JP5240798B2 - Refractive index improver, and resin composition, polymerization or curable composition and optical material containing the same - Google Patents

Description

  The present invention relates to a refractive index improver, and a resin composition, a polymerization or curable composition containing the same, and an optical material.

  Plastic optical materials are advantageous in that they are lighter, harder to break, and easier to process than inorganic materials. In recent years, plastic optical materials are rapidly spreading as various optical members including glasses and camera lenses. As an example of such a plastic optical material, Patent Document 1 includes resins such as acrylic resin and polycarbonate resin. However, although the refractive index of these resins is certainly high as a resin material, it is less than 1.6. Therefore, when these resins are used as lenses, there is a problem that the thickness of the lenses is larger than that of glass.

  Under such circumstances, aromatic sulfur-containing polymers are useful as engineering plastics with excellent heat resistance and chemical resistance, and are expected as high refractive materials because of the high molecular refraction of sulfur and aromatic rings. . However, since sulfide-based polymers such as polyphenylene sulfide, which is an aromatic sulfur-containing polymer, are highly colored and have poor transparency, problems still remain for use as optical applications.

  As an aromatic sulfur-containing polymer with improved transparency, for example, Patent Document 2 discloses a polymer having a diphenylsulfone structure and a diphenylsulfide structure in the molecule.

JP-A 61-28513 JP-A-8-134204

  By the way, dinaphthothiophene, which is a sulfur-containing polynuclear aromatic compound, is a sulfur-containing component present in petroleum residues and is a compound exhibiting high heat resistance, but has not been found industrially useful so far. It was only a subject of academic interest.

  However, as a result of the investigation by the present inventors, the compound having a dinaphthothiophene skeleton has a refractive index that is rare as an organic compound, alone or in a blended body with a resin, and is polymerizable. It has been found that such optical properties are maintained even when a substituent is introduced and polymerized. Therefore, an object of the present invention is to provide a novel refractive index improver based on an organic compound, a resin composition containing the same, a polymerization or curable composition, and an optical material based on the above knowledge.

  More specifically, the present invention provides the following.

（上記一般式（Ｉ）中、（Ｒ）_ｍ又は（Ｒ）_ｎは、それぞれｍ個又はｎ個の同一又は異なる置換基を意味し、当該置換基は、それらが結合するナフタレン環における置換可能な炭素原子のいずれに結合してもよく、各Ｒは、それぞれ独立に、炭素数１〜２０でヘテロ原子を含んでもよいアルキル基、シクロアルキル基、アリール基若しくはアラルキル基、ビニル基、スチリル基、アリル基、（メタ）アクリロイルオキシメチル基、メチル（メタ）アクリロイルオキシメチル基、カルボキシル基、ヒドロキシメチル基、ヒドロキシエチル基、ホルミル基、メチルカルボニル基、メトキシカルボニル基、Ｎ−エチルアミノカルボニル基、トリフルオロメチル基、トリメチルシリル基、シアノ基、シアノエチル基、イソシアナト基、チオイソシアナト基、ベンジリデンアミノ基、水酸基、アミノ基、ニトロ基、チオール基、スルホ基、ハロゲン原子、又は置換されてもよいシリル基を表す。また、上記一般式（Ｉ）中、ｍは、０〜６の整数であり、ｎは、０〜６の整数である。） (1) A refractive index improver comprising a dinaphthothiophene compound represented by the following general formula (I).

(In the above general formula (I), (R) _m or (R) _n means m or n identical or different substituents, respectively, which can be substituted in the naphthalene ring to which they are bonded. Each R may independently be an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a vinyl group, a styryl group, which may have 1 to 20 carbon atoms and may contain a hetero atom. Allyl group, (meth) acryloyloxymethyl group, methyl (meth) acryloyloxymethyl group, carboxyl group, hydroxymethyl group, hydroxyethyl group, formyl group, methylcarbonyl group, methoxycarbonyl group, N-ethylaminocarbonyl group, Trifluoromethyl group, trimethylsilyl group, cyano group, cyanoethyl group, isocyanato group, thioisocyanate DOO group, benzylidene amino group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. In addition, in the above general formula (I), m is 0 6 is an integer, and n is an integer of 0 to 6.)

（上記一般式（ＩＩ）中、（Ｒ）_ｐ又は（Ｒ）_ｑは、それぞれｐ個又はｑ個の同一又は異なる置換基を意味し、当該置換基は、それらが結合するナフタレン環における置換可能な炭素原子のいずれに結合してもよく、各Ｒは、それぞれ独立に、炭素数１〜２０でヘテロ原子を含んでもよいアルキル基、シクロアルキル基、アリール基若しくはアラルキル基、ビニル基、スチリル基、アリル基、（メタ）アクリロイルオキシメチル基、メチル（メタ）アクリロイルオキシメチル基、カルボキシル基、ヒドロキシメチル基、ヒドロキシエチル基、ホルミル基、メチルカルボニル基、メトキシカルボニル基、Ｎ−エチルアミノカルボニル基、トリフルオロメチル基、トリメチルシリル基、シアノ基、シアノエチル基、イソシアナト基、チオイソシアナト基、ベンジリデンアミノ基、水酸基、アミノ基、ニトロ基、チオール基、スルホ基、ハロゲン原子、又は置換されてもよいシリル基を表す。また、上記一般式（ＩＩ）中、ｐは、０〜５の整数であり、ｑは、０〜５の整数である。また、上記一般式（ＩＩ）中、Ｘは、単結合、ヘテロ原子を含んでもよいアルキレン基、アラルキレン基、アルケニレン基、エステル結合、アミド結合、イミド結合又はこれらの結合を主鎖に含むアルキレン基、アリーレン基、アラルキレン基、二価の置換芳香族基、二価の置換へテロ芳香族基、二価の置換シリル基、又は二価の原子である。） (2) refractive index improvers include polymers, a containing as a repeating unit a structure represented by following formula (II).

(In the above general formula (II), (R) _p or (R) _q means p or q identical or different substituents, respectively, which can be substituted on the naphthalene ring to which they are bonded. Each R may independently be an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a vinyl group, a styryl group, which may have 1 to 20 carbon atoms and may contain a hetero atom. Allyl group, (meth) acryloyloxymethyl group, methyl (meth) acryloyloxymethyl group, carboxyl group, hydroxymethyl group, hydroxyethyl group, formyl group, methylcarbonyl group, methoxycarbonyl group, N-ethylaminocarbonyl group, Trifluoromethyl group, trimethylsilyl group, cyano group, cyanoethyl group, isocyanato group, thioisocyanate Isocyanato group, benzylidene amino group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. In addition, in the above general formula (II), p is 0 And q is an integer of 0 to 5. In the general formula (II), X is a single bond, an alkylene group which may contain a hetero atom, an aralkylene group, an alkenylene group or an ester bond. , An amide bond, an imide bond, or an alkylene group containing these bonds in the main chain, an arylene group, an aralkylene group, a divalent substituted aromatic group, a divalent substituted heteroaromatic group, a divalent substituted silyl group, or It is a divalent atom.)

（上記一般式（ＩＩＩ）中、（Ｒ）_ｒは、ｒ個の同一又は異なる置換基を意味し、当該置換基は、ジナフトチオフェン骨格における置換可能な炭素原子のいずれに結合してもよく、各Ｒは、それぞれ独立に、炭素数１〜２０でヘテロ原子を含んでもよいアルキル基、シクロアルキル基、アリール基若しくはアラルキル基、ビニル基、スチリル基、アリル基、（メタ）アクリロイルオキシメチル基、メチル（メタ）アクリロイルオキシメチル基、カルボキシル基、ヒドロキシメチル基、ヒドロキシエチル基、ホルミル基、メチルカルボニル基、メトキシカルボニル基、Ｎ−エチルアミノカルボニル基、トリフルオロメチル基、トリメチルシリル基、シアノ基、シアノエチル基、イソシアナト基、チオイソシアナト基、ベンジリデンアミノ基、水酸基、アミノ基、ニトロ基、チオール基、スルホ基、ハロゲン原子、又は置換されてもよいシリル基を表す。また、上記一般式（ＩＩＩ）中、ｒは、０〜１１の整数である。また、上記一般式（ＩＩＩ）中、Ｙは、単結合、エステル結合、アミド結合、イミド結合、エーテル結合、スルフィド結合、又はこれらの結合を主鎖に含むアルキレン基、又は二価の原子であり、Ｒ^１は、水素原子又はメチル基である。） (3) a polymer as a repeating unit a structure represented by the following formula (III), or a refractive index enhancing agent comprising a copolymer, comprising as a repeating unit structure represented by the following general formula (III).

(In the general formula (III), (R) _r means r identical or different substituents, and the substituents may be bonded to any substitutable carbon atom in the dinaphthothiophene skeleton. And each R is independently an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a vinyl group, a styryl group, an allyl group, a (meth) acryloyloxymethyl group, which has 1 to 20 carbon atoms and may contain a hetero atom. Methyl (meth) acryloyloxymethyl group, carboxyl group, hydroxymethyl group, hydroxyethyl group, formyl group, methylcarbonyl group, methoxycarbonyl group, N-ethylaminocarbonyl group, trifluoromethyl group, trimethylsilyl group, cyano group, Cyanoethyl group, isocyanato group, thioisocyanato group, benzylideneamino group , water It represents an acid group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group, and r is an integer of 0 to 11 in the general formula (III). In the general formula (III), Y is a single bond, an ester bond, an amide bond, an imide bond, an ether bond, a sulfide bond, or an alkylene group containing these bonds in the main chain, or a divalent atom. , R ¹ is a hydrogen atom or a methyl group.)

  (4) A resin composition comprising the refractive index improver according to any one of items (1) to (3) and a resin.

