesitylene, naphthalene, anisole, nitrobenzene, aniline, tetralin, durene, etc. Halogenated aromatic hydrocarbons: chlorobenzene, dichlorobenzene, chloronaphthalene, etc. Aliphatic hydrocarbons: pentane, hexane, heptane, etc. Halogenated aliphatic hydrocarbons: dichloromethane , chloroform, 1,2-dichloroethane, tetrachloroethane, etc. Ethers: diethyl ether, diisopropyl ether, methyl t-butyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, dioxane, etc. Alcohols: methanol, ethanol, propanol, isopropanol, butanol, t-Butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, hexafluoroisopropanol, etc. Glyme: methyl diglyme, ethyl diglyme, triglyme, diethylene glycol butyl methyl ether, etc. Esters: methyl acetate, ethyl acetate, propyl acetate, acetic acid Butyl, etc. Aliphatic nitriles: acetonitrile, etc. Sulfoxides: dimethyl sulfoxide, sulfolane, etc. Amides: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

The temperature of the reaction between compound (II) and compound (III) is, for example, -80 to 200°C, preferably 0 to 150°C. The compound represented by formula (I) in which A in formula (1a) is an O atom obtained by the reaction may be isolated or may be subjected to the second step without being isolated. .

The reaction carried out in the second step involves replacing the oxygen atom of the epoxy group or oxetanyl group of the compound represented by formula (I) in which A in formula (1a) is an O atom with a sulfur atom using a sulfurizing agent. , a reaction that forms a thiirane group (episulfide group) or a thietane group. Examples of the sulfurizing agent include thiourea, methylthiourea, dimethylthiourea, trimethylthiourea, tetramethylthiourea, tetraethylthiourea, ethylenethiourea, sodium thiocyanate, potassium thiocyanate, and the like. The amount of the sulfurizing agent used is, for example, 0.01 to 20 mol, preferably 0.01 to 20 mol, per 1 mol of the compound represented by formula (I) in which A in formula (1a) is an O atom. The amount is 5 to 10 moles.

The reaction between the compound represented by formula (I) in which A in formula (1a) is an O atom and the sulfurizing agent is preferably carried out in a solvent. As the solvent, the organic solvents exemplified above can be used. Two or more types of organic solvents may be used in combination. The temperature of the reaction of the compound represented by formula (I) in which A in formula (1a) is an O atom with a sulfurizing agent is, for example, -80 to 200°C, preferably 0 to 100°C.

In the second step, a polymerization inhibitor may be added in order to suppress the polymerization of the produced compound represented by formula (I) in which A is an S atom. Examples of the polymerization inhibitor include acids, acid anhydrides, and the like. Specifically, nitric acid, hydrochloric acid, perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, fuming sulfuric acid, sulfuryl chloride, boric acid, arsenic acid, arsenous acid, pyroarsenic acid, phosphoric acid, phosphorous acid, Hypophosphorous acid, phosphorus oxychloride, phosphorus oxybromide, phosphorus sulfide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrocyanic acid, chromic acid, nitric anhydride, sulfuric anhydride, boron oxide, arsenic pentoxide, Inorganic acidic compounds such as phosphorous oxide, chromic anhydride, silica gel, silica alumina, aluminum chloride, zinc chloride, formic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid, valeric acid, caprone Acid, caprylic acid, naphthenic acid, methylmercaptopropionate, malonic acid, glutaric acid, adipic acid, cyclohexanecarboxylic acid, thiodipropionic acid, dithiodipropionic acid acetic acid, maleic acid, benzoic acid, phenylacetic acid, o-toluyl Acid, m-toluic acid, p-toluic acid, salicylic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, benzylic acid, α-naphthalenecarboxylic acid, Organic carboxylates such as β-naphthalenecarboxylic acid, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, trifluoroacetic anhydride, etc. Acids, phosphoric acids such as mono, di and trimethyl phosphate, mono, di and triethyl phosphate, mono, di and triisobutyl phosphate, mono, di and tributyl phosphate, mono, di and trilauryl phosphate and these phosphate moieties are phosphites. phosphorous acids, organic phosphorus compounds such as dialkyldithiophosphoric acids represented by dimethyldithiophosphoric acid, phenol, catechol, t-butylcatechol, 2,6-di-t-butylcresol, 2,6-di-t -Butylethylphenol, resorcinol, hydroquinone, phloroglucin, pyrogallol, cresol, ethylphenol, butylphenol, nonylphenol, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetamide, methyl hydroxyphenylacetate, ethyl hydroxyphenylacetate, hydroxyphenethyl alcohol, Hydroxyphenethylamine, hydroxybenzaldehyde, phenylphenol, bisphenol-A, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), bisphenol-F, bisphenol-S, α-naphthol, β-naphthol, amino Phenols such as phenol, chlorophenol, 2,4,6-trichlorophenol, methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, p-Toluenesulfonic acid, ethylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, p-phenolsulfonic acid, o-cresolsulfonic acid, metanilic acid, sulfanilic acid, 4B-acid, diaminostilbenzenesulfonic acid, biphenylsulfonic acid , α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, peric acid, laurentic acid, phenyl J acid, and other sulfonic acids, and it is also possible to use a plurality of them in combination. The amount of the polymerization inhibitor used is, for example, 0.0001 to 1.0 mol, preferably 0.0001 to 1.0 mol, per 1 mol of the compound represented by formula (I) in which A in formula (1a) is an O atom. is 0.01 to 0.2 mol. As the polymerization inhibitor, acetic acid, acetic anhydride, maleic acid, and maleic anhydride are preferred.

In the second step, the product solution after the reaction is washed with an acidic aqueous solution to improve the stability over time of the compound represented by formula (I) in which A in formula (1a) is an S atom. Can be done. Specific examples of acids used in the acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, peracetic acid, thioacetic acid, oxalic acid, Examples include tartaric acid, succinic acid, and maleic acid. These may be used alone or in combination of two or more. Aqueous solutions of these acids are usually effective at a pH of 6 or less, but are more effective at a pH of 3 or less. Preferred are hydrochloric acid and sulfuric acid.

Furthermore, in the second step, a hydrogen sulfide adsorbent can also be used to improve the stability of the compound represented by formula (I) in which A in formula (1a) is an S atom. Examples of hydrogen sulfide adsorbents include iron (III) hydroxide, zinc oxide, KNK-301 (zinc oxide-based adsorbent, manufactured by Kureha Yushi Kogyo), Nionon 202A (iron oxide-based adsorbent, manufactured by Ibuki Tadashi Co., Ltd.), Examples include Rimonic (iron hydroxide type, manufactured by Nippon Rimonic). The hydrogen sulfide adsorbent may be added during the second step reaction, or may be used in purification after the reaction.

<Resin (I)>
Resin (I) has a refractive index of 1.60 or more at a wavelength of 550 nm, and is not particularly limited as long as it is other than compound (I). Resin (I) may have a refractive index of 1.60 or more, 1.62 or more, 1.65 or more, or 1.67 or more at a wavelength of 550 nm. The refractive index at a wavelength of 550 nm is, for example, 1.80 or less, and may be 1.78 or less.

As the resin (I), at least one monomer (hereinafter referred to as "monomeric Examples include resins having a structural unit derived from the resin (hereinafter sometimes referred to as "resin (B)").

