JP2007238884A - Optical article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an optical article that has excellent transparency, a high refractive index and a low optical anisotropy. <P>SOLUTION: The optical article is formed from a composition comprising a resin containing at least one kind of a structural unit represented by any of general formulas [ring α is an aromatic ring-containing ring; ring β and ring γ are each a monocyclic or monocyclic ring; L is difunctional connecting group; n is 0 or 1] and metal fine particles. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is an optical article (for example, spectacle lens, lens for various optical devices (lens for pickup, lens for vehicle camera) formed of a sulfur-containing resin and metal fine particles having a high refractive index, excellent transparency and low optical anisotropy. , Portable camera lenses, digital camera lenses, OHP lenses, etc.), microlens arrays, prisms, prism sheets, optical fiber communication devices (optical waveguides, optical amplifiers, etc.), LED sealants, etc.).

  In recent years, optical articles, which have been exclusively used for glass, have been replaced with plastic materials having excellent characteristics such as economy, easy moldability, breakage resistance, and light weight in recent years. For example, in digital camera lenses, mobile phone lenses, CDs, optical lenses typified by Blu-ray pickup lenses, disk bases, light guide plates, prism sheets, etc., polymethyl methacrylate (PMMA), polycarbonate (PC), Or the use of cycloolefin polymer is progressing. Moreover, introduction of sulfur-containing resins is also progressing in spectacle lenses.

  On the other hand, as for resin materials for optical articles, no material has yet been provided that satisfies all the requirements of high refractive index, high transparency, and low birefringence. However, the present situation is that improvement of characteristics is required.

  As a high refractive index resin material, for example, a technique for introducing a sulfur atom into a polymer (Patent Documents 1 to 6, etc.), a technique for introducing a halogen atom or an aromatic ring into a polymer (Patent Document 7), etc. are proposed. Has been. As an attempt to achieve both high refractive index and low anisotropy, a fluorene skeleton and a sulfur atom-containing polymer have been proposed (Patent Document 8). Furthermore, introduction of a spiro structure has been proposed as a technique for reducing the birefringence of an aromatic polycarbonate (Patent Document 9).

In addition, a technique for forming a high refractive index material by dispersing fine particles of titanium oxide having a high refractive index in a resin matrix has been reported (Patent Document 10). However, even with this method, it has been difficult to produce a sufficiently transparent matrix having a high refractive index.
JP 2002-131502 A Japanese Patent Laid-Open No. 10-298287 Japanese Patent Laid-Open No. 3-56525 Japanese Patent Laid-Open No. 5-208950 JP-A-8-208975 JP-A-10-319201 JP 2004-244444 A JP 2001-106761 A JP 2000-298776 A JP 2003-73559 A

However, even in the above attempt, there has been no material that sufficiently satisfies the characteristics required for plastic lenses such as high refractive index, high transparency, low optical anisotropy, and easy formation.
This invention is made | formed in view of the said actual condition, The objective is to provide the optical article which has a high refractive index, the outstanding transparency, and low optical anisotropy.

  As a result of intensive studies, the present inventors have found that the problems of the prior art can be solved by using a resin containing a specific structural unit and metal fine particles in combination. That is, the following present invention has been provided as means for solving the problems.

[1] An optical article formed by a composition comprising a resin containing a structural unit represented by the following general formula (1) or general formula (2) and metal fine particles.

［一般式（１）中、２つの環αはそれぞれ独立に芳香環を含む環を表し、２つの環はスピロ結合によって結合している。２つのＬはそれぞれ独立に２価の連結基を表し、２つのｎはそれぞれ独立に０または１を表す。］

[In the general formula (1), the two rings α each independently represent a ring containing an aromatic ring, and the two rings are connected by a spiro bond. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. ]

［一般式（２）中、環βおよび環γはそれぞれ独立に単環式または多環式の環を表し、２つの環γは環β上の１つの４級炭素に連結している。２つのＬはそれぞれ独立に２価の連結基を表し、２つのｎはそれぞれ独立に０または１を表す。］

[In general formula (2), ring β and ring γ each independently represent a monocyclic or polycyclic ring, and two rings γ are linked to one quaternary carbon on ring β. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. ]

[2] The resin is a polyaddition product of a dithiol compound corresponding to the general formula (1) or the general formula (2) and a compound having two or more reactive groups capable of addition by thiol in one molecule. [1] The optical article according to [1].

[3] The optical article according to [2], wherein the compound having two or more reactive groups is a polyisocyanate compound or a polyisothiocyanate compound.

[4] The optical unit according to any one of [1] to [3], wherein the structural unit is a structural unit represented by any one of the following general formulas (3) to (6). Goods.

［一般式（３）中、Ｒ¹¹、Ｒ¹²それぞれ独立に水素原子または置換基を表し、Ｒ¹³はそれぞれ独立に置換基を表す。また、Ｒ¹¹〜Ｒ¹³で表わされるそれぞれの置換基は連結して環を形成してもよい。ｐおよびｑはそれぞれ独立に０〜３の整数を表す。２つのＬはそれぞれ独立に２価の連結基を表し、２つのｎはそれぞれ独立に０または１を表す。］

[In General Formula (3), R ¹¹ and R ¹² each independently represents a hydrogen atom or a substituent, and R ¹³ each independently represents a substituent. Moreover, each substituent represented by R ^{11 to} R ¹³ may be linked to form a ring. p and q each independently represents an integer of 0 to 3. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. ]

［一般式（４）中、Ｒ³¹はそれぞれ独立に水素原子または置換基を表し、Ｒ³²はそれぞれ独立に置換基を表す。また、Ｒ³¹、Ｒ³²で表わされるそれぞれの置換基は連結して環を形成してもよい。ｐおよびｑはそれぞれ独立に０〜３の整数を表す。２つのＬはそれぞれ独立に２価の連結基を表し、２つのｎはそれぞれ独立に０または１を表す。Ｘは酸素原子または硫黄原子を表す。］

[In General Formula (4), each R ³¹ independently represents a hydrogen atom or a substituent, and each R ³² independently represents a substituent. Moreover, each substituent represented by R ³¹ and R ³² may be linked to form a ring. p and q each independently represents an integer of 0 to 3. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. X represents an oxygen atom or a sulfur atom. ]