  (5) The resin is a poly (meth) acrylic acid ester, polystyrene, polyvinyl ether, polyolefin and a copolymer of monomers constituting these, polycarbonate, polyester, polyimide, polyamide, polysulfide, polyurethane, polyether, phenol resin, The resin composition according to (4), comprising at least one selected from the group consisting of a urea resin, a melamine resin, an epoxy resin, and an oxetane resin.

  (6) The resin composition according to item (5), wherein the resin has a branched structure.

  (7) m + n is an integer of 1 or more, and at least one R is a substituent having an ethylenically unsaturated group, the refractive index improver according to the item (1), and the ethylenically unsaturated by heating or light irradiation. A polymerizable composition comprising a polymerization initiator for polymerizing a saturated group.

  (8) The polymerizable composition as set forth in (7), further comprising a compound having an ethylenically unsaturated group separately from the refractive index improver.

  (9) A polymerizable composition comprising the refractive index improver according to any one of items (1) to (3), a monomer, and a polymerization initiator for polymerizing the monomer.

  (10) m + n is an integer of 1 or more, and at least one R is a substituent having an epoxy group or oxetanyl group. The refractive index improver according to claim 1, and the epoxy group or oxetanyl by heating or light irradiation. A curable composition comprising a reaction initiator for opening a group.

  (11) The curable composition according to item (10), further comprising a monomer, oligomer or resin having an epoxy group or an oxetanyl group separately from the refractive index improver.

  (12) A curable composition comprising the refractive index improver according to any one of items (1) to (3), a curable resin, and a curing agent that cures the curable resin.

  (13) The curable composition according to any one of (10) to (12), wherein the polymerizable composition according to any one of (7) to (9) is polymerized. A resin composition obtained by curing.

  (14) The refractive index improver according to any one of items (1) to (3), or the resin composition according to any one of items (4) to (6) and (13), An optical material having at least a part thereof.

（上記一般式（Ｉ）中、（Ｒ）_ｍ又は（Ｒ）_ｎは、それぞれｍ個又はｎ個の同一又は異なる置換基を意味し、当該置換基は、それらが結合するナフタレン環における置換可能な炭素原子のいずれに結合してもよく、各Ｒは、それぞれ独立に、炭素数１〜２０でヘテロ原子を含んでもよいアルキル基、シクロアルキル基、アリール基若しくはアラルキル基、ビニル基、スチリル基、アリル基、（メタ）アクリロイルオキシメチル基、メチル（メタ）アクリロイルオキシメチル基、カルボキシル基、ヒドロキシメチル基、ヒドロキシエチル基、ホルミル基、メチルカルボニル基、メトキシカルボニル基、Ｎ−エチルアミノカルボニル基、トリフルオロメチル基、トリメチルシリル基、シアノ基、シアノエチル基、イソシアナト基、チオイソシアナト基、ベンジリデンアミノ基、水酸基、アミノ基、ニトロ基、チオール基、スルホ基、ハロゲン原子、又は置換されてもよいシリル基を表す。また、上記一般式（Ｉ）中、ｍは、０〜６の整数であり、ｎは、０〜６の整数である。） (15) A method of using a dinaphthothiophene compound represented by the following general formula (I) as an organic refractive index improver.

(In the above general formula (I), (R) _m or (R) _n means m or n identical or different substituents, respectively, which can be substituted in the naphthalene ring to which they are bonded. Each R may independently be an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a vinyl group, a styryl group, which may have 1 to 20 carbon atoms and may contain a hetero atom. Allyl group, (meth) acryloyloxymethyl group, methyl (meth) acryloyloxymethyl group, carboxyl group, hydroxymethyl group, hydroxyethyl group, formyl group, methylcarbonyl group, methoxycarbonyl group, N-ethylaminocarbonyl group, Trifluoromethyl group, trimethylsilyl group, cyano group, cyanoethyl group, isocyanato group, thioisocyanate DOO group, benzylidene amino group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. In addition, in the above general formula (I), m is 0 6 is an integer, and n is an integer of 0 to 6.)

(16) The method according to item (15 ), wherein the organic material has a refractive index of 1.5 to 1.9.

  ADVANTAGE OF THE INVENTION According to this invention, the novel refractive index improver by an organic compound, the resin composition containing the same, a polymerization or curable composition, and an optical material are provided.

It is a spectrum which shows the transmittance | permeability of the ultraviolet-ray and visible light in the chloroform solution (0.1 mass%) of the refractive index improver (Polymer D) of Example 9. FIG.

  The refractive index improver of the present invention includes a compound having a dinaphthothiophene skeleton represented by the following general formula (I) (hereinafter also referred to as “dinaphthothiophene compound”). That is, the refractive index improver of the present invention may be the dinaphthothiophene compound itself or may contain other components. The refractive index improver of the present invention becomes, for example, a resin composition having a large refractive index by being mixed with a resin base material. In addition, the refractive index improver of the present invention includes a dinaphthothiophene compound into which a substituent having polymerizability or curability is introduced, thereby polymerizing or curing together with a polymerization initiator or a curing agent, and if necessary. In the presence of the compound, the resin composition has a large refractive index. And an optical material with a large refractive index can be produced by molding these resin compositions. As described above, the refractive index improver of the present invention may be used by mixing with a resin base material, or the refractive index improver itself may be used with a high molecular weight. It may be solidified by a molding means, and the solidified refractive index improver may be used as an optical material. The optical material thus produced also has a large refractive index. Furthermore, an optical material mainly composed of an optical substrate such as glass or plastic, which partially contains the refractive index improver of the present invention itself or a resin composition containing the refractive index improver of the present invention, also has a large refractive index. Have. Examples of such optical materials include those in which the refractive index improver of the present invention itself or a resin composition containing the refractive index improver of the present invention is applied and vapor-deposited on the surface of an optical substrate, or two or more optical materials Are bonded with a resin composition containing the refractive index improver of the present invention.

  As already described, as a result of the study by the present inventors, the dinaphthothiophene compound represented by the following general formula (I) shows a high refractive index, while its basic structure is hardly colored in the visible light region. Not found out. The refractive index improver of the present invention has been completed based on the above findings, and exhibits a large refractive index improving effect by including a dinaphthothiophene compound represented by the following general formula (I).

In the above general formula (I), (R) _m or (R) _n means m or n identical or different substituents, respectively, which can be substituted in the naphthalene ring to which they are bonded. It may be bonded to any carbon atom, and each R independently represents an organic group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. Moreover, in the said general formula (I), m is an integer of 0-6 and n is an integer of 0-6.

  In the said general formula (I), an organic group is a substituent containing a carbon atom, and in addition to this carbon atom, hetero atoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, may be included.

  As such an organic group, an alkyl group having 1 to 20 carbon atoms, which may contain a hetero atom, a cycloalkyl group, an aryl group or an aralkyl group, a vinyl group, a styryl group, an allyl group, a (meth) acryloyloxymethyl group, Methyl (meth) acryloyloxymethyl group, carboxyl group, hydroxymethyl group, hydroxyethyl group, formyl group, methylcarbonyl group, methoxycarbonyl group, N-ethylaminocarbonyl group, trifluoromethyl group, trimethylsilyl group, cyano group, cyanoethyl Group, isocyanato group, thioisocyanato group, benzylideneamino group and the like. In addition, as described later, the organic group may include a main chain of a polymer chain.

  The alkyl group having 1 to 20 carbon atoms and including a hetero atom may be linear or branched. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, methoxy, ethoxy, and methoxy. Examples include a methyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, and the like.

  In addition, the cycloalkyl group having 1 to 20 carbon atoms and including a hetero atom may be a monocyclic structure or a multicyclic structure. Examples of such a cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

  The aryl group having 1 to 20 carbon atoms and including a hetero atom may be a monocyclic structure or a condensed ring structure. Examples of such an aryl group include a phenyl group, a naphthyl group, and a pyridyl group.

  Examples of the aralkyl group having 1 to 20 carbon atoms and including a hetero atom include a benzyl group and a phenethyl group.

  In the general formula (I), examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Each substituent represented by R may be appropriately determined in consideration of the solubility required for the refractive index improver, the compatibility with the resin substrate, and the like.

  As a method for introducing the substituent R into the dinaphthothiophene skeleton, known methods can be mentioned without particular limitation. For example, when an alkyl group is introduced into a dinaphthothiophene skeleton, an alkyl boronic acid compound may be reacted with a brominated product of dinaphthothiophene in the presence of a palladium catalyst.

  The dinaphthothiophene compound represented by the above general formula (I) is not particularly limited, but may be dinaphthothiophene (dinaphtho [2,1-b: 1 ′, 2′-d] thiophene) itself. In addition, one or more hydrogen atoms of dinaphthothiophene may be substituted with an organic group or a halogen atom. Dinaphthothiophene can be obtained by separating and purifying what is contained in the petroleum residue, or can be obtained by organic synthesis. As an example of a method for obtaining dinaphthothiophene by organic synthesis, 1,1′-binaphthol is reacted with dimethylthiocarbamoyl chloride in the presence of a base to form a dimethylthiocarbamate, and this dimethylthiocarbamate is then converted to sulfolane. Heating under reflux (boiling point: 285 ° C.) can be mentioned.

  Examples of dinaphthothiophene compounds represented by the above general formula (I) include dinaphthothiophene, dinaphthothiophene-6-carboxaldehyde, 6-hydroxymethyldinaphthothiophene, 5-benzyldinaphthothiophene, 6-acetoxy Examples include methyldinaphthothiophene, 5,8-diethyldinaphthothiophene, and 6-vinyldinaphthothiophene.

  Since the dinaphthothiophene compound represented by the general formula (I) has a dinaphthothiophene skeleton, the refractive index is improved, and the solid state refractive index is 1.6 to 1.9. Here, the solid state of the dinaphthothiophene compound includes, in addition to the crystalline state and amorphous state of the monomolecular dinaphthothiophene compound, a solidified polymer dinaphthothiophene compound described below.