The resin (I) may contain one polymerizable group selected from the group consisting of a (meth)acryloyl group, a mercapto group, a cyclic ether group having 2 to 4 carbon atoms, and a cyclic sulfide group having 2 to 4 carbon atoms. preferable. By using such a resin, excellent curability can be exhibited. The resin (I) preferably contains one polymerizable group selected from the group consisting of a mercapto group, a cyclic ether group having 2 to 4 carbon atoms, and a cyclic sulfide group having 2 to 4 carbon atoms. This is because by using such a resin, it becomes easy to obtain resin (I) having a refractive index of 1.60 or more at a wavelength of 550 nm. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. Examples of the cyclic sulfide group include a thiirane group and a thietane group.

Novolak resin is a resin obtained by condensing a phenol compound and an aldehyde in the presence of a catalyst. Examples of phenolic compounds include phenol; o-cresol, m-cresol, or p-cresol; 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, or 3,5-xylenol; - Trimethylphenol; 2-tert-butylphenol, 3-tert-butylphenol or 4-tert-butylphenol; 2-tert-butyl-4-methylphenol- or 2-tert-butyl-5-methylphenol; 2-dimethoxyphenol, 4 -dimethoxyphenol or 5-methylresorcinol; 2-methoxyphenol, 3-methoxyphenol or 4-methoxyphenol; 2,3-dimethoxyphenol, 2,5-dimethoxyphenol- or 3,5-dimethoxyphenol; 2-methoxyresorcinol; 4-tert-butylcatechol; 2-ethylphenol, 3-ethylphenol or 4-ethylphenol; 2,5-diethylphenol or 3,5-diethylphenol; 2,3,5-triethylphenol; 2-naphthol; 1 , 3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, or 1,7-dihydroxynaphthalene; and polyhydroxytriphenylmethane compounds obtained by condensation of xylenol and hydroxybenzaldehyde. Two or more of these phenol compounds may be used in combination. Among them, phenolic compounds include o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5- Trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol, and 2-tert-butyl-5-methylphenol are preferred.

Examples of aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, acrolein, or crotonaldehyde; alicyclic aldehydes such as cyclohexanaldehyde, cyclopentanaldehyde, furfural, or furyl acrolein; benzaldehyde; , o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4- or 3,5-dimethylbenzaldehyde, o-hydroxybenzaldehyde, m- Aromatic aldehydes such as hydroxybenzaldehyde or p-hydroxybenzaldehyde; araliphatic aldehydes such as phenylacetaldehyde or cinnamic aldehyde. Two or more of these aldehydes may also be used in combination. Among these aldehydes, formaldehyde is preferred because it is industrially easily available.

Examples of catalysts used for the condensation of phenolic compounds and aldehydes include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid or phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid or p-toluenesulfonic acid; acetic acid. Examples include divalent metal salts such as zinc, zinc chloride, and magnesium acetate. Two or more of these catalysts may be used in combination. The amount of such catalyst used is usually 0.01 to 1 mol per 1 mol of aldehyde.

The condensation reaction between the phenol compound and the aldehyde can be carried out, for example, by mixing the phenol compound and the aldehyde and then reacting the mixture at a temperature of 60 to 120° C. for 2 to 30 hours. The condensation reaction may be performed in the presence of a solvent. Examples of the solvent in the condensation reaction include methyl ethyl ketone, methyl isobutyl ketone, and acetone. After completion of the reaction, the novolac resin can be taken out by, for example, adding a water-insoluble solvent to the reaction mixture as needed, washing the reaction mixture with water, and then concentrating it.

The weight average molecular weight of the novolak resin is usually 3,000 to 50,000, preferably 4,000 to 40,000, more preferably 5,000 to 30,000. When the weight average molecular weight of the novolac resin is within the above range, it is possible to effectively prevent formation of a thin film and the remaining of residue after development.

The resin having polymerized units derived from hydroxystyrene is typically polyvinylphenol, preferably polyp-vinylphenol.

［式（Ａ）中、
Ｒは１価の炭化水素基を表し、Ｒが複数ある場合、複数のＲは同一であっても異なっていてもよく、
ｎは平均値で１以上の数を表し、
ＡはＯ原子又はＳ原子を表し、複数あるＡは同一であっても異なっていてもよい。］ When the resin (I) is a novolac resin, a preferable example is a resin represented by the formula (A) (hereinafter also referred to as "resin (A)").The resin (A) has a high refractive index. It is possible to provide a cured product that exhibits excellent curability.

[In formula (A),
R represents a monovalent hydrocarbon group, and when there are multiple R's, the multiple R's may be the same or different,
n represents an average value of 1 or more,
A represents an O atom or an S atom, and multiple A's may be the same or different. ]

Formula (A) represents that the group containing the A atom may be present at any position from the 1st to 8th positions of the naphthalene ring. Furthermore, the group R can be present at any position from 2 to 6 on the benzene ring.

As R representing a monovalent hydrocarbon group, when there are multiple R's, each independently includes, for example, a monovalent aliphatic chain hydrocarbon group that may have a substituent, a monovalent aliphatic chain hydrocarbon group that may have a substituent, A monovalent alicyclic hydrocarbon group which may have a substituent, a monovalent aromatic hydrocarbon group which may have a substituent, and a monovalent group consisting of a combination thereof (aralkyl group, etc.). valent hydrocarbon groups. -CH ₂ - contained in the monovalent hydrocarbon group is -O-, -S-, -NR ^1A - (R ^1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, It may be substituted with -SO ₂ -.

Examples of the monovalent aliphatic chain hydrocarbon group include saturated or unsaturated aliphatic chain hydrocarbon groups, and specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group. , alkyl groups such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. can be mentioned. The monovalent aliphatic chain hydrocarbon group may be linear or branched. The number of carbon atoms in the monovalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, even more preferably 1 or 2. be.

Examples of substituents that the monovalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, hydroxy group, amino group, acetyl group, and cyano group. Examples include groups.

Examples of the monovalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups, specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group. , cyclononyl group, monocyclic alicyclic hydrocarbon group such as cyclodecyl group; bicyclo[1.1.0]butyl group, tricyclo[2.2.1.0]heptyl group, bicyclo[3.2.1] Octyl group, bicyclo [2.2.2. ] Polycyclic alicyclic hydrocarbon groups such as an octyl group, an adamantyl group, a bicyclo[4.3.2]undecyl group, and a tricyclo[5.3.1.1]dodecyl group. The monovalent alicyclic hydrocarbon group usually has 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 5 or 6 carbon atoms.

Examples of substituents that the monovalent alicyclic hydrocarbon group may have include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as decyl groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, hydroxy groups, amino groups, acetyl groups, cyano Examples include groups.

The monovalent aromatic hydrocarbon group may be monocyclic or polycyclic, and includes, for example, a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and the like. The monovalent aromatic hydrocarbon group usually has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms.

Examples of the substituents that the monovalent aromatic hydrocarbon group may have include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as decyl groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, hydroxy groups, amino groups, acetyl groups, cyano Examples include groups.

R is preferably a monovalent aliphatic chain hydrocarbon group that may have a substituent, more preferably an alkyl group that may have a substituent, and still more preferably, It is an alkyl group having 1 to 6 carbon atoms, even more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

R may be present at any position from 2 to 6 of the benzene ring, but is preferably present at the para position to the group containing the A atom.

n represents an average value of 1 or more. Here, the resin (A) may be one type of resin represented by the formula (A), or a mixture of two or more types of resins represented by the formula (A). The above "average value" means the value of n (an integer of 1 or more) that the resin has when the resin (A) is a type of resin represented by the formula (A), and When it is a mixture of two or more resins represented by (A), it is the average value of n values of the two or more resins. When resin (A) is one type of resin represented by formula (A), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5. . When the resin (A) is a mixture of two or more resins represented by formula (A), n is an average value, preferably in the range of 1 to 10, more preferably in the range of 1 to 5. It is within. Note that the two or more types of resins may have the same value of n but differ in other configurations.

