JP2005298717A - Thermoplastic resin material, its production method and optical element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin material having high transmittance by using an inorganic particulate which is excellent in dispersion stability in a host material, its production method and an optical element using the same. <P>SOLUTION: In the production method of the thermoplastic resin material wherein the absolute value of temperature change rate of refractive index dn/dT satisfies the relation: 0≤¾dn/dT¾≤9.0×10<SP>-5</SP>, the inorganic particulate having an average particle size of 1-50 nm is dispersed in the host material comprising an organic polymer. The inorganic particulate is subjected to a surface treatment with an organic compound without undergoing a dried state at particle formation. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin material suitably used as a lens, a filter, a grating, an optical fiber, a flat optical waveguide, etc., and having a small refractive index temperature change rate, a method for producing the same, and an optical element using the same.

  Information equipment such as a player, a recorder, and a drive for reading and recording information on an optical information recording medium (hereinafter also simply referred to as a medium) such as MO, CD, and DVD is provided with an optical pickup device. The optical pickup device includes an optical element unit that irradiates a medium with light having a predetermined wavelength emitted from a light source, and receives the reflected light with a light receiving element. The optical element unit receives the light from a reflection layer or a light receiving medium of the medium. An optical element such as a lens for condensing light by the element is included.

  The optical element of the optical pickup device is preferably made of plastic as a material in that it can be manufactured at low cost by means such as injection molding. As a plastic applicable to an optical element, a copolymer of a cyclic olefin and an α-olefin (for example, Patent Document 1) is known.

  By the way, in the case of an information device capable of reading and writing information on a plurality of types of media such as a CD / DVD player, for example, the optical pickup device responds to differences in the shape of both media and the wavelength of light to be applied. It is necessary to make it the structure. In this case, it is preferable from the viewpoint of cost and pickup characteristics that the optical element unit is common to all the media.

  On the other hand, an optical element unit using plastic as a material is required to be a substance having optical stability such as a glass lens. For example, optical plastic materials such as cyclic olefins have significantly improved refractive index stability with respect to humidity, whereas the improvement in refractive index stability with temperature is not yet sufficient. .

  As one of methods for correcting the optical refractive index of the plastic lens as described above, various methods using a fine particle filler have been proposed.

  This fine particle filler is used to modify the refractive index of optical plastics, and by using a filler whose particle size is sufficiently small, no light scattering is caused by the filler. As a result, sufficient transparency can be maintained. For example, technical literature describing the addition of fine particles to increase the refractive index of plastic includes C.I. Becker and P.M. Mueller and H.M. Schmidt, “Optical and Thermodynamic Investigations in Thermoplastic Microsynthetic Materials with Surfaces Modified with Silica Fine Particles”, SPIE Proceedings Vol. 3469, July 1998, pages 88-98; Braune and P.M. Mueller and H.M. Schmidt, “Tantalum Oxide Nanomers for Optical Applications”, SPIE Proceedings Vol. 3469, July 1998, pages 124-132 and the like.

  As described above, since transparent plastic materials are lighter and cheaper than glass, they are used in various applications in optical systems. However, since the refractive index stability with respect to temperature and humidity is inferior to that of glass, improvement is desired. The stability of the refractive index with respect to temperature can be expressed by the temperature dependence dn / dT of the refractive index expressed by the following formula (A).

Formula (A)
dn / dT = (n−1) {(1 / ρ) (dρ / dT) + (1 / [R]) (d [R] / dT)}
In the formula, ρ represents the density of the substance, and [R] represents the molecular refractive index of the substance.

The refractive index of organic polymers decreases with increasing temperature (dn / dT <0) almost without exception. For example, as shown below, dn / dT of organic polymer materials generally used for optical applications is approximately equal to −10 ⁻⁴ / K.

<< Organic Polymer Material >><< dn / dT (10 _-4 / K) >>
Polymethyl methacrylate -1.1
Polycarbonate -1.2
Polystyrene -1.1
As a method of providing a thermoplastic resin material having a small absolute value of dn / dT, there is a method of reducing the thermal properties of the material itself, that is, dρ / dT in the formula (A), specifically, the temperature dependence of density. Conceivable. As this method, a method of mixing an additive such as a crosslinking agent in order to reinforce the matrix of the resin material can be considered, but an additive sufficient to improve dn / dT has not yet been found. Is the current situation.

On the other hand, for example, a method of reducing the absolute value of dn / dT by mixing a substance having dn / dT> 0 in a host material having dn / dT <0 can be considered. Since some inorganic materials are known to have dn / dT> 0 as a result of temperature-dependent changes in intramolecular coordination, a host material comprising an organic polymer with dn / dT <0. It is considered that the absolute value of dn / dT can be reduced by mixing inorganic fine particles satisfying dn / dT> 0, and a temperature-sensitive polymeric host material and dispersed fine particle substance A fine synthetic optical product having a reduced temperature sensitivity has been proposed (see, for example, Patent Documents 2 to 8). However, for example, as shown by Formula 2 described in Patent Document 6, it is shown that in order to reduce the dn / dT of the host material by 50%, it is necessary to mix 40% by mass or more of inorganic fine particles. Yes. In such a resin material in which a large amount of inorganic fine particles are mixed, there is a problem that the specific gravity is large and the transparency is low. In addition, there is a problem that the inorganic fine particles dispersed in the resin aggregate and the performance changes when stored for a long period of time, and it is only possible to provide a resin material that is not suitable for practical use. In order to disperse the inorganic fine particles of the order in the thermoplastic resin material, the surface treatment of the inorganic fine particles is essential. Usually, the inorganic particles using the sol-gel method are taken out in a dry state and then subjected to a desired surface treatment so that they can be dispersed in the resin material. However, in the production of thermoplastic resin materials using inorganic fine particles once produced through a drying process, local refractive index and light scattering abnormalities are caused by the occurrence of partial aggregation of inorganic fine particles of nano order. For example, it becomes a defect in the case of an optical element.
JP 2002-105131 A (page 4) JP 2002-207101 A (Claims) JP 2002-240901 A (Claims) JP 2002-241560 A (Claims) JP-A-2002-241692 (Claims) JP-A-2002-241492 (Claims) JP 2002-241612 A (Claims) JP 2002-303701 A (Claims)

  The present invention has been made in view of the above problems, and its purpose is to use inorganic fine particles having excellent dispersion stability in a host material, a thermoplastic resin material having high transmittance, a method for producing the same, and a method for producing the same. The optical element used is provided.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
Inorganic particles having an average particle diameter of 1 nm or more and 50 nm or less are dispersed in a host material made of an organic polymer, and the absolute value of dn / dT of the temperature change rate of the refractive index is defined by the following formula (A). A method for producing a thermoplastic resin material that satisfies a condition, characterized in that the inorganic fine particles are subjected to a surface treatment with an organic compound, and the surface treatment is performed without passing through a dry state at the time of particle formation. A method for producing a thermoplastic resin material.

Formula (A)
0 ≦ | dn / dT | ≦ 9.0 × 10 ⁻⁵
(Claim 2)
The method for producing a thermoplastic resin material according to claim 1, wherein dn / dT of the inorganic fine particles satisfies a condition defined by the following formula (B).

Formula (B)
0 ≦ dn / dT ≦ 1.0 × 10 ⁻³
(Claim 3)
The method for producing a thermoplastic resin material according to claim 1 or 2, wherein the inorganic fine particles are a semiconductor crystal composition, an inorganic oxide, or a mixture of a semiconductor crystal composition and an inorganic oxide.

(Claim 4)
The host material made of the organic polymer is at least one selected from an acrylic resin, a cyclic olefin resin, a polycarbonate resin, a polyester resin, a polyether resin, a polyamide resin, and a polyimide resin. The manufacturing method of the thermoplastic resin material of any one of these.

(Claim 5)
A thermoplastic resin material produced by the method for producing a thermoplastic resin material according to any one of claims 1 to 4.

(Claim 6)
An optical element formed by using the thermoplastic resin material according to claim 5.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin material which has the high transmittance | permeability using the inorganic fine particle excellent in the dispersion stability in host material, its manufacturing method, and an optical element using the same can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventors have dispersed inorganic fine particles having an average particle diameter of 1 nm or more and 50 nm or less in a host material made of an organic polymer, and the temperature change rate of the refractive index. Is a method for producing a thermoplastic resin material in which the absolute value of dn / dT satisfies the condition defined by the following formula (A), which is surface-treated with an organic compound, and has passed through a dry state during particle formation. Production of thermoplastic resin material with high transmittance using inorganic fine particles with excellent dispersion stability in the host material by the method for producing thermoplastic resin materials using surface-treated inorganic fine particles It is up to the present invention that the method can be realized.

  That is, one of the features of the thermoplastic resin material of the present invention is a thermoplastic resin material having a small absolute value of the refractive index temperature change rate (dn / dT).

  In the present invention, dn / dT, which is an index of the temperature change rate of the refractive index, indicates that the refractive index (n) of the material changes at a rate of dn / dT with respect to the change of temperature (T). The value of dn / dT is obtained by measuring the refractive index of the thermoplastic resin material at each temperature and reading the temperature change rate of the refractive index. As a method for measuring the refractive index, for example, a preferred method can be selected according to the form of the thermoplastic resin material from ellipsometry, spectral reflectance method, optical waveguide method, Abbe method, minimum deviation method, and the like. Since the temperature change rate of the refractive index is expressed by the following formula (A), it can also be obtained by calculation from the temperature change rate of the density of the substance and the molecular refractive index of the substance.

Formula (1)
dn / dT = (n−1) {(1 / ρ) (dρ / dT) + (1 / [R]) (d [R] / dT)}
Here, ρ represents the density of the substance, and [R] represents the molecular refractive index of the substance.

The present invention is characterized in that it is a thermoplastic resin material in which | dn / dT |, which is the absolute value of dn / dT, is 0 or more and 9.0 × 10 ⁻⁵ or less, preferably | dn / dT | Is 0 or more and 5.0 × 10 ⁻⁵ or less, more preferably a thermoplastic resin material having a dn / dT of −2.5 × 10 ⁻⁵ or more and 1.0 × 10 ⁻⁶ or less.

As described above, the refractive index of the organic polymer greatly decreases with increasing temperature (dn / dT≈−10 ⁻⁴ / K) almost without exception. Therefore, by using the thermoplastic resin material of the present invention, it is possible to provide an optical element that is more excellent in temperature stability than in the past.

  As a method for providing a thermoplastic resin material having a small absolute value of dn / dT as in the present invention, the thermal property of the material itself, that is, the temperature dependence of the density represented by dρ / dT in the above formula (A) is used. A method of reducing the size is conceivable. As this method, a method of mixing an additive such as a cross-linking agent in order to reinforce the matrix of the resin material can be considered, but sufficient addition to achieve dn / dT satisfying the conditions specified in the present invention. Things are not found.

  On the other hand, for example, a method of reducing the absolute value of dn / dT by mixing a substance having dn / dT> 0 in a host material having dn / dT <0 can be considered. Inorganic materials are known to have dn / dT> 0 as a result of temperature-dependent changes in intramolecular coordination, and therefore, in host materials made of organic polymers where dn / dT <0. In addition, it is considered that the absolute value of dn / dT can be reduced by mixing inorganic fine particles with dn / dT> 0. Japanese Patent Application Laid-Open Nos. 2002-207101, 2002-241492, etc. describe an invention based on this concept, and in order to reduce the dn / dT of the host material by 50% as shown by Formula 2 in the specification. It is shown that it is necessary to mix 40% by mass or more of inorganic fine particles. Therefore, in order to obtain the thermoplastic resin material of the present invention according to the present invention, inorganic fine particles having a very large dn / dT are found, or the specific gravity is large and the transparency is low due to the large mixed mass of the inorganic fine particles. It can be seen that it is only possible to provide a resin material that is not suitable for conversion.