［一般式（５）中、Ｒ²¹はそれぞれ独立に水素原子または置換基を表し、Ｒ²²はそれぞれ独立に置換基を表す。また、Ｒ²¹、Ｒ²²で表わされるそれぞれの置換基は連結して環を形成してもよい。ｐおよびｑはそれぞれ独立に０〜３の整数を表す。２つのＬはそれぞれ独立に２価の連結基を表し、２つのｎはそれぞれ独立に０または１を表す。Ｘは酸素原子または硫黄原子を表す。］

[In General Formula (5), each R ²¹ independently represents a hydrogen atom or a substituent, and each R ²² independently represents a substituent. Moreover, each substituent represented by R ²¹ and R ²² may be linked to form a ring. p and q each independently represents an integer of 0 to 3. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. X represents an oxygen atom or a sulfur atom. ]

［一般式（６）中、Ｒ⁶¹、Ｒ⁶²はそれぞれ独立に置換基を表す。また、それぞれが連結して環を形成してもよい。ｊおよびｋはそれぞれ独立に０〜４の整数を表す。２つのＬはそれぞれ独立に２価の連結基を表し、２つのｎはそれぞれ独立に０または１を表す。］

[In General Formula (6), R ⁶¹ and R ⁶² each independently represents a substituent. In addition, each may be linked to form a ring. j and k each independently represents an integer of 0 to 4. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. ]

[5] The optical article according to any one of [1] to [4], wherein the metal fine particles are zirconia or titania fine particles.

[6] The optical article according to any one of [1] to [5], wherein the optical article is a plastic lens.

  The optical article of the present invention has a high refractive index, excellent transparency, and low optical anisotropy.

  Hereinafter, the optical article of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

1. Matrix-forming composition <resin material>
The optical article of the present invention is characterized in that it is formed by combining a resin containing at least a partial structure represented by the general formula (1) or (2) and metal fine particles. In the following, first, general formulas (1) and (2) will be described in detail.

The ring α in the general formula (1) represents a ring including an aromatic ring, and the two rings are connected by a spiro bond. The two rings α may be the same or different. The ring α may be monocyclic or polycyclic, and may or may not have a substituent.
Examples of the ring α include an indane ring derivative, an indanone ring derivative, a chroman ring derivative, a dihydrobenzofuran ring derivative, a dihydrobenzothiophene ring derivative, etc., preferably an indane ring derivative, a chroman ring derivative or a dihydrobenzofuran ring derivative. Particularly preferred are indane ring derivatives.
L represents a divalent linking group, preferably a linking group having 1 to 10 carbon atoms, more preferably an aliphatic linking group having 1 to 10 carbon atoms, and more preferably an aliphatic linking group having 1 to 5 carbon atoms. Represents a group linking group. Examples include methylene group, ethylene group, propylene group, butylene group, oxyethylene group, oxybutylene group, thioethylene group, thiobutylene group, aminomethylene group, aminobutylene group, carbonylene group, and more preferably oxyethylene. Group, an oxyalkylene group such as oxybutylene group or a thioalkylene group such as thioethylene group and thiobutylene group, particularly preferably a thioalkylene group. Two Ls may be the same or different.
n represents 0 or 1, and is preferably 0. Two n's may be the same or different.

  More preferred examples of the partial structure represented by the general formula (1) include structures represented by the general formulas (3) to (5).

In general formula (3), R ¹¹ and R ¹² each independently represent a hydrogen atom or a substituent, and R ¹³ each independently represents a substituent. Moreover, each substituent represented by R ^{11 to} R ¹³ may be linked to form a ring. p and q each independently represent an integer of 0 to 3, preferably 0. m and n each independently represent an integer of 1 to 3.
Examples of preferred substituents are a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. More preferred examples of R ¹¹ and R ¹² are hydrogen atom, methyl group and phenyl group, and more preferred examples of R ¹³ are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, tert-butyl group and phenyl group. , Allyl group, and ethynyl group. L and n represent the same meaning as in the general formula (1), and specific examples and preferred examples are also the same.

In general formula (4), each R ³¹ independently represents a hydrogen atom or a substituent, and each R ³² independently represents a substituent. The substituents represented by R ³¹ and R ³² may be linked to form a ring. Preferred examples of R ³¹ include the groups listed as preferred examples of R ¹¹ in the general formula (3). Preferred examples of R ³² are listed as preferred examples of R ¹³ in the general formula (3). The group which was made can be mentioned. p and q each independently represent an integer of 0 to 3, preferably 0. L and n represent the same meaning as in the general formula (1), and specific examples and preferred examples are also the same. X represents an oxygen atom or a sulfur atom.

In general formula (5), each R ²¹ independently represents a hydrogen atom or a substituent, and each R ²² independently represents a substituent. Moreover, each substituent represented by R ²¹ and R ²² may be linked to form a ring. Preferred examples of R ²¹ include the groups listed as examples of R ¹¹ in the general formula (3). Preferred examples of R ²² are listed as preferred examples of R ¹³ in the general formula (3). The group can be mentioned. p and q each independently represent an integer of 0 to 3, preferably 0. L and n represent the same meaning as in general formula (1), and specific examples and preferred examples are also the same. X represents an oxygen atom or a sulfur atom.

In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different, and one quaternary ring on ring β. Linked to carbon. Ring β and ring γ may each be monocyclic or polycyclic, and may or may not have a substituent.
Examples of the ring β include a fluorene ring, an indandione ring, an indanone ring, an indene ring, an indane ring, a tetralone ring, an anthrone ring, a cyclohexane ring, a cyclopentane ring, and preferably a fluorene ring.
Examples of ring γ include benzene ring, naphthalene ring, anthracene ring, fluorene ring, cyclohexane ring, cyclopentane ring, pyridine ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, benzothiazole ring, indane ring, chroman Examples thereof include a ring, an indole ring and an α-pyrone ring, and a benzene ring is preferred.
L represents a divalent linking group, preferably a linking group having 1 to 10 carbon atoms, more preferably an aliphatic linking group having 1 to 10 carbon atoms, and more preferably an aliphatic linking group having 1 to 5 carbon atoms. Represents a group linking group. Examples include methylene group, ethylene group, propylene group, butylene group, oxyethylene group, oxybutylene group, thioethylene group, thiobutylene group, aminomethylene group, aminobutylene group, carbonylene group, and more preferably oxyethylene. Group, an oxyalkylene group such as oxybutylene group or a thioalkylene group such as thioethylene group and thiobutylene group, particularly preferably a thioalkylene group. Two Ls may be the same or different.
n represents 0 or 1, and is preferably 0. Two n's may be the same or different.

  A more preferred example of the partial structure represented by the general formula (2) includes a structure represented by the following general formula (6).

