thermosetting components

Abstract

To provide a thermosetting composition that yields a cured product with a high refractive index and superior solvent resistance, a method for producing a cured product using the thermosetting composition, a cured product of the thermosetting composition, a film composed of the cured product, a micro lens composed of the cured product, and an optical element comprising the micro lens.SOLUTION: A thermosetting composition comprises a polymer with a constitutional unit of a specific structure, wherein an aromatic group with a carboxy group protected by a tert-butoxy carbonyloxy group or an acid-dissociable group is bound to a triazine ring through a specific linking group, and a crosslinkable compound of a specific structure comprising two or more cross-linkable groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting composition comprising a triazine ring-containing polymer containing a specific structural unit, a method for producing a cured product using the thermosetting composition, a cured product of the aforementioned thermosetting composition, a film made from the aforementioned cured product, a microlens made from the aforementioned cured product, and an optical element equipped with the microlens. [Background technology]

[0002] Traditionally, cameras, video cameras, and the like have used solid-state image sensors. These solid-state image sensors include CCD (charge-coupled device) image sensors and CMOS (complementary metal-oxide semiconductor) image sensors. The image sensor is equipped with a tiny focusing lens (hereinafter referred to as a microlens) to improve light-gathering efficiency.

[0003] In recent years, CCD and CMOS image sensors have become even more high-resolution. As a result, microlenses are becoming smaller in diameter. Even with small-diameter microlenses, a high refractive index is necessary for the microlens material to efficiently focus light onto the photodiode in the image sensor. For example, linear polymers containing triazine rings are known as highly refractive materials that can be molded into various forms (see Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2014-162829 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] By using the linear polymer described in Patent Document 1, high refractive index microlenses can be formed. However, elements equipped with microlenses are often exposed to chemical solutions such as organic solvents when manufacturing devices that incorporate these elements. Therefore, materials such as microlenses also require excellent solvent resistance.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a thermosetting composition that gives a cured product having a high refractive index and excellent solvent resistance, a method for producing a cured product using the thermosetting composition, a cured product of the aforementioned thermosetting composition, a film made of the aforementioned cured product, a microlens made of the aforementioned cured product, an optical element equipped with the microlens, and an optical element equipped with the microlens. [Means for solving the problem]

[0007] The present inventors have discovered that the above problems can be solved by using a thermosetting composition comprising a polymer containing a specific structural unit having an aromatic group having a tert-butoxycarbonyloxy group, a tert-butoxycarbonylamino group, or a carboxyl group protected by an acid-dissociable group, bonded to a triazine ring via a specific linking group, and a crosslinkable compound of a specific structure containing two or more crosslinkable groups, leading to the present invention. Specifically, the present invention provides the following.

[0008] A first aspect of the present invention is a thermosetting composition comprising a triazine ring-containing polymer (A), a crosslinkable compound (B), and an organic solvent (S), A triazine ring-containing polymer is given by the following formula (A1): [ka] (In formula (A1), Ar 1 , and Ar 2 R is an aromatic group-containing group, a1is a tert-butoxycarbonyloxy group, a tert-butoxycarbonylamino group, or a carboxy group protected by an acid-dissociable group, and X 1 and X 2 are each independently -NR a2 -, -O-, or -S-, and R a2 is a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic hydrocarbon group, and X 1 is bonded to the aromatic ring in the aromatic group-containing group as Ar 1 , and X 2 is bonded to the aromatic ring in the aromatic group-containing group as Ar 2 .) comprising a structural unit represented by, the crosslinkable compound (B) comprises two or more crosslinkable groups, at least one of the two or more crosslinkable groups is an epoxy group or an episulfide group, when R a1 is a carboxy group protected by said acid-dissociable group, said thermosetting composition further comprises a thermal acid generator (C).

[0009] A second aspect of the present invention is a method for producing a cured product, comprising: molding the thermosetting composition according to the first aspect; and heating the molded thermosetting composition to cure it.

[0010] A third aspect of the present invention is a cured product of the thermosetting composition according to the first aspect.

[0011] A fourth aspect of the present invention is a film formed of the cured product according to the first aspect.

[0012] A fifth aspect of the present invention is a microlens formed of the cured product according to the first aspect.

[0013] A sixth aspect of the present invention is an optical element comprising the microlens according to the fifth aspect. Effects of the Invention

[0014] According to the present invention, it is possible to provide a thermosetting composition that gives a cured product having a high refractive index and excellent solvent resistance, a method for producing a cured product using the thermosetting composition, a cured product of the aforementioned thermosetting composition, a film made of the aforementioned cured product, a microlens made of the aforementioned cured product, an optical element equipped with the microlens, and an optical element equipped with the microlens. [Modes for carrying out the invention]

[0015] ≪Thermosetting composition≫ The thermosetting composition comprises a triazine ring-containing polymer (A), a crosslinkable compound (B), and an organic solvent (S). The triazine ring-containing polymer is given by the following formula (A1): [ka] (In formula (A1), Ar 1 , and Ar 2 R is an aromatic group-containing group, a1 X is a carboxyl group protected by a tert-butoxycarbonyloxy group, a tert-butoxycarbonylamino group, or an acid-dissociable group. 1 , and X 2 These are, independently, -NR a2 -, -O-, or -S-, R a2 X is a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic hydrocarbon group, 1 Ar 1 Attached to the aromatic ring in the aromatic group containing the aromatic group, X 2 Ar 2 (As an aromatic group, it attaches to the aromatic ring in the aromatic group-containing group.) It includes constituent units represented by . The crosslinkable compound (B) contains two or more crosslinkable groups. Of the two or more crosslinkable groups, at least one is an epoxy group or an episulfide group. R a1 However, if the carboxyl group is protected by an acid-dissociable group, the thermosetting composition further comprises a thermal acid generator (C).

[0016] The following describes the essential and optional components that the thermosetting composition may contain.

[0017] <Triadine ring-containing polymer (A)> The triazine ring-containing polymer is (A), given by the following formula (A1): [ka] (In formula (A1), Ar 1 , and Ar 2 R is an aromatic group-containing group, a1 X is a carboxyl group protected by a tert-butoxycarbonyloxy group, a tert-butoxycarbonylamino group, or an acid-dissociable group. 1 , and X 2 These are, independently, -NR a2 -, -O-, or -S-, R a2 X is a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic hydrocarbon group, 1 Ar 1 Attached to the aromatic ring in the aromatic group containing the aromatic group, X 2 Ar 2 (As an aromatic group, it attaches to the aromatic ring in the aromatic group-containing group.) It includes constituent units represented by . A triazine ring-containing polymer (A) that includes the constituent unit represented by formula (A1) exhibits a high refractive index. Hereafter, the triazine ring-containing polymer (A) will also be referred to as "polymer (A)".

[0018] Polymer (A) has a carboxyl group protected by a tert-butoxycarbonyloxy group, a tert-butoxycarbonylamino group, or an acid-dissociable group. The acid-dissociable group is a group that can dissociate from the protected carboxyl group by the action of an acid, thereby regenerating the carboxyl group. Such polymers are soluble in various organic solvents, such as nitrogen-containing polar organic solvents and ketone solvents. However, the polymer (A) becomes poorly soluble in organic solvents when the carboxyl group protected by a tert-butoxycarbonyloxy group, a tert-butoxycarbonylamino group, or an acid-dissociable group is deprotected. Polymer (A') derived from polymer (A) and having a phenolic hydroxyl group, an amino group, or a carboxyl group generated by deprotection becomes even more poorly soluble in organic solvents when crosslinked with a crosslinkable compound (B) that can react with a phenolic hydroxyl group, an amino group, or a carboxyl group.

[0019] Therefore, the polymer (A) described above is easily processed as a solution. On the other hand, a cured product produced using a liquid curable composition containing the aforementioned polymer (A) and an organic solvent (S) under conditions in which a carboxyl group protected by a tert-butoxycarbonyloxy group, a tert-butoxycarbonylamino group, or an acid-dissociable group is deprotected is poorly soluble in the organic solvent.

[0020] Polymer (A) may contain the constituent units represented by formula (A1) as well as other constituent units other than those represented by formula (A1). Hereafter, the constituent unit represented by formula (A1) will also be referred to as "unit (A1)". Other constituent units not represented by formula (A1) will also be referred to as "unit (A2)". The amount of unit (A1) in polymer (A) is not particularly limited as long as the desired effect is not impaired. The amount of unit (A1) in polymer (A) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass, relative to the mass of polymer (A).

[0021] <Unit (A1)> In formula (A1), Ar 1 , and Ar 2 This is an aromatic group-containing group. An aromatic group-containing group may consist only of an aromatic group, or it may have both an aromatic group and a non-aromatic group. The aromatic group-containing group may contain only one aromatic group or two or more aromatic groups. The aromatic group contained in the aromatic group-containing group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. It is preferable that the aromatic group contained in the aromatic group-containing group is an aromatic hydrocarbon group.

[0022] The aromatic group contained in the aromatic group-containing group may be a monocyclic group or a polycyclic group. The polycyclic group may be a fused cyclic group, or a group in which one or more rings selected from monocyclic and polycyclic groups are linked by a single bond. The fused cyclic group may be a group formed by the fusion of aromatic groups, or a group formed by the fusion of an aromatic group and an aliphatic cyclic group.

