JP2005146116A - Resin composition, optical material, and optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which is easy-to-manufacture and has the sufficient transparency and optical performance, to provide an optical material formed of this resin composition, and to provide an optical film obtained from the above resin composition. <P>SOLUTION: The resin composition contains a resin and an inorganic filler which is dispersed in this resin, with the above inorganic filler supporting an organic functional agent and with a haze value per 1 mm of an optical path length of the resin composition molded body being 10% or less. The optical material is formed of the resin composition. The optical film is formed by molding the resin composition into a film form. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin composition in which an inorganic filler carrying an organic functional agent is dispersed in a resin, an optical material comprising the resin composition, and an optical film formed by molding the resin composition into a film. .

Conventionally, these functions are provided for the purpose of imparting various functions such as oxidation prevention, light stabilization, ultraviolet absorption, infrared absorption, low friction, antistatic, flame retardancy, and retardation adjustment to resin materials. An organic compound (hereinafter referred to as “organic functional agent”) is added. Many of these organic functional agents have insufficient compatibility with the resin to be used, and may volatilize during molding or bleed out. Improvements in the molecular structure of organic functional agents to improve compatibility with polymer materials, and addition of functions to polymers by polymerizing polymerizable organic functional agents with monomers and polymers. Has been made.
However, there is a problem that combinations of functional agents and resins that can be used are limited.

  In order to solve this problem, Patent Document 1 contains a resin, a layered silicate, a hindered amine light stabilizer and / or an ultraviolet absorber in a predetermined ratio, and the layered silicate is at least part of the layered crystal. A weather-resistant resin composition is described in which the single layers of the two layers are slightly displaced from each other on the center of the surface of the single layer, and are apparently dispersed in the form of a flat plate having a thickness of 5 to 50 nm and a length of 500 nm or more. . Patent Document 2 discloses 100 parts by mass of a thermoplastic resin or rubber (a), 1 to 50 parts by mass of an ester compound (b) having an ether bond in the molecule, and 1 to 20 parts by mass of a specific quaternary ammonium salt (c). And an antistatic resin composition comprising 1 to 50 parts by mass of layered silicate (d). Patent Document 3 discloses an organic-inorganic composite characterized in that (A) a part of a positively charged organic compound and (B) a part of a light stabilizer coexist between layers of a layered silicate. Is described.

On the other hand, in recent years, optical films such as retardation films and infrared cut filters are frequently used for various optical members.
However, since the resin composition described in Patent Document 1 has poor moldability (fluidity), it is difficult to form a film and light scattering occurs. In addition, films obtained from the resin compositions described in Patent Documents 2 and 3 are not suitable for use as optical materials because of poor transparency and large optical distortion.
Therefore, there has been a demand for the development of a new optical material that gives a molded article having sufficient transparency without causing the organic functional agent to evaporate or bleed out during molding.

JP 2003-105202 A JP 2003-192922 A JP 2000-053805 A

  The present invention has been made in view of the state of the prior art, and the organic functional agent does not volatilize or bleed out during molding, has sufficient transparency, and has little optical distortion. It aims at providing the resin composition which gives a molded object, the optical material which consists of this resin composition, and the optical film obtained from the said resin composition.

  As a result of diligent research to solve the above problems, the present inventors have found that in a resin composition in which an inorganic filler carrying an organic functional agent is dispersed in a resin, the filler has an inorganic length of 500 nm or less. The resin composition using the layered compound or the inorganic fine particles having a particle diameter of 20 nm or less does not cause the organic functional agent to be volatilized or bleed out during molding, is extremely excellent in transparency, and has optical distortion. Since a small number of molded products can be obtained, it has been found that it can be suitably used as an optical material, and the present invention has been completed.

  Thus, according to the first aspect of the present invention, the resin contains an inorganic filler dispersed in the resin, the filler carries an organic functional agent, and the haze at an optical path length of 1 mm of the resin composition molded body. A resin composition having a value of 10% or less is provided.

  In the resin composition of the present invention, the inorganic filler is preferably an inorganic layered compound having a length of 500 nm or less or inorganic fine particles having a number average particle diameter of 20 nm or less.

In the resin composition of the present invention, the organic functional agent is preferably a light absorber or a light stabilizer.
In the resin composition of the present invention, the organic functional agent is preferably covalently bonded, ionic bond, coordinate bond or hydrogen bond to the inorganic filler.
Moreover, in the resin composition of this invention, it is preferable that the said resin is an alicyclic structure containing polymer, and it is more preferable that it is an alicyclic structure containing polymer which has a polar group.

According to a second aspect of the present invention, there is provided an optical material comprising the resin composition of the present invention.
According to the third aspect of the present invention, there is provided an optical film formed by molding the resin composition of the present invention into a film.

  According to the present invention, a resin composition that is easy to produce and has sufficient transparency and optical performance is provided. The resin composition of the present invention is suitable as an optical material for producing an optical member such as an optical film.

1) Resin composition The resin composition of the present invention comprises a resin and an inorganic filler dispersed in the resin, the filler carries an organic functional agent, and the optical path length of the resin composition molded article The haze value at 1 mm is 10% or less.