In general formula (6), R ⁶¹ and R ⁶² each independently represent a substituent. In addition, each may be linked to form a ring. Preferable examples of R ⁶¹ and R ⁶² include the groups listed as preferred examples of R ¹³ in the general formula (3). j and k each independently represents an integer of 0 to 3. L and n represent the same meaning as in general formula (1).

  The resin having the partial structure represented by the general formula (1) or the general formula (2) can be added and substituted with thiol in one molecule using the dithiol derivative having the partial structure as one kind of raw material monomers. A polymer using a compound having two or more reactive groups as a copolymerization monomer is preferable.

  Examples of the dithiol derivative having the partial structure include a diol having a spirobiindane skeleton (for example, synthesized by the method described in US Pat. No. 3,544,638 and JP-A-62-10030), and a spirobichroman skeleton. Diols having a spirobibenzofuran skeleton (for example, Japanese Patent Application Laid-Open No. 2005-225996), and diols having a spirobibenzofuran skeleton (for example, Journal of Chemical Society, Volume 111, page 4953 (1989); Can be synthesized according to the method described in Journal of Polymer Science, Part A: Polymer Chemistry (2001), 39 (7), 1040-1050 or JP-A-2002-338540. It can be synthesized by a technique such as conversion to a group.

  Examples of reactive groups that can be added by thiol include unsaturated groups such as isocyanate groups, isothiocyanate groups, vinyl groups, and acryloyl groups, epoxy groups, and episulfide groups. Examples of reactive groups that can be substituted with thiol include activated acyl groups (acyl halides such as acyl chloride and acyl bromide, active ester groups such as phenoxycarbonyl group and acetoxycarbonyl group), and active sulfonyl groups (eg sulfonyl chloride, phenyl). Sulfonates, etc.) and halides (eg fluorides, iodides, etc.).

  By appropriately adding and polymerizing a compound in which two or more of these groups are present in one molecule, the above dithiol compound, and other monomer components from the viewpoint of moldability and the like, general formula (1) or general formula A resin having the structural unit represented by (2) can be synthesized. The ratio of sulfur atoms in the resin used in the present invention is preferably 1 to 60% by mass, more preferably 5 to 55% by mass, and particularly preferably 10 to 50% by mass.

  The resin used in the present invention may be a thermoplastic resin suitable for injection molding or a curable resin suitable for a molding method in which molding is performed while reacting.

  In the case of a thermoplastic resin suitable for injection molding, it is preferably a polycondensate or polyadduct of the above monomer having two functional groups capable of addition / condensation with the above dithiol and thiol, Examples include polythioester, polythiocarbonate, polythioether and the like.

  As a method for producing these resins, a method described in “Experimental Methods for Polymer Synthesis” by Takayuki Otsu and Masaaki Kinoshita, edited by Kagaku Dojin (1996) can be applied.

  Although the example of the preferable thermoplastic resin used by this invention below is shown, resin which can be used by is not limited to these.

  The number average molecular weight of the thermoplastic resin used in the present invention is preferably in the range of 1,000 to 5,000,000, more preferably in the range of 5,000 to 1,000,000, and in the range of 10,000 to 500,000. Is more preferable. From the viewpoint of heat resistance and moldability, the glass transition temperature is preferably 80 ° C to 280 ° C, more preferably 100 ° C to 250 ° C, and particularly preferably 120 ° C to 230 ° C.

  Examples of the curable resin include compounds having three or more functional groups reactive with the dithiol derivative and thiol in one molecule (for example, trifunctional or higher polyisocyanate compound, polyisothiocyanate compound, polyacyl chloride, polysulfonyl chloride). , Polyepoxy, polyepisulfide compound, polyvinyl compound, poly (meth) acryloyl compound) are preferable, but a prepolymer in which a curable group such as a (meth) acryloyl group or an epoxy group is introduced into the thermoplastic resin. It may be.

  Specific examples of the curable resin composition are exemplified below in the form of a combination of monomers, but the curable resin that can be used in the present invention is not limited thereto.

<Metal fine particles>
Examples of the metal fine particles used in the present invention include oxide fine particles, sulfide fine particles, selenide fine particles, telluride fine particles and the like. More specifically, for example, zirconium oxide, titanium oxide fine particles, zinc oxide fine particles, tin oxide, zinc sulfide fine particles and the like can be mentioned, more preferably zirconium oxide fine particles and titanium oxide fine particles, particularly preferably zirconium oxide. Fine particles.

The method for producing metal fine particles used in the present invention is not particularly limited, and any known method can be used. Desired oxide fine particles can be obtained by using a metal halide or alkoxy metal as a raw material and hydrolyzing in a reaction system containing water.
For example, a method for producing zirconium oxide fine particles includes a method in which an aqueous solution containing a zirconium salt is neutralized with an alkali to obtain hydrated zirconium, then dried and fired, and dispersed in a solvent to obtain a zirconium oxide suspension. A method of hydrolyzing an aqueous solution containing zirconium to obtain a zirconium oxide suspension, a method of hydrolyzing an aqueous solution containing a zirconium salt to obtain a zirconium oxide suspension, and then ultrafiltration, and hydrolyzing a zirconium alkoxide A method for obtaining a zirconium oxide suspension and a method for obtaining a zirconium oxide suspension by heat treatment of an aqueous solution containing a zirconium salt under hydrothermal pressure are known, and any of these methods may be used. .

  Further, for example, titanyl sulfate is exemplified as a synthesis raw material for titanium oxide nanoparticles, and zinc salts such as zinc acetate and zinc nitrate are exemplified for synthesis of zinc oxide nanoparticles. Metal alkoxides such as tetraethoxysilane and titanium tetraisopropoxide can also be suitably used as a raw material. For example, a known method described in Japanese Journal of Applied Physics, 37, 4603-4608 or (1998) Langmuir, 16: 1 241-246 (2000) can be used. In particular, when oxide nanoparticles are synthesized by a sol formation method, for example, titanium oxide nanoparticles using titanyl sulfate as a raw material are synthesized and then dehydrated with an acid or alkali via a precursor such as hydroxide. Procedures that condense or peptize to form a hydrosol are also possible. In the procedure via such a precursor, it is preferable from the viewpoint of the purity of the final product that the precursor is isolated and purified by any method such as filtration or centrifugation. An appropriate surfactant such as sodium dodecylbenzenesulfonate (abbreviated as DBS) or dialkylsulfosuccinate monosodium salt (manufactured by Sanyo Chemical Industries, Ltd., trade name is Eleminol JS-2) is added to the hydrosol to obtain a sol The particles may be isolated by making them water-insoluble. For example, a known method described in Coloring Materials, Vol. 57, No. 6, 305-308 (1984) can be used.