[0023] The number of aromatic monorings contained in the aromatic group-containing group is not particularly limited as long as the desired effect is not impaired. If the aromatic group-containing group is an aromatic fused ring group, the number of monorings constituting the aromatic fused ring shall be considered the number of aromatic monorings contained in the aromatic group-containing group. Specifically, if the aromatic group-containing group is a naphthalene diyl group, the number of aromatic monorings contained in the aromatic group-containing group shall be 2. The number of aromatic monorings contained in the aromatic group-containing group is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0024] Preferred examples of aromatic group-containing groups include those represented by the following formulas (a-1) to (a-11). [ka]

[0025] In equations (a-1) to (a-11), R a01 Each of these groups is independently selected from the group consisting of halogen atoms, sulfonic acid groups, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms. W a1 , and W a2 These are, independently, single bonds and -CR bonds. a02 R a03Groups represented by -, carbonyl groups, -O-, -S-, -SO-, -SO2-, -NR a04 It is a base represented by -. R a02 , and R a03 This is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. -CR a02 R a03 - In the group represented by R a02 , and R a03 These elements may be joined together to form a ring. R a04 This is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms. X a1 , and X a2 Each of these independently consists of a single bond, an alkylene group with 1 to 10 carbon atoms, and -Y a1 -Ph-Y a2 It is a base represented by -. Ph is a phenylene group which may have substituents of 1 to 4. The substituents which the phenylene group may have are groups selected from the group consisting of halogen atoms, sulfonic acid groups, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms. Y a1 , and Y a2 Each of these is independently either a single bond or an alkylene group having 1 to 10 carbon atoms. n1 is an integer between 0 and 4 (inclusive). n2 and n3 are independent integers between 0 and 3, inclusive. n4 is an integer between 0 and 2 (inclusive). n5 is an integer between 0 and 3 (inclusive). n6 and n7 are independent integers between 0 and 3, inclusive. n8 is an integer between 0 and 3 (inclusive). n9 is an integer between 0 and 5 (inclusive). n10 and n11 are independent integers between 0 and 3, inclusive. n12 is an integer between 0 and 3 (inclusive). n13 is an integer between 0 and 4 (inclusive). n14, n15, and n16 are each independent integers between 0 and 4 (inclusive). n17 is an integer between 0 and 3 (inclusive). n18 is an integer between 0 and 4 (inclusive). n19 is an integer between 0 and 5 (inclusive). n20 and n21 are integers between 0 and 4 (inclusive). n22 and n23 are integers between 0 and 4 (inclusive).

[0026] R a01 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Among these, fluorine, chlorine, and bromine atoms are preferred.

[0027] R a01 The alkyl group having 1 to 10 carbon atoms may be linear or branched. a01 Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, and n-decyl group.

[0028] R a01 The alkoxy group, having 1 to 10 carbon atoms, may be linear or branched. a01 Specific examples of alkoxy groups having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethyl-n-hexyloxy group, n-nonyloxy group, and n-decyloxy group.

[0029] Wa1 , and W a2 These are, independently, single bonds and -CR bonds. a02 R a03 Groups represented by -, carbonyl groups, -O-, -S-, -SO-, -SO2-, -NR a04 It is a base represented by -. W a1 , and W a2 However, -CR a02 R a03 If the group is represented by -, R a02 , and R a03 This is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms. R a02 , and R a03 Alkyl alkyl groups with 1 to 10 carbon atoms as R a01 It is similar to an alkyl group having 1 to 10 carbon atoms. R a02 , and R a03 These elements may be joined together to form a ring. W a1 , and W a2 However, -NR a04 If the group is represented by -, R a04 This is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms. R a04 Alkyl alkyl groups with 1 to 10 carbon atoms as R a01 It is similar to an alkyl group having 1 to 10 carbon atoms.

[0030] X a1 , and X a2 Each of these independently consists of a single bond, an alkylene group with 1 to 10 carbon atoms, and -Y a1 -Ph-Y a2 It is a base represented by -. X a1 , and X a2Specific examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethane-1,2-diyl group (ethylene group), an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, and a decane-1,10-diyl group. X a1 , and X a2 is -Y a1 -Ph-Y a2 When the group is represented by -Ph-, Ph is a phenylene group that may have 1 to 4 substituents. The substituent that the phenylene group may have is a group selected from the group consisting of a halogen atom, a sulfonic acid group, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms and the alkoxy group having 1 to 10 carbon atoms as the optional substituent of the phenylene group are the same as the alkyl group having 1 to 10 carbon atoms and the alkoxy group having 1 to 10 carbon atoms as R a01 . Y a1 , and Y a2 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms. Y a1 , and Y a2 The alkylene group having 1 to 10 carbon atoms as is the same as the alkylene group having 1 to 10 carbon atoms as X a1 , and X a2 .

[0031] Specific examples of the groups represented by formula (a-1) to formula (a-11) are given below. **[Chemical Formula]**

[0032] **[Chemical Formula]**

[0033] Among the above groups, the following groups are preferred. [ka]

[0034] In equation (A1), R a1 This is a carboxyl group protected by a tert-butoxycarbonyloxy group, a tert-butoxycarbonylamino group, or an acid-dissociable group. The tert-butoxycarbonyloxy group and the tert-butoxycarbonylamino group can be deprotected by heating alone to generate a phenolic hydroxyl group or an amino group. On the other hand, deprotection of a carboxyl group protected by an acid-dissociable group by heating alone is difficult. To deprotect a carboxyl group protected by an acid-dissociable group by heating, it is advantageous to heat the protected carboxyl group in the presence of a thermal acid generator (C), as described later. In this case, the acid generated by the thermal acid generator (C) upon heating easily deprotects the carboxyl group protected by the acid-dissociable group. As mentioned above, R is easily deprotected by heating alone. a1 The preferred members are tert-butoxycarbonyloxy groups and tert-butoxycarbonylamino groups.

[0035] The acid-dissociable group is well known in the fields of organic synthesis and photoresists, and is not particularly limited as long as it can protect a carboxyl group. Preferred examples of acid-dissociable groups include acetal protecting groups and tertiary carbon-carbon-containing groups.

[0036] As an acetal protecting group, -CR A1 -OR A2 A base represented by is preferred. R A1 R is a hydrogen atom or an alkyl group. A2 R is an alkyl group. A1 , and RA2 These elements may be joined together to form a ring. R A1 , and R A2 The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 4. A1 , and R A2 The alkyl group may be linear or branched, but linear is preferred. R A1 , and R A2 Suitable examples of alkyl groups include methyl, ethyl, n-propyl, and n-butyl groups.

[0037] -CR A1 -OR A2 Specific examples of the group represented by include the methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, n-butyloxymethyl group, 1-methoxyethyl group, 1-ethoxymethyl group, 1-n-propyloxyethyl group, 1-n-butyloxyethyl group, tetrahydropyran-2-yl group, and tetrahydrofuran-2-yl group.

[0038] As for tertiary carbon atom-containing groups, -C(R A3 )(R A4 )(R A5 A base represented by ) is preferred. R A3 , R A4 , and R A5 Each of these is independently an alkyl group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, or an aliphatic cyclic group having 5 to 20 carbon atoms. R A3 , R A4 , and R A5 Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, and n-hexyl group. R A3 , R A4 , and R A5A fluorinated alkyl group is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. R A3 , R A4 , and R A5 Specific examples of aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, these include groups obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. In particular, groups obtained by removing one hydrogen atom from cyclohexane and adamantane (which may have further substituents) are preferred.

[0039] -C(R A3 )(R A4 )(R A5 The following are specific examples of groups represented by ): [ka]

[0040] In equation (A1), X 1 , and X 2 These are, independently, -NR a2 It is -, -O-, or -S-. a2 This is a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic hydrocarbon group.

[0041] R a2 The number of carbon atoms in the alkyl group is not particularly limited. a2 The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 4. a2 The alkyl group may be linear or branched, but linear is preferred. R a2Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl groups. R a2 The substituents that the alkyl group may have include halogen atoms, hydroxyl groups, alkoxy groups, mercapto groups, and cyano groups.

[0042] R a2 The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited. a2 The number of carbon atoms in the alkyl group is preferably 6 to 12. R a2 Specific examples of aromatic hydrocarbon groups include the phenyl group, naphthalene-1-yl group, naphthalene-2-yl group, 4-phenylphenyl group, 3-phenylphenyl group, and 2-phenylphenyl group. R a2 The substituents that the aromatic hydrocarbon group may have include halogen atoms, alkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, and cyano groups.

[0043] X in equation (A1) 1 Ar 1 X in formula (A1) is bonded to the aromatic ring in the aromatic group-containing group. 2 Ar 2 It attaches to the aromatic ring in the aromatic group-containing group.

[0044] The following are examples of preferred structural units of unit (A1). Structural units in which the amino group bonded to the triazine ring in the following structural units is changed to -O- or -S- are also preferred. Constituent units in which the tert-butoxycarbonyl group in the following constituent units is replaced with a methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, n-butyloxymethyl group, 1-methoxyethyl group, 1-ethoxymethyl group, 1-n-propyloxyethyl group, 1-n-butyloxyethyl group, tetrahydropyran-2-yl group, or tetrahydrofuran-2-yl group are also preferred. In the following structural units, the tert-butoxycarbonyloxy group is replaced with a tert-butoxycarbonylamino group or a carboxyl group protected by the aforementioned acid-dissociable group, and structural units in which this group is replaced are also preferred. [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] <Unit (A2)> As mentioned above, polymer (A) may contain other constituent units other than the constituent unit represented by formula (A1), namely unit (A2). The structure of unit (A2) is not particularly limited as long as the desired effect is not impaired.

[0049] Polymer (A) is produced by polymerizing a dihalotriazine compound with an aromatic diamine compound, an aromatic diol, or an aromatic dithiol, as described later. Therefore, the constituent unit (A2) is preferably the one represented by the following formula (A2). [ka]

[0050] In formula (A2), X 1 , X 2 , and Ar 2 These are the same as those in equation (A1). In equation (A2), Ar 3 Ar is an aromatic group which may have substituents. 3 The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. 3 As the aromatic group, an aromatic hydrocarbon group is preferred. Ar 3 Specific examples of aromatic hydrocarbon groups include the phenyl group, naphthalene-1-yl group, naphthalene-2-yl group, 4-phenylphenyl group, 3-phenylphenyl group, and 2-phenylphenyl group. Ar 3 The substituents that the aromatic hydrocarbon group may have include halogen atoms, alkyl groups, alkoxy groups, and cyano groups.