  According to the method of the present invention, there is provided a thermoplastic resin material having a specific gravity and transparency that are low in temperature dependence of the refractive index of the present invention, which has been difficult to achieve by the method described in JP-A-2002-207101, and that can be practically used. Can be provided.

  Details of the present invention will be described below.

《Inorganic fine particles》
The inorganic fine particles according to the present invention have an average particle diameter of 1 nm or more and 50 nm or less, and are characterized by being subjected to a surface treatment with an organic compound without passing a dry state at the time of particle formation.

  The inorganic fine particles according to the present invention preferably have an average particle size of 1 nm or more and 30 nm or less, more preferably 1 nm or more and 20 nm or less, and further preferably 1 nm or more and 10 nm or less. If the average particle size is less than 1 nm, it is difficult to disperse the inorganic fine particles, so that the desired performance may not be obtained. If the average particle size exceeds 50 nm, the resulting thermoplastic material composition becomes turbid. As a result, the transparency is lowered and the light transmittance may be less than 70%. The average particle diameter here refers to the diameter when converted to a sphere having the same volume as the particles.

  The shape of the inorganic fine particles used in the present invention is not particularly limited, but preferably spherical fine particles are used. Further, the particle size distribution is not particularly limited, but in order to achieve the effect of the present invention more efficiently, a particle having a relatively narrow distribution is preferably used rather than a particle having a wide distribution. Used.

The dn / dT of the inorganic fine particles used in the present invention is preferably 0 or more and 1 × 10 ⁻³ or less, more preferably 5 × 10 ⁻⁵ or more and 1 × 10 ⁻³ or less.

  The inorganic fine particles used in the present invention are not particularly limited, but are preferably a semiconductor crystal composition, an inorganic oxide, or a mixture of a semiconductor crystal composition and an inorganic oxide, such as oxide fine particles. More specifically, for example, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, hafnium oxide, niobium oxide, tantalum oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, yttrium oxide, lanthanum oxide, cerium oxide, Phosphate and sulfate formed in combination with oxides such as indium oxide, tin oxide, lead oxide, and lithium oxides of double oxide such as lithium niobate, potassium niobate, and lithium tantalate Etc.

Further, the semiconductor crystal composition that can be used as the inorganic fine particles according to the present invention is not particularly limited, but a semiconductor crystal composition that does not generate absorption, light emission, fluorescence, or the like in a wavelength region used as an optical element is desirable. Specific examples of the composition include simple elements of Group 14 elements of the periodic table such as carbon, silicon, germanium and tin, simple elements of Group 15 elements of the periodic table such as phosphorus (black phosphorus), and periodic tables such as selenium and tellurium. A group 16 element simple substance, a compound composed of a plurality of Group 14 elements such as silicon carbide (SiC), tin (IV) (SnO ₂ ), tin sulfide (II, IV) (Sn (II) Sn (IV ) S _3), tin sulfide (IV) (SnS _2), tin sulfide (II) (SnS), selenium tin (II) (SnSe), tellurium tin (II) (SnTe), lead sulfide (II) ( PbS), lead selenide (II) (PbSe), lead telluride (II) (PbTe) periodic table group 14 element and periodic table group 16 element compound, boron nitride (BN), boron phosphide (BP), boron arsenide (BAs), aluminum nitride (AlN), aluminum phosphide (AlP) Aluminum arsenide (AlAs), aluminum antimonide (AlSb), gallium nitride (GaN), gallium phosphide (GaP), gallium arsenide (GaAs), gallium antimonide (GaSb), indium nitride (InN), indium phosphide (InP) ), Indium arsenide (InAs), indium antimonide (InSb), etc., a compound of a periodic table group 13 element and a periodic table group 15 element (or group III-V compound semiconductor), aluminum sulfide (Al ₂ S ₃ ) , Aluminum selenide (Al ₂ Se ₃ ), gallium sulfide (Ga ₂ S ₃ ), gallium selenide (Ga ₂ Se ₃ ), gallium telluride (Ga ₂ Te ₃ ), indium oxide (In ₂ O ₃ ), sulfide indium (In ₂ S _3), indium selenide (In ₂ Se _3), telluride, indium (I ₂ Te ₃₎ Periodic Table compounds of a Group 13 element and Periodic Table Group 16 element such as, thallium chloride (I) (TlCl), thallium bromide (I) (TlBr), thallium iodide (I) (TlI ), Etc., a compound of a periodic table group 13 element and a periodic table group 17 element, zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), cadmium oxide (CdO) ), Cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), mercury sulfide (HgS), mercury selenide (HgSe), mercury telluride (HgTe) and the like Compounds with Group 16 elements (or II-VI group compound semiconductors), Arsenic sulfide (III) (As ₂ S ₃ ), Arsenic selenide (III) (As ₂ Se ₃ ), Arsenic telluride (III) (As ₂ Te ₃ ), antimony sulfide (III) (Sb ₂ S ₃ ), antimony selenide (III) (Sb ₂ Se ₃ ), antimony telluride (III) (Sb ₂ Te ₃ ), bismuth sulfide (III) (Bi ₂ ) S ₃ ), bismuth selenide (III) (Bi ₂ Se ₃ ), bismuth telluride (III) (Bi ₂ Te ₃ ) and other compounds of group 15 elements of the periodic table and group 16 elements of the periodic table, copper oxide (I) (Cu ₂ O), copper selenide (I) (Cu ₂ Se) periodic table group 11 element and periodic table group 16 element compound, copper chloride (I) (CuCl), bromide Compounds of Group 11 elements of the periodic table and Group 17 elements of the periodic table such as copper (I) (CuBr), copper iodide (I) (CuI), silver chloride (AgCl), silver bromide (AgBr), oxidation Compound of periodic table group 10 element and periodic table group 16 element such as nickel (II) (NiO), etc. Preparative (II) (CoO), compounds of cobalt sulfide (II) (CoS) periodic table Group 9 element and Periodic Table Group 16 element such as, triiron tetraoxide (Fe ₃ O _4), iron sulfide (II ) Compound of periodic table group 8 element such as (FeS) and periodic table group 16 element, Compound of periodic table group 7 element such as manganese (II) (MnO) and periodic table group 16 element, Compounds of Periodic Table Group 6 elements and Periodic Table Group 16 elements such as molybdenum sulfide (IV) (MoS ₂ ), tungsten oxide (IV) (WO ₂ ), vanadium oxide (II) (VO), vanadium oxide ( IV) (VO ₂ ), tantalum oxide (V) (Ta ₂ O ₅ ) and other periodic table group 5 elements and periodic table group 16 elements, titanium oxide (TiO ₂ , Ti ₂ O ₅ , Ti ₂₎ O _3, Ti ₅ O _9, etc.) compounds of the periodic table group 4 element and periodic table group 16 element such as, sulfide magnesium (MgS), compounds of Group 2 elements and Periodic Table Group 16 element such as magnesium selenide (MgSe), cadmium (II) oxide Chromium _{(III) (CdCr 2 O 4} ), cadmium selenide (II ) Chalcogen spinels such as chromium (III) (CdCr ₂ Se ₄ ), copper sulfide (II) chromium (III) (CuCr ₂ S ₄ ), mercury (II) selenide (III) (HgCr ₂ Se ₄ ), Examples thereof include barium titanate (BaTiO ₃ ). In addition, G. Schmid et al .; Adv. Mater. 4, 494 (1991) (BN) ₇₅ (BF ₂ ) ₁₅ F ₁₅ and D. Fenske et al .; Angew. Chem. Int. Ed. Engl. 29, page 1452 (1990), a semiconductor cluster having a fixed structure such as Cu146Se73 (triethylphosphine) 22 reported in the same manner is also exemplified.

  As these fine particles, one kind of inorganic fine particles may be used, or a plurality of kinds of inorganic fine particles may be used in combination.

<< Production method of inorganic fine particles, surface modification >>
The method for producing inorganic fine particles according to the present invention is characterized in that the surface of the inorganic fine particles is subjected to a surface treatment (also referred to as surface modification) without passing through a dry state. By producing surface-treated inorganic fine particles without passing through the dry state, the dispersion stability of the inorganic fine particles in the thermoplastic resin composition as the host material is excellent, and the ratio of the aggregates of the inorganic fine particles is also dried. By not taking the state, it can be kept low, and as a result, it is possible to obtain a thermoplastic resin material that has a small refractive index variation due to temperature change, no turbidity, and high transmittance.

  The method for producing inorganic fine particles according to the present invention is not particularly limited as long as it does not pass through a dry state during the surface treatment, and any known method can be used. For example, desired oxide fine particles can be obtained by using a metal halide or an alkoxy metal as a raw material and hydrolyzing in a reaction system containing water. At this time, a method of using an organic acid, an organic amine or the like in combination is also used for stabilizing the fine particles. More specifically, for example, in the case of titanium dioxide fine particles, Journal of Chemical Engineering of Japan Vol. 31, No. 1, pages 21-28 (1998), and in the case of zinc sulfide, the Journal of Physical. A known method described in Chemistry Vol. 100, 468-471 (1996) can be used. For example, according to these methods, titanium oxide having an average particle diameter of 5 nm is obtained by adding an appropriate surface modifier when hydrolyzed in an appropriate solvent using titanium tetraisopropoxide or titanium tetrachloride as a raw material. It can be manufactured easily. Zinc sulfide having an average particle diameter of 40 nm can be produced by adding a surface modifier when dimethylzinc or zinc chloride is used as a raw material and sulfurized with hydrogen sulfide or sodium sulfide. The method for surface modification is not particularly limited, and any known method can be used. For example, there is a method of modifying the surface of the fine particles by hydrolysis under conditions where water is present without passing through a drying process. In this method, a catalyst such as an acid or an alkali is preferably used, and it is generally considered that a hydroxyl group on the surface of fine particles and a hydroxyl group generated by hydrolysis of a surface modifier dehydrate to form a bond.

  In the present invention, one feature is that the inorganic fine particles according to the present invention are surface-treated.

  In the present invention, examples of the surface modifier used for the surface treatment of inorganic fine particles include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetraphenoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, and propyltrimethoxysilane. , Methyltriethoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, 3-methylphenyltrimethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiphenoxysilane, trimethylmethoxysilane , Triethylethoxysilane, triphenylmethoxysilane, triphenylphenoxysilane, cyclopentyltrimethoxylane, cyclohextrie Xysilane, benzyldimethylethoxysilane, octyltriethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane , Γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacrylic Xylpropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane , Γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, aminosilane compound, and the like. Instead of aluminum, titanium, zirconia or the like can be used, and in this case, for example, aluminum triethoxide, aluminum triisoproxide or the like.

  Also, fatty acids such as isostearic acid, stearic acid, cyclopropane carboxylic acid, cyclohexane carboxylic acid, cyclopentane carboxylic acid, cyclohexane propionic acid, octylic acid, palmitic acid, behenic acid, undecylenic acid, oleic acid, hexahydrophthalic acid and the like Any of the surface treatment agents of the metal salts and organic phosphoric acid surface treatment agents can be used, and these can be used alone or in admixture of two or more.