In addition to the method of hydrolyzing in water, the metal fine particles may be prepared in an organic solvent or an organic solvent in which the resin used in the present invention is dissolved.
Examples of the solvent used in these methods include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone, anisole and the like. These may be used alone or as a mixture of two or more.

  If the number average particle size of the metal fine particles used in the present invention is too small, the characteristics specific to the substance constituting the fine particles may change. Conversely, if the number average particle size is too large, the effect of Rayleigh scattering becomes significant. The transparency of the material composition may be extremely lowered. Therefore, the lower limit value of the number average particle size of the metal fine particles used in the present invention is preferably 1 nm, more preferably 2 nm, still more preferably 3 nm, and the upper limit value is preferably 15 nm, more preferably 10 nm, still more preferably 5 nm. It is.

  The refractive index range of the metal fine particles used in the present invention is preferably 1.90 to 3.00, more preferably 1.90 to 2.70, and 2.00 to 2.70. Is more preferable. If metal fine particles having a refractive index of 1.90 or more are used, a material composition having a refractive index greater than 1.70 can be easily produced. If metal fine particles having a refractive index of 3.00 or less are used, the transmittance is 80% or more. The material composition tends to be easy to produce.

  The amount of the metal fine particles used in the present invention is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 60% by mass with respect to the total solid content. .

<Dispersant>
The fine particles used in the present invention are preferably dispersed in the resin using a dispersant. The molecular weight of the dispersant used in the present invention is usually 50 to 10,000, more preferably 100 to 5,000, and still more preferably 200 to 1,000. If the molecular weight is too large, it tends to be difficult to increase the refractive index of the material composition.

  When the fine particles used in the present invention are coordinated or modified with an organic compound (referred to as “dispersing agent” in the present invention) having compatibility with the resin matrix mainly composed of the resin, the fine particles on the resin matrix Dispersibility may be improved, and transparency and mechanical strength of the material composition of the present invention may be improved. The effect of such a dispersant is considered to be due to a combination of an effect of suppressing aggregation of fine particles and an effect of improving compatibility with the resin matrix.

A preferred structure of such a dispersant is represented by the following general formula (7).
General formula (7)
A-R
Here, A represents a functional group capable of forming an arbitrary chemical bond with the surface of the fine particles, and R represents a monovalent group or polymer having 1 to 30 carbon atoms having compatibility or reactivity with the resin matrix. The chemical bond is, for example, a covalent bond, an ionic bond, a coordination bond, a hydrogen bond, or the like.

  Although there is no limitation on the method of coordination of the dispersant to the metal fine particles and the modification method by covalent bond and the molecular structure of the organic substance used therefor, specific examples of A coordinated to the fine particles include thiol and sulfonic acids. A sulfur-containing organic compound, a phosphorus-containing organic ligand having phosphine or phosphine oxide, a nitrogen-containing ligand having an alkylamine or an aromatic amine, or a ligand having a carboxylic acid is effective. Among these examples, a phosphorus-containing organic ligand is preferably used. For example, KAYAMER PM-21 (trade name) manufactured by Nippon Kayaku is suitable.

  Specific examples of A modified by covalent bonding include silane coupling agents, titanate coupling agents, aluminum coupling agents and the like conventionally used for surface treatment of oxides such as silica, alumina, and titania. A metal alkoxide group which is an active functional group is effective. Among these, a silane coupling agent is preferable, and methods described in JP-A-5-221640, JP-A-9-100111, JP-A-2002-187721, and the like can be used.

On the other hand, when R is a group having compatibility or reactivity with the resin matrix, the chemical structure thereof is the same as or similar to part or all of the chemical structure of the resin that is the main component of the resin matrix. Is preferred.
These dispersants may be used alone or in combination of two or more. The amount of the dispersant used in the present invention is preferably 1 to 80% by mass, more preferably 3 to 50% by mass, and further preferably 5 to 30% by mass with respect to the total solid content. .

<Plasticizer>
If the glass transition temperature of the resin is high, molding may not always be easy. For this reason, a plasticizer may be used to lower the molding temperature. As a plasticizer used by this invention, what has the structure represented by General formula (8) is preferable.

［式中、Ｂ¹およびＢ²はそれぞれ独立に炭素数６〜１８のアルキル基またはアラルキル基、ｍは０または１、Ｘは

[Wherein, B ¹ and B ² are each independently an alkyl group or aralkyl group having 6 to 18 carbon atoms, m is 0 or 1, and X is

のうちのいずれかであり、Ｒ¹ およびＲ² はそれぞれ独立に水素原子または炭素数４以下のアルキル基を示す。］

R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 4 or less carbon atoms. ]

In the compound represented by the general formula (8), B ¹ and B ² can independently select any alkyl group or aralkyl group within the range of 6 to 18 carbon atoms. If the number of carbon atoms is less than 6, the molecular weight may be too low to boil at the melting temperature of the polymer and generate bubbles. On the other hand, when the number of carbon atoms exceeds 18, the compatibility with the polymer is deteriorated, so that the effect of addition may be insufficient.
Specific examples of the groups B ¹ and B ² include n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and the like. Straight alkyl groups, branched alkyl groups such as 2-hexyldecyl group and methyl-branched octadecyl group, and aralkyl groups such as benzyl group and 2-phenylethyl group. Specific examples of the compound represented by the general formula (8) used in the present invention include the following compounds, among which W-1 (trade name [KP-L155] manufactured by Kao Corporation) is preferable.

  The amount of the plasticizer used in the present invention is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 10% by mass with respect to the total solid content. .

<Curing catalyst>
The curable resin may appropriately coexist with a curing accelerator corresponding to the reaction mechanism.
Curing accelerators that accelerate the addition reaction by heat include, for example, inorganic Bronsted acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic Bronsted acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid, and paratoluenesulfonic acid; dibutyltin dilaurate Lewis acids such as dibutyltin diacetate, dibutyltin dioctate, triisopropoxyaluminum and tetrabutoxyzirconium; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; organic bases such as triethylamine, pyridine and tetramethylethylenediamine Quaternary ammonium salts such as benzyltriethylammonium chloride and tetrabutylammonium chloride can be used.

  Organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used as curing accelerators that promote radical reactions by heat. Specifically, organic peroxides include benzoyl peroxide, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide, etc .; Ammonium persulfate, potassium persulfate, etc .; azo compounds such as 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile; diazo compounds such as diazoaminobenzene, Examples thereof include p-nitrobenzenediazonium.

  Examples of curing acceleration that promotes an addition reaction by light include compounds that generate an acid or a base by the action of active energy rays.

Various examples of compounds that generate acids by the action of active energy rays are described in, for example, “Organic Materials for Imaging” p187-198 edited by Organic Electronics Materials Research Group (Bunshin Publishing), Japanese Patent Laid-Open No. 10-282644. These known compounds can be appropriately selected and used. Specifically, RSO ₃ ⁻ (R represents an alkyl group, aryl group), AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ^{− and the} like, a diazonium salt, ammonium salt, phosphonium salt, Various onium salts such as iodonium salts, sulfonium salts, selenonium salts, arsonium salts, organic halides such as oxadiazole derivatives and S-triazine derivatives substituted with a trihalomethyl group, o-nitrobenzyl esters of organic acids, benzoin esters, Examples include imino esters and disulfone compounds, preferably onium salts, particularly preferably sulfonium salts and iodonium salts. Known compounds that generate a base by the action of active energy rays can be used, and specific examples thereof include nitrobenzyl carbamates and dinitrobenzyl carbamates.

  Compounds that promote radical reactions by the action of active energy rays include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyl Examples include dione compounds, disulfide compounds, fluoroamine compounds, and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  When a compound that accelerates curing by the action of these active energy rays is added, a sensitizing dye can also be used in combination in order to efficiently use the light having the irradiation light wavelength.

  The optimum addition amount of the curing accelerator and the sensitizing dye varies depending on the type of curing reaction, the type of catalyst, the heating temperature, or the irradiation wavelength when irradiated with light, but in the optical article-forming composition. 0.1-15 mass% is preferable with respect to the total solid content, More preferably, it is about 0.5-5 mass%.

<Other additives>
The resin composition used in the optical article of the present invention may be appropriately blended with other resins depending on the purpose. The resin material to be blended may be thermoplastic or curable resin.

  As thermoplastic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin , Polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modified polycarbonate resin, acryloyl compound, etc. However, the thermoplastic resin that can be added in the present invention is not limited thereto.

  The glass transition temperature (Tg) of the resin is preferably 100 ° C. or higher.

  Examples of these resins (indicated in parentheses are Tg), polycarbonate resin (PC: 140 ° C.), alicyclic polyolefin resin (for example, ZEONOR 1600: 160 ° C., manufactured by Nippon Zeon Co., Ltd., Arton: 170 manufactured by JSR Co., Ltd.) ° C), polyarylate resin (PAr: 200 ° C), polyethersulfone resin (PES: 220 ° C), polysulfone resin (PSF: 190 ° C), polyester resin (for example, O-PET: 125 ° C manufactured by Kanebo Co., Ltd.), polyethylene Terephthalate, polyethylene naphthalate), cycloolefin copolymer (COC: compound of Example 1 of JP 2001-150584 A: 162 ° C.), fluorene ring-modified polycarbonate resin (BCF-PC: implementation of JP 2000-227603 A) Compound of Example-4: 225 ° C.), alicyclic modified polycar Nate resin (IP-PC: compound of Example-5 of JP-A No. 2000-227603: 205 ° C.), acryloyl compound (compound of Example-1 of JP-A No. 2002-80616: 300 ° C. or more), etc. Can be mentioned.

  As the resin blended with the resin of the present invention, a crosslinked resin can also be preferably used from the viewpoint of solvent resistance, heat resistance and the like. As the kind of the cross-linked resin, various known ones can be used without particular limitation for both the thermosetting resin and the active energy ray curable resin. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin and the like. Any other crosslinking method can be used without particular limitation as long as it is a reaction that forms a covalent bond, and a system in which the reaction proceeds at room temperature using a polyalcohol compound and a polyisocyanate compound to form a urethane bond is also particularly limited. It can be used without. However, such a system often has a problem of pot life before film formation, and is usually used as a two-component mixed type in which a polyisocyanate compound is added immediately before film formation. On the other hand, when used as a one-component type, it is effective to protect the functional group involved in the crosslinking reaction, and it is also commercially available as a block type curing agent. As commercially available block type curing agents, B-882N manufactured by Mitsui Takeda Chemical Co., Ltd., Coronate 2513 manufactured by Nippon Polyurethane Industry Co., Ltd. (above block polyisocyanate), Cymel 303 manufactured by Mitsui Cytec Co., Ltd. (methylated melamine resin) ) Etc. are known. Further, a blocked carboxylic acid such as the following B-1 that protects a polycarboxylic acid that can be used as a curing agent for an epoxy resin is also known.

  The active energy ray curable resins are roughly classified into radical curable resins and cationic curable resins. As the curable component of the radical curable resin, a compound having a plurality of radical polymerizable groups in the molecule is used. As a typical example, a polyfunctional acrylate monomer having 2 to 6 acrylate groups in the molecule And compounds having a plurality of acrylate groups in the molecule called urethane acrylate, polyester acrylate, and epoxy acrylate. As a typical curing method of the radical curable resin, there are a method of irradiating an electron beam and a method of irradiating ultraviolet rays. Usually, in the method of irradiating with ultraviolet rays, a polymerization initiator that generates radicals upon irradiation with ultraviolet rays is added. In addition, if the polymerization initiator which generate | occur | produces a radical by heating is added, it can also be used as a thermosetting resin. As the curable component of the cationic curable resin, a compound having a plurality of cationic polymerizable groups in the molecule is used. As a typical curing method, a photoacid generator that generates an acid upon irradiation with ultraviolet rays is added, and ultraviolet rays are added. And a method of curing by irradiation. Examples of the cationically polymerizable compound include a compound containing a ring-opening polymerizable group such as an epoxy group and a compound containing a vinyl ether group.

  The resins used in the present invention may be used singly or in combination of a plurality of types, and also for resins that can be blended with the resin of the present invention listed above, a plurality of types may be mixed and used. Also good.

  Furthermore, in the present invention, plasticizers, dyes and pigments, antioxidants, antistatic agents, ultraviolet absorbers, inorganic fine particles, mold release agents, leveling agents, lubricants, etc., as long as the effects of the present invention are not impaired. These various additives (resin modifiers) can also be added. The addition amount of these resin modifiers is appropriately selected according to the purpose, but it is generally added in the range of 0.01 to 10% by mass with respect to the total solid content, preferably It is about 0.1-5 mass%.