[0051] The weight-average molecular weight of polymer (A) is not particularly limited as long as the desired effect is not impaired. A weight-average molecular weight of 500 to 100,000 is preferred. From the viewpoint of high solvent resistance of polymer (A) in a heated state, a weight-average molecular weight of 5,000 or more is preferred. From the viewpoint of high solubility of the polymer in various solvents, a weight-average molecular weight of 30,000 or less is preferred.

[0052] <Method for producing polymer (A)> The polymer (A) method described above is not particularly limited as long as the resulting polymer contains unit (A1). Typically, the above polymers are produced by condensing a triazine compound represented by the following formula (A3) with an aromatic diamine compound represented by the following formula (A5-1), an aromatic diol represented by the following formula (A5-2), or an aromatic dithiol represented by the following formula (A5-3).

[0053] [ka]

[0054] In formula (A3), Ar 1 , X 1 , and R a1 These are the same as those in formula (A1). Hal is a halogen atom. Examples of Hal include fluorine, chlorine, bromine, and iodine atoms. Of these, chlorine and bromine atoms are preferred, and chlorine atoms are more preferred.

[0055] Ar 2 -(NR a2 H)2···(A5-1) Ar 2 -(OH)2···(A5-2) Ar 2 -(SH)2···(A5-3) In formulas (A5-1) to (A5-3), Ar 2 , and R a2 These are similar to those in equation (A1).

[0056] Specific examples of aromatic diamine compounds represented by formula (A5-1) include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 9,10-diaminoanthracene, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4 ,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2, 2-Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)ben Zen, 1,3-bis(3-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 4,4'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(4-aminophenoxy)biphenyl, 3,3'-Bis(4-aminophenoxy)biphenyl, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]ketone, 2,2-bis[4-{4-amino-2-(trifluoromethyl)phenoxy}phenyl]hexafluoropropane, 9,9-bis(4-amino Phenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, 2,7-diaminofluorene, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(3-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-6-aminobenzoxazole, 2-(3-aminophenyl)-6-aminobenzoxazole, 1,4-bis(5-amino-2-benzoxazolyl)benzene, 1,4-bis(6-amino-2 -Benzoxazolyl)benzene, 1,3-bis(5-amino-2-benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5-benzoxazolyl], bis[(4-aminophenyl)-5-benzoxazolyl], bis[(3-aminophenyl)-6-benzoxazolyl] Examples include zolyl, bis[(4-aminophenyl)-6-benzoxazolyl], 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline, 4-aminobenzoic acid 4-aminophenyl ester, 1,3-bis(4-anilino)tetramethyldisiloxane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, etc.

[0057] Specific examples of aromatic diols represented by formula (A5-2) include hydroquinone, resorcinol, 2,4-dihydroxytoluene, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 9,10-dihydroxyanthracene, 9,10-bis(4-hydroxyphenyl)anthracene, 4,4'-dihydroxy-2, 2'-Bis(trifluoromethyl)biphenyl, 4,4'-dihydroxybenzophenone, 3,3'-dihydroxybenzophenone, 3,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfone, 3,3'-dihydroxydiphenylsulfone, 3,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 3,3'-dihydroxydiphenylsulfide, 3,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylmethane, 3,3'-di Aminodiphenylmethane, 3,4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis[4-(4-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(4-hydroxyphenoxy)phenyl]hexafluoropropane, propane, 4,4'-dihydroxydiphenyl ether, 3,4'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzanilide, 3,3'-dihydroxy Roxybenzanilide, 1,4-bis(4-hydroxyphenyl)benzene, 1,3-bis(4-hydroxyphenyl)benzene, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 1,3-bis(3-hydroxyphenoxy)benzene, 1,2-bis(4-hydroxyphenoxy)ethane, 1,3-bis(4-hydroxyphenoxy)propane, 1,4-bis(4-hydroxyphenoxy)butane, 1,5-bis(4-hydroxyphenoxy)pentane, 1,6-Bis(4-hydroxyphenoxy)hexane, bis[4-(4-hydroxyphenoxy)phenyl]ether, bis[4-(3-hydroxyphenoxy)phenyl]ether, 4,4'-bis(4-hydroxyphenoxy)biphenyl, 3,4'-bis(4-hydroxyphenoxy)biphenyl, 3,3'-bis(4-hydroxyphenoxy)biphenyl, bis(4-hydroxyphenoxyphenyl)sulfone, bis(3-hydroxyphenoxyphenyl)sulfone, bis[4-(4-hydroxyphenoxy)phenyl]sulfone, bis[4 -(3-hydroxyphenoxy)phenyl]sulfone, bis[4-(4-hydroxyphenoxy)phenyl]ketone, 2,2-bis[4-{4-hydroxy2-(trifluoromethyl)phenoxy}phenyl]hexafluoropropane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 2,7-dihydroxyfluorene, 2-(4-hydroxyphenyl)-5-hydroxybenzoxazole, 2-(3-hydroxyphenyl)-5-hydroxybenzoxazole, 2 -(4-hydroxyphenyl)-6-hydroxybenzoxazole, 2-(3-hydroxyphenyl)-6-hydroxybenzoxazole, 1,4-bis(5-hydroxy-2-benzoxazolyl)benzene, 1,4-bis(6-hydroxy-2-benzoxazolyl)benzene, 1,3-bis(5-hydroxy-2-benzoxazolyl)benzene, 1,3-bis(6-hydroxy-2-benzoxazolyl)benzene, 2,6-bis(4-hydroxyphenyl)benzobisoxazole, 2,6-bis(3-hydroxyphenyl)ben Zobisoxazole, bis[(3-hydroxyphenyl)-5-benzoxazol], bis[(4-hydroxyphenyl)-5-benzoxazol], bis[(3-hydroxyphenyl)-6-benzoxazol], bis[(4-hydroxyphenyl)-6-benzoxazol], 3,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline, 4-hydroxyphenyl ester of 4-hydroxybenzoic acid, 1,Examples include 3-bis(4-anilino)tetramethyldisiloxane.

[0058] Specific examples of aromatic dithiols represented by formula (A5-3) include 1,4-dimercaptobenzene, 1,3-dimercaptobenzene, 2,4-dimercaptotoluene, 4,4'-dimercaptobiphenyl, 3,3'-dimercaptobiphenyl, 3,4'-dimercaptobiphenyl, 1,4-dimercaptonaphthalene, 1,5-dimercaptonaphthalene, 2,6-dimercaptonaphthalene, 2,7-dimercaptonaphthalene, 9,10-dimercaptoanthracene, 9,10-bis(4-mercaptophenyl)anthracene, and 4,4 '-Dimercapto-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-Dimercaptobenzophenone, 3,3'-Dimercaptobenzophenone, 3,4'-Dimercaptobenzophenone, 4,4'-Dimercaptodiphenylsulfone, 3,3'-Dimercaptodiphenylsulfone, 3,4'-Dimercaptodiphenylsulfone, 4,4'-Dimercaptodiphenylsulfide, 3,3'-Dimercaptodiphenylsulfide, 3,4'-Dimercaptodiphenylsulfide, 4,4'-Dimercaptodiphenylmethane ,3,3'-diaminodiphenylmethane, 3,4'-dimercaptodiphenylmethane, 2,2-bis(4-mercaptophenyl)propane (bisphenol A), 2,2-bis[4-(4-mercaptophenoxy)phenyl]propane, 2,2-bis[4-(4-mercaptophenoxy)phenyl]hexafluoropropane, propane, 4,4'-dimercaptodiphenyl ether, 3,4'-dimercaptodiphenyl ether, 3,3'-dimercaptodiphenyl ether, 4,4'-dimercaptobenzanilide, 3,3' -Dimercaptobenzanilide, 1,4-bis(4-mercaptophenyl)benzene, 1,3-bis(4-mercaptophenyl)benzene, 1,4-bis(4-mercaptophenoxy)benzene, 1,3-bis(4-mercaptophenoxy)benzene, 1,3-bis(3-mercaptophenoxy)benzene, 1,2-bis(4-mercaptophenoxy)ethane, 1,3-bis(4-mercaptophenoxy)propane, 1,4-bis(4-mercaptophenoxy)butane, 1,5-bis(4-mercaptophenoxy)pentane, 1,6-Bis(4-mercaptophenoxy)hexane, bis[4-(4-mercaptophenoxy)phenyl]ether, bis[4-(3-mercaptophenoxy)phenyl]ether, 4,4'-bis(4-mercaptophenoxy)biphenyl, 3,4'-bis(4-mercaptophenoxy)biphenyl, 3,3'-bis(4-mercaptophenoxy)biphenyl, bis(4-mercaptophenoxyphenyl)sulfone, bis(3-mercaptophenoxyphenyl)sulfone, bis[4-(4-mercaptophenoxy)phenyl]sulfone, bis[ 4-(3-mercaptophenoxy)phenyl]sulfone, bis[4-(4-mercaptophenoxy)phenyl]ketone, 2,2-bis[4-{4-mercapto2-(trifluoromethyl)phenoxy}phenyl]hexafluoropropane, 9,9-bis(4-mercaptophenyl)fluorene, 9,9-bis(4-mercapto3-methylphenyl)fluorene, 2,7-dimercaptofluorene, 2-(4-mercaptophenyl)-5-mercaptobenzoxazole, 2-(3-mercaptophenyl)-5-mercaptobenzoxazole, 2 -(4-mercaptophenyl)-6-mercaptobenzoxazole, 2-(3-mercaptophenyl)-6-mercaptobenzoxazole, 1,4-bis(5-mercapto-2-benzoxazol)benzene, 1,4-bis(6-mercapto-2-benzoxazol)benzene, 1,3-bis(5-mercapto-2-benzoxazol)benzene, 1,3-bis(6-mercapto-2-benzoxazol)benzene, 2,6-bis(4-mercaptophenyl)benzobisoxazole, 2,6-bis(3-mercaptophenyl)benn Zobisoxazole, bis[(3-mercaptophenyl)-5-benzoxazol], bis[(4-mercaptophenyl)-5-benzoxazol], bis[(3-mercaptophenyl)-6-benzoxazol], bis[(4-mercaptophenyl)-6-benzoxazol], 3,4'-dimercaptodiphenyl sulfide, 4,4'-dimercaptodiphenyl sulfide, 4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline, 4-mercaptobenzoic acid 4-mercaptophenyl ester, 1,Examples include 3-bis(4-anilino)tetramethyldisiloxane.