  These compounds have different characteristics such as reaction rate, and compounds suitable for surface modification conditions can be used. Further, only one type may be used or a plurality of types may be used in combination. Furthermore, the properties of the surface-modified fine particles obtained may vary depending on the compound used, and the affinity with the thermoplastic resin used to obtain the material composition can be achieved by selecting the compound used for the surface modification. is there. The ratio of the surface modification is not particularly limited, but the ratio of the surface modifier is preferably 10 to 99% by mass and more preferably 30 to 98% by mass with respect to the fine particles after the surface modification. preferable.

"Thermoplastic resin"
In the thermoplastic resin of the present invention, the surface-treated inorganic fine particles are dispersed in a host material made of an organic polymer, whereby the temperature dependency of the refractive index of the host material is improved, and | dn / dT | Is 0 or more and 9.0 × 10 ⁻⁵ or less.

  Examples of the organic polymer host material include transparent resin materials generally used as optical materials, and examples thereof are listed below.

(1) Polymers derived from hydrocarbons having one or two unsaturated bonds For example, polyethylene, polypropylene, polymethylbut-1-ene, poly-4-methylpent-1-ene, polybut-1-ene and polystyrene And the like. These polyolefins may have a crosslinked structure.

(2) Halogen-containing vinyl polymer Examples include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, and chlorinated rubber.

(3) Polymers derived from α, β-unsaturated acids and derivatives thereof For example, polyacrylate, polymethacrylate, polyacrylamide, polyacrylonitrile, or a copolymer with a monomer constituting the polymer, for example, acrylonitrile -Butadiene / styrene copolymer, acrylonitrile / styrene copolymer, acrylonitrile / styrene / acrylic acid ester copolymer, and the like.

(4) Polymers derived from unsaturated alcohols and amines, or acyl derivatives or acetals of unsaturated alcohols, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl polybenzoate, vinyl maleate, polyvinyl butyral, Examples include polyallyl phthalate, polyallyl melamine, or a copolymer with a monomer constituting the polymer, such as an ethylene / vinyl acetate copolymer. (5) A polymer derived from an epoxide, for example, polyethylene oxide or bis And polymers derived from glycidyl ether.

(6) Polyacetal Examples include polyoxymethylene, polyoxyethylene, and polyoxymethylene containing ethylene oxide as a comonomer.

(7) Polyphenylene oxide (8) Polycarbonate (9) Polysulfone (10) Polyurethane and urea resin (11) Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams, for example nylon 6, nylon 66, nylon 11, nylon 12 and the like.

(12) Polyesters derived from dicarboxylic acids and dialcohols and / or oxycarboxylic acids or corresponding lactones, for example, polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol / cyclohexane terephthalate.

(13) Polymers having a crosslinked structure derived from aldehyde and phenol, urea or melamine Examples of the polymer include phenol / formaldehyde resins, urea / formaldehyde resins, and melamine / formaldehyde resins.

(14) Alkyd resin Examples include glycerin and phthalic acid resins.

  (15) Unsaturated polyester resins and halogen-containing modified resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and obtained using vinyl compounds as crosslinking agents.

(16) Natural polymer For example, cellulose, rubber, protein, or derivatives thereof, for example, cellulose acetate, cellulose propionate, cellulose ether and the like.

(17) Soft polymer For example, a soft polymer containing a cyclic olefin component, an α-olefin copolymer, an α-olefin / diene copolymer, an aromatic vinyl hydrocarbon / conjugated diene soft copolymer, Examples thereof include a soft polymer or copolymer comprising isobutylene or isobutylene / conjugated diene.

  Among them, the host material according to the present invention is preferably at least one selected from acrylic resins, cyclic olefin resins, polycarbonate resins, polyester resins, polyether resins, polyamide resins and polyimide resins. The compounds described in Table 1 of 2003-73559 can be mentioned, and preferred compounds are shown in Table 1.

  Further, as the host material according to the present invention, the following thermoplastic resins are particularly preferable.

  One of the thermoplastic resins that can be preferably used in the present invention is an α-olefin having 2 to 20 carbon atoms and an olefin having a cyclic structure represented by the following general formula (1) or (2). It is a cyclic olefin polymer obtained by hydrogenating a copolymer.

In the above general formula (1), n represents 0 or 1, m represents 0 or an integer of 1 or more, q represents 0 or 1, and R ^{1 to} R ¹⁸ , R ^a and R ^b are each independently Represents a hydrogen atom, a halogen atom or a hydrocarbon group, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond In addition, R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group.

In the general formula (1), p and q each represent 0 or an integer of 1 or more, m and n each represent 0, 1 or 2, and R ^{1 to} R ¹⁹ each independently represent a hydrogen atom, a halogen atom, Represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, a carbon atom to which R ⁹ and R ¹⁰ are bonded, and a carbon atom to which R ¹³ or R ¹¹ is bonded May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other. A ring or polycyclic aromatic ring may be formed.

In the general formula (1), n is 0 or 1, m is 0 or an integer of 1 or more, and q is 0 or 1. In addition, when q is 1, R ^a and R ^b are each independently the atoms or hydrocarbon groups shown below, and when q is 0, there is no bond between R ^a and R ^b , The carbon atoms on both sides are combined to form a 5-membered ring.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C3-C15 cycloalkyl group, and an aromatic hydrocarbon group are mentioned normally each independently. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group, and the cycloalkyl group includes a cyclohexyl group. Group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. In these hydrocarbon groups, the hydrogen atom may be substituted with a halogen atom.

Furthermore, in the general formula (1), R ^{15 to} R ¹⁸ may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed The polycycle may have a double bond. Here, specific examples of the monocyclic or polycyclic ring formed are shown below.

In the above example, the carbon atom numbered 1 or 2 indicates the carbon atom to which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) in general formula (1) is bonded. R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and examples of such an alkylidene group include an ethylidene group, a propylidene group, and an isopropylidene group.

  Next, the cyclic olefin represented by the general formula (2) will be described.

In the general formula (2), p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group. The halogen atom has the same meaning as the halogen atom in the general formula (1).

  Examples of the hydrocarbon group independently include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. . More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. As the cycloalkyl group, Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group.

  Examples of the alkoxy group include methoxy group, ethoxy group, and propoxy group. These hydrocarbon groups and alkoxy groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. It may be connected via. That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ , or the groups represented by R ¹⁰ and R ¹¹ , , An alkylene group of any one of a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH ₂ CH ₂ —) is formed.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Examples of the monocyclic or polycyclic aromatic ring in this case include the following groups in which R ¹⁵ and R ¹² further form an aromatic ring.

  Here, q is synonymous with q in the general formula (2).

  The more specific example of the cyclic olefin represented by the above general formula (1) or general formula (2) is shown below. As an example,

A bicyclo [2.2.1] hept-2-ene (also referred to as norbornene. In the above formula, the numbers 1 to 7 represent carbon position numbers) and this compound was substituted with a hydrocarbon group. Derivatives.

  As this substituted hydrocarbon group, 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5-phenyl , 5-benzyl, 5-tolyl, 5- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (anthracenyl) 5,6-diphenyl.

  Furthermore, as other derivatives, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a-hexahydro Bicyclo [2.2.1] hept-2-ene derivatives such as anthracene can be exemplified.

In addition, tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene, 2-methyl-tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene, 5-methyl-tricyclo [4.3.0.1 ^{2, 5]} tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene derivatives such as deca-3-ene, tricyclo [4.4.0.1 ^{2, 5]} undec-3-ene, 10-methyltricyclo [4.4.0.1 ^{2, 5]} tricyclo undec-3-en [4.4.0.1 ^{2, 5]} undec-3-ene Derivatives,

Tetracyclo [4.4.0.1 ² , ⁵ . 1 ⁷ , ¹⁰ ] dodec-3-ene (hereinafter, also simply referred to as tetracyclododecene. In the above formula, the numbers 1 to 12 represent carbon position numbers) and derivatives substituted with a hydrocarbon group Is mentioned.

  Examples of the hydrocarbon group for the substituent include 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2, 10-dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9-isobutyl-2,7- Dimethyl, 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-9 -Methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 8- -Propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8- Benzyl, 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl, 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- (Anthracenyl), 5,6-diphenyl and the like can be exemplified.

  Still other derivatives include adducts of (cyclopentadiene-acenaphthylene adduct) and cyclopentadiene.

Also, tetracyclo [4.4.0.1 ² , ⁵ . 1 ⁷ , ¹⁰ ] dodec-3-ene derivative, pentacyclo [6.5.1.1 ³ , ⁶ . 0 ² , ⁷ . 0 ⁹ , ¹³ ] pentadec-4-ene and its derivatives, pentacyclo [7.4.0.1 ² , ⁵ . 1 ⁹ , ¹² . 0 ⁸ , ¹³ ] pentadec-3-ene and its derivatives, pentacyclo [6.5.1.1 ³ , ⁶ . 0 ² , ⁷ . 0 ⁹ , ¹³ ] pentadeca-4,10-diene compound, pentacyclo [8.4.0.1 ² , ⁵ . 1 ⁹ , ¹² . 0 ⁸ , ¹³ ] hexadec-3-ene and derivatives thereof, pentacyclo [6.6.1.1 ³ , ⁶ . 0 ² , ⁷ . 0 ⁹ , ¹⁴ ] hexadec-4-ene and its derivatives, hexacyclo [6.6.1.1 ³ , ⁶ . 1 ¹⁰ , ¹³ . 0 ² , ⁷ . 0 ⁹ , ¹⁴ ] heptadec-4-ene and its derivatives, heptacyclo [8.7.0.1 ² , ⁹ . 1 to ^{4, 7. 111} , ¹⁷ . 0 ³ , ⁸ . 0 ¹² , ¹⁶ ] eicosa-5-ene and its derivatives, heptacyclo [8.7.0.1 ³ , ⁶ . 1 ¹⁰ , ¹⁷ . 1 ¹² , ¹⁵ . 0 ² , ⁷ . 0 ^{11, 16]} eicosa-4-ene and its derivatives, heptacyclo [8.8.0.1 ^{2, 9.} 1 to ^{4, 7.} 1 ¹¹ , ¹⁸ . 0 ³ , ⁸ . 0 ^{12, 17]} Hen'eikosa-5-ene and derivatives thereof, octacyclo [8.8.0.1 ^{2, 9.} 1 to ^{4, 7.} 1 ¹¹ , ¹⁸ . 1 ¹³ , ¹⁶ . 0 ³ , ⁸ . 0 ^{12, 17]} docosa-5-ene and derivatives thereof, Nonashikuro [10.9.1.1 ^{4, 7.} 1 ¹³ , ²⁰ . 1 ¹⁵ , ¹⁸ . 0 ² , ¹⁰ . 0 ³ , ⁸ . 0 ¹² , ²¹ . 0 ^{14, 19]} Pentakosa-5-ene and derivatives thereof, Nonashikuro [10.10.1.1 ^{5, 8.} 1 ¹⁴ , ²¹ . 1 ¹⁶ , ¹⁹ . 0 ² , ¹¹ . 0 ⁴ , ⁹ . 0 ¹³ , ²² . 0 ¹⁵ , ²⁰ ] hexacosa-6-ene and derivatives thereof.

  Specific examples of the cyclic olefin represented by the general formula (1) or the general formula (2) that can be used in the present invention are as described above, but more specific structures of these compounds are as follows. It is shown in paragraph numbers [0032] to [0054] of JP-A-7-145213, and those exemplified in the publication can also be used as cyclic olefins in the present invention.