(1) Resin The resin used in the present invention is not particularly limited as long as it is excellent in transparency. For example, an alicyclic structure-containing polymer, a chain olefin polymer such as polyethylene or polypropylene, triacetyl cellulose, Examples thereof include polyvinyl alcohol, polyimide, polyarylate, polyester, polycarbonate, polysulfone, polyethersulfone, amorphous polyolefin, modified acrylic polymer, and epoxy resin. Among these, an alicyclic structure-containing polymer or a chain olefin polymer is preferable, and an alicyclic structure-containing polymer is particularly preferable from the viewpoints of transparency, low hygroscopicity, dimensional stability, lightness, and the like.

  The alicyclic structure-containing polymer is a polymer containing an alicyclic structure in the repeating unit of the polymer. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure. From the viewpoint of thermal stability of a resin composition or a molded product obtained from the composition, a cycloalkane structure is preferable.

  Carbon number which forms an alicyclic structure is 4-30 normally, Preferably, it is 5-20, More preferably, it is 5-15. When the carbon number is in this range, a molded product obtained from a resin composition having excellent heat resistance and flexibility or this alicyclic structure-containing polymer composition is obtained. This alicyclic structure may be present in either the main chain or the side chain of the polymer.

  The content ratio of the repeating unit containing the alicyclic structure in the alicyclic structure-containing polymer is not limited, and is appropriately selected according to the properties, physical properties, and the like of the resin composition to be obtained. Preferably it is 70 mass% or more, More preferably, it is 90 mass% or more. When the content ratio of this repeating unit is too small, the heat resistance of the resulting resin composition may be lowered, which is not desirable. In addition, the alicyclic structure containing polymer used for this invention may contain repeating units other than the repeating unit containing an alicyclic structure.

  Examples of the alicyclic structure-containing polymer used in this invention include a norbornene polymer (A), a monocyclic olefin polymer (B), a cyclic conjugated diene polymer (C), and a vinyl alicyclic hydrocarbon heavy polymer. A combination (D) and a mixture thereof can be exemplified. Among these polymers, from the viewpoint of heat resistance and mechanical strength of the resulting alicyclic structure-containing polymer composition, hydrides of norbornene polymers, vinyl alicyclic hydrocarbon polymers, and vinyl alicyclic carbonizations. Hydrogenated hydrides are preferred.

  Examples of the norbornene polymer (A) include a ring-opening polymer of a norbornene-based monomer, a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with this monomer, and a hydride of these polymers. And addition polymers of norbornene monomers and addition copolymers of norbornene monomers and other monomers copolymerizable with the monomers. Among these polymers and copolymers, a hydride of a ring-opening polymer of a norbornene monomer is particularly preferable from the viewpoint of heat resistance and mechanical strength of the resulting alicyclic structure-containing polymer composition.

Examples of the norbornene-based monomer include bicyclo [2.2.1] -hept-2-ene (common name: norbornene) and derivatives thereof (having substituents in the ring, the same shall apply hereinafter), tricyclo [4.3. .0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene) and derivatives thereof, 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3- Ene (common name: metatetrahydrofluorene) and its derivatives, tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene (common name: tetracyclododecene) and its derivatives.

  Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, and an alkoxycarbonyl group. The norbornene-based monomer may have one or more of these substituents. May be.

As the norbornene-based monomer having these substituents, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like. These norbornene monomers can be used alone or in combination of two or more.

  The ring-opening polymer of the norbornene-based monomer or the ring-opening copolymer of the norbornene-based monomer and another monomer capable of ring-opening copolymerization with this monomer polymerizes the monomer in the presence of a known ring-opening polymerization catalyst. Can be manufactured. Examples of other monomers capable of ring-opening copolymerization with the norbornene monomer include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

  A hydride of a ring-opening polymer of the norbornene-based monomer or a hydride of a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with this monomer is usually the ring-opening polymer or It can manufacture by adding the well-known hydrogenation catalyst containing transition metals, such as nickel and palladium, to the polymerization liquid containing a ring-opening copolymer, and hydrogenating a carbon-carbon unsaturated bond.

  The addition polymer of the norbornene monomer or the addition polymer of the norbornene monomer and another monomer copolymerizable with the monomer can be produced by polymerizing the monomer in the presence of a known addition polymerization catalyst. it can.

  Examples of other monomers capable of addition copolymerization with norbornene-based monomers include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, and derivatives thereof; cyclobutene, cyclopentene, 3a, 5,6,7a- Examples thereof include cycloolefins such as tetrahydro-4,7-methano-1H-indene and derivatives thereof; non-conjugated dienes such as 1,4-hexadiene and 4-methyl-1,4-hexadiene. Among these monomers, α-olefins, particularly ethylene is preferable. Other monomers capable of addition copolymerization with the norbornene-based monomer may be used alone or in combination of two or more.

  In addition copolymerization of a norbornene monomer and another monomer that can be addition copolymerized with this monomer, the structural unit derived from the norbornene monomer in the resulting copolymer, and another copolymerizable monomer The amount of each monomer used is selected so that the ratio of the structural unit derived from is usually 50:50 to 99: 1, preferably 70:30 to 95: 5 in terms of mass ratio.

  Examples of the monocyclic olefin polymer (B) include addition polymers of monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene, and hydrides thereof.

  Examples of the cyclic conjugated diene polymer (C) include 1,2- or 1,4-addition polymers of cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene, and hydrides thereof.