A represents an O atom or an S atom, and multiple A's may be the same or different. The larger the ratio of the number of A as S atoms to the total number of A (hereinafter also referred to as "S atom content ratio"), the higher the refractive index of the cured product can be. When at least one A is an S atom, it is called an episulfidized resin (A). From the viewpoint of increasing the refractive index, the average S atom content ratio of the resin (A) is preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.7 or more, and even more preferably It is 0.8 or more, particularly preferably 0.9 or more, and most preferably 1.0. The S atom content ratio may be less than 1.0. The average value here has the same meaning as above.

In formula (A), the bonding position of the group containing the A atom bonded to the naphthalene ring is not particularly limited, but is preferably the 1st or 2nd position of the naphthalene ring.

Examples of the resin represented by formula (A) include compounds represented by formula (Aa). R, n and A in formula (Ia) have the same meanings as above.

As mentioned above, resin (A) may be a mixture of two or more resins represented by formula (A). The mixture includes, for example, formulas (A) that differ from each other in any one or more of the S atom content ratio, the position of the group containing the A atom in the naphthalene ring, the type of R, the position of R in the benzene ring, and the value of n. A mixture of two or more kinds of compounds represented by:

The weight average molecular weight Mw of the resin (A) is, for example, 500 to 10,000, preferably 750 to 3,000, as calculated by gel permeation chromatography (GPC) in terms of polystyrene.

The resin (B) has a structure derived from at least one monomer (hereinafter sometimes referred to as "monomer (a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. It has a unit. The resin (B) has a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b)"). A monomer copolymerizable with monomer (a) (however, it is different from monomer (a) and monomer (b).Hereinafter, referred to as "monomer (c)") may have a structural unit derived from (in some cases).

In this specification, "(meth)acrylic acid" represents at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" have similar meanings.

Examples of the monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-Carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Bicyclounsaturated compounds containing a carboxyl group such as hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;
Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyhydric carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate. ;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, o-, m-, p-vinylbenzoic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in aqueous alkali solutions.

The monomer (b) has a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. refers to a polymerizable compound that has
Monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

As the monomer (b), for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b1)"), an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b2)"), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "monomer (b3)") ), etc.

As the monomer (b1), for example, a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter referred to as "monomer (b1-1)") ), and a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (b1-2)").

The monomer (b1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond.
Examples of the monomer (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzylglycidyl ether, m-vinyl Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis( glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris( 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2, Examples include 4,6-tris(glycidyloxymethyl)styrene.

Examples of the monomer (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxy Cyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel Corporation) ), a compound represented by formula (BI), a compound represented by formula (BII), and the like.

［式（ＢＩ）及び式（ＢＩＩ）中、Ｒ^a及びＲ^bは、互いに独立に、水素原子、又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｘ^a及びＸ^bは、互いに独立に、単結合、＊－Ｒ^c－、＊－Ｒ^c－Ｏ－、＊－Ｒ^c－Ｓ－又は＊－Ｒ^c－ＮＨ－を表す。
Ｒ^cは、炭素数１～６のアルカンジイル基を表す。
＊は、Ｏとの結合手を表す。］

[In formula (BI) and formula (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. may be replaced with .
X ^a and X ^b each independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S-, or *-R ^c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxypropyl group, -hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, and the like.

Preferred examples of R ^a and R ^b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, Examples include hexane-1,6-diyl group.

Preferably, X ^a and X ^b include a single bond, a methylene group, an ethylene group, *-CH ₂ -O-, *-CH ₂ CH ₂ -O-, and more preferably a single bond, *-CH ₂ Examples include CH ₂ -O- (* represents a bond with O).

Examples of the compound represented by formula (BI) include compounds represented by any of formulas (BI-1) to (BI-15). Among them, formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) and formula (BI-11) to formula (BI-15) Compounds represented by formula (BI-1), formula (BI-7), formula (BI-9) and formula (BI-15) are more preferred.

Examples of the compound represented by formula (BII) include compounds represented by any one of formula (BII-1) to formula (BII-15), among which compounds represented by formula (BII-1) and formula (BII-15) are preferred. (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) and formulas (BII-11) to (BII-15), and more. Preferred are compounds represented by formula (BII-1), formula (BII-7), formula (BII-9) and formula (BII-15).

The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone, or two or more types may be used in combination. The compound represented by formula (BI) and the compound represented by formula (BII) may be used together. When the compound represented by formula (BI) and the compound represented by formula (BII) are used together, their content ratio [compound represented by formula (BI): compound represented by formula (BII)] is On a molar basis, the ratio is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, even more preferably 20:80 to 80:20.

As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable.
Examples of the monomer (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, and 3-methyl-3-(meth)acryloyl. Examples include oxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyloxetane, and the like.

As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable.
Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (eg, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As the monomer (b), monomer (b1) is preferable because it can further improve the reliability of the heat resistance, chemical resistance, etc. of the obtained cured product. Furthermore, monomer (b1-2) is more preferred in that composition (I) has excellent storage stability.

Examples of the monomer (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl. (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo [5.2. 1.0 ^2,6 ] Decan-8-yl (meth)acrylate (commonly referred to as "dicyclopentanyl (meth)acrylate" in the technical field. Also, "tricyclodecyl (meth)acrylate") ), tricyclo[5.2.1.0 ^2,6 ]decane-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth) ) acrylate (commonly referred to as “dicyclopentenyl (meth)acrylate” in the technical field), tricyclo[5.2.1.0 ^2,6 ]decen-9-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, Cyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate (Meth)acrylic acid esters such as acrylates;
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
Halogen atom-containing (meth)acrylic acid ester such as 2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;
Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2 .1] hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy -5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2 .2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyl) bicyclounsaturated compounds such as (oxycarbonyl)bicyclo[2.2.1]hept-2-ene;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 - dicarbonylimide derivatives such as maleimidopropionate and N-(9-acridinyl)maleimide;
Vinyl group-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, N-vinylcarbazole and p-methoxystyrene; vinyl group-containing nitriles such as (meth)acrylonitrile; chloride Halogenated hydrocarbons such as vinyl and vinylidene chloride; Vinyl group-containing amides such as (meth)acrylamide; Esters such as vinyl acetate; Dienes such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene ; etc.

The content of resin (I) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, even more preferably 13 to 80% by mass, based on 100% by mass of the solid content of composition (I). The content is 70% by mass, and even more preferably 15 to 60% by mass. When the content of resin (I) is within the above range, the refractive index of the cured product can be improved.

<Other ingredients>
Examples of the other components contained in composition (I) include polymerizable compounds other than compound (I), resins other than resin (I) (hereinafter also referred to as "resin (II)") ), a polymerization initiator, a polymerization initiation aid, a leveling agent, an antioxidant, a curing agent, etc. Examples of the curing agent include polycarboxylic acids and imidazole compounds.

(1) Polymerizable compound Composition (I) can contain one or more polymerizable compounds in addition to compound (I). By containing the polymerizable compound in the composition (I), the viscosity or curability of the composition (I) can be adjusted, and the mechanical properties and/or optical properties of the obtained cured product and molded products containing the same can be adjusted. It is possible to do this.

The polymerizable compound is not limited as long as it is a compound other than compound (I) and has polymerizability. The polymerizable compound is a monomer that reacts with heat or the action of a polymerization initiator, and examples of the monomer include compounds having an ethylenically unsaturated bond, preferably (meth)acrylic compounds, and more preferably Examples include compounds having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.