  Examples of the method for producing the cyclic olefin represented by the general formula (1) or the general formula (2) include the Diels-Alder reaction between cyclopentadiene and olefins having a corresponding structure. it can.

  These cyclic olefins can be used alone or in combination of two or more.

  The pre-treatment polymer comprising a cyclic olefin used in the present invention is a cyclic olefin represented by the above general formula (1) or general formula (2), for example, JP-A-60-168708, 61- According to the methods proposed in publications such as No. 120816, No. 61-115912, No. 61-115916, No. 61-271308, No. 61-272216, No. 62-252406 and No. 62-252407, It can manufacture by selecting conditions.

Among them, the α-olefin / cyclic olefin random copolymer having 2 to 20 carbon atoms is generally 5 to 95 mol%, preferably 20 to 80 mol% of structural units derived from the α-olefin. The structural unit derived from a cyclic olefin is usually contained in an amount of 5 to 95 mol%, preferably 20 to 80 mol%. The composition ratio of α-olefin and cyclic olefin is measured by ¹³ C-NMR.

  Here, the α-olefin having 2 to 20 carbon atoms constituting the α-olefin / cyclic olefin random copolymer will be described.

  The α-olefin may be linear or branched, and ethylene, propylene, but-1-ene, penta-1-ene, hexa-1-ene, octa-1-ene, deca-1-ene, dodeca Linear α-olefins having 2 to 20 carbon atoms such as -1-ene, tetradec-1-ene, hexadec-1-ene, octadec-1-ene, eicosa-1-ene; 3-methylbuta-1 -Ene, 3-methylpent-1-ene, 3-ethylpent-1-ene, 4-methylpent-1-ene, 4-methylhex-1-ene, 4,4-dimethylhex-1-ene, 4,4- Examples thereof include branched α-olefins having 4 to 20 carbon atoms such as dimethylpent-1-ene, 4-ethylhex-1-ene, and 3-ethylhex-1-ene. Among these, a linear α-olefin having 2 to 4 carbon atoms is preferable, and ethylene is particularly preferable. Such linear or branched α-olefins can be used singly or in combination of two or more.

  In this α-olefin / cyclic olefin random copolymer, the structural unit derived from the α-olefin having 2 to 20 carbon atoms and the structural unit derived from the cyclic olefin are randomly arranged. And have a substantially linear structure. The fact that this copolymer is substantially linear and does not have a gel-like cross-linked structure means that when this copolymer is melted in an organic solvent, the solution contains insolubles. It can be confirmed by not. For example, when the intrinsic viscosity [η] is measured, this copolymer can be confirmed by completely melting in 135 ° C. decalin.

  In the α-olefin / cyclic olefin random copolymer used in the present invention, at least a part of the cyclic olefin represented by the general formula (1) or the general formula (2) is represented by the following general formula (3) or the general formula: It is thought that it constitutes the repeating unit represented by (4).

In the general formula (3), n, m, q, R 1 ~R 18 and R ^a and R ^b are as defined respectively in formula (1).

In the said General formula (4), n, m, p, q, and R < ¹ > -R < ¹⁹ > are synonymous with each in the said General formula (2).

  In addition, the α-olefin / cyclic olefin random copolymer according to the present invention has structural units derived from other copolymerizable monomers as long as the purpose and effects of the present invention are not impaired. It may be.

  Examples of such other monomer include α-olefins having 2 to 20 carbon atoms as described above or olefins other than cyclic olefins. Specifically, cyclobutene, cyclopentene, cyclohexene, 3,4 Cycloolefins such as dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) cyclohex-1-ene and cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, hexa Non-conjugated such as -1,4-diene, 4-methyl-1,4-hexadiene, 5-methylhexa-1,4-diene, octa-1,7-diene, dicyclopentadiene and 5-vinyl-2-norbornene Dienes can be mentioned.

  When the α-olefin / cyclic olefin random copolymer contains a structural unit derived from another monomer as described above, it is usually at most 20 mol% and at most 10 mol%. Is preferred.

  The α-olefin / cyclic olefin random copolymer used in the present invention uses an α-olefin having 2 to 20 carbon atoms and the cyclic olefin represented by the general formula (1) or the general formula (2). Thus, it can be manufactured by the manufacturing method disclosed in the aforementioned publication. Among these, a production method using the catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent and carrying out the copolymerization reaction in a hydrocarbon solvent is preferable.

  In this copolymerization reaction, a metallocene catalyst belonging to Group 4 of the periodic table can also be used. Here, the solid metallocene-based catalyst of Group 4 of the periodic table is composed of a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organoaluminum oxy compound, and an organoaluminum compound blended as necessary. It is a catalyst. Here, examples of the transition metal of Group 4 of the periodic table include zirconium, titanium, and hafnium, and these transition metals are catalysts having a ligand containing at least one cyclopentadienyl skeleton. is there. Examples of the ligand containing a cyclopentadienyl skeleton include a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and a fluorenyl group. Here, the cyclopentadienyl group may be substituted with an alkyl group. These groups may be bonded via other groups such as an alkylene group. Examples of the ligand other than the ligand containing a cyclopentadienyl skeleton include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

  Moreover, what is normally used for manufacture of polyolefin can be used for an organoaluminum oxy compound and an organoaluminum compound. As such a solid metallocene catalyst belonging to Group 4 of the periodic table, for example, those described in JP-A Nos. 61-221206, 64-106 and 2-173112 are used. be able to.

  In the present invention, the graft modified product used as the pre-treatment polymer for the hydrogenation treatment is a graft modified product of the above-mentioned α-olefin / cyclic olefin random copolymer.

  Examples of the modifier used here include usually unsaturated carboxylic acids, specifically, (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. , Unsaturated carboxylic acids such as endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid (registered trademark)), and derivatives of these unsaturated carboxylic acids such as unsaturated carboxylic acids Examples thereof include acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and ester compounds of unsaturated carboxylic acids.

  Specific examples of the unsaturated carboxylic acid derivative include maleic anhydride, citraconic anhydride, maleyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like.

  Among these, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic anhydrides such as maleic acid, Nadic acid (registered trademark) and anhydrides of these acids are preferably used. These modifiers can also be used in combination of two or more.

  Such an α-olefin / cyclic olefin random copolymer graft-modified product can be produced by blending a modifier with the copolymer so as to obtain a desired modification rate, and by graft polymerization. It can also be produced by preparing a modified product having a high modification rate, and then mixing the modified product with an unmodified ethylene / cyclic olefin random copolymer so as to obtain a desired modification rate.

  In order to obtain a graft modified product from an α-olefin / cyclic olefin random copolymer and a modifier, conventionally known polymer modification methods can be widely applied. For example, a method in which a modifier is added to a molten ethylene / cyclic olefin random copolymer and graft polymerization (reaction), or a modifier is added to a solvent solution of ethylene / cyclic olefin random copolymer to perform a graft reaction. A graft-modified product can be obtained by a method of making it.

  Such a grafting reaction is usually performed at a temperature of 60 to 350 ° C. The graft reaction can be carried out in the presence of a radical initiator such as an organic peroxide and an azo compound.

  In the present invention, any of the α-olefin / cyclic olefin random copolymer as described above and a graft-modified product thereof can be used alone as the pretreatment polymer for the hydrogenation treatment. Two or more species or two or more different groups can be used in combination.

  The cyclic olefin polymer according to the present invention preferably has a glass transition temperature (Tg) measured by DSC (temperature increase rate of 10 ° C./min) of 60 to 230 ° C., more preferably 70 to 210 ° C. Preferably there is.

  The cyclic olefin polymer is amorphous or low crystalline, and the crystallinity measured by X-ray diffraction method is usually 20% or less, preferably 10% or less, more preferably 2%. It is as follows.

  The intrinsic viscosity [η] measured in decalin at 135 ° C. is preferably 0.01 to 20 dl / g, more preferably 0.05 to 10 dl / g, still more preferably 0.08 to 5 dl / g. is there.

  The softening point is usually 30 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 90 to 250 ° C., particularly preferably 100 to 100 ° C., as the softening point (TMA) measured with a thermomechanical analyzer. 200 ° C. Here, the measurement of the softening point was performed by the thermal deformation behavior of a sheet having a thickness of 1 mm using a Thermo Mechanical Analyzer manufactured by DuPont. That is, a quartz needle having a load of 49 g was placed on the sheet, the temperature was raised at a rate of 5 ° C./min, and the temperature at which the needle penetrated 0.635 mm into the sheet was defined as the softening point (TMA).

  Among the above cyclic olefin polymers, an α-olefin / cyclic olefin random copolymer is obtained by hydrogenation, has a softening point (TMA) of 80 ° C. or higher, and has an intrinsic viscosity [η] of 0. Those having a viscosity of 0.05 to 10 dl / g are preferred.

  In the hydrogenation treatment in the present invention, it is preferable to hydrogenate the above-mentioned pre-treatment polymer in a solvent mainly containing a cyclic saturated hydrocarbon in the presence of a hydrogenation catalyst. Examples of the solvent for the polymer before treatment include cyclohexane, n-hexane, decalin, cycloheptane, cyclopentane, n-heptane, and n-octane. These can be used alone or in combination of two or more.

  Among these, cyclohexane and n-hexane are preferable, and a solvent containing 50% by mass or more of cyclohexane is particularly preferable.

  Examples of the hydrogenation catalyst metal include Pt, Rh, Pd, Cu, Y, Fe, Ru, W, and Zn. Preferably, Raney nickel, palladium on activated carbon, and Wilkinson complex are used.

  The method of hydrogenation is, for example, 1 to 30% by mass of the polymer before treatment, preferably 3 to 20% by mass in the solvent for hydrogenation, and 0.5 to 10% by mass with respect to this polymer. A concentration of catalyst (as metal) is added and the reaction is carried out at a reaction temperature of 20 to 200 ° C., preferably 40 to 120 ° C. and a hydrogen partial pressure of 0.1 to 20 MPa, preferably 0.5 to 10 MPa. The reaction time is appropriately selected according to the required degree of improvement in hue, but is usually selected from 5 minutes to 12 hours, preferably from 5 minutes to 6 hours. After the reaction, the catalyst is removed by filtration or the like.

  Another thermoplastic resin that can be preferably used in the present invention is a polymer having a weight average molecular weight (Mw) of 1,000 to 1,000,000 in a repeating unit of the following general formula ( A repeating unit (a) having an alicyclic structure represented by I) and at least one chain structure selected from the following general formula (II), the following general formula (III) and the following general formula (IV): An alicyclic hydrocarbon system containing the repeating unit (b) so that the total content is 90% by mass or more, and the content of the repeating unit (b) is 1% by mass or more and less than 10% by mass. It is a copolymer.

In the above general formula (I), X is an alicyclic hydrocarbon group, and in general formula (I) to general formula (IV), R _{1 to} R ₁₃ are each independently a hydrogen atom or a chain hydrocarbon group. , Halogen atom, alkoxy group, hydroxy group, ether group, ester group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, alkoxy group, hydroxy group, ether group, ester group, cyano group, An amide group, an imide group, or a silyl group). n1 to n4 each represent mass%, and at least n2 represents 1 mass% or more and less than 10 mass%.

In the general formulas (I) to (IV), R _{1 to} R ₁₃ are each independently a hydrogen atom, a chain hydrocarbon group, a halogen atom, an alkoxy group, a hydroxy group, an ether group, an ester group, or a cyano group. , A chain hydrocarbon substituted with an amide group, an imide group, a silyl group, or a polar group (halogen atom, alkoxy group, hydroxy group, ether group, ester group, cyano group, amide group, imide group, or silyl group) Represents a group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, for example. Examples of the chain hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. Examples of the chain hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 carbon atoms. -6 alkenyl groups.