  The dinaphthothiophene compound represented by the general formula (I) includes a polymer containing a structure represented by the following general formula (II) as a repeating unit. By using such a polymer as a refractive index improver, the compatibility of the refractive index improver with the resin base material can be improved, and the refractive index improver itself is molded into a high-strength optical material. It is preferable in that it can be performed.

In the above general formula (II), (R) _p or (R) _q means p or q identical or different substituents, respectively, which can be substituted in the naphthalene ring to which they are bonded. It may be bonded to any carbon atom, and each R independently represents an organic group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. Moreover, in the said general formula (II), p is an integer of 0-5 and q is an integer of 0-5. In the above general formula (II), X is a single bond, a divalent organic group or a divalent atom.

  The dinaphthothiophene compound containing the repeating unit represented by the general formula (II) is a compound in which two Rs in the general formula (I) constitute the main chain of the polymer chain. Therefore, in the general formula (II), the number of carbon atoms into which substituents can be introduced is 5 per naphthalene ring, which is 10 in total. Any of these 10 carbon atoms can be independently or without any substituent R introduced. In this case, each substituent R to be introduced is independently determined and may be the same as or different from each other. In the general formula (II), examples of the organic group represented by R include the same groups as those described in the general formula (I). In the general formula (II), examples of the halogen atom represented by R include the same as those described in the general formula (I). Each substituent represented by R includes solubility required for a refractive index improver, compatibility with a resin base material, strength required for an optical material formed by molding a dinaphthothiophene compound, and the like. What is necessary is just to select suitably in consideration of various characteristics.

  In the above general formula (II), X is a single bond, a divalent organic group or a divalent atom. When X is a divalent organic group, X is an alkylene group, an aralkylene group, an alkenylene group, an ester bond, an amide bond, an imide bond, or any of these which may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. Examples thereof include an alkylene group having a bond in the main chain, an arylene group, an aralkylene group, a divalent substituted aromatic group, a divalent substituted heteroaromatic group, and a divalent substituted silyl group. When X is a divalent atom, X is an oxygen atom, a sulfur atom, a tin atom that may have a bond with another atom, or a phosphorus atom that may have a bond with another atom. Illustrated.

  The method for synthesizing the dinaphthothiophene compound containing the repeating unit represented by the general formula (II) is not particularly limited. An example of such a synthesis method is a method of reacting dinaphthothiophene with paraformaldehyde in the presence of a boron trifluoride diethyl ether complex. In this case, the dinaphthothiophene compound having a repeating unit represented by the general formula (II) is a polymer obtained by crosslinking dinaphthothiophene with a methylene group. The method for obtaining dinaphthothiophene is as described above.

  When the dinaphthothiophene compound having the repeating unit represented by the general formula (II) is a polymer of dinaphthothiophene, the mass average molecular weight is preferably 700 to 200000, and more preferably 1000 to 50000. 1000 to 20000 is most preferable. If the mass average molecular weight is 700 or more, the film-forming property, volatilization resistance, compatibility and solvent resistance are good. If the mass average molecular weight is 200,000 or less, the solubility in a solvent is lowered and the solution viscosity is increased. It is suppressed.

  In the dinaphthothiophene compound represented by the general formula (I), a polymer containing a structure represented by the following general formula (III) as a repeating unit, or a structure represented by the following general formula (III) is repeated. Copolymers including units are also included (hereinafter, these are collectively referred to as “a dinaphthothiophene compound having a repeating unit represented by the general formula (III)”). By using such a polymer or copolymer as a refractive index improver, the compatibility of the refractive index improver with respect to the resin substrate can be improved, and further, optical properties such as birefringence can be improved. It is preferable in that the refractive index improver itself can be molded into an optical material having high strength.

In the general formula (III), (R) _r means r same or different substituents, and the substituents may be bonded to any substitutable carbon atom in the dinaphthothiophene skeleton, Each R independently represents an organic group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. Moreover, r is an integer of 0-11 in the said general formula (III). In the general formula (III), Y is a single bond, a divalent organic group or a divalent atom, and R ¹ is a hydrogen atom or a methyl group.

  The dinaphthothiophene compound containing the repeating unit represented by the general formula (III) is a compound in which one R in the general formula (I) constitutes a bonding group to the polymer main chain. Therefore, in the general formula (III), the number of carbon atoms into which a substituent can be introduced is 11 in the dinaphthothiophene skeleton. Any substituent R may or may not be introduced independently on any of these 11 carbon atoms. In this case, each substituent R to be introduced is independently determined and may be the same as or different from each other. In the general formula (III), examples of the organic group represented by R include the same groups as those described in the general formula (I). In the general formula (III), examples of the halogen atom represented by R include the same as those described in the general formula (I). Each substituent represented by R includes solubility required for a refractive index improver, compatibility with a resin base material, strength required for an optical material formed by molding a dinaphthothiophene compound, and the like. What is necessary is just to select suitably in consideration of various characteristics.

  In the above general formula (III), Y is a single bond, a divalent organic group or a divalent atom. When Y is a divalent organic group, examples of Y include an ester bond, an amide bond, an imide bond, an ether bond, a sulfide bond, or an alkylene group containing these bonds in the main chain. When Y is a divalent atom, examples of Y include an oxygen atom, a sulfur atom, and a tin atom that may have a bond with other atoms.

  The method for synthesizing the dinaphthothiophene compound containing the repeating unit represented by the general formula (III) is not particularly limited. As an example of such a synthesis method, (A) a monomer derivative in which a polymerizable unsaturated group such as a vinyl group or (meth) acryloyl group is bonded to dinaphthothiophene is prepared, and the monomer derivative is used alone. Or with other monomers. Further, (B) a resin having a reactive group such as a carboxyl group or a hydroxyl group in the side chain, and a dinaphthothiophene derivative having a substituent capable of reacting with and binding to the reactive group. The method of making it react is mentioned.

  As an example of the above (A), after dinaphthothiophene is formylated, the formyl group is converted into a vinyl group by Wittig reaction, thereby introducing a vinyl group into dinaphthothiophene, and polymerization or polymerization with a radical polymerization initiator. Examples thereof include a method of copolymerizing with other vinyl monomers. Other vinyl monomers include (meth) acrylic acid esters, (meth) acrylic acid amides, (meth) acrylonitrile, acrylate monomers such as glycidyl (meth) acrylate, vinyl esters such as vinyl acetate, and hydroxyl groups such as hydroxyethyl acrylate. Examples thereof include vinyl monomers having vinyl monomers, vinyl ethers, vinyl chloride and the like, and aromatic vinyl monomers such as styrene, vinyl pyridine, vinyl benzophenone and vinyl imidazole.

  As an example of the above (B), a method of reacting a saponified copolymer containing poval or vinyl acetate as a monomer with a dinaphthothiophene derivative having a glycidyl group, a polymer of (meth) acrylic acid or Examples thereof include a method of reacting a copolymer containing (meth) acrylic acid as a monomer with a dinaphthothiophene derivative having a hydroxyl group.

  When the dinaphthothiophene compound having a repeating unit represented by the general formula (III) is a copolymer, the monomer component constituting the copolymer has a structure represented by the general formula (III). The proportion of the corresponding monomer component is preferably 5 to 95 mol%, more preferably 30 to 90 mol%, and most preferably 50 to 90 mol%. If the ratio of the monomer component corresponding to the structure represented by the general formula (III) among the monomer components constituting the copolymer is 5 mol% or more, good performance as a refractive index improver can be obtained. If it is 95 mol% or less, the heat resistance, mechanical strength, birefringence reduction effect or compatibility improvement effect brought about by copolymerization will be good.

  More specifically, examples of the dinaphthothiophene compound having a repeating unit represented by the general formula (III) include a compound represented by the following general formula (IV).

In the general formula (IV), R, R ¹ , Y and r are the same as those in the general formula (III), R ² and R ³ represent a hydrogen atom or a methyl group, and W and Z are Each independently represents OCOR ⁴ , OCONR ⁵ R ⁶ , a cyano group or a substituted aromatic group, and R ⁴ represents an alkyl group, an aralkyl group or an aryl group, and an oxygen atom, sulfur atom, nitrogen atom in the structure thereof R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom in the structure. May be included. In the general formula (IV), s represents an integer from 1 to 1000, t represents an integer from 0 to 1000, and u represents an integer from 0 to 1000. Moreover, in the compound represented by the general formula (IV), each repeating unit containing R ¹ , R ² or R ³ is present in a ratio of s: t: u, and the order in which each repeating unit is bonded. Is not particularly limited and is arbitrary.

  As already explained, the dinaphthothiophene compound explained above is contained in the refractive index improver of the present invention. The refractive index improver of the present invention may be mixed with another resin base material to form a resin composition for an optical material, or the refractive index improver itself may be solidified by a molding means to form an optical material. May be.

  When the refractive index improver of the present invention is mixed with another resin base material to produce a resin composition for an optical material, the resin used as the resin base material is not particularly limited, but is a thermoplastic resin or uncured The thermosetting resin is preferred. As thermoplastic resins, poly (meth) acrylic acid resins, polystyrene resins, polyvinyl ether resins, polyolefin resins, polycarbonate resins, polyester resins, polyimide resins, polyamide resins, polysulfide resins, polyurethane resins Examples thereof include resins and polysiloxane resins. Examples of the resin also include a copolymer of monomers constituting poly (meth) acrylic acid, polystyrene, polyvinyl ether, and polyolefin. Examples of the uncured thermosetting resin include phenol resin, urea resin, melamine resin epoxy resin, and oxetane resin. These resins may be used alone or in combination as a resin base material, or may be mixed with other resins to form a resin base material. When the resin used as the resin substrate is an uncured thermosetting resin, if necessary, a curing agent for curing the resin may be added to the resin.