<Material composition>
The optical article of the present invention is formed from a material composition in which metal fine particles are dispersed in a resin having a high refractive index. The method for producing the material composition is not particularly limited. Specifically, a method of independently synthesizing a resin and metal fine particles and mixing them, a method of synthesizing a resin in the presence of a pre-synthesized metal fine particle, and a metal fine particle in the presence of a pre-synthesized resin Examples thereof include a method of synthesizing both the resin and the metal fine particles at the same time, and any of these methods may be used.

  For example, when adopting a method in which metal fine particles are independently synthesized in a resin and mixed together, the metal fine particles and the resin solution may be stirred and mixed, or the metal fine particle dispersion and the resin solution may be stirred and mixed. May be. At this time, the metal fine particles or a dispersion thereof may be mixed with the resin solution all at once, or may be gradually dropped into the resin solution. Further, a plasticizer or a dispersant may be present during the stirring and mixing. Such a plasticizer or dispersant may be added in advance to the resin solution or the metal fine particle dispersion, or may be added to a mixture of the resin solution and the metal fine particles.

2. Molding The method of making the optical article of the present invention into a molded product such as an optical lens is not particularly limited, and known techniques (injection molding method, injection compression molding method, compression molding method, vacuum molding method, casting polymerization method, Transfer molding method, blow molding method, extrusion molding method, pressure molding method, casting molding method, etc.) can be used. In the case of a thermoplastic resin, it is generally manufactured by an injection molding method in which the resin is melted, poured into a mold, and then cooled and removed from the mold. In the case of a curable resin, thermosetting is performed. The mold is preferred, and it is generally produced by a casting polymerization method in which a mixture of raw materials containing a reactive compound is poured into a glass or metal mold, polymerized and cured, and then the mold is removed.

  It is preferable to degas and dry the main raw material and auxiliary raw material in advance, add them to the same container at the same time, mix them under stirring, and then inject them into the mold. It may be injected into the mold after mixing, or several components may be mixed separately and then mixed again in the same container and then injected into the mold. Examples of the mixer include a ribbon type, a helical type, a paddle type, and a screw, but are not particularly limited. The raw material may be introduced into the molding machine in the form of powder, but it is preferable to introduce the raw material after it is once pelletized.

  In the case of injection molding of thermoplastic resin, it is desirable that the resin temperature be about 150 ° C. higher than the glass transition temperature (Tg) of the resin. In practice, a temperature range of 200 to 380 ° C. is preferable, and about 230 to 350 ° C. It is more preferable to make it into the temperature range. The mold temperature is preferably about Tg to (Tg-20) ° C, more preferably (Tg-2) ° C to (Tg-10) ° C, specifically 80 to 300. ° C is preferred, more preferably about 100 to 250 ° C.

When the thermosetting resin is cured, the curing time is usually 1 minute to 100 hours, preferably 1 to 48 hours, and the curing temperature is usually 30 to 350 ° C, preferably 50 to 300 ° C, more preferably 80. ~ 250 ° C. It is preferable to carry out an annealing treatment for about 1 minute to 5 hours at a temperature of about 50 to 200 ° C. after the curing is completed in order to reduce the optical anisotropy of the optical article.
In the case of a thermosetting resin, the mixing is usually about -10 to 150 ° C, preferably -10 to 100 ° C, more preferably -5 to 50 ° C, usually about 1 minute to 5 hours, preferably 5 It is carried out in a time of about minutes to 2 hours, more preferably about 5 minutes to 30 minutes.

  In the present invention, a known method can be adopted as a method for molding the resin composition into a film or sheet shape, and preferred examples include a solution casting method and an extrusion molding method (melt molding method).

Regarding the casting and drying methods in the solution casting method, US Pat. No. 2,336,310, US Pat. No. 2,367,603, US Pat. No. 2,429,078, US Pat. No. 2,429,297, US Pat. No. 2,429,978, US Pat. No. 2,607,704, US Pat. No. 2739070, British Patent No. 640731, British Patent No. 736892, Japanese Examined Patent Publication No. 45-4554, Japanese Examined Patent Publication No. 49-5614, Japanese Unexamined Patent Publication No. 60-176634, Japanese Unexamined Patent Publication No. 60-203430, Japanese Unexamined Patent Publication No. There is description in each gazette of 62-1115035. The resin solution is preferably cast on a drum or band having a surface temperature of 30 ° C. or lower, and the metal support temperature is preferably 10 to 20 ° C.
Examples of the manufacturing apparatus manufactured by the solution casting method include the manufacturing apparatuses described in JP-A-2002-189126, paragraph numbers 0061 to 0068, FIGS. 1 and 2, and the like. The manufacturing apparatus that can be used is not limited to these.

  The solvent used in the solution casting method may be any type as long as it dissolves the resin of the present invention. In particular, a solvent that can dissolve at a solid content concentration of 10% by mass or more at 25 ° C. is used. preferable. The solvent used preferably has a boiling point of 200 ° C. or lower, more preferably 150 ° C. or lower. When the boiling point is high, the solvent may be insufficiently dried and may remain in the film.

  Examples of the solvent preferably used in the present invention include methylene chloride, chloroform, tetrahydrofuran, benzene, cyclohexane, toluene, xylene, 1,2-dichloroethane, ethyl acetate, acetone, chlorobenzene, dimethylformamide, methanol, ethanol and the like. The solvent that can be used in the invention is not limited to these.

Moreover, you may use a solvent in mixture of 2 or more types.
Examples of the mixed solvent include a solvent in which one to several kinds of alcohol having 1 to 5 carbon atoms are mixed in methylene chloride. In this case, the content of the alcohol is preferably 5 to 20% by mass with respect to the whole solvent. Furthermore, a solvent in which an appropriate mixture of an ether, a ketone and an ester each having 3 to 12 carbon atoms is mentioned as a preferred example. In this case, one to several alcohols having 1 to 5 carbon atoms may be mixed.
In addition, examples of the organic solvent described in Paragraph 6 of the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention) are also preferable examples.

  The resin concentration in the solution used for solution casting is usually 5 to 60% by mass, preferably 10 to 40% by mass, and more preferably 10 to 30% by mass. If the concentration of the resin is too low, the viscosity may be low and it may be difficult to adjust the thickness, and if it is too high, the film forming property may be poor and unevenness may be increased.