Examples of (meth)acrylic compounds having two (meth)acryloyl groups include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol Bis(acryloyloxyethyl) ether of A, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, 3-methylpentanediol diol Examples include (meth)acrylate.

Examples of (meth)acrylic compounds having three or more (meth)acryloyl groups include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, Ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri Pentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol tri(meth)acrylate Reaction product of acrylate and acid anhydride, reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride, reaction product of tripentaerythritol hepta(meth)acrylate and acid anhydride, caprolactone-modified trimethylolpropane tri (meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate ) acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol tetra(meth)acrylate, caprolactone-modified tripentaerythritol penta(meth)acrylate, caprolactone-modified tripentaerythritol hexa(meth)acrylate, caprolactone-modified tri- Pentaerythritol hepta(meth)acrylate, caprolactone-modified tripentaerythritol octa(meth)acrylate, reaction product of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride, caprolactone-modified dipentaerythritol penta(meth)acrylate and acid anhydride Examples include reaction products with caprolactone-modified tripentaerythritol hepta(meth)acrylate and acid anhydrides.

As the (meth)acrylic compound, a (meth)acrylic compound having three or more (meth)acryloyl groups is preferable, and dipentaerythritol hexa(meth)acrylate is more preferable.

When composition (I) contains a polymerizable compound, the content of the polymerizable compound is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total solid content of composition (I). It is preferably 30% by mass or less, more preferably 20% by mass or less.

(2) Resin (II)
Composition (I) can contain one or more resins (II). Composition (I) containing resin (II) imparts developability to the cured product of composition (I) and improves the mechanical and/or optical properties of the cured product and molded products containing it. It is possible to make adjustments. Resin (II) is not limited as long as it is a resin other than resin (I), and includes thermoplastic resins and curable resins. The curable resin may be a photocurable resin that is cured by irradiation with active energy rays, or a thermosetting resin that is cured by heat.

Examples of thermoplastic resins include olefin resins such as polyethylene resins, polypropylene resins, and polycycloolefin resins, (meth)acrylic resins such as poly(meth)acrylate resins, polystyrene resins, and styrene-acrylonitrile resins. Resin, acrylonitrile-butadiene-styrene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol resin, polyethylene Examples include polyester resins such as terephthalate resin, polybutylene terephthalate resin, and liquid crystal polyester resin, polyacetal resin, polyamide resin, polycarbonate resin, polyurethane resin, and polyphenylene sulfide resin. One or more of these resins may be used as a polymer blend or polymer alloy.

Examples of the curable resin include resins having a photopolymerizable group or a thermopolymerizable group, such as (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenolic resins, urea resins, and alkyd resins. , polyimide resin, etc.

(3) Polymerization initiator Composition (I) can contain one or more types of polymerization initiator. The polymerization initiator is not particularly limited as long as it can initiate the polymerization of compound (I), and includes, for example, radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, radical and cationic polymerization initiators, etc. and can be selected and used as appropriate. These polymerization initiators generate radicals, acids, or bases by at least one of active energy ray irradiation and heat, and advance radical polymerization, cationic polymerization, or anionic polymerization of the polymerizable compound.

The polymerization initiator is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds; More preferred are polymerization initiators containing. These polymerization initiators tend to have high sensitivity and high transmittance in the visible light region.

The O-acyloxime compound is a compound having a structure represented by formula (D1). Hereinafter, * represents a bond.

Examples of O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- 1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-( 2-Methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4 -dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1 -one-2-imine is mentioned. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may be used.

The alkylphenone compound is a compound having a structure represented by formula (D2-1) or a structure represented by formula (D2-2). In these structures, the benzene ring may have a substituent.

Examples of the compound having the structure represented by formula (D2-1) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-( 4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1- One example is on. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (all manufactured by BASF Corporation) may be used. Furthermore, a polymerization initiator having a group capable of causing chain transfer, which is described in Japanese Patent Publication No. 2002-544205, may be used. Examples of the compound having the structure represented by formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomer, α,α-di Examples include ethoxyacetophenone and benzyl dimethyl ketal. In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (D2-1).

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl) naphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl) )-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2) -methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine It will be done.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by BASF Japan Co., Ltd.) may be used.

Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4 , 4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4, 4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis( 2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxy phenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-open No. 62-174204, etc.), in which the phenyl group at the 4,4', 5,5'-positions is substituted with a carbalkoxy group. Examples include biimidazole compounds (see, for example, JP-A-7-10913).

Furthermore, as a polymerization initiator, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'- Benzophenone compounds such as methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Examples include quinone compounds such as anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These can be used in combination with a polymerization initiation aid (especially an amine compound) described below.

As the polymerization initiator, an acid generator can also be used. Examples of acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, and 4-acetoxyphenyl methyl sulfonate. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin Examples include tosylate.

When composition (I) contains a polymerizable compound and a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total content of the resin and the polymerizable compound. parts, more preferably 0.5 to 15 parts by weight, still more preferably 1 to 8 parts by weight. When the content of the polymerization initiator is within the above range, the visible light transmittance of the resulting cured product tends to be high.

(4) Polymerization initiation aid The polymerization initiation aid is a compound or sensitizer used together with the polymerization initiator to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator.

Examples of the polymerization initiation aid include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the thiazoline compound include compounds represented by formulas (H1-1) to (H1-3), compounds described in JP-A No. 2008-65319, and the like.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoate. 2-ethylhexyl dimethylaminobenzoate, N,N-dimethylpara-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis( Examples include ethylmethylamino)benzophenone, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may also be used.

Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxy Examples include anthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Examples of carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When composition (I) contains a polymerizable compound, a polymerization initiator, and a polymerization initiation aid, the content of the polymerization initiation aid is based on 100 parts by mass of the total content of the resin (I) and the polymerizable compound. , preferably 0.1 to 30 parts by weight, more preferably 0.2 to 10 parts by weight. When the amount of the polymerization initiation aid is within the above range, the sensitivity tends to be even higher when forming a cured product.

(5) Leveling agent Examples of the leveling agent include silicone surfactants, fluorine surfactants, and silicone surfactants containing fluorine atoms. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (product name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC). .

Examples of the above-mentioned fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, Florado (registered trademark) FC430, Florado FC431 (manufactured by Sumitomo 3M Ltd.), Megafac (registered trademark) F142D, Florado (registered trademark) F171, Florado F172, Florado F173, Florado F177, Florado F183, Florado F554, Megafac (registered trademark) R30, RS-718-K (manufactured by DIC Corporation), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, Megafac (registered trademark) BL20, Megafac (registered trademark) F475, Megafac (registered trademark) F477, and Megafac (registered trademark) F443 (manufactured by DIC Corporation) may be mentioned.

When containing a leveling agent, its content is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass, based on the total amount of the resin composition. It is not more than 0.005% by mass and not more than 0.07% by mass.

(6) Antioxidant Examples of the antioxidant include phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among these, phenolic antioxidants are preferred in that the resulting film is less colored.

Examples of phenolic antioxidants include 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy -3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5 -methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methyl phenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6- tert-butyl-4-methylphenol), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H, 3H,5H)-trione, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-tolyl)tri- p-cresol, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol and 6-[3-( Examples include 3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine. As the phenolic antioxidant, commercially available products may be used. Examples of commercially available phenolic antioxidants include Sumilizer (registered trademark) BHT, GM, GS, and GP (all of the above). (manufactured by Sumitomo Chemical Co., Ltd.), and Irganox (registered trademark) 1010, 1076, 1330, and 3114 (all manufactured by BASF Corporation).