[0059] The triazine compound represented by formula (A3) can be produced by condensing a cyanuryl halogen with an aromatic amine compound represented by formula (A3-1), a hydroxyaromatic compound represented by formula (A3-2), or a mercaptoaromatic compound represented by formula (A3-3). R a1 -Ar 1 -NR a2 H···(A3-1) R a1 -Ar 1 -OH···(A3-2) R a1 -Ar 1 -SH···(A3-3)

[0060] In formulas (A3-1) to (A3-3), Ar 1 , R a1 , and R a2 These are similar to those in equation (A1).

[0061] Examples of cyanuryl halogens include cyanuryl fluoride, cyanuryl chloride, and cyanuryl bromide. Of these, cyanuryl chloride is preferred.

[0062] When producing the triazine compound represented by formula (A3), the amount of the aromatic amine compound represented by formula (A3-1), the hydroxyaromatic compound represented by formula (A3-2), or the mercaptoaromatic compound represented by formula (A3-3) used is preferably 0.8 moles or more and 1.2 moles or less, more preferably 0.9 moles or more and 1.1 moles or less, and even more preferably 0.95 moles or more and 1.05 moles or less, per mole of cyanuric halogenate.

[0063] The reaction between cyanuric halogens and aromatic amine compounds represented by formula (A3-1), hydroxyaromatic compounds represented by formula (A3-2), or mercaptoaromatic compounds represented by formula (A3-3) is usually carried out by mixing the two in an organic solvent. The organic solvent used in this reaction is not particularly limited as long as the reaction proceeds well. As an organic solvent, solvents that do not contain hydroxyl groups, mercapto groups, or amino groups are preferred because they do not react with cyanuric halogens. Specific examples of organic solvents include, for example, ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, and styrene; monoalkyl ether acetates of glycols such as ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; dialkyl ethers of glycols such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether; esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate; and lactones such as γ-butyrolactone. The amount of organic solvent used is not particularly limited as long as the reaction proceeds well. Preferably, the amount of organic solvent used is 100 parts by mass or more and 5000 parts by mass or less, and more preferably 200 parts by mass or more and 4000 parts by mass or less, per 100 parts by mass of the reaction raw material.

[0064] The temperature at which the cyanuryl halogen is reacted with the aromatic amine compound represented by formula (A3-1), the hydroxyaromatic compound represented by formula (A3-2), or the mercaptoaromatic compound represented by formula (A3-3) is preferably -20°C to 150°C, and more preferably -10°C to 50°C. An aromatic amine compound represented by formula (A3-1), a hydroxyaromatic compound represented by formula (A3-2), or a mercaptoaromatic compound represented by formula (A3-3) is R a1If the material contains a tert-butoxycarbonyloxy group or a tert-butoxycarbonylamino group, the reaction temperature is preferably -10°C to 50°C in order to prevent thermal deprotection of the tert-butoxycarbonyloxy group or the tert-butoxycarbonylamino group. The reaction time is not particularly limited. For example, the reaction time is preferably 30 minutes to 50 hours, and more preferably 1 hour to 30 hours.

[0065] The following compounds are suitable examples of aromatic amine compounds represented by formula (A3-1), hydroxyaromatic compounds represented by formula (A3-2), and mercaptoaromatic compounds represented by formula (A3-3). a1 R in equation (A1) is a1 It is similar to that. [ka]

[0066] [ka]

[0067] [ka]

[0068] Units (A1) and (A2) can be obtained by using a triazine compound represented by formula (A3) along with a dihalotriazine compound other than the triazine compound represented by formula (A3). As a dihalotriazine compound other than the triazine compound represented by formula (A3), the dihalotriazine compound represented by the following formula (A2-1) is preferred. By using the dihalotriazine compound represented by the following formula (A2-1), the constituent unit represented by formula (A2) is introduced into the polymer (A) as unit (A2).

[0069] [ka]

[0070] X in equation (A2-1) 1 This is X in equation (A1). 1 It is the same as the Ar in equation (A2-1). 3 In equation (A2), Ar 3 It is the same as in equation (A2-1). Hal in equation (A3) is the same as Hal in equation (A3).

[0071] The method for condensing a dihalotriazine compound, including a triazine compound represented by formula (A3), with an aromatic diamine compound represented by formula (A5-1), an aromatic diol represented by formula (A5-2), or an aromatic dithiol represented by formula (A5-3) is not particularly limited. Typically, the aforementioned polymer (A) can be produced by mixing a dihalotriazine compound containing a triazine compound represented by formula (A3) with an aromatic diamine compound represented by formula (A5-1), an aromatic diol represented by formula (A5-2), or an aromatic dithiol represented by formula (A5-3) in an organic solvent.

[0072] The organic solvent used in the condensation reaction is preferably an organic solvent in which the polymer (A) to be produced is soluble. Examples of such organic solvents include nitrogen-containing polar organic solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methylformamide, N,N-dimethylpropionic acid amide, N,N-dimethylisobutylamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-2-piperidone, N-acetylpyrrolidine, N,N'-dimethylethyleneurea (1,3-dimethyl-2-imidazolidinone), N,N'-dimethylpropyleneurea, N,N,N',N'-tetramethylmalonamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea; sulfoxides such as dimethyl sulfoxide; hexamethyl phosphate triamide; ketone solvents such as cyclopentanone, cyclohexanone, and methyl isobutyl ketone; and ethers such as tetrahydrofuran and dioxane. The amount of organic solvent used is not particularly limited as long as the reaction proceeds well. Preferably, the amount of organic solvent used is 100 parts by mass or more and 5000 parts by mass or less, and more preferably 200 parts by mass or more and 4000 parts by mass or less, per 100 parts by mass of the reaction raw material.

[0073] When producing polymer (A), the amount of aromatic diamine compound represented by formula (A5-1), aromatic diol represented by formula (A5-2), or aromatic dithiol represented by formula (A5-3) used is preferably 0.8 moles or more and 1.2 moles or less, more preferably 0.9 moles or more and 1.1 moles or less, and even more preferably 0.95 moles or more and 1.05 moles or less, per mole of dihalotriazine compound containing the triazine compound represented by formula (A3).

[0074] The reaction temperature when producing polymer (A) is preferably between 0°C and 200°C, and more preferably between 20°C and 150°C. The reaction time is not particularly limited. For example, the reaction time is preferably 5 minutes to 24 hours, more preferably 10 minutes to 18 hours, and even more preferably 30 minutes to 12 hours.

[0075] <Crosslinkable compound (B)> The crosslinkable compound (B) has two or more crosslinkable groups. Of the two or more crosslinkable groups, at least one is an epoxy group or an episulfide group. Preferably, the crosslinkable compound (B) has two or more groups selected from epoxy groups and episulfide groups as crosslinkable groups. Preferably, the crosslinkable compound (B) does not have any crosslinkable groups other than epoxy groups and episulfide groups. As the crosslinkable compound (B), epoxy compounds having only epoxy groups as crosslinkable groups and episulfide compounds having only episulfide groups as crosslinkable groups are preferred, and epoxy compounds having only epoxy groups as crosslinkable groups are more preferred. Other crosslinkable groups besides epoxy groups and episulfide groups are not particularly limited, as long as they can reactively crosslink with phenolic hydroxyl groups, amino groups, or carboxyl groups. Examples of crosslinkable groups other than epoxy groups and episulfide groups include isocyanate groups.

[0076] Preferred examples of the crosslinkable compound (B) include an aromatic compound (Bi) containing two or more crosslinkable groups and a triazine ring, an optionally substituted fluorene ring, or an optionally substituted binaphthalene ring; a sulfur-containing compound (Bii) containing two or more crosslinkable groups; and an aliphatic compound (Biii) containing two or more crosslinkable groups. Sulfur-containing compounds (Bii) are compounds that do not fall under the category of aromatic compounds (Bi). Furthermore, episulfide compounds that do not contain sulfur atoms other than those contained in the episulfide group do not fall under the category of sulfur-containing compounds (Bii). Aliphatic compounds (Biii) are compounds that do not fall under the categories of aromatic compounds (Bi) or sulfur-containing compounds (Bii). By using a thermosetting composition containing a crosslinkable compound (B) selected from the above aromatic compounds (Bi), sulfur-containing compounds (Bii), and aliphatic compounds (Biii), a cured product with a high refractive index can be formed.

[0077] Hereinafter, compounds containing two or more crosslinkable groups and a triazine ring will also be referred to as "crosslinkable triazine compounds (Bi-1)". Compounds containing two or more crosslinkable groups and a fluorene ring will also be referred to as "crosslinkable fluorene compounds (Bi-2)". Compounds containing two or more crosslinkable groups and a binaphthalene ring will also be referred to as "crosslinkable binaphthalene compounds (Bi-3)".

[0078] [Cross-linkable triazine compound (B1)] As the crosslinkable triazine compound, the compound represented by the following formula (b1) is preferred. [ka]

[0079] In equation (b1), Ar b1 Ar b2 , and Ar b3 These are, independently, aromatic group-containing groups. b1 , R b2 , and R b3X is a hydrogen atom, alkyl group, alkoxy group, halogen atom, nitro group, cyano group, glycidyloxy group, or thiran-2-ylmethyloxy group. b1 , X b2 , and X b3 These are, independently, -NR b4 It is -, -O-, or -S-. b1 , R b2 , and R b3 Two or three of these are glycidyloxy groups or thiran-2-ylmethyloxy groups. b4 X is a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic hydrocarbon group. b1 Ar b1 It attaches to the aromatic ring in the aromatic group-containing group as X. b2 Ar b2 It attaches to the aromatic ring in the aromatic group-containing group as X. b3 Ar b3 It attaches to the aromatic ring in the aromatic group-containing group.