  X in the said general formula (I) represents an alicyclic hydrocarbon group, and the carbon number which comprises it is 4-20, Preferably it is 4-10, More preferably, it is 5-7. is there. By setting the number of carbon atoms constituting the alicyclic structure within this range, birefringence can be reduced, which is preferable. The alicyclic structure is not limited to a monocyclic structure, and may be a polycyclic structure such as a norbornane ring or a dicyclohexane ring.

  n1 to n4 each represent mass%, and at least n2 represents 1 mass% or more and less than 10 mass%.

  Next, the details of the alicyclic hydrocarbon copolymer according to the present invention will be described.

  The alicyclic hydrocarbon group may have a carbon-carbon unsaturated bond, but its content is 10% or less, preferably 5% or less, more preferably 3% or less of the total carbon-carbon bonds. is there. By making the carbon-carbon unsaturated bond of an alicyclic hydrocarbon group into this range, transparency and heat resistance can be improved, which is preferable. The carbon constituting the alicyclic hydrocarbon group includes, for example, a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxy group, an ether group, an ester group, a cyano group, an amide group, an imide group, and a silyl group. A chain hydrocarbon group substituted with a polar group (for example, a halogen atom, alkoxy group, hydroxy group, ether group, ester group, cyano group, amide group, imide group, silyl group, etc.) Of these, a hydrogen atom or a chain hydrocarbon group having 1 to 6 carbon atoms is preferred in terms of heat resistance and low water absorption.

  Moreover, in the said general formula (III), although it has a carbon-carbon unsaturated bond in a principal chain, when transparency and heat resistance are requested | required strongly, the content rate of a carbon-carbon unsaturated bond is , 10% or less, preferably 5% or less, more preferably 3% or less of the total carbon-carbon bonds constituting the main chain.

  In particular, among the repeating units represented by the general formula (I), the repeating unit represented by the following general formula (V) is excellent in terms of heat resistance and low water absorption.

  Among the repeating units represented by the general formula (II), the repeating unit represented by the following general formula (VI) is excellent in terms of heat resistance and low water absorption.

  Of the repeating units represented by the general formula (III), the repeating unit represented by the following general formula (VII) is excellent in terms of heat resistance and low water absorption.

  Among the repeating units represented by the general formula (IV), the repeating unit represented by the following general formula (VIII) is excellent in terms of heat resistance and low water absorption.

In the above general formula (V), general formula (VI), general formula (VII), and general formula (VIII), R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h , R _i , R _j , R _k , R _m , R _n , R _p each independently represents a hydrogen atom or a lower chain hydrocarbon group, and is a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, It is preferable from the viewpoint of excellent heat resistance and low water absorption.

  n5 to n8 each represents mass%.

  Of the repeating units having a chain structure represented by the general formula (II) and the general formula (III), the repeating unit having a chain structure represented by the general formula (III) is a hydrocarbon obtained. It is preferable at the point which is excellent in the intensity | strength characteristic of a polymer.

  In the present invention, the repeating unit (a) having an alicyclic structure represented by the general formula (I) in the hydrocarbon copolymer, the general formula (II), the general formula (III), and One of the characteristics is that the total content with the repeating unit (b) of at least one chain structure selected from the general formula (IV) is 90% or more on a mass basis, preferably 95 % Or more, more preferably 97% or more. By setting the total content within the range specified above, an alicyclic hydrocarbon copolymer having a high balance of low birefringence, heat resistance, low water absorption, and mechanical strength can be obtained.

  The content of the repeating unit (b) of the chain structure in the alicyclic hydrocarbon-based copolymer according to the present invention is one of the features that it is 1% or more and less than 10% on a mass basis, The range is preferably 1% or more and 8% or less, more preferably 2% or more and 6% or less. By setting the content of the repeating unit (b) within the range specified above, an alicyclic hydrocarbon-based copolymer in which low birefringence, heat resistance, and low water absorption are highly balanced can be obtained. .

  The chain length of the repeating unit (a) is sufficiently shorter than the molecular chain length of the alicyclic hydrocarbon copolymer, and specifically, the weight average molecular weight of the repeating unit chain having an alicyclic structure. And (weight average molecular weight (Mw) of alicyclic hydrocarbon copolymer) × (number of repeating units having alicyclic structure / total number of repeating units constituting alicyclic hydrocarbon copolymer) ) Is B, A is preferably 30% or less of B, more preferably 20% or less, still more preferably 15% or less, and particularly preferably 10% or less. When A is outside this range, the low birefringence is poor.

  Furthermore, it is preferable that the chain length of the repeating unit (a) has a specific distribution. Specifically, when the weight average molecular weight of the repeating unit chain having an alicyclic structure is A and the number average molecular weight of the repeating unit chain having an alicyclic structure is C, A / C is preferably 1.3. As described above, the range is more preferably 1.3 to 8, and most preferably 1.7 to 6. When A / C is excessively small, the degree of block increases, and when it is excessively large, the degree of randomness increases, and in any case, low birefringence is inferior.

  The molecular weight of the alicyclic hydrocarbon copolymer according to the present invention is a polystyrene (or polyisoprene) equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter referred to as GPC), The range is from 000 to 1,000,000, preferably from 5,000 to 500,000, more preferably from 10,000 to 300,000, and most preferably from 50,000 to 250,000. If the weight average molecular weight (Mw) of the alicyclic hydrocarbon copolymer is excessively small, the strength characteristics of the molded product are inferior. Conversely, if the molecular weight is excessively large, the birefringence of the molded product increases.

  The molecular weight distribution of the alicyclic hydrocarbon copolymer according to the present invention can be appropriately selected depending on the purpose of use, but the weight average molecular weight (Mw) and number average in terms of polystyrene (or polyisoprene) measured by GPC. The ratio (Mw / Mn) to the molecular weight (Mn) is usually 2.5 or less, preferably 2.3 or less, more preferably 2 or less. When Mw / Mn is in this range, mechanical strength and heat resistance are highly balanced.

  The glass transition temperature (Tg) of the alicyclic hydrocarbon-based copolymer according to the present invention may be appropriately selected according to the purpose of use, but is usually 50 ° C to 250 ° C, preferably 70 ° C to 200 ° C, More preferably, it is 90 to 180 ° C.

  Subsequently, the manufacturing method of the alicyclic hydrocarbon type copolymer which concerns on this invention is demonstrated.

  As a method for producing an alicyclic hydrocarbon copolymer according to the present invention, (Method 1) copolymerizing an aromatic vinyl compound and another monomer copolymerizable with the main chain and aromatic ring carbon- Examples thereof include a method of hydrogenating a carbon unsaturated bond, (Method 2) a method of copolymerizing an alicyclic vinyl compound and other monomers copolymerizable, and hydrogenating as necessary.

  When the alicyclic hydrocarbon copolymer according to the present invention is produced by the above method, other monomer (b) copolymerizable with the aromatic vinyl compound or the alicyclic vinyl compound (a ′). And the repeating unit derived from the compound (a ′) in the copolymer is D = (weight average of repeating unit chain derived from the aromatic vinyl compound and / or the alicyclic vinyl compound) Molecular weight), E = (Weight average molecular weight of hydrocarbon copolymer (Mw) × (Number of repeating units derived from aromatic vinyl compound and / or alicyclic vinyl compound / Hydrocarbon copolymer) The main chain of the copolymer having a chain structure in which D is 30% or less, preferably 20% or less, more preferably 15% or less, and most preferably 10% or less of E. , And aromatic rings and cycloalkene rings It can be efficiently obtained by a method for hydrogenating carbon-carbon unsaturated bond - unsaturated carbon ring. When D is outside the conditions specified above, the low birefringence of the resulting alicyclic hydrocarbon-based copolymer is poor.

  In the present invention, among the above production methods, the method described in (Method 1) is preferable in that an alicyclic hydrocarbon copolymer can be obtained more efficiently.

  As the copolymer before hydrogenation, the D / F is constant when the number average molecular weight of the chain of repeating units derived from the aromatic vinyl compound and / or the alicyclic vinyl compound is F. A range is preferred. Specifically, the D / F is preferably 1.3 or more, more preferably 1.3 or more and 8 or less, and most preferably 1.7 or more and 6 or less. When D / F is outside this range, the low birefringence of the resulting alicyclic hydrocarbon copolymer is poor.

  The weight average molecular weight and the number average molecular weight of the chain of repeating units derived from the compound (a ′) are, for example, unsaturated dicarboxylic acid in the main chain of the aromatic vinyl-based copolymer described in the document Macromolecules 1983, 16, 1925-1928. It can be confirmed by, for example, a method of measuring the molecular weight of the aromatic vinyl chain taken out by reductive decomposition after adding a heavy bond with ozone.

  The molecular weight of the copolymer before hydrogenation is 1,000 to 1,000,000, preferably 5,000 to 500,000 in terms of polystyrene (or polyisoprene) equivalent weight average molecular weight (Mw) measured by GPC. More preferably, it is in the range of 10,000 to 300,000. When the weight average molecular weight (Mw) of the copolymer is excessively small, the strength characteristics of the molded product of the alicyclic hydrocarbon copolymer obtained therefrom are inferior. Conversely, when the copolymer is excessively large, the hydrogenation reactivity is inferior.

  Specific examples of the aromatic vinyl compound used in the above (Method 1) include, for example, styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, Examples include dichlorostyrene, monofluorostyrene, 4-phenylstyrene, and styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, and the like are preferable.

  Specific examples of the alicyclic vinyl compound used in the above (Method 2) include, for example, cyclobutylethylene, cyclopentylethylene, cyclohexylethylene, cycloheptylethylene, cyclooctylethylene, norbornylethylene, dicyclohexylethylene, α- Methylcyclohexylethylene, α-t-butylcyclohexylethylene, cyclopentenylethylene, cyclohexenylethylene, cycloheptenylethylene, cyclooctenylethylene, cyclodecenylethylene, norbornenylethylene, α-methylcyclohexenylethylene, and α- Examples include t-butylcyclohexenylethylene, and among these, cyclohexylethylene and α-methylcyclohexylethylene are preferable.

  These aromatic vinyl compounds and alicyclic vinyl compounds can be used alone or in combination of two or more.

  Other monomers that can be copolymerized are not particularly limited, but chain vinyl compounds and chain conjugated diene compounds are used. When chain conjugated dienes are used, the operability in the production process is excellent. The resulting alicyclic hydrocarbon copolymer is excellent in strength properties.

  Specific examples of the chain vinyl compound include chain olefin monomers such as ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene; 1-cyanoethylene (acrylonitrile), 1-cyano- Nitrile monomers such as 1-methylethylene (methacrylonitrile) and 1-cyano-1-chloroethylene (α-chloroacrylonitrile); 1- (methoxycarbonyl) -1-methylethylene (methacrylic acid methyl ester), 1- (Ethoxycarbonyl) -1-methylethylene (methacrylic acid ethyl ester), 1- (propoxycarbonyl) -1-methylethylene (methacrylic acid propyl ester), 1- (butoxycarbonyl) -1-methylethylene (methacrylic) Acid butyl ester), 1-methoxycarboni (Meth) acrylic acid such as ethylene (acrylic acid methyl ester), 1-ethoxycarbonylethylene (acrylic acid ethyl ester), 1-propoxycarbonylethylene (acrylic acid propyl ester), 1-butoxycarbonylethylene (acrylic acid butyl ester) Ester monomers, 1-carboxyethylene (acrylic acid), 1-carboxy-1-methylethylene (methacrylic acid), unsaturated fatty acid monomers such as maleic anhydride, and the like are mentioned, among which chain olefin monomers are preferable, Most preferred are ethylene, propylene and 1-butene.