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityltetrakis (3 -laurylthiopropionate). As the sulfur-based antioxidant, commercially available products may be used. Examples of commercially available sulfur-based antioxidants include Sumilizer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris(nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra(tridecyl)-1,1, 3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite is mentioned. As the phosphorus antioxidant, a commercially available product may be used. Examples of commercially available phosphorus antioxidants include Irgafos (registered trademark) 168, 12, and 38 (all manufactured by BASF Corporation), ADEKA STAB 329K, and ADEKA STAB PEP36 (all manufactured by ADEKA Corporation). can be mentioned.

Examples of amine antioxidants include N,N'-di-sec-butyl-p-phenylenediamine, N,N'-di-isopropyl-p-phenylenediamine, and N,N'-dicyclohexyl-p-phenylene. Examples include diamine, N,N'-diphenyl-p-phenylenediamine, and N,N'-bis(2-naphthyl)-p-phenylenediamine. As the amine antioxidant, a commercially available product may be used. Examples of commercially available amine antioxidants include Sumilizer (registered trademark) BPA, BPA-M1, and 4ML (all manufactured by Sumitomo Chemical Co., Ltd.).

When composition (I) contains an antioxidant, the content thereof is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the total content of the resin and the polymerizable compound. is 0.5 parts by mass or more and 3 parts by mass or less. When the content of the antioxidant is within the above range, the resulting cured product tends to have excellent heat resistance and pencil hardness.

(7) Curing agent <polyhydric carboxylic acid>
A polycarboxylic acid can be used as a curing agent. The polycarboxylic acid is at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids. A polyvalent carboxylic acid is a compound having two or more carboxy groups, and a polyvalent carboxylic acid anhydride is an anhydride of a polyvalent carboxylic acid. The molecular weight of the polyvalent carboxylic acid is preferably 3,000 or less, more preferably 1,000 or less.

Examples of the polyhydric carboxylic anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, 2-(2-octaconic anhydride) -3-enyl)succinic anhydride, 2-(2,4,6-trimethylnon-3-enyl)succinic anhydride, tricarballylic anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride Chain polyvalent carboxylic acid anhydrides such as anhydrides; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydro Phthalic anhydride, 4-methylhexahydrophthalic anhydride, norbornenedicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane -2,3-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-5-ene-2, Alicyclic polycarboxylic anhydrides such as 3-dicarboxylic anhydride and cyclopentanetetracarboxylic dianhydride; phthalic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, pyromellitic anhydride , trimellitic anhydride, benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, ethylene glycol bis(anhydrotrimellitate), glycerin tris(anhydrotris) trimellitate), glycerin bis(anhydrotrimellitate) monoacetate, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1, 2-c] Aromatic polycarboxylic acid anhydrides such as furan-1,3-dione; ADEKA HARDONA (registered trademark) -EH-700 (product name (the same applies hereinafter), manufactured by ADEKA Co., Ltd.), RIKACID (registered trademark) -HH, RIKACID (registered trademark) -TH, ADEKA -MH, MH-700 (product name (the same applies hereafter), manufactured by ADEKA Co., Ltd.) Commercially available products such as Epikinia 126, Epikinia YH-306, and Epiquinia DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.) may also be used.

Examples of the polyvalent carboxylic acids include chain polyvalent carboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polyvalent carboxylic acids that lead to chain polyvalent carboxylic acid anhydrides. Acids; cyclohexanedicarboxylic acid, alicyclic polycarboxylic acids such as polycarboxylic acids that lead to alicyclic polycarboxylic acid anhydrides; isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, Aromatic polyvalent carboxylic acids such as polyvalent carboxylic acids leading to aromatic polyvalent carboxylic acid anhydrides; and the like.

Among these, chain carboxylic acid anhydrides and alicyclic polycarboxylic acid anhydrides are preferred, since the resulting film has excellent heat resistance and is less likely to reduce transparency, especially in the visible light region. Carboxylic acid anhydrides are more preferred.

When the composition (I) contains a polyhydric carboxylic acid, the content thereof is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, based on 100 parts by mass of the total content of the resin and the polymerizable compound. Parts by weight, more preferably 2 to 15 parts by weight. When the content of polycarboxylic acid is within the above range, the resulting film will have excellent heat resistance and adhesion.

<Imidazole compound>
An imidazole compound can be used as a curing agent. The imidazole compound is not particularly limited as long as it has an imidazole skeleton, and examples thereof include compounds known as epoxy curing agents. Among these, the compound represented by formula (G2-1) is preferred.

[In formula (G2-1), R ³¹ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbon atoms.
R ³² to R ³⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group, or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group The hydrogen atom contained in may be substituted with a hydroxy group. ]

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, heptadecyl group. , undecyl group.
Examples of the cyanoalkyl group having 2 to 5 carbon atoms include a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group, and a cyanopentyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, and stearoyl group.

Examples of imidazole compounds include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole, 2-ethylimidazole, 2-methylimidazole, and 2-methylimidazole. Undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxymethylimidazole , 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2-(p-hydroxyphenyl)imidazole, 1-cyanomethyl-2-methylimidazole, 1- (2-cyanoethyl)-2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4-methylimidazole, 1-cyanomethyl-2-phenylimidazole , 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole. Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole are preferred.

When composition (I) contains an imidazole compound, its content is preferably 0.1 parts by mass or more and 25 parts by mass or less, more preferably The content is 0.2 parts by mass or more and 15 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less. When the content of the imidazole compound is within the above range, the resulting cured product tends to have excellent transparency in the visible light region.

(8) Solvent Composition (I) contains a solvent. The solvent is not particularly limited, and includes solvents commonly used in the field. For example, ester solvents (solvents that contain -COO- but no -O- in the molecule), ether solvents (solvents that contain -O- but no -COO- in the molecule), and ether ester solvents (solvents that contain -O- but no -COO- in the molecule). solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- in the molecule but not -COO-), alcohol solvents (solvents containing OH in the molecule, -O-, - (CO- and -COO--free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, and methylanisole.

Ether ester solvents include methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Examples include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Examples include.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Among the above-mentioned solvents, organic solvents having a boiling point of 100° C. or more and 200° C. or less at 1 atm are preferred from the viewpoint of coating properties and drying properties. As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, cyclohexanone, methoxybutanol and methoxybutyl acetate are preferred, and propylene glycol monomethyl ether More preferred are acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol and methoxybutyl acetate.

The content of the solvent in composition (I) is preferably 60 to 95% by mass, more preferably 70 to 95% by mass, based on the total amount of composition (I). In other words, the solid content of the composition (I) of the present invention is preferably 5 to 40% by weight, more preferably 5 to 30% by weight.

(9) Other components Composition (I) may contain additives known in the technical field, such as fillers, other polymer compounds, ultraviolet absorbers, chain transfer agents, adhesion promoters, etc., as necessary. May contain.

(10) Method for producing composition (I) Composition (I) consists of compound (I), resin (I), and a solvent, a polymerizable compound, a polymerization initiator, and a polymerization initiation promoter, which are used as necessary. It can be manufactured by mixing the agent, leveling agent, antioxidant, curing agent, and other components by a known method. After mixing, it is preferable to filter through a filter with a pore size of about 0.05 to 1.0 μm.

<Cured products and molded products>
The present invention provides a cured product of composition (I) and a molded article containing the cured product. Since the composition (I) has excellent curability, it is suitable as a curable material for producing a cured product or a molded product containing the same. The cured product can be obtained by curing composition (I) using at least one of active energy ray irradiation and heat. The shape of the molded product containing the cured product is not particularly limited, and may include film (membrane), plate, lens, powder, granules, non-spherical particles, crushed particles, porous, continuous lumps, and fibers. The shape may be any shape depending on the purpose of the molded product, including shape, tubular shape, hollow fiber shape, etc.