[0080] In equation (b1), Ar b1 Ar b2 , and Ar b3 The aromatic group containing the aromatic group is, in the above formula (a1), Ar 1 It is similar to an aromatic group containing Ar. b1 Ar b2 , and Ar b3 It is preferable that these are the same aromatic group-containing groups. In equation (b1), R b4 In the aforementioned equation (a1), R a2 It is similar to that.

[0081] R b1 , R b2 , and R b3 The number of carbon atoms in the alkyl group is not particularly limited. b1 , R b2 , and R b3 The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 4. R b1 , Rb2 , and R b3 Specific examples of the alkyl group as include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.

[0082] R b1 , R b2 , and R b3 The number of carbon atoms in the alkoxy group as is not particularly limited. R b1 , R b2 , and R b3 The number of carbon atoms in the alkoxy group as is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less. R b1 , R b2 , and R b3 Specific examples of the alkoxy group as include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, and an n-hexyloxy group.

[0083] Preferable examples of the compound represented by formula (b1) include the following compounds.

[0084]

Chemical Formula

[0085]

Chemical Formula

[0086]

Chemical Formula

[0087]

Chemical Formula

[0088] [Cross-linkable fluorene compound (Bi-2)] As a crosslinkable fluorene compound (Bi-2), the compound represented by the following formula (b2) is preferred because it is easy to synthesize and obtain, has good crosslinking reactivity, and makes it easy to obtain a cured product with a high refractive index. [ka] (In formula (b2), W 1 and W 2 Each of these is independently expressed in the following equation (b2-1): [ka] It is a base represented by, In formula (b2-1), ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by -S-, and R 1 R represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an alkylene oxy group having 1 to 4 carbon atoms. 1 If it is an alkylene oxy group, the oxygen atom in the alkylene oxy group is bonded to ring Z, and R 2 is a monovalent hydrocarbon group, a hydroxyl group, -OR 4a The base indicated by -SR 4b The groups represented by -NHR, acyl groups, alkoxycarbonyl groups, halogen atoms, nitro groups, cyano groups, mercapto groups, carboxyl groups, amino groups, carbamoyl groups, -NHR 4c The base shown by -N(R 4d ) The group shown in 2, a sulfo group, or a monovalent hydrocarbon group, -OR 4a The base indicated by -SR 4b The group indicated by -NHR, acyl group, alkoxycarbonyl group, 4c The group indicated by, or -N(R 4d )2 At least some of the hydrogen atoms bonded to the carbon atoms in the group indicated by are monovalent hydrocarbon groups, hydroxyl groups, -OR 4a The base indicated by -SR 4b The groups represented by -NHR, acyl groups, alkoxycarbonyl groups, halogen atoms, nitro groups, cyano groups, mercapto groups, carboxyl groups, amino groups, carbamoyl groups, -NHR 4c The base shown by -N(R4d )2 indicates a group substituted with a mesyloxy group or a sulfo group, R 4a ~R 4d represents a monovalent hydrocarbon group independently, m represents an integer greater than or equal to 0, and R 3 This is a thiran-2-ylmethyl group or a glycidyl group. Ring Y 1 and ring Y 2 R represents the same or different aromatic hydrocarbon rings. 3a and R 3b (where n1 and n2 independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, and n1 and n2 independently represent integers between 0 and 4.)

[0089] In the above formula (b2-1), ring Z may be, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a naphthalene ring, etc.)]. 8-20 A condensed bicyclic hydrocarbon ring, preferably C 10-16 Examples include condensed bicyclic hydrocarbon rings, condensed tricyclic aromatic hydrocarbon rings (e.g., anthracene rings, phenanthrene rings, etc.), and condensed 2- to 4-cyclic aromatic hydrocarbon rings. Ring Z is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring. Note that W in formula (b2) 1 and W 2 Since each of these is an independent base represented by formula (b2-1), W 1 and W 2 Each of these contains ring Z. 1 The rings Z and W included in this ring 2 The ring Z contained in may be the same or different rings; for example, one ring may be a benzene ring and the other a naphthalene ring, but it is particularly preferable that both rings are naphthalene rings.

[0090] Also, W 1 and W 2 The substitution position of ring Z, which is bonded via X to the carbon atom to which both are directly connected, is not particularly limited. For example, if ring Z is a naphthalene ring, the group corresponding to ring Z bonded to the carbon atom may be a 1-naphthyl group, a 2-naphthyl group, etc.

[0091] In formula (b2-1), X independently represents a single bond or a group denoted by -S-, and is typically a single bond.

[0092] In equation (b2-1), R 1 Examples include single bonds; alkylene groups with 1 to 4 carbon atoms, such as methylene groups, ethylene groups, trimethylene groups, propylene groups, and butane-1,2-diyl groups; and alkylene oxy groups with 1 to 4 carbon atoms, such as methyleneoxy groups, ethyleneoxy groups, and propyleneoxy groups. 2-4 Alkylene groups (especially ethylene groups, propylene groups, etc.) 2-3 Alkylene group; C 2-4 Alkylene oxy groups (especially ethylene oxy groups, propylene oxy groups, etc.) 2-3 An alkylene group is preferred, and a single bond is more preferred. 1 If is an alkylene oxy group, the oxygen atom in the alkylene oxy group bonds with ring Z. Also, W in formula (b2) 1 and W 2 Since each of these is an independent base represented by formula (b2-1), W 1 and W 2 These are the divalent groups R 1 Includes W 1 R included 1 and W 2 R included 1 These may be the same or they may be different.

[0093] In equation (b2-1), R 2 Examples include alkyl groups (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.). 1-12 Alkyl alkyl group, preferably C 1-8 Alkyl alkyl groups, more C 1-6 Alkyl alkyl groups, etc., cycloalkyl groups (Cyclohexyl group, etc.) 5-10 Cycloalkyl groups, preferably C 5-8 Cycloalkyl groups, more preferably C 5-6C(Cycloalkyl groups, etc.), aryl groups (e.g., phenyl group, tolyl group, xylyl group, naphthyl group, etc.) 6-14 Aryl group, preferably C 6-10 Aryl group, more preferably C 6-8 (Aryl group, etc.), Aralkyl group (benzyl group, phenethyl group, etc.) 6-10 Aryl-C 1-4 Monovalent hydrocarbon groups such as alkyl groups; hydroxyl groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups (C) 1-12 Alkoxy group, preferably C 1-8 Alkoxy group, more preferably C 1-6 (such as alkoxy groups), cycloalkoxy groups (such as cyclohexyloxy groups) 5-10 Cycloalkoxy groups, etc., aryloxy groups (such as phenoxy groups) 6-10 (aryloxy group), aralkyloxy group (e.g., benzyloxy group, etc.) 6-10 Aryl-C 1-4 -OR groups such as alkyloxy groups 4a The base shown by [wherein R 4a indicates a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). ]; alkylthio group (such as methylthio group, ethylthio group, propylthio group, butylthio group, etc.) 1-12 Alkylthio group, preferably C 1-8 Alkylthio group, more preferably C 1-6 C (such as alkylthio groups), cycloalkylthio groups (such as cyclohexylthio groups) 5-10 Cycloalkylthio groups, etc., arylthio groups (phenylthio groups, etc.) 6-10 (arylthio group), aralkylthio group (for example, benzylthio group, etc.) 6-10 Aryl-C 1-4 -SR (alkylthio group, etc.) 4b The base shown by [wherein R 4b indicates a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). ]; Acyl group (such as an acetyl group C 1-6 Acyl group, etc.; Alkoxycarbonyl group (C such as methoxycarbonyl group) 1-4Alkoxycarbonyl groups, etc.); halogen atoms (fluorine, chlorine, bromine, iodine, etc.); nitro groups; cyano groups; mercapto groups; carboxyl groups; amino groups; carbamoyl groups; alkylamino groups (methylamino, ethylamino, propylamino, butylamino, etc.) 1-12 Alkylamino group, preferably C 1-8 Alkylamino group, more preferably C 1-6 C (such as alkylamino groups), cycloalkylamino groups (such as cyclohexylamino groups) 5-10 Cycloalkylamino groups, etc., arylamino groups (phenylamino groups, etc.) 6-10 (arylamino group), aralkylamino group (e.g., benzylamino group, etc.) 6-10 Aryl-C 1-4 -NHR (Alkylamino group, etc.) 4c The base shown by [wherein R 4c indicates a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). ]; dialkylamino group (such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, etc. (C 1-12 Alkyl)amino group, preferably di(C) 1-8 Alkyl)amino group, more preferably di(C) 1-6 (Alkyl)amino group, etc., dicycloalkylamino group (dicyclohexylamino group, etc.) 5-10 (Cycloalkyl)amino group, etc., diarylamino group (diphenylamino group, etc.) 6-10 (aryl)amino group), dialkylamino group (for example, dibenzylamino group, etc.) 6-10 Aryl-C 1-4 -N(R) 4d )2 is the base shown in the formula [wherein R 4d represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). ]; (meth)acryloyloxy group; sulfo group; the above monovalent hydrocarbon group, -OR 4a The base indicated by -SR 4b The group indicated by -NHR, acyl group, alkoxycarbonyl group, 4c The group indicated by, or -N(R 4d)2 At least some of the hydrogen atoms bonded to the carbon atoms in the group indicated by are the above monovalent hydrocarbon group, hydroxyl group, -OR 4a The base indicated by -SR 4b The groups represented by -NHR, acyl groups, alkoxycarbonyl groups, halogen atoms, nitro groups, cyano groups, mercapto groups, carboxyl groups, amino groups, carbamoyl groups, -NHR 4c The base shown by -N(R 4d ) Groups substituted with the group shown in 2, (meth)acryloyloxy group, mesyloxy group, or sulfo group [for example, alkoxyaryl group (for example, methoxyphenyl group, etc.) C 1-4 Alkoxy C 6-10 (aryl group), alkoxycarbonylaryl group (e.g., methoxycarbonylphenyl group, ethoxycarbonylphenyl group, etc.) 1-4 Alkoxy-carbonyl C 6-10 Examples include aryl groups, etc.