  The method for casting the solution is not particularly limited, but it can be cast on a flat plate or a roll using a bar coater, a T die, a T die with a bar, a doctor blade, a roll coat, a die coat or the like.

The temperature at which the solvent is dried varies depending on the boiling point of the solvent used, but it is preferable to dry the solvent in two stages. As a first step, drying is performed at 30 to 100 ° C. until the mass concentration of the solvent becomes 10% or less, more preferably 5% or less. Next, as a second step, the film is peeled off from the flat plate or roll and dried in the range of 60 ° C. or higher and the glass transition temperature of the resin or lower.
When peeling a film from a flat plate or a roll, it may be peeled off immediately after completion of drying in the first stage, or may be peeled off after being cooled.

  The conditions of the extrusion molding method are the same as the conditions used for general optical resins, and the preferred range for the injection molding method is used as the melting temperature.

  In the optical article of the present invention, when an active energy ray-curable compound is contained in the resin, polymerization is accelerated by irradiating active energy rays after or during molding as described above. It can also be made.

  Examples of active energy rays include ionizing active energy rays such as electron beams, α rays, β rays, and γ rays, ultraviolet rays, visible rays, infrared rays, microwaves, etc. In the present invention, the handling is easy and the irradiation efficiency is high. From the viewpoint of good, ultraviolet rays or electron beams are more preferable, and electron beams are particularly preferable. The irradiation conditions in the case of irradiating with an electron beam are as follows: the irradiation dose is usually 1 to 80 Mrad, preferably 5 to 60 Mrad, more preferably 10 to 40 Mrad, and the acceleration voltage is usually 50 to 500 KV, preferably 100 to 400 KV. Preferably it is the range of 150-300 KV.

3. Optical Article The refractive index (Nd) of the optical article of the present invention is preferably 1.65 or more, more preferably 1.67 or more, and particularly preferably 1.69 or more.
The total light transmittance of the optical article of the present invention is preferably 80% or more, more preferably 85% or more, and still more preferably 87% or more.
The retardation in the in-plane direction of the optical article of the present invention is preferably 25 nm or less, more preferably 20 nm or less, and further preferably 15 nm or less.

  The optical article of the present invention includes various plastic lenses (glass lenses, camera lenses, binocular lenses, microscope lenses, projector lenses, Fresnel lenses, lenticular lenses, fθ lenses, headlamp lenses, pickup lenses, finder lenses, spherical and aspherical surfaces, etc. Including a lens), a disk substrate, a light guide plate, a prism sheet, and an optical waveguide.

  That is, the optical article of the present invention can be made into an optical article having a use value independently by itself, or can be made into a useful optical article after being combined with other articles. In the latter case, the types and structures of other articles to be combined are not particularly limited. For example, a layered material such as an antireflection film or a hard coat layer may be appropriately installed on the surface of the substrate of the optical article of the present invention, or a frame body such as a lens frame may be fitted into the optical article of the present invention. May be installed. Further, the optical article of the present invention may be incorporated in devices such as a camera and a sensor.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1] Production of film sample 1) Synthesis of resin As raw material monomers for the resin used below, for example, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane-6,6' -Dithiol is based on the method described in Journal of Polymer Science, Part A: Polymer Chemistry (2001), 39 (7), 1040-1050, and 3,3,3 ', 3'-tetramethyl-1,1'-Spirobiindane-6,6'-diol was synthesized as a starting material. Other dithiol monomers were synthesized in the same manner.
Furthermore, polythiourethane, polythiocarbonate, and polythioester were synthesized using the dithiol monomer as a raw material according to the method described in JP-A No. 2001-106761.

2) Synthesis of metal fine particles <Preparation of titanium oxide nanoparticles>
While stirring the 0.1 mol / L aqueous solution of titanyl sulfate, the same volume of 1.5 mol / L aqueous sodium carbonate solution was added dropwise at room temperature over 10 minutes. The white ultrafine particle suspension thus obtained was purified by repeating the steps of removing the supernatant by decantation and washing with water at 3500 rpm. The white precipitate thus obtained was heated at 50 ° C. for about 1 hour with stirring and dispersing in 0.3 mol / L of dilute hydrochloric acid to obtain a transparent acidic hydrosol. The acidic hydrosol was ice-cooled, and an aqueous solution of sodium dodecylbenzenesulfonate was added. As a result, a white precipitate was formed. Then, extraction with toluene was performed to obtain a toluene dispersion of titanium oxide nanoparticles. The residue obtained after drying the dispersion was subjected to X-ray diffraction (XRD) spectrum measurement at 23 ° C. using RINT 1500 (X-ray source: copper Kα ray, wavelength 1.5418 mm) manufactured by Rigaku Corporation. Hitachi Co., Ltd. H-9000UHR type transmission electron microscope by performing a transmission electron microscope (TEM) observation using a (acceleration voltage 200 kV, vacuum of about 7.6 × 10- ⁹ Pa at observation) The production of anatase-type titanium oxide fine particles (number average particle size is about 5 nm) was confirmed. Further content: of TiO ₂ in the residue was confirmed to be 75% by mass. The refractive index of the obtained fine particles was 2.50.

<Preparation of zirconium oxide fine particles>
A zirconium oxychloride solution having a concentration of 50 g / l was neutralized with a 48% aqueous sodium hydroxide solution to obtain a hydrated zirconium suspension. The suspension was filtered and then washed with ion exchanged water to obtain a hydrated zirconium cake. This cake was adjusted to a concentration of 15% by mass in terms of zirconium oxide using ion-exchanged water as a solvent, placed in an autoclave, and hydrothermally treated at 150 ° C. and 150 ° C. for 24 hours to obtain a zirconium oxide fine particle suspension. Formation of zirconium oxide fine particles having a number average particle size of 5 nm was confirmed by TEM. The refractive index of the obtained fine particles was 2.10.
Prepare a toluene solution in which the zirconium oxide aqueous dispersion prepared above and KAYAMER PM-21 manufactured by Nippon Kayaku are dissolved so that the mass ratio of the solid content of zirconium oxide and PM-21 is 3: 1. After stirring at 50 ° C. for 8 hours, the toluene solution was extracted to prepare a zirconium oxide fine particle toluene dispersion.

3) Production of plastic film sample Each of the resins (P-11, P-27, P-31, P-41) of the present invention was individually dissolved in methylene chloride, and the above-described titanium oxide fine particles or zirconium oxide toluene dispersion And it mixed so that it might become the metal oxide content of Table 1, and prepared the 10 mass% solution. The solution was filtered through a 5 μm filter and cast on a glass substrate using a doctor blade. After casting, the film was heat-dried at 80 ° C. for 2 hours and then at 120 ° C. for 8 hours, and then the film was peeled from the glass substrate to produce film samples (F-1 to 6).