The method for obtaining a molded article from composition (I) is not particularly limited, and examples thereof include a method in which a film is formed on a substrate and then molded by etching or the like, an injection molding method, a cast polymerization molding method, and the like.

In the cast polymerization method, for example, the composition (I) is injected into a mold, defoamed etc. as necessary, and then cured by heating in an oven, etc., and the obtained molded product is taken out. . The removed molded product may be further irradiated with active energy rays to additionally cure the molded product.

When forming a film as a molded article on a substrate, the composition (I) is applied to the substrate, dried as necessary to form a coating layer, and the coating layer is cured to form a cured film. can get things. The molded article may be a patterned cured film. A patterned cured film can be obtained by patterning by a method such as a photolithography method, an inkjet method, or a printing method. The patterning method is preferably a photolithography method. The photolithography method is a method in which composition (I) is applied to a substrate, dried if necessary to form a coating layer, exposed to light through a photomask, and then developed.

Substrates include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass whose surface is coated with silica, resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and the above substrates. A material in which a thin film of aluminum, silver, silver/copper/palladium alloy, etc. is formed can be used. Examples of the method for applying the composition (I) to the substrate include a spin coating method, a slit coating method, and a slit and spin coating method.

The light source used for exposure is preferably a light source that generates light with a wavelength of 250 nm or more and 450 nm or less. For example, from the light of this wavelength, depending on the absorption wavelength of the photopolymerization initiator, light around 436 nm, around 408 nm, or around 365 nm may be selectively extracted using a bandpass filter. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp. Heating (pre-development bake) may be performed after pattern exposure and before development.

Examples of the developer used for development include aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide, and organic solvents. Examples of organic solvents include ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glymes, esters, aliphatic Examples include organic solvents such as nitriles, sulfoxides, and amides. Two or more types of solvents may be used in combination. The developer may contain a surfactant. The developing method may be any of the paddle method, dipping method, spray method, etc. The patterned film obtained by development may be further heated (post-baked).

Since the cured product or the molded product containing the same is formed from the composition (I), it can exhibit a high refractive index, and the refractive index depends on the composition of the composition (I), etc. By adjusting the refractive index, it is possible to control the refractive index to a desired value. The cured product or the molded product containing the same may have a refractive index of 1.70 or more, 1.72 or more, or even 1.75 or more at a wavelength of 550 nm. The refractive index at a wavelength of 550 nm is, for example, 1.80 or less, and may be 1.78 or less.

[Application]
According to the present invention, a cured product or molded product having a high refractive index, or a cured product or molded product having a desired refractive index can be obtained. Applications of the cured product or molded product include, for example, glass substitutes and their surface coating materials; coating materials for window glass, lighting glass, and light source protection glass for residences, facilities, transportation equipment, etc.; residences, facilities, transportation equipment, etc. Window films such as; interior and exterior materials and interior and exterior paints for houses, facilities, transportation equipment, etc., and coatings formed by such coatings; alkyd resin lacquer paints and coatings formed by such coatings; acrylic lacquer paints and coatings formed by such coatings. Coating film formed; Materials for light sources that emit ultraviolet rays such as fluorescent lamps and mercury lamps; Materials for blocking electromagnetic waves, etc. generated from precision machinery, electronic and electrical equipment materials, and various displays; Containers or packaging for foods, chemicals, drugs, etc. Materials; Bottles, boxes, blisters, cups, special packaging, compact disk coatings, agricultural and industrial sheet or film materials; Anti-fading agents for printed matter, dyed products, dyes and pigments; For polymer supports (e.g. machinery and automobile parts) Print overcoats; Inkjet media coatings; Laminated matte; Optical light films; Safety glass/windshield interlayers; Electrochromic/photochromic applications; Overlaminate films; Solar thermal control coatings; Cosmetics such as sunscreen creams, shampoos, conditioners, and hair conditioners; Textile products and fibers for clothing such as sportswear, stockings, and hats; Home interior products such as curtains, carpets, and wallpaper; Plastic lenses, contact lenses, and artificial eyes, etc. Medical instruments; Optical products such as optical filters, backlight display films, prisms, lenses (e.g., eyeglass lenses, camera lenses, and microlenses and pickup lenses described below), mirrors, and photographic materials; mold films, transfer type Examples include stationery such as stickers, anti-graffiti films, tapes, and inks; sign boards, signage devices, etc. and their surface coating materials; substrates used in optical devices, etc.; optical waveguides; holograms; LED sealing materials; and the like.

The molded product is suitably used as a lens, which is an optical article used in optical equipment. Examples of optical devices include solid-state image sensors, display devices, and the like. Lenses are used in solid-state image sensors to improve the efficiency of light collection to each photoelectric conversion element, and lenses are used in display devices to improve the efficiency of light extraction from pixels. The lens may be a microlens. As a display device, it is suitably used for a liquid crystal display device, an organic EL display device, etc.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the examples, % and parts indicating content or amount used are based on mass unless otherwise specified.

ジムロート冷却管及び温度計を設置した４つ口フラスコ内を窒素雰囲気とし、式（ＩＩｂ－１）で表される化合物（１，６－ナフタレンジチオール）３０部、アセトン１６５部、純水４５部、及び式（ＩＩＩ－１）で表される化合物（エピクロロヒドリン）１３９部を上記フラスコに加えて氷浴中で１５分撹拌した。続いて、別のフラスコに水酸化ナトリウム１５部、アセトン６６部、及び純水２０３部を加えて完溶させたのちに、上記４つ口フラスコに１時間かけて滴下した。滴下したのちに３０℃まで昇温し、３０℃で２時間撹拌した。得られた混合物を精製し、式（ＩＶｂ－１）で表される化合物４６部を得た。 [Synthesis example of compound (I)]
<Synthesis Example 1: Synthesis of compound represented by formula (Ib-1)>
Synthesis of compound represented by formula (IVb-1)

A four-neck flask equipped with a Dimroth condenser and a thermometer was set in a nitrogen atmosphere, and 30 parts of the compound represented by formula (IIb-1) (1,6-naphthalenedithiol), 165 parts of acetone, 45 parts of pure water, 139 parts of the compound represented by formula (III-1) (epichlorohydrin) were added to the flask and stirred for 15 minutes in an ice bath. Subsequently, 15 parts of sodium hydroxide, 66 parts of acetone, and 203 parts of pure water were added to another flask to completely dissolve them, and then added dropwise to the four-necked flask over 1 hour. After the dropwise addition, the temperature was raised to 30°C and stirred at 30°C for 2 hours. The resulting mixture was purified to obtain 46 parts of a compound represented by formula (IVb-1).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that a compound represented by formula (IVb-1) was produced.
¹ H-NMR (deuterated chloroform) δ: 8.37-8.39 (1H), 7.85 (1H), 7.39-7.70 (4H), 3.08-3.29 (5H), 2.94-2.98 (1H), 2.57-2.81 (3H), 2.39-2.41 (1H)
LC-MS; [M+H] ⁺ =305.5

ジムロート冷却管及び温度計を設置した４つ口フラスコ内を窒素雰囲気とし、式（ＩＶｂ－１）で表される化合物３部、メタノール３０部、トルエン３０部、無水酢酸０．０５部、及びチオ尿素３．８部を上記フラスコに加えて室温下で２４時間撹拌した。得られた混合物を精製し、式（Ｉｂ－１）で表される化合物２．５部を得た。 (2) Synthesis of compound represented by formula (Ib-1)