  The resin contained in the resin base material may be linear or branched. The branched resin means a resin having a branched structure in the molecule. By using a branched resin for the resin substrate, it is possible to impart amorphousness and high solubility to the resin substrate. And the resin composition which added the refractive index improvement agent of this invention to such a resin base material is anticipated by the birefringence reduction effect by the orientation prevention effect of the refractive index improvement agent by a resin base material. The branched resin can be obtained by using part or all of the monomer used in the synthesis as a polyfunctional monomer. Of the branched resins, those having a large degree of branching are sometimes referred to as hyperbranched polymers. However, the term branched resin in the present invention means one having a branched structure in the molecule. Of course, the resin called a polymer includes a resin whose degree of branching is not so high as a hyperbranched polymer.

  The content of the dinaphthothiophene compound in the resin composition may be appropriately determined in consideration of the required refractive index. As an example, the content of the dinaphthothiophene compound in the resin composition is preferably 5 to 95% by mass, more preferably 30 to 90% by mass, and most preferably 50 to 90% by mass. preferable. It is preferable that the content of the dinaphthothiophene compound in the resin composition is 5% by mass or more because a practical refractive index as an optical material can be imparted to the resin substrate, and dinaphtho in the resin composition is preferable. When the content of the thiophene compound is 95% by mass or less, it is preferable in that the strength of the molded body can be maintained well when the resin composition is molded. In the case where the refractive index improver contains a component other than the dinaphthothiophene compound, the refractive index improver for the resin substrate is adjusted so that the content of the dinaphthothiophene compound in the resin composition falls within the above range. What is necessary is just to adjust the addition amount suitably.

  The resin composition for optical material thus produced becomes an optical material by being molded. When the resin used in the resin composition for optical materials is a thermoplastic resin, the resin composition is molded into a desired shape while being softened by heating, and then the molded resin composition is It only has to be cooled. Further, when the resin used in the resin composition for optical materials is a thermosetting resin, after molding the resin composition in a desired state in a softened state, the molded resin composition is heated or Any other suitable means may be used for curing. The optical material thus obtained shows a high refractive index because it contains the refractive index improver of the present invention.

  In addition to the resin compositions for optical materials listed above, as a further example of a resin composition for optical materials, a resin composition obtained by polymerizing a polymerizable composition containing a refractive index improver or a refractive index improver The resin composition which hardened the curable composition containing is mentioned. Next, such a resin composition will be described.

  First, a resin composition obtained by polymerizing a polymerizable composition containing a refractive index improver will be described. Two forms are mentioned as a polymeric composition used here.

  The polymerizable composition of the first form includes a dinaphthothiophene compound having a polymerizability that is a refractive index improver and a polymerization initiator that polymerizes the dinaphthothiophene compound by heating or light irradiation. The refractive index improver contained in the polymerizable composition itself has polymerizability and becomes a resin contained in the resin composition. This polymerizable composition can contain a compound that can be copolymerized with a dinaphthothiophene compound having polymerizability, if necessary.

  The dinaphthothiophene compound having a polymerizable property is a substituent in which m + n is an integer of 1 or more and at least one R has an ethylenically unsaturated group among the dinaphthothiophene compounds represented by the general formula (I). Is a compound having Since such a dinaphthothiophene compound has at least one substituent having an ethylenically unsaturated group, it can be polymerized, for example, in the presence of a radical polymerization initiator. The polymerized dinaphthothiophene compound becomes a resin contained in the resin composition.

  The substituent having an ethylenically unsaturated group is not particularly limited, but vinyl group, styryl group, allyl group, (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloyloxymethyl group, (meth) Examples include an acryloylamino group and a (meth) acryloylaminomethyl group.

  More specifically, examples of the dinaphthothiophene compound having polymerizability include compounds represented by the following general formula (V).

In the general formula (V), each X ¹ is independently a single bond, a divalent organic group or a divalent atom, each R ² is independently a hydrogen atom or a methyl group, and c + d Is an integer from 0 to 4, and d is an integer from 0 to 4, provided that is an integer from 1 to 4. When X ¹ is a divalent organic group, X ¹ is an alkylene group, an aralkylene group, an alkenylene group, an ester bond, an amide bond, an imide bond, or a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. Examples thereof include an alkylene group, an arylene group, an aralkylene group, a divalent substituted aromatic group, a divalent substituted heteroaromatic group, and a divalent substituted silyl group containing these bonds in the main chain. In addition, when X ¹ is a divalent atom, X ¹ may be an oxygen atom, a sulfur atom, a tin atom that may have a bond with another atom, or a phosphorus atom that may have a bond with another atom. Atoms are exemplified. In the general formula (V), X ¹ may be bonded to any substitutable carbon atom in the naphthalene ring to which they are bonded. (R) _a or (R) _b means a or b identical or different substituents, respectively, which are attached to any of the substitutable carbon atoms in the naphthalene ring to which they are attached. Each R may independently represent an organic group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. Moreover, in the said general formula (I), a is an integer of 0-5, b is an integer of 0-5.

  The polymerization initiator is a compound that polymerizes the polymerizable dinaphthothiophene compound by addition, heating, or light irradiation, that is, polymerizes the ethylenically unsaturated group of the polymerizable dinaphthothiophene compound. Examples of such compounds include radical polymerization initiators such as benzoyl peroxide, azobisisobutyronitrile, di-tert-butyl peroxide, redox catalysts, benzyl methyl ketals, α-hydroxyalkyls that generate radicals by light irradiation. Examples include photopolymerization initiators such as phenone, titanocene, and oxime ester, and anionic polymerization initiators such as alkylmagnesium chloride and alkyllithium. The addition amount of the polymerization initiator in the polymerizable composition may be appropriately determined in consideration of the desired polymerizability and the characteristics of the resin composition to be obtained, but as an example, a dinaphthothiophene compound having a polymerizability and About 0.1-10 mass% is mentioned with respect to the sum total with the compound which can be copolymerized with the dinaphtho thiophene compound which has the said polymeric property.

  Examples of the compound that can be copolymerized with the polymerizable dinaphthothiophene compound include a compound having an ethylenically unsaturated group, which is different from the polymerizable dinaphthothiophene compound. Such a compound can obtain a linear polymer by copolymerization with a polymerizable dinaphthothiophene compound, or a cured product by crosslinking, and a resin composition to be formed has desired characteristics. Can be. Such compounds include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid amide, (meth) acrylonitrile, styrene, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate. In addition to such monomers, resins having an ethylenically unsaturated group in the side chain are exemplified.

  The polymerizable composition may further contain a solvent. Such solvents are not particularly limited, but alcohols such as methanol, ethanol and isopropanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, aromatics such as benzene, toluene and xylene, dimethylformamide Amides such as, halogen-containing compounds such as chloroform, and the like.

  The polymerizable composition of the second form includes the refractive index improver of the present invention, a monomer, and a polymerization initiator that polymerizes the monomer. Unlike the polymerizable composition of the first form, the refractive index improver contained in this polymerizable composition itself does not need to have polymerizability. Instead, the polymerizable composition includes a monomer and a polymerization initiator that polymerizes the monomer.

  Examples of the combination of the monomer used in this embodiment and the polymerization initiator for polymerizing the monomer include a combination of a (meth) acrylic monomer and a photopolymerization initiator, a monomer having an ethylenically unsaturated bond, and radical polymerization initiation A combination with an agent may be mentioned, but is not particularly limited.

  Examples of the monomer include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid amide, (meth) acrylonitrile, styrene, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. Illustrated. Examples of the radical polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, and ditert-butyl peroxide.

  The polymerizable compositions of the first and second forms are polymerized by heating or light irradiation to form a resin composition. Since this resin composition contains a compound having a dinaphthothiophene skeleton represented by the general formula (I) derived from the refractive index improver of the present invention, it has a high refractive index and forms an optical material. Are preferably used. In order to form a resin composition from a polymerizable composition, after forming the polymerizable composition into a desired shape such as a film or a three-dimensional object, it is heated or irradiated with light, or by means such as coating. Bonding the optical substrate divided into two or more by a method of heating or irradiating the film after forming a film of the polymerizable composition on the surface of the optical substrate such as plastic or plastic, or by means such as coating Examples thereof include a method of heating or irradiating light after forming a film of the polysynthesize composition on the surface. In addition, when a polymerizable composition contains a solvent, it is preferable to remove the solvent contained in the polymerizable composition before heating or light irradiation.

  Next, a resin composition obtained by curing a curable composition containing a refractive index improver will be described. Two forms are mentioned as a curable composition used here.

  The curable composition of the 1st form contains the dinaphtho thiophene compound which has curability which is a refractive index improvement agent, and the reaction initiator which hardens the said dinaphtho thiophene compound by heating or light irradiation. The refractive index improver contained in the curable composition itself has curability and is cured to become a resin composition. The curable composition may further include a monomer, an oligomer, or a resin having an epoxy group or an oxetanyl group, which is a curable compound, as necessary.

  The dinaphthothiophene compound having curability is a substituent in which m + n is an integer of 1 or more and at least one R has an epoxy group or an oxetanyl group among the dinaphthothiophene compounds represented by the general formula (I). Is a compound having Since such a dinaphthothiophene compound has at least one substituent having an epoxy group or an oxetanyl group, the epoxy group or the oxetanyl group is opened in the presence of a reaction initiator that opens the epoxy group or the oxetanyl group. To form bonds with other molecules. As a result, the compound contained in the curable composition has a high molecular weight, and the curable composition becomes a cured resin composition.

  Although it does not specifically limit as a substituent which has an epoxy group or an oxetanyl group, An epoxy group, a glycidyl group, a glycidylmethyl group, an oxetanyl group, an oxetanylmethyl group etc. are illustrated.