[0094] Of these, R is a representative example. 2 is a monovalent hydrocarbon group, -OR 4a The base indicated by -SR 4b The groups represented by -NHR, acyl groups, alkoxycarbonyl groups, halogen atoms, nitro groups, cyano groups, and -NHR groups. 4c The base shown by -N(R 4d )2 may also be the base shown.

[0095] Preferred R 2 Examples include monovalent hydrocarbon groups [for example, alkyl groups (for example, C 1-6 Alkyl alkyl groups, cycloalkyl groups (for example, C 5-8 Cycloalkyl groups), aryl groups (e.g., C 6-10 Aryl group), aralkyl group (for example, C 6-8 Aryl-C 1-2 [Alkyl group, etc.], alkoxy group (C 1-4 Examples include alkoxy groups, etc. In particular, R 2a and R 2b is an alkyl group [C 1-4 Alkyl groups (especially methyl groups), aryl groups [for example, C 6-10It is preferably a monovalent hydrocarbon group (especially an alkyl group) such as an aryl group (especially a phenyl group).

[0096] In addition, when m is an integer of 2 or more, a plurality of R 2 may be different from or the same as each other. In addition, W 1 contained R 2 and R contained in W 2 contained R 2 may be the same or different.

[0097] In formula (b2-1), the number m of R 2 can be selected according to the type of ring Z, and for example, may be 0 or more and 4 or less, preferably 0 or more and 3 or less, more preferably 0 or more and 2 or less. In addition, m in W 1 and m in W 2 may be the same or different.

[0098] In the above formula (b2-1), R 3 is a thiiran-2-ylmethyl group or a glycidyl group.

[0099] W 1 contained R 3 and R contained in W 2 contained R 3 may be the same or different. R contained in W 1 contained R 3 and R contained in W 2 contained R 3 preferably both are a thiiran-2-ylmethyl group or a glycidyl group, and more preferably both are the same group selected from the group consisting of a thiiran-2-ylmethyl group and a glycidyl group.

[0100] In the above formula (b2), ring Y 1 and ring Y 2 include, for example, a benzene ring and a fused polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring (for example, C such as a naphthalene ring 8-20 a fused bicyclic hydrocarbon ring, preferably C 10-16Examples include condensed bicyclic hydrocarbon rings, condensed tricyclic aromatic hydrocarbon rings (e.g., anthracene rings, phenanthrene rings, etc.), and condensed bicyclic to tetracyclic aromatic hydrocarbon rings. 1 and ring Y 2 It is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring. Note that ring Y 1 and ring Y 2 These rings may be the same or different; for example, one ring may be a benzene ring and the other a naphthalene ring.

[0101] In the above equation (a1), R 3a and R 3b Typically, these include non-reactive substituents, such as cyano groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), monovalent hydrocarbon groups [for example, alkyl groups, aryl groups (phenyl groups, etc.)]. 6-10 Examples include aryl groups, etc., and it is preferably a cyano group or an alkyl group, and particularly preferably an alkyl group. Examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, etc. 1-6 Alkyl alkyl groups (for example, C 1-4 Examples include alkyl groups, especially methyl groups. Note that if n1 is an integer greater than or equal to 2, R 3a They may be different from each other, or they may be the same. Also, if n2 is an integer greater than or equal to 2, R 3b They may be different from each other, or they may be the same. Furthermore, R 3a and R 3b They may be the same or they may be different. Also, ring Y 1 and ring Y 2 R for 3a and R 3b The bond position (substitution position) is not particularly limited. Preferred substitution numbers n1 and n2 are 0 or 1, particularly 0. Note that n1 and n2 may be the same or different from each other.

[0102] Among the compounds represented by the above formula (b2), particularly preferred examples include epoxy group-containing fluorene compounds such as 9,9-bis[4-[2-(glycidyloxy)ethoxy]phenyl]-9H-fluorene, 9,9-bis[4-[2-(glycidyloxy)ethyl]phenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3-methylphenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3,5-dimethylphenyl]-9H-fluorene, 9,9-bis(6-glycidyloxynaphthalen-1-yl)-9H-fluorene, and 9,9-bis(5-glycidyloxynaphthalen-2-yl)-9H-fluorene; and compounds represented by the following formula.

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [Cross-linkable binaphthalene compound (Bi-3)] Suitable specific examples of crosslinkable binaphthalene compounds (Bi-3) include 2,2'-diglycidyloxy-1,1'-binaphthalene, 2,2'-diglycidyloxy-3,3'-diglycidyloxycarbonyl-1,1'-binaphthalene, 2,2'-diglycidyloxy-6,6'-diglycidyloxycarbonyl-1,1'-binaphthalene, 2,2'-di(thiran-2-ylmethyl)oxy-1,1'-binaphthalene, 2,2'-di(thiran-2-ylmethyl)oxy-3,3'-di(thiran-2-ylmethyl)oxycarbonyl-1,1'-binaphthalene, and 2,2'-di(thiran-2-ylmethyl)oxy-6,6'-di(thiran-2-ylmethyl)oxycarbonyl-1,1'-binaphthalene.

[0109] [Sulfur-containing compound (Bii)] Sulfur-containing compounds (Bii) are sulfur-containing compounds that contain two or more crosslinking groups. However, compounds that do not contain sulfur atoms other than those contained in the episulfide group do not fall under the category of sulfur-containing compounds (B4).

[0110] The crosslinking groups of the sulfur-containing compound (Bii) are preferably a glycidyl group and a thiran-2-ylmethyl group, with the thiran-2-ylmethyl group being more preferred.

[0111] A suitable example of a sulfur-containing compound (Bii) is the compound represented by the following formula (b4-1). R b5 -CH2-S-[-(CH2) p -S-] q -CH2-R b5 ...(b4-1) In equation (b4-1), R b5 is a thiiran-2-yl group. p is an integer between 0 and 4 (inclusive). q is an integer between 0 and 2 (inclusive). Specific examples of compounds represented by formula (b4-1) include bis(thiran-2-ylmethyl) sulfide, bis(thiran-2-ylmethyl) methane, 1,2-bis(thiran-2-ylmethyl) ethane, 1,3-bis(thiran-2-ylmethyl) propane, 1,4-bis(thiran-2-ylmethyl) butane, and bis(thiran-2-ylmethylthioethyl) sulfide.

[0112] A suitable example of a sulfur-containing compound (Bii) is the compound represented by the following formula (b4-2). R b5 -CH2-S-(CH2) r -CHX-(CH2) s -S-CH2-R b5 ...(b4-2) In equation (b4-2), R b5 is a thiran-2-yl group. CHX is a cyclohexanediyl group. r and s are each independently integers between 0 and 4 (inclusive). Specific examples of compounds represented by formula (b4-2) include 1,3-bis(thiran-2-ylmethylthio)cyclohexane, 1,4-bis(thiran-2-ylmethylthio)cyclohexane, 1,3-bis(thiran-2-ylmethylthiomethyl)cyclohexane, and 1,4-bis(thiran-2-ylmethylthiomethyl)cyclohexane.

[0113] A suitable example of a sulfur-containing compound (Bii) is the compound represented by the following formula (b4-3). R b5 -CH2-S-(CH2) t -DTA-(CH2) u -S-CH2-R b5 ...(b4-3) In equation (b4-3), R b5 is a thiran-2-yl group. DTA is a 1,4-dithiandiyl group. t and u are each independent integers between 0 and 4 (inclusive). Specific examples of compounds represented by formula (b4-3) include 2,5-bis(thiran-2-ylmethylthio)-1,4-dithiane and 2,5-bis(thiran-2-ylmethylthiomethyl)-1,4-dithiane.

[0114] A suitable example of a sulfur-containing compound (Bii) is the compound represented by the following formula (b4-4). R b5 -CH2-S-(CH2) v -Ph-(CH2) w -S-CH2-R b5 ...(b4-4) In equation (b4-4), R b5 is a thiran-2-yl group. Ph is a phenylene group. v and w are each independent integers between 0 and 4 (inclusive). Specific examples of compounds represented by formula (b4-4) include 1,3-bis(thiran-2-ylmethylthio)benzene, 1,4-bis(thiran-2-ylmethylthio)benzene, 1,3-bis(thiran-2-ylmethylthiomethyl)benzene, and 1,4-bis(thiran-2-ylmethylthiomethyl)benzene.

[0115] [Aliphatic compound (Biii)] Aliphatic compounds (Biii) are aliphatic compounds containing two or more crosslinking groups. However, aliphatic compounds (Biii) are compounds that do not fall under the categories of aromatic compounds (Bi) or sulfur-containing compounds (Bii). The structure of the aliphatic compound (Biii) may be a chain structure, a cyclic structure, or a combination of a chain structure and a cyclic structure. The crosslinking groups of the aliphatic compound (Biii) are preferably a glycidyl group and a thiran-2-ylmethyl group.

[0116] Examples of aliphatic compounds (Biii) include compounds in which two or more hydroxyl groups of various aliphatic polyols are replaced by glycidyl groups or thiran-2-ylmethyl groups. Suitable examples of polyols that yield aliphatic compounds (Biii) include ethylene glycol, propylene glycol (propane-1,2-diol), propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, glycerin, diglycerin, triglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, sorbitol, and isosorbide.