A four-necked flask equipped with a Dimroth condenser and a thermometer was set in a nitrogen atmosphere, and 3 parts of the compound represented by formula (IVb-1), 30 parts of methanol, 30 parts of toluene, 0.05 part of acetic anhydride, and thio 3.8 parts of urea was added to the above flask and stirred at room temperature for 24 hours. The resulting mixture was purified to obtain 2.5 parts of a compound represented by formula (Ib-1).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that a compound represented by formula (Ib-1) was produced.
¹ H-NMR (deuterated chloroform) δ: 8.39 to 8.43 (1H), 7.86 (1H), 7.40 to 7.74 (4H), 3.40 to 3.53 (2H), 3.04-3.18 (2H), 2.78-2.96 (2H), 2.47-2.49 (1H), 2.35-2.36 (1H), 2.14-2. 16 (1H), 1.93-1.94 (1H)
LC-MS; [M+H] ⁺ =337.5

ジムロート冷却管及び温度計を設置した４つ口フラスコ内を窒素雰囲気とし、式（ＩＩｄ－１）で表される化合物（２，７－ナフタレンジチオール）１５部、アセトン８３部、純水２３部、及び式（ＩＩＩ－１）で表される化合物（エピクロロヒドリン）６９部を上記フラスコに加えて氷浴中で１５分撹拌した。続いて、別のフラスコに水酸化ナトリウム７．５部、アセトン３３部、及び純水１０１部を加えて完溶させたのちに、前記４つ口フラスコに１時間かけて滴下した。滴下したのちにオイルバスで６５℃まで昇温し、６５℃で１時間撹拌した。得られた混合物を精製し、式（ＩＶｄ－１）で表される化合物２４部を得た。 <Synthesis Example 2: Synthesis of compound represented by formula (Id-1)>
(1) Synthesis of compound represented by formula (IVd-1)

A four-necked flask equipped with a Dimroth condenser and a thermometer was set in a nitrogen atmosphere, and a compound represented by formula (IId-1) (2,7-naphthalenedithiol) 15 parts, acetone 83 parts, pure water 23 parts, 69 parts of the compound represented by formula (III-1) (epichlorohydrin) were added to the flask and stirred for 15 minutes in an ice bath. Subsequently, 7.5 parts of sodium hydroxide, 33 parts of acetone, and 101 parts of pure water were added to another flask to completely dissolve them, and then added dropwise to the four-necked flask over 1 hour. After the dropwise addition, the temperature was raised to 65°C in an oil bath, and the mixture was stirred at 65°C for 1 hour. The resulting mixture was purified to obtain 24 parts of a compound represented by formula (IVd-1).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that a compound represented by formula (IVd-1) was produced.
¹ H-NMR (deuterated chloroform) δ: 7.70-7.76 (4H), 7.43-7.45 (2H), 3.21-3.27 (4H), 3.05-3.11 (2H), 2.78-2.80 (2H), 2.57-2.58 (2H)
LC-MS; [M+H] ⁺ =305.5

ジムロート冷却管及び温度計を設置した４つ口フラスコ内を窒素雰囲気とし、式（ＩＶｄ－１）で表される化合物２０部、メタノール３２０部、ジクロロメタン８０部、及びチオ尿素２５部を上記フラスコに加えて室温下で２４時間撹拌した。得られた混合物を精製し、式（Ｉｄ－１）で表される化合物１８．１部を得た。 (2) Synthesis of compound represented by formula (Id-1)

A four-necked flask equipped with a Dimroth condenser and a thermometer was set in a nitrogen atmosphere, and 20 parts of the compound represented by formula (IVd-1), 320 parts of methanol, 80 parts of dichloromethane, and 25 parts of thiourea were added to the flask. In addition, the mixture was stirred at room temperature for 24 hours. The resulting mixture was purified to obtain 18.1 parts of a compound represented by formula (Id-1).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that a compound represented by formula (Id-1) was produced.
¹ H-NMR (deuterated chloroform) δ: 7.73-7.79 (4H), 7.46-7.48 (2H), 3.52-3.57 (2H), 3.14-3.18 (2H), 2.90-2.96 (2H), 2.49-2.51 (2H), 2.15-2.17 (2H)
LC-MS; [M+H] ⁺ =337.5

［式中、Ａ及びｎは前記と同じ意味を表す。］ [Synthesis example of resin (I)]
<Synthesis Example 3: Synthesis of resin represented by formula (Aa-2)>

[In the formula, A and n represent the same meanings as above. ]

A four-necked flask equipped with a Dimroth condenser and a thermometer was set in a nitrogen atmosphere, and a resin represented by formula (Aa-1) (naphthol-cresol novolac type epoxy resin "NC-7000L" manufactured by Nippon Kayaku Co., Ltd.) was added. ), 320 parts of dichloromethane, 80 parts of methanol, and 33 parts of thiourea were added to the flask and stirred at room temperature for 72 hours. The resulting mixture was purified to obtain 14 parts of a resin represented by formula (Aa-2).

¹ H-NMR analysis was performed and it was confirmed that a resin represented by formula (Aa-2) was produced. The peak at 2.56 to 2.96 ppm derived from epoxy completely disappeared, and the formation of a new peak at 2.40 to 2.65 ppm due to thiirane was confirmed.

From the above ¹ H-NMR analysis, the ratio of the number of A as S atoms to the total number of A (S atom content ratio) was determined, and the average value was 1.0. Further, the weight average molecular weight Mw of the resin represented by formula (Aa-2) was 1500 and Mn was 600 by GPC.
Device: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40℃
Solvent: Tetrahydrofuran Flow rate: 1.0 mL/min
Detector; RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The refractive index at a wavelength of 550 nm of the resins represented by formulas (Aa-1) and (Aa-2) was calculated according to the following procedure.
100 parts by mass of the resin represented by formula (Aa-1) or the resin represented by formula (Aa-2) and 310 parts by mass of cyclopentanone as a solvent were placed in a flask and stirred to obtain a liquid composition. Ta. Visual inspection of the composition revealed that it was transparent and that the ingredients were uniformly dissolved. Approximately 3 cc of the composition prepared above was dropped onto non-alkali glass (Eagle A coating layer was formed by spin coating. The alkali-free glass plate on which the coating layer was formed was heated at 60° C. for 5 minutes to dry the solvent, thereby obtaining an alkali-free glass on which a coating film containing no solvent was formed. The thickness of the coating film on the alkali-free glass was measured using a stylus-type film thickness meter (DekTak XT, manufactured by Bruker) and found to be 1.5 μm.
For the alkali-free glass on which the coating film was formed, the reflection spectrum from wavelength 300 nm to 800 nm was measured using a visible and ultraviolet spectrophotometer (V-650, manufactured by JASCO Corporation) with an integrating sphere unit (ISV-922, manufactured by JASCO Corporation) and the transmission spectrum. Measure the reflection spectrum, subtract the increase/decrease due to interference in the reflection spectrum from the transmission spectrum and reflection spectrum, and smooth the true reflection spectrum. Among the true reflection spectra, calculate the value at a wavelength of 550 nm and alkali-free glass (EagleXG, manufactured by Corning). From the refractive index of The refractive index of the resin represented by formula (Aa-2) at a wavelength of 550 nm was 1.63 and 1.66, respectively.

[Example 1: Preparation of composition]
70 parts by mass of the compound represented by formula (Ib-1) obtained in Synthesis Example 1, 30 parts by mass of the resin represented by formula (Aa-2), 5 parts by mass of polymerization initiator A, and a solvent. 310 parts by mass of cyclopentanone was placed in a flask and stirred to obtain a liquid composition. Visual inspection of the composition revealed that it was transparent and that the ingredients were uniformly dissolved.