  Examples of the chain conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Of these chain vinyl compounds and chain conjugated dienes, chain conjugated dienes are preferable, and butadiene and isoprene are particularly preferable. These chain vinyl compounds and chain conjugated dienes can be used alone or in combination of two or more.

  These chain vinyl compounds can be used alone or in combination of two or more.

  The method for polymerizing the compound (a ′) is not particularly limited. However, the batch polymerization method (batch method) and the monomer sequential addition method (after the polymerization is started using a part of the total amount of monomers used, And the like, and a method of proceeding the polymerization by sequentially adding the above monomers). Particularly, when the sequential monomer addition method is used, a hydrocarbon copolymer having a preferable chain structure can be obtained. The copolymer before hydrogenation has a more random chain structure, so that the above-mentioned D value is smaller and / or the D / F shows a larger value. The degree of randomness of the copolymer is determined by the speed ratio between the polymerization rate of the aromatic vinyl compound and the polymerization rate of other copolymerizable monomers, and the smaller this speed ratio, the more It has a random chain structure.

  According to the monomer sequential addition method, since the uniformly mixed monomer is sequentially added into the polymerization system, unlike the batch method, the polymerization selectivity of the monomer is further lowered during the growth process by polymer polymerization. The resulting copolymer has a more random chain structure. In addition, since the accumulation of polymerization reaction heat in the polymerization system is small, the polymerization temperature can be kept low and stable.

  In the case of the monomer sequential addition method, the initial amount of the monomer is usually 0.01 to 60% by mass, preferably 0.02 to 20% by mass, more preferably 0.05 to 10% by mass, out of the total amount of monomers used. Polymerization is started by adding an initiator in the state of being previously present in the polymerization reactor as a monomer. When the initial monomer amount is in such a range, the reaction heat generated in the initial reaction after the initiation of polymerization can be easily removed, and the resulting copolymer can have a more random chain structure.

  When the reaction is continued until the polymerization conversion of the initial monomer is 70% or more, preferably 80% or more, more preferably 90% or more, the chain structure of the resulting copolymer becomes more random. Thereafter, the remainder of the monomer is continuously added, and the rate of addition is determined in consideration of the consumption rate of the monomer in the polymerization system.

  Usually, when the time required for the polymerization rate of the initial monomer to reach 90% is T, and the ratio (%) of the initial monomer to the total used monomer is I, the relational expression [(100−I) × T / I ] Is determined so that the addition of the remaining monomer is completed within a range of 0.5 to 3 times, preferably 0.8 to 2 times, more preferably 1 to 1.5 times the time given by Specifically, the initial monomer amount and the rate of addition of the remaining monomer are determined so that it is usually in the range of 0.1 to 30 hours, preferably 0.5 to 5 hours, more preferably 1 to 3 hours. Further, the total monomer polymerization conversion immediately after completion of the monomer addition is usually 80% or more, preferably 85% or more, and more preferably 90% or more. When the total monomer polymerization conversion rate immediately after the completion of monomer addition is within the above range, the chain structure of the resulting copolymer becomes more random.

  The polymerization reaction is not particularly limited, such as radical polymerization, anionic polymerization, and cationic polymerization. However, the polymerization operation, the ease of the hydrogenation reaction in the post-process, and the mechanical properties of the finally obtained hydrocarbon copolymer are not limited. In view of strength, the anionic polymerization method is preferable.

  In the case of radical polymerization, methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used in the presence of an initiator, usually at 0 to 200 ° C., preferably 20 to 150 ° C. In the case where it is necessary to prevent impurities from being mixed into the resin, bulk polymerization and suspension polymerization are desirable. Examples of the radical initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl-peroxy-2-ethylhexanoate, azoisobutyronitrile, 4,4-azobis-4-cyano. Azo compounds such as pentanoic acid and azodibenzoyl, water-soluble catalysts such as potassium persulfate and ammonium persulfate, redox initiators and the like can be used.

  In the case of anionic polymerization, bulk polymerization, solution polymerization, slurry polymerization in the temperature range of usually 0 ° C. to 200 ° C., preferably 20 ° C. to 100 ° C., particularly preferably 20 ° C. to 80 ° C. in the presence of an initiator. However, solution polymerization is preferable in view of removal of reaction heat. In this case, an inert solvent capable of dissolving the polymer and its hydride is used. Examples of the inert solvent used in the solution reaction include aliphatic hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane, and iso-octane; cyclopentane, cyclohexane, and methylcyclopentane. , Alicyclic hydrocarbons such as methylcyclohexane and decalin; aromatic hydrocarbons such as benzene and toluene, etc., among which aliphatic hydrocarbons and alicyclic hydrocarbons are used for the hydrogenation reaction. Can also be used as an inert solvent. These solvents can be used alone or in combination of two or more, and are usually used at a ratio of 200 to 10,000 parts by mass with respect to 100 parts by mass of all the monomers used.

  Examples of the initiator for the anionic polymerization include monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium, dilithiomethane, 1,4-diobane, and 1,4-dilithio. Polyfunctional organolithium compounds such as -2-ethylcyclohexane can be used.

  In the polymerization reaction, a polymerization accelerator or a randomizer (an additive having a function of preventing a chain of a certain component from becoming long) can be used. In the case of anionic polymerization, for example, a Lewis base compound can be used as a randomizer. Specific examples of the Lewis base compound include ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol methyl phenyl ether; tetramethylethylenediamine, trimethylamine, triethylamine, pyridine Tertiary amine compounds such as potassium; t-amyl oxide, alkali metal alkoxide compounds such as potassium t-butyl oxide; and phosphine compounds such as triphenylphosphine. These Lewis base compounds can be used alone or in combination of two or more.

  The polymer obtained by radical polymerization or anionic polymerization can be recovered by a known method such as a steam stripping method, a direct desolvation method, or an alcohol coagulation method. In addition, when an inert solvent is used in the hydrogenation reaction during the polymerization, the polymer is not recovered from the polymerization solution and can be used as it is in the hydrogenation step.

  Hereinafter, the hydrogenation method of an unsaturated bond is demonstrated in detail.

  When conducting hydrogenation reactions such as carbon-carbon double bonds of unsaturated rings such as aromatic rings and cycloalkene rings of the copolymer before hydrogenation, and unsaturated bonds of the main chain, the reaction method and reaction form are special. There is no particular limitation, and it may be carried out according to a known method. However, a hydrogenation method that can increase the hydrogenation rate and has little polymer chain scission reaction that occurs simultaneously with the hydrogenation reaction is preferable. The method is performed using a catalyst containing at least one metal selected from cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, and rhenium. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used.

  The heterogeneous catalyst can be used in the form of a metal or a metal compound or supported on a suitable carrier. Examples of the carrier include activated carbon, silica, alumina, calcium carbide, titania, magnesia, zirconia, diatomaceous earth, silicon carbide and the like. The amount of the catalyst supported is usually 0.01 to 80% by mass, preferably 0. It is the range of 05-60 mass%. The homogeneous catalyst is a catalyst in which a nickel, cobalt, titanium or iron compound and an organometallic compound (for example, an organoaluminum compound or an organolithium compound) are combined, or an organometallic complex catalyst such as rhodium, palladium, platinum, ruthenium or rhenium. Can be used. Examples of the nickel, cobalt, titanium, or iron compound include acetylacetone salts, naphthene salts, cyclopentadienyl compounds, cyclopentadienyl dichloro compounds, and the like of various metals. As the organic aluminum compound, alkylaluminum such as triethylaluminum and triisobutylaluminum, aluminum halide such as diethylaluminum chloride and ethylaluminum dichloride, alkylaluminum hydride such as diisobutylaluminum hydride and the like are preferably used.

  As an example of the organometallic complex catalyst, metal complexes such as γ-dichloro-π-benzene complex, dichloro-tris (triphenylphosphine) complex, hydrido-chloro-triphenylphosphine complex of the above metals are used. These hydrogenation catalysts can be used alone or in combination of two or more, and the amount used is usually 0.01 to 100 parts, preferably on the mass basis with respect to the polymer. 0.05 to 50 parts, more preferably 0.1 to 30 parts.

  The hydrogenation reaction is usually 10 ° C. to 250 ° C., but preferably 50 ° C. to 200 ° C. because the hydrogenation rate can be increased and the polymer chain scission reaction occurring simultaneously with the hydrogenation reaction can be reduced. More preferably, it is 80 degreeC-180 degreeC. The hydrogen pressure is usually 0.1 MPa to 30 MPa, but in addition to the above reasons, from the viewpoint of operability, it is preferably 1 MPa to 20 MPa, more preferably 2 MPa to 10 MPa.

The hydrogenation rate of the hydride obtained in this way is determined by ¹ H-NMR, as determined by carbon-carbon unsaturated bond of the main chain, carbon-carbon double bond of aromatic ring, carbon of unsaturated ring Any of the carbon double bonds is usually 90% or more, preferably 95% or more, more preferably 97% or more. When the hydrogenation rate is low, the low birefringence, thermal stability, etc. of the resulting copolymer are lowered.

  The method for recovering the hydride after completion of the hydrogenation reaction is not particularly limited. Usually, after removing the hydrogenation catalyst residue by a method such as filtration or centrifugation, the solvent is removed directly from the hydride solution by drying, the hydride solution is poured into a poor solvent for the hydride, and the hydride A method of coagulating can be used.

<Mixing of thermoplastic resin and surface-treated inorganic fine particles>
The thermoplastic material of the present invention comprises a thermoplastic resin and surface-treated inorganic fine particles, but the production method is not particularly limited. That is, a method of preparing the thermoplastic resin and the surface-treated inorganic fine particles independently, and then mixing both, a method of producing a thermoplastic resin under the condition that the surface-treated inorganic fine particles prepared in advance exist, Any method can be employed, such as a method of preparing inorganic fine particles that have been surface-treated in the presence of a thermoplastic resin prepared in advance, or a method of simultaneously producing both thermoplastic resin and surface-treated inorganic fine particles. Specifically, for example, two solutions of a solution in which a thermoplastic resin is dissolved and a dispersion in which surface-treated inorganic fine particles are uniformly dispersed are uniformly mixed, and the solution is poor in solubility in the thermoplastic resin. A method for obtaining a target material composition can be suitably exemplified by meeting with, but is not limited thereto.
In the thermoplastic material composition of the present invention, the degree of mixing of the thermoplastic resin and the surface-treated inorganic fine particles is not particularly limited, but in order to achieve the effects of the present invention more efficiently, uniformly. It is desirable that they are mixed. If the degree of mixing is insufficient, there is a concern that it may affect the optical properties such as refractive index, Abbe number, and light transmittance, and it will also adversely affect resin processability such as thermoplasticity and melt moldability. There is a fear. The degree of mixing is considered to be affected by the production method, and it is important to select a method in consideration of the characteristics of the thermoplastic resin to be used and the surface-treated inorganic fine particles. In order to more uniformly mix both the thermoplastic resin and the surface-treated inorganic fine particles, a method of directly bonding the thermoplastic resin and the inorganic fine particles can be suitably used in the present invention.