[0117] Preferred specific examples of aliphatic compounds having an epoxy group (Biii) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, propane-1,3-diol diglycidyl ether, butane-1,4-diol diglycidyl ether, pentane-1,5-diol diglycidyl ether, hexane-1,6-diol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, and dipropylene glycol diglycidyl ether. Triglycerin ether, tripropylene glycol diglycidyl ether, glycerin-1,3-diglycidyl ether, glycerin-1,2-diglycidyl ether, diglycerin diglycidyl ether, diglycerin triglycidyl ether, diglycerin tetraglycidyl ether, triglycerin diglycidyl ether, triglycerin triglycidyl ether, triglycerin tetraglycidyl ether, triglycerin pentaglycidyl ether, triglycerin, triglycerin hexaglycidyl ether Examples include trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol diglycidyl ether, dipentaerythritol triglycidyl ether, dipentaerythritol tetraglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, 1,4-cyclohexanediol diglycidyl ether, 1,3-cyclohexanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,3-cyclohexanedimethanol diglycidyl ether, sorbitol diglycidyl ether, sorbitol triglycidyl ether, sorbitol tetraglycidyl ether, sorbitol pentaglycidyl ether, sorbitol hexaglycidyl ether, and isosorbide diglycidyl ether.

[0118] A suitable example of an aliphatic compound having an episulfide group (Biii) is a compound obtained by substituting the glycidyl group with a thiirane-2-ylmethyl group in the above-mentioned compound as a specific example of an aliphatic compound having an epoxy group (Biii).

[0119] The amount of crosslinking compound (B) used in the thermosetting composition is not particularly limited as long as the desired effect is not impaired. In terms of good curability of the thermosetting composition and excellent solvent resistance of the cured product, the amount of crosslinking compound (B) used in the thermosetting composition is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 30 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of polymer (A). Furthermore, the ratio of moles of polymer (A) to moles of crosslinkable compound (B) is preferably 50:50 to 80:20, given that the refractive index of the cured product is high.

[0120] <Organic solvent (S)> As the organic solvent (S), any solvent capable of dissolving the polymer (A) can be preferably used. Suitable organic solvents (S) include N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N-methylformamide, N,N-dimethylpropionic acid amide, N,N-dimethylisobutylamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-2-piperidone, N-acetylpyrrolidine, N,N'-dimethylethyleneurea (1,3-dimethyl-2-imidazolidinone), N,N'-dimethylpropyleneurea, and N,N,N',N'-tetramethylmalopropyl alcohol. Nitrogen-containing polar organic solvents such as acid amides, N-methyl caprolactam, and N,N,N',N'-tetramethylurea; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclopentanone, and cyclohexanone; ethers such as tetrahydrofuran and 1,4-dioxane; aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, and styrene; ethylene glycol methyl ether Monoalkyl ether acetates of glycols such as telacetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; monoalkyl ethers of glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and 1-methoxy-2-butanol; dialkyl ethers of glycols such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether;Examples include glycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, hexylene glycol, and diethylene glycol; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 1-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 2-methyl-1-pentanol, 1-octanol, 2-ethylhexanol, allyl alcohol, 1-methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, and benzyl alcohol; esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate; and lactones such as γ-butyrolactone. Since polymer (A) dissolves particularly well, it is preferable that the organic solvent (S) includes a ketone-based solvent or a nitrogen-containing polar organic solvent.

[0121] The amount of organic solvent (S) used is not particularly limited as long as the thermosetting composition can be molded into the desired shape. The organic solvent (S) is used such that the solid content concentration of the thermosetting composition is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less.

[0122] <Thermal acid generator (C)> Polymer (A) is R a1 If the thermosetting composition has a carboxyl group protected by an acid-dissociable group, it further comprises a thermal acid generator (C). The thermal acid generator (C) is not particularly limited as long as it is a compound that generates acid upon heating. Known thermal acid generators can be appropriately selected as the thermal acid generator (C). As the thermal acid generator (C), an onium salt type thermal acid generator is preferred in terms of its ability to generate acid upon heating. Examples of onium salts include sulfonium ions, ammonium ions, iodonium ions, and phosphonium ions. These are preferred because they are stable and easy to handle. Among these onium salts, sulfonium ions and iodonium ions are more preferred, with sulfonium ions being even more preferred.

[0123] The amount of the thermal acid generator (C) used is not particularly limited as long as the desired effect is not impaired. The amount of the thermal acid generator (C) used is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less, relative to the mass of the solid content of the thermosetting composition.

[0124] <Surfactant (D)> The thermosetting composition may further contain surfactants (surface modifiers) to improve film-forming properties, coatability, defoaming properties, leveling properties, etc. The surfactant may be used alone or in combination of two or more types. Examples of surfactants include silicone-based surfactants, fluorine-based surfactants, and polymer wetting and dispersing agents, with polymer wetting and dispersing agents being particularly preferred from the viewpoint of improving film-forming properties.

[0125] Examples of silicone-based surfactants include BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, and BYK-390 (manufactured by BYK Chemie).

[0126] Fluorine-based surfactants include, specifically, F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D, and MCF-350. Examples include SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF-1132, TF-1027SF, TF-1441, TF-1442 (manufactured by DIC); and the Polyfox series PF-636, PF-6320, PF-656, PF-6520 (manufactured by Omnova).

[0127] Examples of polymer wetting and dispersing agents include BYK-140, BYK-145, BYK-161, BYK-162, BYK-163, BYK-164, BYK-167, BYK-168, BYK-170, BYK-171, BYK-174, BYK-180, BYK-182, BYK-184, BYK-185, BYK-2050, BYK-2055, BYK-2015, and BYK-9077 (manufactured by BYK Chemie).

[0128] The amount of surfactant used is not particularly limited. From the viewpoint of film-forming properties, coatability, defoaming properties, and leveling properties of the thermosetting composition, the amount of surfactant used is preferably, for example, 0.01% to 2% by mass, and more preferably 0.05% to 1% by mass, relative to the mass of the solid content of the thermosetting composition.

[0129] <Other ingredients> The thermosetting composition may optionally contain additives such as defoamers, silane coupling agents, colorants (pigments, dyes), and crosslinking agents. Any of these additives can be conventionally known compounds.

[0130] <Method for producing thermosetting compositions> A thermosetting composition can be prepared by mixing the essential components described above with any optional components as needed, and then uniformly dissolving each component in an organic solvent (S). The thermosetting composition may be filtered using a filter of a desired mesh size, if necessary.

[0131] ≪Method for manufacturing hardened products≫ The aforementioned thermosetting composition is molded, A cured product can be produced by a method that includes heating and curing a molded thermosetting composition.

[0132] The molding method is not particularly limited and is selected appropriately depending on the shape of the cured product. Examples of molding methods include coating and casting into a mold. Furthermore, the thermosetting composition can be formed into a desired three-dimensional shape using so-called 3D printing methods. Below, we will describe a film manufacturing method as a representative example of a cured product manufacturing method.

[0133] First, a thermosetting composition is applied to a desired substrate to form a coating film.

[0134] The method for applying the thermosetting composition onto the substrate is not particularly limited. For example, a coating film can be formed by applying the thermosetting composition to the substrate to a desired thickness using contact transfer type coating devices such as roll coaters, reverse coaters, bar coaters, and slit coaters, or non-contact type coating devices such as spinners (rotary coating devices) and curtain flow coaters.

[0135] Next, the coated film is heated to remove the organic solvent (S) from the film while curing the thermosetting composition. The heating temperature is determined appropriately, taking into consideration the boiling point of the organic solvent (S) and the temperature at which the acid generator (C) generates acid. The heating temperature for the coated film is preferably between 100°C and 400°C, and more preferably between 150°C and 300°C. The heating time is preferably between 30 seconds and 30 minutes, and more preferably between 1 minute and 10 minutes.

[0136] The cured product obtained in this way exhibits a high refractive index. Specifically, the refractive index of the cured product is preferably 1.72 or higher, and more preferably 1.74 or higher, as measured by the refractive index of light with a wavelength of 550 nm. Cured materials exhibiting such high refractive indices are suitably used as cured films or microlens materials. Cured films can be used as high refractive index films in various optical elements. Cured materials as microlenses are particularly suitable for use in optical elements such as CCDs and CMOS sensors.

[0137] As described above, the inventors provide the following (1) to (11). (1) A thermosetting composition comprising a triazine ring-containing polymer (A), a crosslinkable compound (B), and an organic solvent (S), A triazine ring-containing polymer is given by the following formula (A1): [ka] (In formula (A1), Ar 1 , and Ar 2 R is an aromatic group-containing group, a1 X is a carboxyl group protected by a tert-butoxycarbonyloxy group or an acid-dissociable group, 1 , and X 2 These are, independently, -NR a2 -, -O-, or -S-, R a2 X is a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic hydrocarbon group, 1 Ar 1 Bonded to the aromatic ring in the aromatic group containing the aforementioned aromatic group, X 2 Ar 2 (It bonds to the aromatic ring in the aforementioned aromatic group-containing group.) Includes constituent units represented by Crosslinkable compound (B) contains two or more crosslinkable groups, Of the two or more crosslinkable groups, at least one is an epoxy group or an episulfide group. R a1However, if the carboxyl group is protected by an acid-dissociable group, the thermosetting composition further comprises a thermoacid generator (C). (2)R a1 The thermosetting composition described in (1), wherein the group is a tert-butoxycarbonyloxy group. (3) The thermosetting composition according to either (1) or (2), wherein the organic solvent (S) is a ketone solvent or a nitrogen-containing polar organic solvent. (4) Molding the thermosetting composition described in any one of (1) to (3), A method for producing a cured product, comprising heating and curing a molded thermosetting composition. (5) The method for producing a cured product according to (4), wherein the thermosetting composition is formed into a film by applying the thermosetting composition onto a substrate. (6) A cured product of any one of the thermosetting compositions described in (1) to (3). (7) The cured product described in (6), wherein the refractive index of light with a wavelength of 550 nm is 1.72 or higher. A cured film comprising the cured product described in (8), (6), or (7). A microlens made of the cured material described in (9), (6), or (7). An optical element comprising the microlenses described in (10)(9). [Examples]

[0138] The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to these examples.