[Examples 2 to 6, Comparative Examples 1 to 3]
A liquid composition was obtained in the same manner as in Example 1, except that the types of ingredients and the amounts added in the composition were as shown in Table 1. The compositions of Examples 2 to 6 and Comparative Examples 1 to 3 were transparent when visually observed, and it was confirmed that the ingredients were uniformly dissolved.

〔４〕（Ｙ１）：式（Ｙ１）で表される化合物（１，６－ビス（グリシジルオキシ）ナフタレン、ＤＩＣ株式会社製「ＥＰＩＣＬＯＮ ＨＰ－４０３２Ｄ」）

〔５〕（Ａａ－１）：式（Ａａ－１）で表される樹脂（日本化薬株式会社製のナフトール－クレゾールノボラック型エポキシ樹脂「ＮＣ－７０００Ｌ」）
〔６〕（Ａａ－２）：式（Ａａ－２）で表される樹脂
〔７〕重合開始剤Ａ：スルホニウム塩タイプの光カチオン重合開始剤（サンアプロ株式会社製「ＶＣ－１Ｓ」）
〔８〕重合開始剤Ｂ：スルホニウム塩タイプの光カチオン重合開始剤（サンアプロ株式会社製「ＶＣ－１ＦＧ」）
〔９〕重合開始剤Ｃ：オニウム塩タイプの熱カチオン重合開始剤（サンアプロ株式会社製「ＴＡ－１００」） Details of the abbreviations of the ingredients shown in Table 1 are as follows.
[1] (1b-1): Compound represented by formula (1b-1) [2] (1d-1): Compound represented by formula (1d-1) [3] (IB): Formula (IB ) compound represented by

[4] (Y1): Compound represented by formula (Y1) (1,6-bis(glycidyloxy)naphthalene, "EPICLON HP-4032D" manufactured by DIC Corporation)

[5] (Aa-1): Resin represented by formula (Aa-1) (naphthol-cresol novolac type epoxy resin "NC-7000L" manufactured by Nippon Kayaku Co., Ltd.)
[6] (Aa-2): Resin represented by formula (Aa-2) [7] Polymerization initiator A: Sulfonium salt type photocationic polymerization initiator (“VC-1S” manufactured by San-Apro Co., Ltd.)
[8] Polymerization initiator B: Sulfonium salt type photocationic polymerization initiator (“VC-1FG” manufactured by San-Apro Co., Ltd.)
[9] Polymerization initiator C: Onium salt type thermal cationic polymerization initiator (“TA-100” manufactured by San-Apro Co., Ltd.)

[Evaluation test]
(1) Refractive index of cured product Approximately 3 cc of the composition prepared above was dropped onto non-alkali glass (Eagle B100 (manufactured by Mikasa) was spin coated to form a coating layer. The alkali-free glass plate on which the coating layer was formed was heated at 60° C. for 2 minutes. Next, the alkali-free glass plate on which the coating layer was formed was exposed to light at an irradiation energy of 1000 mJ/cm ² in an atmospheric atmosphere using a high-pressure mercury lamp Proximity UV exposure device (UV-3300SC, manufactured by Ushio). Subsequently, the alkali-free glass plate on which the exposed coating layer was formed was heated at 120° C. for 5 minutes to obtain alkali-free glass on which a cured film was formed. The thickness of the cured film on the alkali-free glass was measured using a stylus-type film thickness meter (DekTak XT, manufactured by Bruker) and found to be 1.5 μm.

For the alkali-free glass on which the cured film was formed, the reflection spectrum in the wavelength range from 300 nm to 800 nm was measured using a visible and ultraviolet spectrophotometer (V-650, manufactured by JASCO Corporation) with an integrating sphere unit (ISV-922, manufactured by JASCO Corporation) and the transmission spectrum. Reflection spectra were measured. Among the true reflection spectra obtained by subtracting and smoothing the increase or decrease due to interference in the reflection spectra from the transmission spectrum and reflection spectrum, the wavelength of 550 nm is determined from the value at wavelength 550 nm and the refractive index of alkali-free glass (EagleXG, manufactured by Corning). The refractive index of the cured film was calculated based on Fresnel's formula (Hecto Optics I original 5th edition, Maruzen Publishing, 2018, p. 209-p. 226). The results are shown in Table 1.

(2) Curability Approximately 3 cc of the composition prepared above was dropped onto non-alkali glass (Eagle A coated layer was formed by spin coating using a commercially available commercially available product (manufactured by Co., Ltd.). The alkali-free glass plate on which the coating layer was formed was heated at 60° C. for 2 minutes. Next, the alkali-free glass plate on which the coating layer was formed was exposed to light using a high-pressure mercury lamp Proximity UV exposure device (UV-3300SC, manufactured by Ushio) in an atmospheric atmosphere at the irradiation energy shown in Table 1. Subsequently, the alkali-free glass plate on which the exposed coating layer was formed was heated at the post-baking temperature and time shown in Table 1 to obtain alkali-free glass on which a cured film was formed. The thickness of the cured film on the alkali-free glass was measured using a stylus-type film thickness meter (DekTak XT, manufactured by Bruker) and found to be 1.5 μm.

The curability of the obtained cured film was evaluated according to the following evaluation criteria. The results are shown in Table 1. Curability was determined by immersing alkali-free glass with a cured film in acetone at 23°C for 10 minutes, and using the film thickness retention rate before and after immersion (thickness retention rate = film thickness after immersion ÷ film thickness before immersion). evaluated.
A: Film thickness retention rate is 100% or less and 90% or more B: Film thickness retention rate is less than 90% and 80% or more C: Film thickness retention rate is less than 80%

Claims (8)

A composition comprising a compound represented by formula (I) and a resin having a refractive index of 1.60 or more at a wavelength of 550 nm.

[In formula (I),
n represents any integer from 0 to 6,
L represents a single bond or a divalent group, and multiple Ls may be the same or different,
R ¹¹ represents a monovalent substituent, and when there are multiple R ^11s , the multiple R ^11s may be the same or different,
R ¹² is selected from the group consisting of a hydrogen atom, formula (1a), and formula (1b), and a plurality of R ^12s may be the same or different.

In formula (1a),
A represents an O atom or an S atom, and when there are multiple A's in formula (I), the multiple A's may be the same or different,
m ^a represents 0 or 1, and when there is a plurality of m ^a in formula (I), the plural m ^a may be the same or different,
R ² represents a hydrogen atom or a monovalent substituent, and when there is a plurality of R ² , the plurality of R ² may be the same or different,
* represents a bond with L.
In formula (1b),
R ¹³ represents a monovalent substituent, and when there are multiple R ^13s , the multiple R ^13s may be the same or different,
* represents a bond with L. ] 1. The resin contains one polymerizable group selected from the group consisting of a (meth)acryloyl group, a mercapto group, a cyclic ether group having 2 to 4 carbon atoms, and a cyclic sulfide group having 2 to 4 carbon atoms. The composition described in . The composition according to claim 1, wherein the resin is a resin represented by formula (A).

[In formula (A),
R represents a monovalent hydrocarbon group, and when there are multiple R's, the multiple R's may be the same or different,
n represents an average value of 1 or more,
A represents an O atom or an S atom, and multiple A's may be the same or different. ] The composition according to claim 1, further comprising a polymerization initiator. The composition according to claim 1, wherein the compound represented by formula (I) includes a compound in which a plurality of R ^12s in formula (I) are represented by formula (1a). A cured product of the composition according to claim 1. A display device comprising the cured product according to claim 5. A solid-state imaging device comprising the cured product according to claim 7.