  Examples of the vinyl alicyclic hydrocarbon polymer (D) include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane, and hydrides thereof, and vinyl aromatics such as styrene and α-methylstyrene. Hydrides obtained by hydrogenating aromatic moieties contained in polymers of aromatic hydrocarbon monomers, vinyl alicyclic hydrocarbon monomers or vinyl aromatic hydrocarbon monomers and other monomers copolymerizable with these monomers And a copolymer such as a random copolymer, a block copolymer, and a hydride thereof. Examples of the block copolymer include diblock, triblock or more multiblock, and gradient block copolymer.

  In the present invention, since the affinity with the inorganic layered compound can be improved and the heat resistance can be improved without impairing the light transmittance of the optical film obtained from the resin composition, the alicyclic ring used The structure-containing polymer preferably has a polar group.

  Examples of the polar group include heteroatoms or atomic groups having heteroatoms. Examples of the heteroatoms include oxygen atoms, nitrogen atoms, silicon atoms, and halogen atoms. Among these heteroatoms, an oxygen atom and a nitrogen atom are preferable from the viewpoint of dispersibility and compatibility with the inorganic layered compound. Specific examples of the polar group include a carboxyl group, a carbonyloxycarbonyl group, an epoxy group, a hydroxyl group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.

  The method for obtaining the alicyclic structure-containing polymer having a polar group is not particularly limited, but when the alicyclic structure-containing polymer is a norbornene polymer, for example, (1) selected from various norbornene monomers A method of reacting (modifying) a compound having a polar group with an unmodified polymer obtained by polymerizing a norbornene-based monomer having no polar group, and (2) from among various norbornene-based monomers A method of copolymerizing a selected norbornene monomer having no polar group and a norbornene monomer having a polar group; and (3) a polar group having a polar group selected from various norbornene monomers. A polymer obtained by polymerizing a norbornene-based monomer which is not subjected to the polymerization, and a nor group having a polar group obtained by the method (1) or (2) It can be mentioned a method of mixing the Runen polymer. The alicyclic structure-containing polymer other than the norbornene polymer is the same as that of the norbornene polymer.

  Examples of the alicyclic structure-containing polymer having a polar group include chlorinated products of alicyclic structure-containing polymers, chlorosulfonated products, and graft modified products of polar group-containing unsaturated compounds. A graft modified product with a polar group-containing unsaturated compound is preferred.

  Examples of the polar group-containing unsaturated compound include unsaturated epoxy compounds such as glycidyl acrylate, glycidyl methacrylate, glycidyl p-styrylcarboxylate, allyl glycidyl ether, and glycidyl ether of 2-methylallyl glycidyl ether; acrylic acid, methacrylic acid , Α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, and the like; monomethyl maleate, dimethyl maleate, glycidyl malate, etc. Unsaturated ester compounds; unsaturated alcoholic compounds such as allyl alcohol, 2-allyl-6-methoxyphenol and 4-allyloxy-2-hydroxybenzophenone; chlorodimethylvinylsilane, trimethylsilyl Acetylene, 5-trimethylsilyl-1,3-cyclopentadiene, 3-trimethylsilylallyl alcohol, and the like unsaturated silane compounds, such as trimethylsilyl meth click relay Bok.

  Among these polar group-containing unsaturated compounds, unsaturated epoxy compounds and unsaturated carboxylic acid compounds are particularly preferable from the viewpoint of uniformly dispersing the filler. In order to efficiently modify the alicyclic structure-containing polymer with the polar group-containing unsaturated compound, it is preferable to carry out the reaction in the presence of a general-purpose radical initiator, and as this suitable radical initiator, Organic peroxide, organic perester, etc. are mentioned.

  The alicyclic structure-containing polymer having a polar group is preferably one having an amount of the polar group of at least 0.01 mmol / g, more preferably 0.01 to 0.8 mmol / g. What is 01-0.5 mmol / g is still more preferable. When the amount of the polar group is within the above range, the affinity with the inorganic layered compound can be further improved.

  The amount of the polar group depends on the introduction rate of the polar group by the reaction of the compound having a polar group in the method (1), and depends on the copolymerization ratio of the monomer having a polar group in the method (2). In the method (3), it can be adjusted by the mixing ratio of the polymer having no polar group and the polymer having a polar group.

  Although there is no restriction | limiting in particular in the molecular weight of resin used for this invention, The weight average molecular weight of polystyrene conversion is 5,000-500,000 normally, Preferably, 8,000-200,000, More preferably, it is 10,000. 000-100,000. When the weight average molecular weight is in this range, the molding processability of the resulting resin composition is improved, and the mechanical strength of the molded body can be improved. This weight average molecular weight can be measured by gel permeation chromatography (GPC) of a cyclohexane solution or a toluene solution.

  Although there is no restriction | limiting in particular also in the glass transition temperature (Tg) of resin used for this invention, Usually, 80 degreeC or more, Preferably it is 130-250 degreeC. When the glass transition temperature is in this range, it is possible to obtain a resin composition that can withstand use at high temperatures and does not cause thermal deformation, stress concentration, or the like, and provides a molded article having excellent durability.

(2) Inorganic filler The resin composition of this invention contains an inorganic filler in the form disperse | distributed in resin. The inorganic filler used in the present invention is not particularly limited as long as it can be uniformly dispersed in the resin and can carry the organic functional agent described below, but is preferably an inorganic layered compound or inorganic fine particles, More preferably, it is an inorganic layered compound.