  More specifically, examples of the curable dinaphthothiophene compound include compounds represented by the following general formula (VI).

In the general formula (VI), each X ² is independently a single bond, a divalent organic group or a divalent atom, and g is 0 on the condition that g + h is an integer of 1 to 4. Is an integer of -4, h is an integer of 0-4, p is independently 1 or 2, and q is 1 or 2 each independently. When X ² is a divalent organic group, X ² includes an alkylene group, an aralkylene group, an alkenylene group, an ester bond, an amide bond, an imide bond, or a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. Examples thereof include an alkylene group, an arylene group, an aralkylene group, a divalent substituted aromatic group, a divalent substituted heteroaromatic group, and a divalent substituted silyl group containing these bonds in the main chain. In addition, when X ² is a divalent atom, X ² may be an oxygen atom, a sulfur atom, a tin atom that may have a bond with another atom, or a phosphorus that may have a bond with another atom. Atoms are exemplified. In general formula (VI), X ² may be bonded to any substitutable carbon atom in the naphthalene ring to which they are bonded. (R) _e or (R) _f means e or f identical or different substituents, respectively, which are attached to any of the substitutable carbon atoms in the naphthalene ring to which they are attached. Each R may independently represent an organic group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. Moreover, in said general formula (I), e is an integer of 0-5 and f is an integer of 0-5.

  The reaction initiator is a compound that opens a ring of an epoxy group or an oxetanyl group contained in the curable dinaphthothiophene compound by heating or light irradiation. Examples of such compounds include compounds such as photoacid generators such as sulfonium salts, metaphenylenediamine, nadic acid anhydride, and tertiary amine compounds. The addition amount of the reaction initiator in the curable composition may be appropriately determined in consideration of the desired curability and the characteristics of the resin composition to be obtained, but as an example, a dinaphthothiophene compound having curability and And about 0.1 to 10% by mass relative to the total of the monomer, oligomer or resin having an epoxy group or oxetanyl group which is an optional component.

  A monomer, oligomer, or resin having an epoxy group or an oxetanyl group is added as an optional component to the curable composition to adjust the curability of the curable composition and the properties of the resin composition obtained by curing. As the monomer, oligomer or resin having an epoxy group or oxetanyl group, known ones such as bisphenol A diglycidyl ether and phenol novolac polyglycidyl ether can be used without particular limitation. The resin composition obtained by curing may be appropriately used in consideration of the characteristics of the resin composition.

  The curable composition may further contain a solvent. Such solvents are not particularly limited, but alcohols such as methanol, ethanol and isopropanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, aromatics such as benzene, toluene and xylene, dimethylformamide And halogen-containing compounds such as chloroform.

  The curable composition of a 2nd form contains the refractive index improver of this invention, curable resin, and the hardening | curing agent which hardens the said curable resin. Unlike the curable composition of the first form, the refractive index improver contained in the curable composition does not need to have curability itself. Instead, the curable composition includes a curable resin and a curing agent that cures the curable resin.

  Examples of the combination of the curable resin used in this embodiment and the curing agent for curing the curable resin include a combination of an epoxy resin and a photoacid generator, a combination of a urethane resin and an amine curing agent, and a dithiol compound. And a combination of an unsaturated compound and a photoacid generator, but are not particularly limited.

  Examples of the curable resin include epoxy resins, phenol resins, melamine resins, urethane resins, oxetane resins, and silicone resins. Examples of the curing agent include photoacid generators such as sulfonium salts, compounds such as metaphenylenediamine, nadic acid anhydride, and tertiary amine compounds.

  The curable compositions of the first and second forms are cured by heating or light irradiation to form a cured resin composition. Since this resin composition contains a compound having a dinaphthothiophene skeleton represented by the general formula (I) derived from the refractive index improver of the present invention, it has a high refractive index and forms an optical material. Are preferably used. In order to form the resin composition from the curable composition, after molding the curable composition into a desired shape such as a film or a three-dimensional object, the method may be performed by heating or irradiating the glass or by means such as coating. A method of heating or irradiating the film after forming a film of the curable composition on the surface of an optical base material such as plastic, or a method of applying a curable composition to a joint surface for joining two or more divided optical base materials. A method of heating or irradiating light after forming a film is exemplified. In addition, when a curable composition contains a solvent, it is preferable to remove the solvent contained in a curable composition before heating or light irradiation.

  Next, the optical material of the present invention will be described. The optical material of the present invention has at least a part of the already described refractive index improver itself or the already described resin composition for an optical material. Since it is “at least a part”, (1) the refractive index improver or the resin composition itself may be solidified to produce an optical material, or (2) the refractive index improver or the resin composition is made of glass or plastic. An optical material may be produced using an optical substrate such as. Since these optical materials contain the refractive index improver of the present invention, they have a high refractive index.

First, the aspect (1) will be described.
When preparing the optical material by solidifying the refractive index improver itself of the present invention, the dinaphthothiophene compound contained in the refractive index improver is preferably the polymer described above, but the dinaphthothiophene compound is a heavy polymer. Even if it is a monomolecular compound that is not a coalescence, it may be solidified in an amorphous or crystalline state, for example. Such a refractive index improver may be solidified after being molded into a desired shape in a state having fluidity by means such as heating or in a state having fluidity before curing.

  When solidifying the resin composition for an optical material of the present invention to produce an optical material, the resin composition having fluidity may be solidified after being molded into a desired shape. In addition, when the resin composition for optical materials is produced by polymerizing a polymerizable composition, or is produced by curing a curable composition, the resin composition Things become extremely hard and difficult to mold. In these cases, after molding into a desired shape at the stage of the polymerizable composition or the curable composition, the molded product may be solidified by heating or light irradiation.

  When producing an optical material using the refractive index improver itself, the resin composition, or the polymerizable composition or curable composition (hereinafter collectively referred to as “resin composition etc.”). Any known molding method can be used without particular limitation. Therefore, various molding methods may be appropriately selected and used in accordance with the required shape of the optical material.

  As such a molding method, a solution of a resin composition or the like is applied to the surface of a substrate with a spin coater or the like, and then a solvent contained in the applied solution is evaporated to form a film, or a molten resin Examples include an injection molding method in which a composition or the like is poured into a mold and molding, a press molding method in which a molten resin composition is poured into a press mold and pressed, a blow molding method, a melt extrusion method, and the like.

Next, the above aspect (2) will be described.
As a method for producing an optical material by using the refractive index improver or resin composition of the present invention together with an optical substrate such as glass or plastic, the refractive index improver or resin composition of the present invention is used as a configuration of the optical substrate. Examples thereof include a method of molding the optical substrate after using it as a component, and a method of forming a film of the refractive index improver of the present invention on the surface of the molded optical substrate by means such as coating and vapor deposition. These methods can be carried out by appropriately using known means.

  Moreover, as an aspect of said (2), the polymerizable composition of this invention or the bonding surface which joins the optical base material divided | segmented into 2 or more, or the bonding surface which joins an optical base material and another member, or Examples include a method of forming an optical material having a bonded portion by forming a film of these compositions by applying a curable composition, and then bonding a bonding target to the film and heating or irradiating light. It is done. Since the optical material produced by this method includes a resin composition formed from a polymerizable composition or a curable composition at the joint, the resin composition is used with an optical substrate such as glass or plastic. It can be said that the produced optical material. Such an optical material is also included in the present invention because it can be said that it has at least a part of the resin composition of the present invention. Such an optical material exhibits a high refractive index because the resin composition of the present invention is present at the joint.

  The optical material produced as described above contains the dinaphthothiophene compound described above and has a high refractive index. Therefore, this optical material has high refraction, such as eyeglass lenses, camera lenses, pickup lenses, micro lenses for image sensors, retardation compensation plates for liquid crystal display devices, optical fibers, optical waveguides, optical circuit materials, switching materials, optical holographic materials, etc. It is preferably used as an optical material for which a rate is required.

  The resin composition, polymerizable composition and curable composition of the present invention can also be used as a material for three-dimensional modeling using a photocurable coating, varnish, ink, and light. When the resin composition, polymerizable composition and curable composition of the present invention are used in such applications, an optical material having a high refractive index is locally formed by a simple technique such as printing or coating. Can do.

  The present invention also relates to a method of using a compound having a dinaphthothiophene skeleton represented by the above general formula (I) as an organic material refractive index improver. As described above, the refractive index of the optical material is improved by adding the dinaphthothiophene compound represented by the general formula (I) to the optical material composed of an organic material such as a (meth) acrylic resin. In addition, the refractive index of the optical material made of the organic material can be set to 1.5 to 1.9. This numerical value is a numerical value larger than 1.5 which is the refractive index of a normal optical material made of acrylic resin or the like. This shows that the compound having a dinaphthothiophene skeleton represented by the above general formula (I) is effective as a refractive index improver for organic substances.

  Hereinafter, the refractive index improver of the present invention will be described more specifically by showing examples, but the present invention is not limited to the following examples.

[Example 1]
Synthesis of dinaphthothio [2,1-b: 1 ′, 2′-d] thiophene (DNpTh)

  In a three-necked flask, 20.0 g (69.9 mmol) of 1,1′-binaphthol (BNpOH) was weighed, and 150 mL of N, N-dimethylformamide (DMF) was added and dissolved therein to obtain a solution. To this solution, 6.70 g (153.7 mmol) of sodium hydride (purity 55%, oil dispersion) was gradually added while cooling with ice under a nitrogen atmosphere, and stirred for 1 hour. To the obtained reaction solution, 20.0 g (153.7 mmol) of dimethylthiocarbamoyl chloride (purity 95%) was added, and these were heated and stirred at 85 ° C. for 1 hour and then cooled to room temperature, and then 1% by mass of KOH. The solution was poured into 500 mL of an aqueous solution, and the deposited precipitate was separated by filtration and washed thoroughly with water. The precipitate separated by filtration was dissolved in 50 mL of methylene chloride to form a solution, water contained in this solution was removed with magnesium sulfate, and then methylene chloride was distilled off from the solution. The solid remaining after the distillation was recrystallized from methylene chloride / petroleum ether to obtain 27.4 g (59.4 mmol) of BNpOTc. The melting point (mp.) Of the obtained BNpOTc was 206.3 ° C.