  The content of the surface-treated inorganic fine particles according to the present invention is not particularly limited as long as the effects of the present invention can be exhibited, and can be arbitrarily determined depending on the kind of the thermoplastic resin and the surface-treated inorganic fine particles. However, a high content of the surface-treated inorganic fine particles is not preferable because optical properties such as light transmittance deteriorate due to light scattering. Therefore, the content of the surface-treated inorganic fine particles according to the present invention is preferably 40% by mass or less, more preferably 0.1% by mass or more and 30% by mass or less with respect to the mass of the thermoplastic resin. Preferably, it is 0.1 mass% or more and 10 mass% or less.

  The thermoplastic material of the present invention is a material composition that has a low temperature dependency of the refractive index, has high transparency, and is optically excellent, and further has thermoplasticity and / or injection moldability. It is a thermoplastic material with excellent properties. This material having both excellent optical properties and moldability is a property that has not been achieved with the materials disclosed so far, and has been surface-treated with a thermoplastic resin and without undergoing a drying process. It is considered that the inorganic fine particles contribute to this property.

<Other ingredients>
In preparing the thermoplastic resin material of the present invention or in the molding process of the resin composition, various additives (also referred to as compounding agents) can be added as necessary. There are no particular restrictions on the additives, but stabilizers such as antioxidants, heat stabilizers, light stabilizers, weather stabilizers, UV absorbers and near infrared absorbers; resin modifiers such as lubricants and plasticizers An anti-clouding agent such as a soft polymer or an alcohol compound; a colorant such as a dye or a pigment; an antistatic agent, a flame retardant, or a filler. These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not impairing the effects described in the present invention. In the present invention, it is particularly preferable that the polymer contains at least a plasticizer or an antioxidant.

《Plasticizer》
The plasticizer is not particularly limited, however, phosphate ester plasticizer, phthalate ester plasticizer, trimellitic ester plasticizer, pyromellitic acid plasticizer, glycolate plasticizer, citrate ester A plasticizer, a polyester plasticizer, etc. can be mentioned.

  In the phosphate ester plasticizer, for example, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. Trimellitic plasticizers such as diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, etc. For pyromellitic acid ester plasticizers such as phenyl trimellitate, triethyl trimellitate, etc. Examples of glycolate plasticizers such as tilpyromelitate, tetraphenylpyromellitate, and tetraethylpyromellitate include triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, and butylphthalylbutyl glycolate. In the citrate plasticizer, for example, triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate, etc. Can be mentioned.

"Antioxidant"
The antioxidant which can be used for this invention is demonstrated.

  Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. Among them, phenolic antioxidants, particularly alkyl-substituted phenolic antioxidants are preferable. By blending these antioxidants, it is possible to prevent lens coloring and strength reduction due to oxidative degradation during molding without lowering transparency, heat resistance and the like. These antioxidants can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention, but the polymer 100 according to the present invention. Preferably it is 0.001-5 mass parts with respect to a mass part, More preferably, it is 0.01-1 mass part.

  A conventionally well-known thing can be used as a phenolic antioxidant, for example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2 , 4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate and the like, and JP-A Nos. 63-179953 and 1-168643. Acrylate compounds described in Japanese Patent Publication No. 1; octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) ), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5 Di-t-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenylpropionate)) methane [i.e. pentaerythrmethyl- Tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenylpropionate))], triethylene glycol bis (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate) Alkyl-substituted phenolic compounds such as 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 4-bisoctylthio-1, 3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1,3,5-tria Triazine group-containing phenol compounds such emissions; and the like.

  The phosphorus antioxidant is not particularly limited as long as it is usually used in the general resin industry. For example, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) Phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10 Monophosphite compounds such as -dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite ), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite) Like diphosphite compounds such as. Among these, monophosphite compounds are preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferable.

  Examples of the sulfur-based antioxidant include dilauryl 3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodiprote. Pionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc. Can be mentioned.

<Light resistance stabilizer>
The light-resistant stabilizer that can be used in the present invention will be described.

  Examples of the light-resistant stabilizer include benzophenone-based light-resistant stabilizer, benzotriazole-based light-resistant stabilizer, hindered amine-based light-resistant stabilizer, etc., but in the present invention, from the viewpoint of lens transparency, color resistance, etc., hindered amine-based It is preferable to use a light-resistant stabilizer. Among hindered amine light stabilizers (hereinafter referred to as HALS), those having a Mn in terms of polystyrene measured by GPC using tetrahydrofuran (THF) as a solvent are preferably 1,000 to 10,000, and 2,000 What is -5,000 is more preferable, and what is 2,800-3,800 is especially preferable. If Mn is too small, when HALS is blended by heat-melting and kneading into a block copolymer, a predetermined amount cannot be blended due to volatilization, foaming or silver streak occurs during heat-melt molding such as injection molding, etc. Processing stability decreases. Further, when the lens is used for a long time with the lamp turned on, a volatile component is generated as a gas from the lens. Conversely, if Mn is too large, the dispersibility in the block copolymer is lowered, the transparency of the lens is lowered, and the effect of improving light resistance is reduced. Therefore, in the present invention, a lens excellent in processing stability, low gas generation and transparency can be obtained by setting the HALS Mn in the above range.

  Specific examples of such HALS include N, N ′, N ″, N ′ ″-tetrakis- [4,6-bis- {butyl- (N-methyl-2,2,6,6-tetramethylpiperidine. -4-yl) amino} -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine and N, N'-bis (2,2,6 , 6-tetramethyl-4-piperidyl) butylamine, poly [{(1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} { (2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], 1,6-hexanediamine-N, N'-bis (2,2,6,6-tetramethyl- Polypiperidyl) and morpholine-2,4,6-trichloro-1,3,5-triazine, poly [(6-morpholino-s-triazine-2,4-diyl) (2,2, Multiple piperidine rings such as 6,6, -tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino] are bonded via a triazine skeleton. High molecular weight HALS; polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2 , 6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane Such engagement ester, piperidine ring linked to a high molecular weight HALS, and the like via an ester bond.

  Among these, polycondensates of dibutylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4-piperidyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and the like. 5,000 to 5,000 are preferred.

  The blending amount of the thermoplastic resin material of the present invention is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 15 parts by mass, and particularly preferably 0.05 to 100 parts by mass with respect to 100 parts by mass of the polymer. 10 parts by mass. If the amount added is too small, the effect of improving light resistance cannot be obtained sufficiently, and coloring occurs when used outdoors for a long time. On the other hand, when the blending amount of HALS is too large, a part of the HALS is generated as a gas, or the dispersibility in the resin is lowered, so that the transparency of the lens is lowered.

  In addition, by blending the thermoplastic resin material of the present invention with a compound having the lowest glass transition temperature of 30 ° C. or less, it is possible to maintain long properties without deteriorating various properties such as transparency, heat resistance and mechanical strength. It can prevent cloudiness in high temperature and high humidity environment.

<< Method for producing optical resin lens >>
Next, a method for producing an optical resin lens that is one of the optical elements of the present invention will be described.

  The optical resin lens according to the present invention is prepared by first preparing a resin composition (a resin alone or a mixture of a resin and an additive), and then molding the obtained resin composition. The process of carrying out is included.

  The optical resin lens according to the present invention is prepared by first preparing a resin composition (a resin alone or a mixture of a resin and an additive), and then molding the obtained resin composition. The process of carrying out is included.

  The molded product of the thermoplastic resin material of the present invention is obtained by molding a molding material comprising the resin composition. The molding method is not particularly limited, but melt molding is preferable in order to obtain a molded product having excellent characteristics such as low birefringence, mechanical strength, and dimensional accuracy. Examples of the melt molding method include commercially available press molding, commercially available extrusion molding, and commercially available injection molding, and injection molding is preferred from the viewpoints of moldability and productivity.

  The molding conditions are appropriately selected depending on the purpose of use or molding method. For example, the temperature of the resin composition in injection molding (in the case of a resin alone or in a mixture of both a resin and an additive) is appropriate at the time of molding. 150 ° C. to 400 ° C. from the viewpoint of imparting fluidity to the resin to prevent sink marks and distortion of the molded product, preventing the occurrence of silver streak due to thermal decomposition of the resin, and effectively preventing yellowing of the molded product. The range of ° C is preferred, more preferably in the range of 200 ° C to 350 ° C, and particularly preferably in the range of 200 ° C to 330 ° C.

  The molded product according to the present invention can be used in various forms such as a spherical shape, a rod shape, a plate shape, a cylindrical shape, a tubular shape, a tubular shape, a fibrous shape, a film shape or a sheet shape, and has a low birefringence and a transparent property. It is used as an optical resin lens, which is one of the optical elements of the present invention, because of its excellent properties, mechanical strength, heat resistance, and low water absorption, but is also suitable as other optical components.

《Optical resin lens》
The optical resin lens according to the present invention can be obtained by the above-described manufacturing method, and specific examples of application to optical components are as follows.

  For example, as an optical lens or an optical prism, an imaging lens of a camera; a lens such as a microscope, an endoscope or a telescope lens; an all-light transmission lens such as a spectacle lens; a CD, a CD-ROM, or a WORM (recordable optical disk) , MO (rewritable optical disc; magneto-optical disc), MD (mini disc), optical disc pick-up lens such as DVD (digital video disc); laser scanning system lens such as laser beam printer fθ lens, sensor lens; Examples include prism lenses for camera viewfinder systems.

  Examples of optical disc applications include CD, CD-ROM, WORM (recordable optical disc), MO (rewritable optical disc; magneto-optical disc), MD (mini disc), DVD (digital video disc), and the like. Other optical applications include light guide plates such as liquid crystal displays; optical films such as polarizing films, retardation films and light diffusing films; light diffusing plates; optical cards;

  Among these, it is suitable as a pickup lens or a laser scanning system lens that requires low birefringence, and is most suitably used for a pickup lens.

  As an example of the use of the optical resin lens of the present invention, an example used as an objective lens used in a pickup device for an optical disk will be described with reference to FIG.

  In this embodiment, the target is a “high density optical disk” using a so-called blue-violet laser light source having a used wavelength of 405 nm. This optical disk has a protective substrate thickness of 0.1 mm and a storage capacity of about 30 GB.

  FIG. 1 is a schematic diagram showing an example of an optical pickup device used in the present invention.

  In the optical pickup device 1, the laser diode (LD) 2 is a light source, and a blue-violet laser having a wavelength λ of 405 nm is used, but a laser having a wavelength in the range of 390 nm to 420 nm can be appropriately employed.

  The beam splitter (BS) 3 transmits the light source incident from the LD 2 in the direction of the objective optical element (OBL) 4, but the reflected light (returned light) from the optical disk (optical information recording medium) 5 is sensor lens (SL). 6 to collect light on the light receiving sensor (PD) 7.

  The light beam emitted from the LD 2 is incident on the collimator (COL) 8, collimated into infinite parallel light, and then incident on the objective lens OBL 4 via the beam splitter (BS) 3. Then, a condensing spot is formed on the information recording surface 5b via the protective substrate 5a of the optical disc (optical information recording medium) 5. Next, after reflecting on the information recording surface 5b, the polarization direction is changed by the quarter wave plate (Q) 9 along the same path, the path is bent by the BS 3, and the sensor (SL) 6 is passed through the sensor ( Condensed on PD) 7. This sensor photoelectrically converts it into an electrical signal.