  The inorganic layered compound used in the present invention is a compound having a polycrystalline layer structure having a planar structure in the vertical direction in a state (layered) in which the compound has a structure arranged in a plane. In this inorganic layered compound, a crystal layer is bonded to each other by van der Waals force or hydrogen bond force, and a crystal layer charged with a negative charge has a cation between each crystal layer. It can be roughly classified into those coupled by a weak electrostatic force through cations.

Specific examples of the inorganic layered compound as described above include graphite; transition metal dichalcogenides such as TiS ₂ , NbSe ₂ and MoS ₂ ; divalent metal phosphorus chalcogenides such as CrPS ₄ ; MoO ₃ and V ₂ O ₅ . Transition metal oxides; oxyhalides such as FeOCl, VOCl, CrOCl; hydroxides such as Zn (OH) ₂ , Cu (OH) ₂ ; Zr (HPO ₄ ) ₂ .nH ₂ O, Ti (HPO ₄ ) ₃ · nH ₂ O, Na (UO ₂ PO ₄ ) Phosphate such as ₃ · nH ₂ O; Titanate such as Na ₂ Ti ₃ O ₇ , KTiNbO ₅ , RbxMnxTi _2−x O ₄ ; Na ₂ U ₂ O _{7, K} 2 uranium salt such as _{U 2 O 7; KV 3 O} 8, K 3 V 5 O 14, CaV 6 O 16 · nH 2 O, Na (UO 2 V 3 O 9 · NH vanadate such as _{2 O; KNb 3 O 3,} K 4 Nb 6 niobate such _{O 17; Na 2 W 4 O} 13, Ag 4 W 10 tungstate such as _{O 13; Mg 2} Mo 2 Molybdates such as O ₇ · Cs ₂ Mo ₅ O ₁₆ , Cs ₂ Mo ₇ O ₂₂ , Ag ₄ Mo ₁₀ O ₃₃ ; montmorillonite, saponite, hydelite, hectorite, nontronite, stevensite, trioctahedra Le vermiculite, dioctahedral vermiculite, muscovite, Fi logo bytes, biotite, lepidolite, Baragonaito, tetrasilicic chromite, kaolinite, halloysite, _{dickite, H 2 SiO 5, H 2} Si 14 O 29 · 5H 2 O Such as silicates or minerals composed of this silicate Kind, and the like.

  Among these inorganic layered compounds, silicates, phosphates, and molybdates are preferable, and silicates are particularly preferable from the viewpoints of dispersibility in the resin, heat resistance of the resulting resin composition, and mechanical strength.

  The inorganic layered compound has a planar structure in which (i) the inorganic layered compound is distributed in a horizontal direction by aligning the major axes in the horizontal direction, and (ii) the inorganic layered compound is in the vertical direction. The planar structure is repeatedly generated and / or (iii) these are aggregated and dispersed in the resin.

  The inorganic layered compound used in the present invention preferably has a length of 500 nm or less, more preferably has a length of 10 to 500 nm, and still more preferably has a length of 10 to 200 nm. Here, the length refers to the length (D1) in the major axis direction, and when the inorganic layered compound dispersed in the resin in the states (i) to (iii) is viewed, the dispersed inorganic It means that the longest D1 in the layered compound is 500 nm. In the present invention, the inorganic layered compound having a major axis direction length (D1) of 500 nm or less is used, so that light scattering is prevented when the inorganic layered compound is dispersed in the resin. A resin composition molded body having excellent properties can be obtained.

  The layer thickness of the inorganic stratiform compound used in the present invention is preferably 50 nm or less, more preferably 40 nm or less, and further preferably 30 nm or less. When the layer thickness is larger than 50 nm, light scattering occurs and there is a possibility that a resin composition molded article having excellent transparency cannot be obtained.

  In the present invention, in order to improve the dispersibility in the resin, it is preferable to use an inorganic layered compound that has been subjected to an organic treatment using an organic agent. Since the inorganic layered compound originally has hydrophilicity, it can be hydrophobized (organized) by adsorbing or binding the organic agent to the inorganic layered compound. Among them, it is preferable to ion-bond the organic agent to the inorganic layered compound by ion exchange with the metal ion between the layers of the inorganic layered compound.

Examples of the organic agent include at least one selected from organic acids or organic acid salts such as sulfonic acid, phosphonic acid and carboxylic acid; and onium salts such as ammonium salt, phosphonium salt and sulfonium salt. ^R 1 in this ^{R 2 R 3 R 4 N +} X - is preferable to use a quaternary ammonium salt represented by.

In R ¹ R ² R ³ R ⁴ N ⁺ X ⁻ , R ¹ , R ² , R ³ and R ⁴ each independently represents a saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms. Examples of the saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, 21-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group. A saturated aliphatic hydrocarbon group such as a group, dodecyl group, hexadecyl group or octadecyl group; an unsaturated aliphatic hydrocarbon group such as a lauryl group or an oleyl group; an aromatic hydrocarbon group such as a phenyl group or a benzyl group. it can. Examples of X include Cr, Br, NO ₃ , OH, and CH ₃ COO.