  Next, 6.0 g (13.1 mmol) of BNpOTc was dissolved in 12 mL of sulfolane, and the resulting solution was heated to reflux for 2 hours under a nitrogen atmosphere, then cooled to room temperature and poured into distilled water. The solid precipitated in distilled water was filtered off, dried under reduced pressure, and then dissolved in chloroform. The solution thus obtained was decolorized with activated carbon and further recrystallized from chloroform / hexane to obtain 2.63 g (9.3 mmol) of DNpTh. The obtained DNpTh was used as the refractive index improver of Example 1. The obtained DNpTh mp. Was 208.9 ° C.

[Example 2]
Synthesis of dinaphthothiophene-6-carboxaldehyde (6-F-DNpTh)

In a three-necked flask, 1.0 g (3.6 mmol) of DNpTh was weighed, and 200 mL of dehydrated ether was added and dispersed therein. To this dispersion, 6.8 mL (10.6 mmol) of a hexane solution (1.54 M) of n-butyllithium was gradually added dropwise at 0 ° C. under an argon atmosphere, and the mixture was further heated to reflux for 2.5 hours. The obtained reaction solution was cooled to 0 ° C., 0.4 mL (10.6 mmol) of DMF was gradually added dropwise, and the mixture was heated to reflux for 2 hours. Thereafter, 60 mL of distilled water and 50 mL of ethyl acetate were added to the reaction solution under ice cooling, and the mixture was washed with water until the aqueous layer became neutral. After washing with water, the organic layer was separated, the water contained in this organic layer was removed with magnesium sulfate, and then the solvent contained in the organic layer was distilled off. The solid remaining after the distillation was purified by silica gel column chromatography (chloroform: hexane = 3: 1) and recrystallized from ethanol to obtain 0.62 g (2.0 mmol) of 6-F-DNpTh as a yellow solid. The obtained 6-F-DNpTh was used as the refractive index improver of Example 2.
Each physical property value of 6-F-DNpTh is as follows.
mp. 210.4 ° C
¹ H NMR (600 MHz, CDCl ₃ ) δ (ppm): 10.1212 (s, 1H), 8.95 (d, J = 8.4 Hz, 1H), 8.78 (m, 1H), 8.494 (S, 1H), 8.209 (d, J = 8.4 Hz, 1H), 8.05 (m, 2H), 7.980 (d, J = 8.4 Hz, 1H), 7.73 (m , 1H), 7.67 (m, 1H), 7.60 (m, 2H)
IR (film): 1682 cm ⁻¹

[Example 3]
Synthesis of 6-hydroxymethyldinaphthothiophene (6-HM-DNpTh)

In a three-necked flask, 1.1 g (3.2 mmol) of 6-F-DNpTh was weighed, and 10 mL of dehydrated ethanol was added and dispersed therein. Under a nitrogen atmosphere, 0.5 g (13.2 mmol) of sodium borohydride was added to this dispersion, and the mixture was further stirred with heating at 65 ° C. for 1 hour. Under ice-cooling, 30 mL of 1N hydrochloric acid and 50 mL of ethyl acetate were added to the resulting reaction solution, and washed with water until the aqueous layer became neutral. After washing with water, the organic layer was separated, the water contained in this organic layer was removed with magnesium sulfate, and then the solvent contained in the organic layer was distilled off. The solid remaining after the distillation was purified by silica gel column chromatography (chloroform: hexane = 3: 1) to obtain 1.0 g (3.0 mmol) of white solid 6-HM-DNpTh. The obtained 6-HM-DNpTh was used as the refractive index improver of Example 3.
Each physical property value of 6-HM-DNpTh is as follows.
mp. 150.9 ° C
¹ H NMR (600 MHz, CDCl ₃ ) δ (ppm): 8.85 (m, 2H), 8.04 (m, 2H), 7.97 (m, 3H), 7.58 (m, 4H), 5.156 (s, 2H)
IR (film): 3365 cm ⁻¹

[Example 4]
Synthesis of polymer having dinaphthothiophene skeleton (Polymer A)

In a three-necked flask, 1.5 g (5.3 mmol) of DNpTh and 0.16 g (5.3 mmol) of paraformaldehyde were weighed, and 50 mL of dichloroethane was added and dispersed therein. To this dispersion, 0.65 mL of boron trifluoride diethyl ether complex (BF ₃ · OEt ₂ ) was added with good stirring under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 24 hours. Thereafter, this reaction solution was gradually added dropwise to 500 mL of stirring methanol, and the produced solid was separated by filtration and dried to obtain Polymer A (polymer having a dinaphthothiophene skeleton) as a light red powder. The obtained Polymer A was used as the refractive index improver of Example 4.
The physical property values of Polymer A are as follows.
¹ H-NMR (600 MHz, CDCl ₃ ) δ (ppm): 8.8-9.1 (m, Ar), 8.2-8.3 (m, Ar), 7.9-8.1 (m , Ar), 7.4-7.7 (m, Ar), 5.1-5.5 (m, -CH 2 -)
GPC (THF) polystyrene conversion: number average molecular weight 770, mass average molecular weight 1020

[Example 5]
Synthesis of 6-vinyldinaphthothiophene (6-V-DNpTh)

In a three-necked flask, 4.57 g (12.8 mmol) of methyltriphenylphosphonium bromide was weighed, and 50 mL of dehydrated tetrahydrofuran (THF) was added and dispersed therein. 7.9 mL (12.2 mmol) of n-butyllithium (1.54 M, n-hexane solution) was gradually added to this dispersion while cooling with ice in a nitrogen atmosphere, and the mixture was stirred at room temperature for 1 hour. A solution prepared by dissolving 4.57 g (6.4 mmol) of 6-F-DNpTh in 20 mL of THF was gradually added dropwise to the obtained reaction solution under ice cooling, and the mixture was further stirred at room temperature for 3 hours. Under ice-cooling, 100 mL of water was added to this reaction solution and stirred well. Further, 100 mL of ethyl acetate was added, and then the organic layer was separated. Saturated saline was added to the separated organic layer and washed repeatedly until the aqueous layer became neutral. After washing with water, the organic layer was separated, water contained in the organic layer was removed with magnesium sulfate, and then the solvent contained in the organic layer was distilled off. The solid remaining after the distillation was purified by silica gel column chromatography (chloroform) to obtain 3.81 g (12.3 mmol) of 6-V-DNpTh as a pale yellow solid. The obtained 6-V-DNpTh was used for the synthesis of Polymer B described later.
Each physical property value of 6-V-DNpTh is as follows.
mp. 116.8 ° C
¹ H NMR (600 MHz, CDCl ₃ ) δ (ppm): 8.83 (m, 2H), 8.04 (m, 3H), 7.989 (d, J = 7.8 Hz, 1H), 7.943 (D, J = 7.8 Hz, 1H), 7.57 (m, 4H), 7.191 (dd, J = 18.0 Hz, J = 10.8 Hz, 1H), 6.166 (d, J = 18.0 Hz, 1 H), 5.630 (d, J = 10.8 Hz, 1 H)
IR (film): 1623 cm ⁻¹

[Example 6]
Synthesis of polymer having dinaphthothiophene skeleton (Polymer B)

In the polymerization tube, 6-V-DNpTh 1.0 g (3.2 mmol) and azobisisobutyronitrile (AIBN) 26.5 mg (0.16 mmol) were weighed, and 10 mL of dehydrated toluene was added and dissolved therein. . This solution was cooled with liquid nitrogen and subjected to freeze deaeration and nitrogen substitution three times, and then freeze deaerated and sealed, and this solution was stirred at 60 ° C. for 14 hours for a polymerization reaction. The obtained reaction solution was diluted with 3 mL of toluene, and purified by reprecipitation with 200 mL of methanol to obtain 0.62 g (2.0 mmol) of Polymer B as an almost white powder. The obtained Polymer B was used as the refractive index improver of Example 6.
The physical property values of Polymer B are as follows.
¹ H-NMR (600 MHz, CDCl ₃ ) δ (ppm): 8.5 to 6.0 (br, 11H), 3.0 to 0.8 (br, 3H)
GPC (THF) polystyrene conversion: number average molecular weight 7000, mass average molecular weight 15150

[Example 7]
Synthesis of methacrylate monomer (DNTMA) having dinaphthothiophene skeleton

In a three-necked flask equipped with a condenser tube and a Gene Stark tube, 1.3 g (4.1 mmol) of 6-HM-DNpTh and 5 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) were added. Weighed, 20 mL of dehydrated toluene and 4.42 mL (41.3 mmol) of methyl methacrylate were added and dissolved. While this solution was heated to 80 ° C. and nitrogen gas was bubbled, 0.1 mL (1.24 mmol) of sodium methoxide (70% methanol solution) was added dropwise, and further stirred at 80 ° C. for 4.5 hours. Reacted. The obtained reaction solution was returned to room temperature and then washed 3 times with 50 mL of distilled water to separate the organic layer. After water contained in the organic layer was removed with magnesium sulfate, the solvent contained in the organic layer was distilled off. The solid remaining after the distillation was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 4), 10 mL of hexane was added, and the precipitated white solid was collected by filtration to obtain 1.1 g (3.0 mmol) of DNTMA. Obtained. The obtained DNTMA was used for the synthesis of Polymer C described later.
The physical property values of DNTMA are as follows.
mp. 84.7 ° C
¹ H NMR (600 MHz, CDCl ₃ ) δ (ppm): 8.85 (m, 2H), 7.99 (m, 3H), 7.58 (m, 4H), 6.25 (m, 1H), 5.63 (m, 3H), 2.02 (m, 3H)
IR (film): 1719, 1636 cm ⁻¹