  The thermosetting resin composition (M-1, M-4, M-7, M-40) of the present invention is individually dissolved in methylene chloride, and the above-described titanium oxide fine particles or a toluene dispersion of zirconium oxide, A 10% by mass solution was prepared by mixing so as to achieve the metal oxide content shown in Table 1. After casting this solution on a glass substrate, it was heated and dried at room temperature for 1 hour and then at 120 ° C. for 8 hours, and then the film was peeled off from the glass substrate to prepare a film sample (F-7 to 12).

  As comparative samples, Comparative Resin A (resin P-9 described in Examples of JP-A-2001-106761), Comparative Resin B (“Panlite L1225Z”; Teijin Chemicals polycarbonate), and Comparative Resin C (JP The resin described in Example 1 of Japanese Patent No. 2000-298776 was dissolved individually in methylene chloride to prepare a 10 mass% solution. The solution was filtered through a 5 μm filter and cast on a glass substrate using a doctor blade. After casting, the film was heat-dried at 80 ° C. for 2 hours and then at 120 ° C. for 8 hours, and then the film was peeled from the glass substrate to produce film samples (R-1 to R-3).

4) Evaluation of physical properties of film sample The thickness, refractive index, total light transmittance, and in-plane retardation value of the film obtained above were measured according to the methods described below. The obtained results are shown in Table 1.
(1) Film thickness Measured with a dial-type thickness gauge (K402B, manufactured by Anritsu Corporation).
(2) Total light transmittance It measured with the apparatus UV-3100 for ultraviolet visible spectrum measurement (made by Shimadzu Corporation).
(3) Refractive index It measured about the light of wavelength 589nm using the Abbe refractometer (DR-M4 by Atago Co., Ltd.).
(4) Retardation Refractive index at a wavelength of 632.8 nm was measured with an automatic birefringence meter (Oji Scientific Instruments Co., Ltd., KOBRA-21ADH) in the width direction and longitudinal direction in the film plane, and calculated according to the following formula: did.
Retardation = | nMD-nTD | × d
[Where nMD: refractive index in the film width direction, nTD: refractive index in the film longitudinal direction, d: thickness]

  From the results shown in Table 1, the film prepared from the composition of the present invention has a high refractive index and a small retardation value, and is suitable as a high refractive index optical article with little optical distortion. It was confirmed.

[Example 2] Production of lens sample Films F-1 to F-6, R-1, and R-2 in Example 1 were each cut into small pieces, and 30 mm in diameter at a molding temperature of 300 ° C with an injection molding machine. A spherical convex lens having a wall thickness of 1 to 3 mm was prototyped.
Furthermore, from the thermosetting resin composition before producing the films F-7 to F-12 in Example 1, the residues obtained by distilling off the solvent were respectively added to a metal mold having a thickness of 1 mm, and 1 at 30 ° C. Polymerization was carried out for 1 hour at 50 ° C. for 1 hour and then at 100 ° C. for 1 hour to obtain a molded product having a thickness of 1 mm.
When observation was performed under crossed Nicols using a polarizing plate, it was confirmed that the plastic lenses obtained from the comparative resins A and B had a large optical distortion, particularly a large distortion near the gate. The plastic lens obtained from the comparative resin C had a relatively small optical distortion and was good, but the refractive index was not high. On the other hand, the plastic lens obtained from the resin (F-1 to 12) of the present invention has a small optical distortion, it is confirmed that the distortion is small even in an injection molded product, particularly in the vicinity of the gate, and has a high refractive index. It was confirmed to be excellent.

  The optical article of the present invention has a high refractive index, excellent transparency, and low optical anisotropy. For this reason, the optical article of the present invention includes eyeglass lenses, lenses for various optical devices (pickup lenses, in-vehicle camera lenses, portable camera lenses, digital camera lenses, OHP lenses), microlens arrays, prisms, prisms. It can be suitably used for sheets, optical fiber communication devices (optical waveguides, optical amplifiers, etc.), LED sealants, and the like. Therefore, the industrial applicability of the present invention is high.

Claims (6)

An optical article formed of a composition comprising a resin containing a structural unit represented by the following general formula (1) or general formula (2) and metal fine particles.

[In the general formula (1), the two rings α each independently represent a ring containing an aromatic ring, and the two rings are connected by a spiro bond. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. ]

[In general formula (2), ring β and ring γ each independently represent a monocyclic or polycyclic ring, and two rings γ are linked to one quaternary carbon on ring β. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. ]   The resin is a polyaddition product of a dithiol compound corresponding to the general formula (1) or the general formula (2) and a compound having two or more reactive groups capable of addition by thiol in one molecule. The optical article according to claim 1.   The optical article according to claim 2, wherein the compound having two or more reactive groups is a polyisocyanate compound or a polyisothiocyanate compound. The optical article according to any one of claims 1 to 3, wherein the structural unit is a structural unit represented by any one of the following general formulas (3) to (6).

[In General Formula (3), R ¹¹ and R ¹² each independently represent a hydrogen atom or a substituent, and R ¹³ each independently represents a substituent. Moreover, each substituent represented by R ^{11 to} R ¹³ may be linked to form a ring. p and q each independently represents an integer of 0 to 3. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. ]

[In General Formula (4), each R ³¹ independently represents a hydrogen atom or a substituent, and each R ³² independently represents a substituent. Moreover, each substituent represented by R ³¹ and R ³² may be linked to form a ring. p and q each independently represents an integer of 0 to 3. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. X represents an oxygen atom or a sulfur atom. ]

[In General Formula (5), each R ²¹ independently represents a hydrogen atom or a substituent, and each R ²² independently represents a substituent. Moreover, each substituent represented by R ²¹ and R ²² may be linked to form a ring. p and q each independently represents an integer of 0 to 3. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. X represents an oxygen atom or a sulfur atom. ]

[In General Formula (6), R ⁶¹ and R ⁶² each independently represents a substituent. In addition, each may be linked to form a ring. j and k each independently represents an integer of 0 to 4. Two L's each independently represent a divalent linking group, and two n's each independently represent 0 or 1. ]   The optical article according to any one of claims 1 to 4, wherein the metal fine particles are zirconia or titania fine particles.   The optical article according to any one of claims 1 to 5, wherein the optical article is a plastic lens.