  The organic layering treatment of the inorganic layered compound is performed by, for example, preparing an inorganic layered compound dispersion by dispersing the inorganic layered compound in water, adding the organic agent to the dispersion, and stirring at room temperature. Can do. The concentration of the inorganic layered compound in the inorganic layered compound dispersion at this time is preferably adjusted to 0.01 to 70% by mass. The organic agent can also be used as an aqueous solution.

  Examples of the inorganic fine particles used in the present invention include transition metal simple substances such as gold, platinum, silver, palladium, rhodium, zinc, copper, nickel and iron; alloys of these transition metals; semiconductors; These fine particles can be used alone or in combination of two or more.

  The inorganic fine particles used in the present invention preferably have a number average particle diameter of 20 nm or less, more preferably 1 nm to 20 nm, and even more preferably 2 nm to 20 nm. By using such inorganic fine particles having a small particle size as a filler, a resin composition having excellent transparency can be obtained. For the determination of the number average particle diameter and the volume%, numerical values measured from a transmission electron microscope (TEM) observation image are used. That is, the diameter of a circle having the same area as the observed inorganic fine particle image is defined as the particle size of the particle image.

  In addition, in terms of transparency of the resin composition molded article of the present invention, the proportion of inorganic fine particles having a particle size of 60 nm or more is usually 10% by volume or less, preferably 5% by volume or less, based on the volume of all inorganic fine particles. More preferably, it is 3 volume% or less.

  In addition, the smaller the particle size distribution of the inorganic fine particles used in the present invention, the better the homogeneity of dispersibility. When the inorganic fine particles containing semiconductor crystals have an exciton absorption / emission band, the wavelength width becomes smaller. It may be preferable. Accordingly, the particle size distribution is controlled so that the standard deviation is usually 20% or less, preferably 15% or less, more preferably 10% or less. However, such particle size distribution may not be a problem in applications that utilize the high refractive index properties and basic absorption of inorganic fine particles (such as ultraviolet absorption applications, reflection control films, or optical waveguides).

  The inorganic fine particles used in the present invention may have a heterogeneous structure such as a mixed crystal or a core-shell structure described later (a two-layer structure of a core that is an inner core and a shell that is an outer shell that includes the core). In particular, in the case of the core-shell structure, when the core substance has an undesirable action, for example, the photocatalytic ability of the semiconductor crystal as the core promotes the decomposition of the resin matrix, a shell of another substance that does not have such an undesirable action is provided. There may be an excellent effect to improve. Therefore, it is desirable that a chemically relatively inert substance constitutes the shell. Specifically, oxides of non-transition metals such as silica (silicon oxide) and alumina (aluminum oxide), and nitrides such as boron nitride Examples of preferable shell materials include simple carbon such as graphitic carbon and amorphous carbon, or noble metals (silver, gold, platinum, copper, etc.). Further, the inorganic fine particles may be composed of a plurality of types, or even inorganic fine particles made of the same kind of material may have its particle size distribution arbitrarily changed as required, such as a bimodal distribution.

(3) Organic functional agent The organic functional agent used in the present invention is added to the resin composition of the present invention in terms of oxidation prevention, light stabilization, light absorption, low friction, antistatic, retardation adjustment, and refractive index adjustment. An organic compound imparting at least one function selected from Examples thereof include an antioxidant, a light stabilizer, a light absorber, an antistatic agent, a lubricant, and a refractive index adjusting agent. Among these, when the resin composition of the present invention is an optical material, it is preferably a light absorber or a light stabilizer.

  When the inorganic filler is an inorganic layered compound, an organic treatment agent such as a cationic surfactant used to improve dispersibility in the resin, and an organic functional agent that imparts the above function to the resin composition; Are preferably present together.

  The antioxidant is not particularly limited as long as it is an industrially commonly used antioxidant. For example, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a lactone antioxidant, etc. Is mentioned. These antioxidants can be used alone or in combination of two or more.

  Examples of phenolic antioxidants include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-tert-amyl. Acrylates described in JP-A Nos. 63-179953 and 1-168643 such as -6- (1- (3,5-di-tert-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (6-tert-butyl-m-creso) ), 4,4′-thiobis (3-methyl-6-tert-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis (2- (3- (3 3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3- Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,

  1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ′, 5′-di-tertiary) Butyl-4′-hydroxyphenylpropionate) methane [ie, pentaerythrimethyl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionate)), triethylene glycol bis (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate), alkyl-substituted phenolic compounds such as tocophenol; 6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4 -Bisoctylthio-1,3,5-triazine, 6- (4-hydroxy-3,5-dimethylanilino) -2,4-bisoctylthio-1,3,5 Triazine, 6- (4-hydroxy-3-methyl-5-tert-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5 -Triazine group-containing phenol compounds such as di-tert-butyl-4-oxyanilino) -1,3,5-triazine; and the like.

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-). -Tert-butylphenyl) phosphite, tris (2-tert-butyl-4-methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) Octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 10-de Monophosphite compounds such as proxy-9,10-dihydro-9-oxa-10-phospha-phenanthrene;

  4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite ), 4,4′-isopropylidene-bis (diphenylmonoalkyl (C12-C15) phosphite), 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-tert-butyl) Phenyl) butane, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphite, cyclic neopentanetetraylbis (isodecylphosphite), cyclic neopentanetetraylbis ( Nonylphenyl phosphite), cyclic neopentanetetraylbis (2,4-di-tert-butylphenyl phosphite) ), Cyclic neopentanetetraylbis (2,4-dimethylphenylphosphite), diphosphite compounds such as cyclic neopentanetetraylbis (2,6-di-tert-butylphenylphosphite), and the like. Among these, monophosphite compounds are preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite and the like are particularly preferable.