[Example 8]
Synthesis of polymer having dinaphthothiophene skeleton (Polymer C)

In a polymerization tube, 1.25 g (3.3 mmol) of DNTMA and 26.5 mg (0.16 mmol) of azobisisobutyronitrile (AIBN) were weighed, and 10 mL of dehydrated toluene was added and dissolved therein. This solution was cooled with liquid nitrogen, and freeze-degassed nitrogen substitution was repeated three times. Then, the solution was freeze-degassed and sealed, and this solution was stirred at 60 ° C. for 20 hours to cause a polymerization reaction. The obtained reaction solution was diluted with 3 mL of toluene and purified by reprecipitation with 200 mL of a hexane-ethyl acetate mixed solvent (5: 1) to obtain 1.19 g of Polymer C as a white powder. The obtained Polymer C was used as the refractive index improver of Example 8.
The physical property values of Polymer C are as follows.
¹ H-NMR (600 MHz, CDCl ₃ ) δ (ppm): 8.5 to 6.0 (br, 11H), 5.4 to 4.6 (br, 2H), 2.4 to 0.9 (br , 5H)
IR (film): 3047, 1733, 1156 cm ⁻¹
GPC (THF) polystyrene conversion: number average molecular weight 14300, mass average molecular weight 50860

[Examples 9 to 12]
Synthesis of polymer having dinaphthothiophene skeleton (Polymer DG)

To the polymerization tube, 6-V-DNpTh and comonomer X were weighed in the amounts shown in Table 1 below, and 26.5 mg (0.16 mmol) of azobisisobutyronitrile (AIBN) and 10 mL of dehydrated toluene were added thereto. And dissolved. For Example 9 (Polymer D), only 6-V-DNpTh was used as the monomer without adding comonomer X. This solution was cooled with liquid nitrogen, and freeze-degassed nitrogen substitution was repeated three times. Then, the solution was freeze-degassed and sealed, and this solution was stirred at 60 ° C. for 20 hours to cause a polymerization reaction. The obtained reaction solution was diluted with 3 mL of toluene and purified by reprecipitation with 200 mL of ethyl acetate to obtain a substantially white copolymer (Polymer D to G). Polymer D was used as the refractive index improver of Example 9, Polymer E was used as the refractive index improver of Example 10, Polymer F was used as the refractive index improver of Example 11, and Polymer G was used as Example 12. A refractive index improver was used.
The physical property values of Polymers D to G are as follows.

Polymer D (Example 9, 6-V-DNpTh homopolymer)
¹ H-NMR (600 MHz, CDCl ₃ ) δ (ppm): 8.5 to 6.0 (br, 11H), 5.4 to 4.6 (br, 2H), 3.0 to 0.8 (br , 3H)
IR (film): 3050 cm ⁻¹
GPC (THF) polystyrene conversion: number average molecular weight 14200, mass average molecular weight 28310

Polymer E (Example ^{10, R 7: H, R} 8: -C 6 H 5)
¹ H-NMR (600 MHz, CDCl ₃ ) δ (ppm): 8.5 to 6.0 (br), 3.7 to 0.2 (br)
IR (film): 3050, 1937, 1732 cm ⁻¹
GPC (THF) polystyrene conversion: number average molecular weight 7350, mass average molecular weight 21310

Polymer F (Example _{^{11, R 7: -CH 3,}} R 8: -C (O) OCH 3)
¹ H-NMR (600 MHz, CDCl ₃ ) δ (ppm): 8.5 to 6.0 (br), 3.7 to 0.2 (br)
IR (film): 3050, 1729 cm ⁻¹
GPC (THF) polystyrene conversion: number average molecular weight 12480, mass average molecular weight 22430

Polymer G (Example ^{_{12, R 7: -CH 3,}} R 8: -C (O) OCH 2 CH (C 2 H 5) C 4 H 9)
¹ H-NMR (600 MHz, CDCl ₃ ) δ (ppm): 8.5 to 6.0 (br), 3.7 to 0.2 (br)
IR (film): 3050, 1717 cm ⁻¹
GPC (THF) polystyrene conversion: number average molecular weight 4300, mass average molecular weight 10190

[Comparative Example 1]
Dibenzothiophene (manufactured by Wako Pure Chemical Industries, Ltd.) represented by the following formula (V) was used as the refractive index improver of Comparative Example 1.

[Evaluation of refractive index]
Test examples 1-5
For each of the refractive index improvers of Examples 1 to 4 and 6, 20 mg of the refractive index improver was dissolved in 1 mL of chloroform to form a solution, and then this solution was filtered through a membrane filter (0.50 μm). One drop of the obtained filtrate was applied to the surface of a silicon wafer (15 mm square) using a Pasteur pipette, and chloroform contained in the applied filtrate was evaporated to form a film of refractive index improver ( A film thickness of 1 μm) was formed. The obtained refractive index improver films were all uniform and transparent, and for each of the films, the refractive index with respect to light of 632.8 nm was measured using an Ellipson meter (DHA-OLX / S4, manufactured by Mizoji Optical Co., Ltd.). It was measured by. The results are shown in Table 2. Those using the refractive index improver of Example 1 were used in Test Example 1, those using the refractive index improver of Example 2 were used in Test Example 2, and those using the refractive index improver of Example 3 were used. Corresponds to Test Example 3, the one using the refractive index improver of Example 4 corresponds to Test Example 4, and the one using the refractive index improver of Example 6 corresponds to Test Example 5. Moreover, about the test examples 4 and 5 (refractive index improver of Examples 4 and 6), the said test was done using 20 mg of methylene chloride soluble parts.

Test example 6
About the refractive index improvement agent of Example 1, a refractive index improvement agent and polymethyl methacrylate (PMMA, number average molecular weight 3900) were mixed in the ratio shown in Table 2, and the resin composition was produced. 20 mg of the obtained resin composition was dissolved in 1 mL of chloroform to form a solution, and this solution was then filtered through a membrane filter (0.50 μm). One drop of the obtained filtrate was applied to the surface of a silicon wafer (15 mm square) using a Pasteur pipette, and the chloroform contained in the applied filtrate was evaporated to form a film of the resin composition ( A film thickness of 1 μm) was formed. Each of the obtained resin composition films was uniformly transparent, and for each of the films, the refractive index with respect to light of 632.8 nm was measured by an Ellipson meter (DHA-OLX / S4, manufactured by Mizojiri Optical Co., Ltd.). It was measured. The results are shown as Test Example 6 in Table 2.

・ Comparative test example 1
Comparative Test Example 1 was carried out in the same procedure as Test Example 5 except that the refractive index improver of Comparative Example 1 was used as the refractive index improver. The results are shown in Table 2.

・ Comparative test example 2
Using the same PMMA as in Test Example 5 and Comparative Test Example 1, 20 mg of this PMMA was dissolved in 1 mL of chloroform to form a solution, and then this solution was filtered through a membrane filter (0.50 μm). One drop of the obtained filtrate was applied to the surface of a silicon wafer (15 mm square) using a Pasteur pipette, and the chloroform contained in the applied filtrate was evaporated to form a PMMA film (film thickness 100 μm). ) Was formed. About the obtained PMMA film | membrane, the refractive index with respect to the light of 632.8 nm was measured with the Ellipson meter (DHA-OLX / S4, the product made from a Mizoji optical industry company). The results are shown in Table 2.

  As is clear from Table 2, in Test Examples 1 to 6 using any one of the refractive index improvers of Examples 1 to 6, a high refractive index of about 1.70 to 1.81 was obtained. The effectiveness of the refractive index improver is understood. In particular, in Comparative Test Example 1 in which dibenzothiophene, which has been known as a refractive index improver so far, is mixed with PMMA and in Test Example 6 in which the refractive index improver of the present invention is mixed in PMMA, It can be seen that the refractive index is improved by 0.1. Moreover, it turns out that it becomes a refractive index exceeding 1.8 in Test example 4 in which the refractive index improver of Example 4 which is a polymer type is used among the refractive index improvers of this invention. If it is a polymer type refractive index improver, the refractive index improver itself can be molded into an optical material. Therefore, an optical material produced from a refractive index improver that can obtain such a high refractive index is expected to have a high refractive index and is extremely effective.

Test examples 7-11
For each of the refractive index improvers (Polymers C to G) obtained in Examples 8 to 12, 20 mg of the refractive index improver was dissolved in 1 mL of chloroform to form a solution, and then this solution was dissolved in a membrane filter to obtain a solution. Then, this solution was filtered through a membrane filter (0.50 μm). One drop of the obtained filtrate was applied to the surface of a silicon wafer (15 mm square) using a Pasteur pipette, and chloroform contained in the applied filtrate was evaporated to form a film of refractive index improver ( A film thickness of 1 μm) was formed. The obtained refractive index improver films were all uniform and transparent, and for each of the films, the refractive index with respect to light of 632.8 nm was measured using an Ellipson meter (DHA-OLX / S4, manufactured by Mizoji Optical Co., Ltd.). It was measured by. The results are shown in Table 3. In addition, what used the refractive index improver (Polymer C) of Example 8 was used for Test Example 7, and what used the refractive index improver (Polymer D) of Example 9 was used for Test Example 8 and Example 10. The one using the refractive index improver (Polymer E) is used in Test Example 9, the one using the refractive index improver (Polymer F) of Example 11 is used in Test Example 10, and the refractive index improver (Polymer is used in Example 12). Those using G) correspond to Test Example 11, respectively. For reference, the results of Comparative Test Example 2 shown in Table 2 are also shown in Table 3.