  The objective optical element OBL4 is a single lens optical resin lens that is injection-molded with resin. An aperture (AP) 10 is provided on the incident surface side to determine the beam diameter. Here, the incident light beam is reduced to a diameter of 3 mm. The actuator (AC) 11 performs focusing and tracking.

  The numerical aperture required for the objective optical element OBL4 varies depending on the thickness of the protective substrate of the optical information recording medium and the size of the pits. Here, the numerical aperture of the high-density optical disk (optical information recording medium) 5 is 0.85.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

<< Preparation of inorganic fine particles >>
[Preparation of inorganic fine particles A]
Under a nitrogen atmosphere, a solution was prepared by adding 2.5 g of pentaethoxyniobium to 32.31 g of 2-methoxyethanol. To this solution, a mixed solution of 0.35 g of water and 34.45 g of 2-methoxyethanol was added dropwise with stirring. After stirring at room temperature for 16 hours, the mixture was concentrated to an oxide concentration of 5% by mass to obtain a Nb ₂ O ₅ dispersion. When the particle size distribution of the obtained Nb ₂ O ₅ dispersion was measured by a dynamic scattering method, the average particle size was 6 nm.

[Preparation of inorganic fine particles B]
Under a nitrogen atmosphere, a solution was prepared by adding 2.0 g of pentaethoxyniobium to 16.59 g of 2-methoxyethanol. To this solution, a mixed solution of 0.26 g of lithium hydroxide-hydrate and 18.32 g of 2-methoxyethanol was added dropwise with stirring. After stirring at room temperature for 16 hours, the mixture was concentrated to an oxide concentration of 5% by mass to obtain a LiNbO ₃ dispersion. When the particle size distribution of the obtained LiNbO ₃ dispersion was measured by a dynamic scattering method, the average particle size was 5 nm.

[Preparation of inorganic fine particles 1]
After preparing the inorganic fine particles A, 0.1 mol equivalent of cyclopentyltrimethoxysilane to Nb was added in a state where it was not dried, followed by stirring at room temperature for 3 hours and further refluxing for 3 hours. Then, after concentrating at 60 degrees or less with a rotary evaporator, the solvent substitution with cyclohexane was performed to obtain a 5% surface-treated Nb ₂ O ₅ dispersion.

[Preparation of inorganic fine particles 2]
After preparing the inorganic fine particles B, 0.05 mol equivalent of cyclopentyltrimethoxysilane to Nb was added in a state where the inorganic fine particles B were not dried, followed by stirring at room temperature for 3 hours and further refluxing for 3 hours. Then, after concentrating at 60 degrees or less with a rotary evaporator, the solvent was replaced with cyclohexane to obtain a 5% surface-treated LiNbO ₃ dispersion.

[Preparation of inorganic fine particles 3]
After the inorganic fine particles A were prepared, they were once concentrated and dried at 60 ° C. or less with a rotary evaporator, and vacuum dried at room temperature for about 14 hours to obtain a solid powder. Next, methoxyethanol was added to make a 5% by mass dispersion, and after adding 0.1 mol equivalent of cyclopentyltrimethoxysilane to Nb, the mixture was stirred at room temperature for 3 hours and further refluxed for 3 hours. It was. Then, after concentrating at 60 degrees or less with a rotary evaporator, the solvent was replaced with cyclohexane to obtain a 5% surface-treated Nb ₂ O ₅ dispersion.

[Preparation of inorganic fine particles 4]
After the inorganic fine particles B were prepared, they were once concentrated and dried at 60 ° C. or less with a rotary evaporator, and vacuum dried at room temperature for about 14 hours to obtain a solid powder. Next, methoxyethanol was added to make a 5% by mass dispersion, and after adding 0.1 mol equivalent of cyclopentyltrimethoxysilane to Nb, the mixture was stirred at room temperature for 3 hours and further refluxed for 3 hours. It was. Then, after concentrating at 60 degrees or less with a rotary evaporator, the solvent was replaced with cyclohexane to obtain a 5% surface-treated LiNbO ₃ dispersion.

[Preparation of inorganic fine particles 5]
After the inorganic fine particles A were prepared, 10 mol equivalent of cyclohexanecarboxylic acid to Nb was added in a state where the inorganic fine particles A were not dried, followed by stirring at room temperature for 3 hours and further refluxing for 3 hours. Then, after concentrating at 60 degrees or less with a rotary evaporator, the solvent was replaced with cyclohexane to obtain a 5% surface-treated Nb ₂ O ₅ dispersion.

[Preparation of inorganic fine particles 6]
After the inorganic fine particles B were prepared, 5 mol equivalent of cyclohexanecarboxylic acid to Nb was added in a state where the inorganic fine particles B were not dried, followed by stirring at room temperature for 3 hours and further refluxing for 3 hours. Then, after concentrating at 60 degrees or less with a rotary evaporator, the solvent was replaced with cyclohexane to obtain a 5% surface-treated LiNbO ₃ dispersion.

[Preparation of inorganic fine particles 7]
After the inorganic fine particles A were prepared, they were once concentrated and dried at 60 ° C. or less with a rotary evaporator, and vacuum dried at room temperature for about 14 hours to obtain a solid powder. Subsequently, methoxyethanol was added to form a 5% by mass dispersion, and 10 mol equivalent of cyclohexanecarboxylic acid to Nb was added thereto, followed by stirring at room temperature for 3 hours and further refluxing for 3 hours. Then, after concentrating at 60 degrees or less with a rotary evaporator, the solvent was replaced with cyclohexane to obtain a 5% surface-treated Nb ₂ O ₅ dispersion.

[Preparation of inorganic fine particles 8]
After the inorganic fine particles B were prepared, they were once concentrated and dried at 60 ° C. or less with a rotary evaporator, and vacuum dried at room temperature for about 14 hours to obtain a solid powder. Subsequently, methoxyethanol was added to make a 5% by mass dispersion, and after adding 5 mol equivalent of cyclohexanecarboxylic acid to Nb, the mixture was stirred at room temperature for 3 hours and further refluxed for 3 hours. Then, after concentrating at 60 degrees or less with a rotary evaporator, the solvent was replaced with cyclohexane to obtain a 5% surface-treated LiNbO ₃ dispersion.

<< Preparation of resin solution >>
[Preparation of resin solution 1]
1 g of APL5014 as a host material was added to 8 g of cyclohexane, and the mixture was stirred with a stirrer for 6 hours at room temperature. Next, a 5% by mass dispersion of the inorganic fine particles A prepared above was added to this solution in such an amount that the added amount of Nb ₂ 0 ₅ was 60% by mass with respect to APL5014DP, and this mixture was stirred at room temperature all day and night. Resin solution 1 was prepared.

[Preparation of resin solution 2]
1 g of APL5014 as a host material was added to 8 g of cyclohexane, and the mixture was stirred with a stirrer for 6 hours at room temperature. Next, a 5% by mass dispersion of the inorganic fine particles B prepared above was added to this solution in an amount such that the added amount of LiNbO ₃ was 30% by mass with respect to APL5014DP, and this mixture was stirred at room temperature all day and night. Solution 2 was prepared.

[Preparation of resin solutions 3 to 20]
Resin solutions 3 to 20 were prepared in the same manner as in the preparation of the resin solution 1 or 2, except that the type of the host material and the type of the inorganic dispersion were changed as shown in Table 2.

  The details of the host materials listed in Table 2 are as follows.

APL5014DP: manufactured by Mitsui Chemicals, APL5014 (alicyclic hydrocarbon copolymer)
330R: ZEONEX 330R (cyclic olefin polymer) manufactured by ZEON
<Evaluation of resin solution>
The state of each prepared resin solution was visually observed, and the results obtained are shown in Table 2.

<< Production of resin composition >>
Each of the resin solutions 3 to 10 and 13 to 20 prepared above is precipitated in an equal volume mixture of methanol and water using a homogenizer, and resin compositions 3 to 10 and 13 in which inorganic fine particles are dispersed in the host material. ~ 20 was obtained. In addition, since the resin solutions 1, 2, 11, and 12 had caused particle precipitation in the solution state, no resin composition was prepared.

<< Evaluation of Resin Composition >>
[Temperature dependence of refractive index]
Each of the prepared resin compositions and APL5014 and 330R not containing inorganic fine particles as a comparison are melted and heat-molded to prepare 0.5 mm-thick test plates, respectively. Abbe refractometer (DRA manufactured by Atago Co., Ltd.) -M2) is used to measure the refractive index by changing the measurement temperature from 10 ° C. to 50 ° C. at a wavelength of 500 nm, measure the refractive index change rate dn / dT, and evaluate the temperature dependence of the refractive index according to the following criteria: did.

○: Absolute value of dn / dT is 0 or more and 9.0 × 10 ⁻⁵ or less ×: Absolute value of dn / dT exceeds 9.0 × 10 ⁻⁵ [Measurement of light transmittance ]
Each of the prepared resin compositions and, for comparison, APL 5014 and 330R not containing inorganic fine particles were respectively melted and heat-molded to prepare test plates having a thickness of 3 mm. The light transmittance of each sample was measured by using a TURBIDITY METER T-2600DA manufactured by Tokyo Denshoku Co., Ltd. by a method based on ASTM D1003.

  The results obtained as described above are shown in Table 3.

  As is clear from the results shown in Table 3, the resin composition of the present invention has a low refractive index temperature dependency and high transparency compared to the comparative example, and the resin composition does not contain inorganic fine particles. It turns out that it is the light transmittance equivalent to a thing. About the fall of the transmittance | permeability in a comparative example, as a result of performing an electron microscope observation, it was confirmed that it is because the aggregate of 10 nm to several tens of nm is scattered.

It is a schematic diagram which shows an example of the pick-up apparatus for optical discs where the optical resin lens of this invention is used as an objective lens.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical pick-up apparatus 2 Laser diode 3 Beam splitter 4 Objective optical element (also called objective lens)
DESCRIPTION OF SYMBOLS 5 Optical disk 5a Protective board 5b Information recording surface 6 Sensor lens 7 Sensor 8 Collimator 9 1/4 wavelength plate 10 Aperture 11 Actuator

Claims (6)

Inorganic fine particles having an average particle diameter of 1 nm or more and 50 nm or less are dispersed in a host material made of an organic polymer, and the absolute value of dn / dT of the temperature change rate of the refractive index is defined by the following formula (A). A method for producing a thermoplastic resin material that satisfies a condition, characterized in that the inorganic fine particles are subjected to a surface treatment with an organic compound, and the surface treatment is performed without passing through a dry state at the time of particle formation. A method for producing a thermoplastic resin material.
Formula (A)
0 ≦ | dn / dT | ≦ 9.0 × 10 ⁻⁵ The method for producing a thermoplastic resin material according to claim 1, wherein dn / dT of the inorganic fine particles satisfies a condition defined by the following formula (B).
Formula (B)
0 ≦ dn / dT ≦ 1.0 × 10 ⁻³ The method for producing a thermoplastic resin material according to claim 1 or 2, wherein the inorganic fine particles are a semiconductor crystal composition, an inorganic oxide, or a mixture of a semiconductor crystal composition and an inorganic oxide. The host material made of the organic polymer is at least one selected from an acrylic resin, a cyclic olefin resin, a polycarbonate resin, a polyester resin, a polyether resin, a polyamide resin, and a polyimide resin. The manufacturing method of the thermoplastic resin material of any one of these. A thermoplastic resin material produced by the method for producing a thermoplastic resin material according to any one of claims 1 to 4. An optical element formed by using the thermoplastic resin material according to claim 5.

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