  Examples of the sulfur antioxidant include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipropioate. And pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane be able to.

  The lactone antioxidant is not particularly limited as long as it is a compound containing a lactone structure, but an aromatic lactone compound is preferable. Among them, those having a benzofuranone skeleton are more preferable, and 3-arylbenzofuran-2-one having an aryl group as a substituent in the side chain of the furan ring is more preferable. As an example, 5,7-di-tert-butyl-3 -(3,4-Di-methylphenyl) -3H-benzofuran-2-one can be mentioned.

Examples of the light stabilizer include benzophenone light resistance stabilizer, benzotriazole light resistance stabilizer, hindered amine light resistance stabilizer (HALS) and the like, and HALS is particularly preferable.
Specific examples of 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) 6-tetramethyl-4-piperidyl) butylamine polycondensate, 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-4-piperidyl) and mole Polycondensate with oline-2,4,6-trichloro-1,3,5-triazine, poly [(6-morpholino-s-triazine-2,4-diyl) [(2,2,6,6, -Tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and other high molecular weight HALS in which a plurality of piperidine rings are bonded via a triazine skeleton A 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; A mixed ester product of 6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane. Of piperidine ring and the like high molecular weight HALS attached through an ester bond.

Examples of the light absorbent used in the present invention include an ultraviolet absorbent, a near infrared absorbent, an organic colorant, and an infrared absorbent.
The ultraviolet absorber is a compound having absorption in the ultraviolet region. Specific examples of the ultraviolet absorber include salicylic acid compounds such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy -4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- Benzophenone compounds such as methoxy-5-sulfobenzophenone and bis (2-hydroxy-4-methoxybenzoylphenyl) methane;

  2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′- Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′-( 3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] benzotriazol Benzotriazole-based compounds such as 2, 4-di-tert-butylphenyl-3 ′, 5′-di-tert-butyl-4′-hydroxybenzoate; 2-ethylhexyl-2-cyano- Cyanoacrylate compounds such as 3,3′-diphenyl acrylate and ethyl-2-cyano-3,3′-diphenyl acrylate; hindered amines such as bis (2,2,6,6-tetramethylpiperidinyl 4) sebacate Compounds; Organometallic compounds such as nickel bis (octylphenyl) sulfide and [2,2′-thiobis (4-tert-octylphenolate)]-n-butylamine nickel.

  There is no special limitation as a near-infrared absorber, The thing generally used conventionally as a compounding agent of transparent resin can be used. As a near-infrared absorber, in a solution in which 0.1 part by mass thereof is dissolved in 100 parts by mass of a solvent, a light transmittance with respect to a solvent is used in a part or all of a near-infrared wavelength region of 600 to 2500 nm. Those that are 50% or less, preferably 30% or less, are preferably used.

  Suitable compounds as near infrared absorbers include cyanine-based near infrared absorbers, pyrylium-based near infrared absorbers, squarylium-based near infrared absorbers, croconium-based near infrared absorbers, azulenium-based near infrared absorbers, phthalocyanine-based near infrared rays. Examples include an absorbent, a dithiol metal complex-based near infrared absorber, a naphthoquinone-based near infrared absorber, an anthraquinone-based near infrared absorber, an indophenol-based near infrared absorber, and an azimuth-based near infrared absorber.

  These near infrared absorbers are, for example, SIR-103, SIR-114, SIR-128, SIR-130, SIR-132, SIR-152, SIR-159, SIR-162 (above, manufactured by Mitsui Toatsu Dye Co., Ltd.) ), Kayasorb IR-750, Kayasorb IRG-002, Kayasorb IRG-003, IR-820B, Kayasorb IRG-022, Kayasorb IRG-023, Kayasorb CY-2, Kayasorb cCY-4, Kaysorb 9 Etc.) and are commercially available.

The organic colorant used in the present invention is not particularly limited as long as it is an organic colorant generally used by blending with a transparent resin.
Specific examples of the organic colorant include diarylide pigments such as pigment red 38; azo lake pigments such as pigment red 48: 2, pigment red 53, and pigment red 57: 1; pigment red 144, pigment red 166, and pigment red 220. Pigment Red 221 and Pigment Red 248; condensed azo pigments such as Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185 and Pigment Red 208; Quinacridone pigments such as Pigment Red 122; A perylene pigment such as Pigment Red 149, Pigment Red 178, and Pigment Red 179; and an anthraquinone pigment such as Pigment Red 177.

  Examples of infrared absorbers include polymethine dyes, squarylium dyes, thiol nickel complex salts, triallylmethane dyes, immonium dyes, diimmonium dyes, and organic dye compounds such as anthraquinone dyes. Suitable infrared absorbers include, for example, an immonium dye represented by the following formula (a), a diimonium dye represented by the formula (b) (only a cation moiety is shown), and the formula (c) And the like.