  Similar to the refractive index improvers of Examples 1 to 6 shown in Table 2, in Test Examples 7 to 11 using the refractive index improvers of Examples 8 to 12, which are polymer types, 1.70 to 1 A high refractive index of about .74 was obtained. This numerical value is 0.2 or more larger than the refractive index (comparative test example) in PMMA, which is a general-purpose optical polymer. However, it is understood that it is effective. A polymer type refractive index improver is effective for producing an optical material having a high refractive index because the refractive index improver itself can be molded into an optical material.

[Evaluation of transparency]
The transmittance | permeability of the chloroform solution (0.1 mass%) of the refractive index improver (Polymer D) of Example 9 was measured using the spectrophotometer (JASCO V-670, JASCO Corporation make). The result is shown in FIG. FIG. 1 is a spectrum showing the transmittance of ultraviolet and visible light in a chloroform solution (0.1% by mass) of the refractive index improver (Polymer D) of Example 9.

  As shown in FIG. 1, the refractive index improver (Polymer D) of Example 9 has a transmittance of 99.1% at 450 nm, and has high transparency in the visible range despite being a polynuclear aromatic compound. It can be seen that it is useful as an optical material.

[Production of photopolymerizable composition and evaluation of refractive index of photocured film produced using it]
Test examples 12-14
Refractive index improver of Example 5 (6-V-DNpTh; dinaphthothiophene compound having an ethylenically unsaturated double bond) and photocured acrylate composition (bisphenol-based epoxy acrylate / trimethylolpropane triacrylate / photopolymerization) Initiator Darocur 1173 = 75: 25: 1 (mass ratio)) was weighed in amounts shown in Table 4, and dissolved in 1.2 mL of ethyl acetate to obtain a solution of the photopolymerizable composition. The bisphenol epoxy acrylate uses Lipoxy-77-11 manufactured by Showa Polymer Co., Ltd., and Darocur 1173 is a trade name manufactured by Ciba Specialty Chemicals. Next, the obtained solution is filtered through a membrane filter (0.50 μm). One drop of the filtrate is applied to the surface of a silicon wafer (15 mm square) using a Pasteur pipette, and is contained in the applied solution. The ethyl acetate that had been evaporated was evaporated to form a photopolymerizable composition film (film thickness 0.7-0.9 μm).

The film of this photopolymerizable composition was irradiated with light for 30 minutes using a high pressure mercury lamp (6 mW / cm ² ) to obtain a transparent photocured film insoluble in chloroform. This photocured film is not only the resin composition of the present invention but also the optical material of the present invention. About each of the obtained photocuring film, the film thickness after hardening and the refractive index with respect to the light of 632.8 nm were measured with the Ellipson meter (DHA-OLX / S4, the product made from a Mizoji optical industry company). The results are shown in Table 4.

  As is clear from Table 4, in the photocured films (Test Examples 12 to 14) prepared by adding the refractive index improver (6-V-DNpTh) of Example 5, it is about 1.59 to 1.68. A refractive index was obtained, and a refractive index increasing effect of about 0.03 to 0.13 was observed as compared with a comparative photocured film not containing the refractive index improver of the present invention (Comparative Test Example 3). And it turned out that the refractive index raise effect can be adjusted according to the addition amount of the refractive index improvement agent (6-V-DNpTh) of Example 5. FIG.

  As described above, it is clear that the refractive index improver of the present invention has a high refractive index and a high light transmittance, and is understood to be useful for the production of optical materials that require a high refractive index.

Claims (16)

A refractive index improver comprising a dinaphthothiophene compound represented by the following general formula (I).

(In the above general formula (I), (R) _m or (R) _n means m or n identical or different substituents, respectively, which can be substituted in the naphthalene ring to which they are bonded. Each R may independently be an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a vinyl group, a styryl group, which may have 1 to 20 carbon atoms and may contain a hetero atom. Allyl group, (meth) acryloyloxymethyl group, methyl (meth) acryloyloxymethyl group, carboxyl group, hydroxymethyl group, hydroxyethyl group, formyl group, methylcarbonyl group, methoxycarbonyl group, N-ethylaminocarbonyl group, Trifluoromethyl group, trimethylsilyl group, cyano group, cyanoethyl group, isocyanato group, thioisocyanate DOO group, benzylidene amino group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. In addition, in the above general formula (I), m is 0 6 is an integer, and n is an integer of 0 to 6.) Refractive index enhancing agent comprising a polymer, comprising structural repeating units represented by the following general formula (II).

(In the above general formula (II), (R) _p or (R) _q means p or q identical or different substituents, respectively, which can be substituted on the naphthalene ring to which they are bonded. Each R may independently be an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a vinyl group, a styryl group, which may have 1 to 20 carbon atoms and may contain a hetero atom. Allyl group, (meth) acryloyloxymethyl group, methyl (meth) acryloyloxymethyl group, carboxyl group, hydroxymethyl group, hydroxyethyl group, formyl group, methylcarbonyl group, methoxycarbonyl group, N-ethylaminocarbonyl group, Trifluoromethyl group, trimethylsilyl group, cyano group, cyanoethyl group, isocyanato group, thioisocyanate Isocyanato group, benzylidene amino group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. In addition, in the above general formula (II), p is 0 And q is an integer of 0 to 5. In the general formula (II), X is a single bond, an alkylene group which may contain a hetero atom, an aralkylene group, an alkenylene group or an ester bond. , An amide bond, an imide bond, or an alkylene group containing these bonds in the main chain, an arylene group, an aralkylene group, a divalent substituted aromatic group, a divalent substituted heteroaromatic group, a divalent substituted silyl group, or It is a divalent atom.) Polymer to the following general formula (III) repeating the structure represented by the unit, or a refractive index enhancing agent comprising a copolymer, comprising as a repeating unit structure represented by the following general formula (III).

(In the general formula (III), (R) _r means r identical or different substituents, and the substituents may be bonded to any substitutable carbon atom in the dinaphthothiophene skeleton. And each R is independently an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a vinyl group, a styryl group, an allyl group, a (meth) acryloyloxymethyl group, which has 1 to 20 carbon atoms and may contain a hetero atom. Methyl (meth) acryloyloxymethyl group, carboxyl group, hydroxymethyl group, hydroxyethyl group, formyl group, methylcarbonyl group, methoxycarbonyl group, N-ethylaminocarbonyl group, trifluoromethyl group, trimethylsilyl group, cyano group, Cyanoethyl group, isocyanato group, thioisocyanato group, benzylideneamino group , water It represents an acid group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group, and r is an integer of 0 to 11 in the general formula (III). In the general formula (III), Y is a single bond, an ester bond, an amide bond, an imide bond, an ether bond, a sulfide bond, or an alkylene group containing these bonds in the main chain, or a divalent atom. , R ¹ is a hydrogen atom or a methyl group.)   The resin composition containing the refractive index improver of any one of Claims 1-3, and resin.   The resin is a poly (meth) acrylic ester, polystyrene, polyvinyl ether, polyolefin and a copolymer of monomers constituting these, polycarbonate, polyester, polyimide, polyamide, polysulfide, polyurethane, polyether, phenol resin, urea resin, The resin composition according to claim 4, comprising at least one selected from the group consisting of a melamine resin, an epoxy resin, and an oxetane resin.   The resin composition according to claim 5, wherein the resin has a branched structure.   2. The refractive index improver according to claim 1, wherein m + n is an integer of 1 or more, and at least one R is a substituent having an ethylenically unsaturated group, and the ethylenically unsaturated group is polymerized by heating or light irradiation. And a polymerization initiator.   The polymerizable composition according to claim 7, further comprising a compound having an ethylenically unsaturated group separately from the refractive index improver.   A polymerizable composition comprising the refractive index improver according to claim 1, a monomer, and a polymerization initiator for polymerizing the monomer.   2. The refractive index improver according to claim 1, wherein m + n is an integer of 1 or more, and at least one R is a substituent having an epoxy group or oxetanyl group, and the epoxy group or oxetanyl group is opened by heating or light irradiation. A curable composition comprising a reaction initiator to be cyclized.   The curable composition according to claim 10, further comprising a monomer, an oligomer or a resin having an epoxy group or an oxetanyl group separately from the refractive index improver.   A curable composition comprising the refractive index improver according to claim 1, a curable resin, and a curing agent that cures the curable resin.   The resin composition formed by polymerizing the polymerizable composition according to any one of claims 7 to 9, or by curing the curable composition according to any one of claims 10 to 12.   The optical material which has at least one part the refractive index improver of any one of Claims 1-3, or the resin composition of any one of Claims 4-6 and 13. A method of using a dinaphthothiophene compound represented by the following general formula (I) as an organic refractive index improver.

(In the above general formula (I), (R) _m or (R) _n means m or n identical or different substituents, respectively, which can be substituted in the naphthalene ring to which they are bonded. Each R may independently be an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a vinyl group, a styryl group, which may have 1 to 20 carbon atoms and may contain a hetero atom. Allyl group, (meth) acryloyloxymethyl group, methyl (meth) acryloyloxymethyl group, carboxyl group, hydroxymethyl group, hydroxyethyl group, formyl group, methylcarbonyl group, methoxycarbonyl group, N-ethylaminocarbonyl group, Trifluoromethyl group, trimethylsilyl group, cyano group, cyanoethyl group, isocyanato group, thioisocyanate DOO group, benzylidene amino group, a hydroxyl group, an amino group, a nitro group, a thiol group, a sulfo group, a halogen atom, or an optionally substituted silyl group. In addition, in the above general formula (I), m is 0 6 is an integer, and n is an integer of 0 to 6.) The method according to claim 15, wherein the organic material has a refractive index of 1.5 to 1.9.

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