[0139] [Preparation Example 1] A solution was obtained by adding m-nitrophenol (9.74 g, 70 mmol), di-tert-butyl dicarbonate (16.0 g, 74 mmol), and tetrahydrofuran (THF) 140 mL to a 300 mL three-necked flask. Next, 4-N,N-dimethylaminopyridine (DMAP, 1.71 g, 14 mmol) was added to the flask. After the addition of DMAP, the solution in the flask was stirred overnight at room temperature. After stirring overnight, THF was removed from the reaction mixture by distillation to obtain a solid residue. The resulting residue was purified by silica gel chromatography to obtain 16.2 g of 3-tert-butoxycarbonyloxynitrophenol.

[0140] A solution was obtained by adding 3-tert-butoxycarbonyloxynitrophenol (16.2 g, 68 mmol), ammonium formate (21.3 g, 339 mmol), and 330 mL of methanol to a 300 mL three-necked flask. Next, palladium / carbon (5% by weight of palladium, 0.72 g, 0.339 mmol (palladium equivalent)) was added to the flask. After the addition of palladium / carbon, the solution in the flask was stirred overnight at room temperature. After stirring overnight, the reaction mixture was filtered through Celite. Methanol was removed from the resulting filtrate to obtain a solid residue. The resulting residue was purified by silica gel chromatography to obtain 13.1 g of 3-tert-butoxycarbonyloxyaniline.

[0141] In a 500 mL three-necked flask, 11.5 g of cyanuric chloride (63 mmol) dissolved in 90 mL of THF was added, and the solution in the flask was cooled to 0°C using an ice bath. Then, while stirring the solution in the flask, 13.1 g of 3-tert-butoxycarbonyloxyaniline (63 mmol) dissolved in 90 mL of THF was added dropwise to the flask. After dropwise addition, the reaction mixture in the flask was stirred for 2 hours. Potassium carbonate aqueous solution (5.19 g, 38 mmol) dissolved in 60 mL of pure water) was added to the reaction mixture and stirred at room temperature for 20 minutes. The reaction mixture and 400 mL of ethyl acetate were placed in a separatory funnel, and the aqueous phase was removed by liquid-liquid extraction. THF and ethyl acetate were removed from the recovered organic phase to obtain a solid residue. The resulting residue was purified by silica gel chromatography to obtain 19.3 g of 2,4-dichloro-6-(3-tert-butoxycarbonyloxyphenyl)amino-1,3,5-triazine, a dihalotriazine compound with the structure shown below. The obtained compound 1 The results of the 1H NMR measurement are shown below. 1 H NMR (400MHz, CDCl3): δ7.90(brs,1H),7.50(dd,JHH=2.4,2.0Hz,1H),7.35-7.27(m,2H),7.02-6.99 (m,1H),1.59(s,9H) [ka]

[0142] [Preparation Example 2] A solution was obtained by adding bis(4-aminophenyl sulfide) (3.24 g, 15 mmol) and N,N-dimethylacetamide (DMAc) 35 mL to a 500 mL three-necked flask. The solution obtained in the flask was heated to 100 °C using an oil bath. Next, a solution of the dihalotriazine compound obtained in Preparation Example 1 (5.35 g, 15 mmol) dissolved in 55 mL of DMAc was added to the flask to start polymerization. After the reaction was carried out for 3 hours from the start of polymerization, the reaction solution was cooled to room temperature. 4 g of a 28% by mass aqueous ammonia solution, 270 mL of pure water, and 100 mL of methanol were added to a flask, and the polymer produced from the reaction mixture in the flask was precipitated. After recovering the crude polymer by filtration, the crude polymer was washed with 50 mL of hexane. The washed polymer was dried in a vacuum dryer at 100°C for 10 hours to obtain polymer A-1 consisting of the following constituent units. 1.0 g of the obtained polymer A-1 was mixed with 9 g of cyclopentanone, N-methyl-2-pyrrolidone, or propylene glycol monomethyl ether. The mixture was subjected to sonication for 30 minutes to confirm the solubility of polymer A-1 in each solvent. After ultrasonic irradiation, polymer A-1 dissolved uniformly in cyclopentanone and N-methyl-2-pyrrolidone. Polymer A-1 remained partially insoluble in propylene glycol monomethyl ether. [ka]

[0143] [Preparation Example 3] Polymer A-2, consisting of the following constituent units, was obtained in the same manner as in Preparation Example 3, except that the dihalotriazine compound (15 mmol) obtained in Preparation Example 2 was replaced with 2,4-dichloro-6-phenylamino-1,3,5-triazine (15 mmol). [ka]

[0144] [Examples 1-6, Comparative Example 1] A solution was obtained by dissolving the polymer of the type and amount (parts by mass) listed in Table 1, the crosslinkable compound of the type and amount (parts by mass) listed in Table 1, and 0.003 parts by mass of a fluorinated surfactant (PF-656, manufactured by OMNOVA) in 26.4 parts by mass of cyclopentanone. The obtained solution was filtered through a 0.45 μm mesh filter to obtain a thermosetting composition. The light transmittance of the obtained thermosetting composition was evaluated according to the following method. The evaluation results are shown in Table 1. A film was formed using the obtained thermosetting composition by the following method. The light transmittance, refractive index, and residual film percentage after acetone immersion were evaluated according to the following method. These measurement results are shown in Table 1. The crosslinkable compounds listed in Table 1 are as follows. The structures of the crosslinkable compounds are shown below. B-1: Ethylene glycol diglycidyl ether B-2: Sorbitol polyglycidyl ether (sorbitol tetraglycidyl ether) B-3: 1,3-bis(glycidyloxy)-2,2-bis[(glycidyloxy)methyl]propane(pentaerythritol tetraglycidyl ether) (Crosslinkable compound B-1) [ka] (Crosslinkable compound B-2) [ka] (Crosslinkable compound B-3) [ka]

[0145] <Light transmittance measurement> The light transmittance of thermosetting compositions at a wavelength of 400 nm was measured using a UV-Vis spectrophotometer. A light transmittance of 90% or higher was judged as ○. A light transmittance of less than 90% was judged as ×.

[0146] <Film Formation> A thermosetting composition was applied to a glass substrate using a spin coater. The formed coating was heated at 100°C for 1 minute, and then at 200°C for 5 minutes to obtain a film with a thickness of approximately 1 μm.

[0147] <Refractive Index Measurement> The refractive index of the obtained film at a wavelength of 550 nm was measured using a spectroscopic ellipsometer. A refractive index of 1.75 or higher was judged as ◎. A refractive index of 1.71 or higher but less than 1.75 was judged as ○. A refractive index less than 1.71 was judged as ×.

[0148] <Measuring residual film percentage> The obtained film was immersed in acetone at room temperature for 10 minutes. The film thickness T1 before immersion and the film thickness T2 after immersion were measured. The residual film percentage was calculated based on the following formula. A residual film percentage of 90% or more was judged as ○. A residual film percentage of less than 90% was judged as ×. Remaining film rate (%)=T2 / T1×100

[0149] [Table 1]

[0150] Examples 1 to 6 show that by using a polymer containing the unit (A1) represented by the aforementioned formula (A1), it is possible to form a cured product that possesses both a high refractive index and high resistance to organic solvents. On the other hand, Comparative Example 1 shows that when a polymer consisting of structural units that do not correspond to the aforementioned formula (A1) is used, it is difficult to form a cured product that possesses both a high refractive index and high resistance to organic solvents.

Claims

1. A thermosetting composition for forming a cured product with a refractive index of 1.75 or higher at a wavelength of 550 nm, comprising a triazine ring-containing polymer (A), a crosslinkable compound (B), and an organic solvent (S), The ratio of moles of polymer (A) to moles of crosslinkable compound (B) is 50:50 to 80:

20. The triazine ring-containing polymer is defined by the following formula (A1): 【Chemistry 1】 In formula (A1), Ar １ and Ar ２ each are an aromatic group-containing group, R ａ１ is a tert-butoxycarbonyloxy group, a tert-butoxycarbonylamino group, or a carboxy group protected by an acid dissociable group, X １ and X ２ each are independently -NR ａ２ -, -O-, or -S-, R ａ２ is a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic hydrocarbon group, X １ is bonded to the aromatic ring in the aromatic group-containing group as Ar １ , and X ２ is bonded to the aromatic ring in the aromatic group-containing group as Ar ２ .) Includes constituent units represented by The crosslinkable compound (B) comprises two or more crosslinkable groups, Of the two or more crosslinkable groups, at least one is an epoxy group or an episulfide group. The aforementioned R ａ１ However, if the carboxyl group is protected by the acid-dissociable group, the thermosetting composition further comprises a thermoacid generator (C).

2. R ａ１ The thermosetting composition according to claim 1, wherein the group is a tert-butoxycarbonyloxy group.

3. The thermosetting composition according to claim 1 or 2, wherein the organic solvent (S) is a ketone solvent or a nitrogen-containing polar organic solvent.

4. The thermosetting composition according to claim 1 or 2 is molded, A method for producing a cured product, comprising heating and curing the molded thermosetting composition.

5. The method for producing a cured product according to claim 4, wherein the thermosetting composition is formed into a film by applying the thermosetting composition onto a substrate.

6. A cured product of the thermosetting composition according to claim 1 or 2, wherein the refractive index of light with a wavelength of 550 nm is 1.75 or higher.

7. A cured film comprising the cured product described in claim 6.

8. A microlens made of the cured material described in claim 6.

9. An optical element comprising the microlens described in claim 8.

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