  The ultraviolet absorber and infrared absorber serve as a retardation adjusting agent. That is, as the organic functional agent, the resin composition of the present invention containing a dichroic retardation adjusting agent is formed into a film shape and stretched to align the major axis of the molecule in the stretching direction, and the stretching direction. And the light absorption in the direction orthogonal to the extending direction can be varied. Moreover, the retardation film which has arbitrary refractive indexes can be easily manufactured by changing the addition amount of the said retardation regulator. For example, when this retardation film is used for an antireflection film of a reflection type liquid crystal display device in which tolerance of wavelength fraction is severe, coloring of the screen can be prevented. Note that the retardation adjusting agent having dichroism refers to those having different light absorption between the major axis and the minor axis of the molecule.

  Further, it is known from the Kramers-Kronig relational expression that the refractive index changes greatly in the vicinity of the maximum absorption wavelength region of light. That is, it has been shown that a stretched film to which a retardation adjusting agent having dichroism is added can change the refractive index in the direction of stretching and the refractive index in the direction perpendicular to the two stretching directions. When a dichroic retardation adjusting agent having a maximum absorption wavelength of 350 nm is added to a stretched film having a refractive index anisotropy, the refractive index in the stretching direction increases only for light having a wavelength near 350 nm. The phenomenon to be seen is seen. As a result, this stretched film has a large difference (Δn) between the refractive index in the stretching direction and the refractive index in the direction orthogonal to the stretching direction for light having a wavelength near 350 nm, and the retardation defined by Δn × d Will grow.

  The antistatic agent is not particularly limited, and various known ones can be used. Specifically, Bontron N-01 (manufactured by Orient Chemical Co., Ltd.), Nigrosine Base EX (manufactured by Orient Chemical Co., Ltd.), Spiron Black TRH (manufactured by Hodogaya Chemical Co., Ltd.), T-77 (manufactured by Hodogaya Chemical Co., Ltd.) Bontron S-34 (manufactured by Orient Chemical Industries), Bontron E-81 (manufactured by Orient Chemical Industries), Bontron E-84 (manufactured by Orient Chemical Industries), COPY CHARGE NX (manufactured by Clariant), COPY CHARGE NEG ( Quaternary ammonium (salt) group-containing copolymers described in JP-A-11-15192, JP-A-3-175456, JP-A-3-243594, etc. Japanese Laid-Open Patent Publication No. 3-243954, Japanese Laid-Open Patent Publication No. 1-221764, Japanese Laid-Open Patent Publication No. 3-15858 Sulfonic acid (salt) group-containing copolymer antistatic agent such as (charge control resin) and the like according to etc..

  Lubricants include hydrocarbon lubricants such as liquid paraffin, paraffin wax, microcrystalline wax and polyolefin wax; fatty acid lubricants such as stearic acid, behenic acid and 12-hydroxystearic acid; higher alcohols such as cetyl alcohol and stearyl alcohol Lubricants: Fatty acid amide type lubricants such as stearic acid amide, oleic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide; Fatty acid ester type lubricating agents such as butyl stearate, monoglyceride stearate, pentaerythritol tetrastearate, hydrogenated castor oil Metal soap-type lubricants such as calcium stearate, zinc stearate, magnesium stearate; Of these, hydrocarbon lubricants, fatty acid amide lubricants, and fatty acid ester lubricants are preferred. Further, among these, those having a melting point of 80 to 150 ° C. and an acid value of 10 mgKOH / mg or less are particularly preferable. When the melting point exceeds 80 to 150 ° C. and the acid value becomes larger than 10 mgKOH / mg, the haze value tends to increase.

  The refractive index adjusting agent is an additive that gives a refractive index higher or lower than that of the resin alone when added to the resin. As the refractive index adjusting agent, the molecular weight of the refractive index adjusting agent is not particularly limited as long as it provides a desired refractive index distribution and can stably coexist with the resin.

  Examples of the refractive index adjusting agent include diphenyl sulfide (n = 1.635), vinyl benzoate (n = 1.579), benzyl methacrylate (n = 1.568), hexyl acetate (n = 1.408), Bis (3,5,5-trimethylhexyl) phthalate (n = 1.478) can be preferably used.

  In the present invention, as the organic functional agent, a retardation increasing agent disclosed in European Patent 0911656A2, Japanese Patent Application Laid-Open No. 2000-1111914, Japanese Patent Application Laid-Open No. 2000-275434, PCT / JP00 / 02619, or the like. It can also be used. The retardation increasing agent may be used alone or in combination of two or more compounds.

  The retardation increasing agent used for this invention is compoundable with reference to the synthesis method of literature description. As for the synthesis method, many documents (for example, Mol. Cryst. Liq. Cryst., 53, 229 (1979), 89, 93 (1982), 145, 111 (1987). 170, 43 (1989), J. Am. Chem. Soc., 113, 1349 (1991), 118, 5346 (1996), 92, 1582 (1970). J. Org. Chem., 40, 420 (1975), Tetrahedron, 48, 16 (3437) (1992)).

  The present invention is characterized in that an organic functional agent is supported on an inorganic filler. By supporting the organic functional agent on the inorganic filler, it becomes possible to prevent aggregation of the organic functional agent in the resin. The loading method here is not particularly limited as long as it is a loading method having sufficient strength to prevent aggregation of the organic functional agent and sufficient stability under actual use conditions, but the strength and stability of the loading. From the viewpoint of property, it is preferable to support by chemical bond rather than support by physical bond, and it is particularly preferable to intercalate with an inorganic layered compound.

  Examples of the method of supporting by chemical bonding include, for example, a method in which the functional group of the organic functional agent is bonded to the functional group present on the surface of the inorganic filler by ionic bonding or hydrogen bonding, silane coupling agent or titanate coupling. The functional group of the organic functional agent is bonded to the functional group present on the surface of the inorganic filler by a covalent bond, and the organic function is present on the functional group present on the surface of the inorganic filler. There is a method in which functional groups such as sulfide, phosphorus atom, nitrogen atom, carboxylic acid, etc. of the agent are bonded and carried by a coordinate bond.

  In the present invention, it can be confirmed by the following method that the organic functional agent is supported on the inorganic filler. A resin composition in which only an organic functional agent is added to the resin and a resin composition in which an inorganic filler and an organic functional agent are added to the resin are manufactured, and the dispersion state of each organic functional agent in the resin is visually observed. Alternatively, it can be confirmed by comparing the aggregation / dispersion state of the organic functional agent with an optical microscope, an electron microscope or the like. It can be understood that the organic functional agent is not aggregated by the addition of the inorganic filler, whereby the organic functional agent is supported on the inorganic filler and dispersed in the resin.

(4) Resin composition When the inorganic filler used in the resin composition of the present invention is a layered crystal compound, in order to improve the dispersibility in the resin, before blending the resin and the layered compound, the layered crystal It is preferable to organically treat the compound. In selecting the inorganic filler and the organic functional agent to be used in the resin composition of the present invention, each other is covalently bonded, ion-bonded, hydrogenated so that the organic functional agent is sufficiently stably supported on the inorganic filler. It is preferable to select a combination having binding properties, coordination binding properties, and intercalation properties.

As a method of blending these to produce a resin composition, for example, (i) a resin, an inorganic filler, and various functional agents are used using a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, a kneader, and the like. There are a melt mixing method, (ii) a method of blending a resin, a filler and various additives in a solution. Among these, since the dispersibility of the filler can be improved, the method (ii) is preferable, and a layered silicate / organic solvent / organic function using a plunger pump or the like in the above melting process. A method of injecting the mixture of the agent / resin and melt-kneading while removing the organic solvent is preferable. In the case of the method (i), it is particularly preferable to use a kneader with high shear efficiency.

  Although there is no particular limitation on the composition ratio of the resin, the inorganic filler, and the organic functional agent in the resin composition of the present invention, when the total amount of the resin and the inorganic filler is 100 parts by mass, the inorganic filler is Usually, it is 0.01-50 mass parts, Preferably, it is 0.5-30 mass parts, More preferably, it is 1-20 mass parts. If the blending amount of the inorganic filler is less than 0.01 part by mass, the dispersion effect of the organic functional agent may not be sufficient, and if it exceeds 50 parts by mass, the transparency and surface properties may be impaired. Content of an organic functional agent is 0.01-30 mass%, 0.1-20 mass% is preferable, and 0.1-10 mass% is especially suitable. When the content of the organic functional agent is less than 0.01% by mass, the improvement effect by the functional agent such as light stability and infrared absorption ability is poor. On the other hand, when it exceeds 30% by mass, the dispersion state of the resin composition is hindered, which may cause deterioration in physical properties or poor appearance.

  The resin composition of the present invention is excellent in transparency and is suitable as an optical material as described later. The resin composition of the present invention is characterized in that when formed into a molded body, the haze value at an optical path length of 1 mm is 10% or less, preferably 5% or less, particularly preferably 1% or less. The haze value (%) is expressed as a percentage of the transmitted light measured in accordance with JIS K7136, which is shifted by 0.04 rad (2.5 degrees) or more from the incident light due to forward scattering. When a resin composition having a haze of 10% or less at an optical path length of 1 mm when formed into a molded product is used in an optical product, uniform brightness with little scattered light can be ensured.

  The resin composition of the present invention can be molded by a method according to the application, such as an injection molding method, a press molding method, or a cast molding method, utilizing its thermoplasticity. Further, it is possible to form a film from a solution by utilizing the solvent solubility.

2) Optical Material The resin composition of the present invention is particularly suitable as a molding material for optical members that transmit light due to its excellent optical properties. For example, it is used for an optical member in an optical device having a mechanism that transmits light containing a wavelength component of 350 to 650 nm including the visible region. Especially, the resin composition of this invention is suitable as various optical materials for various display elements, such as a display, especially a liquid crystal display element use (for example, liquid crystal display panel), an optical lens use, etc.

  Specific examples of the optical member using the optical material of the present invention are illustrated in more detail. Various lenses such as spectacle lenses, optical connector microlenses, and light-emitting diode condensing lenses, optical switches, optical fibers, and optical branching in optical circuits. , Optical communication parts such as junction circuits, optical multiplex branch circuits, luminous intensity adjusters, various display members such as liquid crystal substrates, touch panels, light guide plates, phase difference plates, optical disc substrates, optical disc films and coatings Various applications such as recording applications, functional films, antireflection films, optical multilayer films (selective reflection films, selective transmission films, etc.), super-resolution films, ultraviolet absorption films, reflection control films, optical waveguides, and identification function printing surfaces Examples include optical film and coating applications.

3) Optical film The optical film of the present invention is formed by molding the resin composition of the present invention into a film.
The optical film of the present invention is used as a member of an optical device such as a liquid crystal display device, an organic EL element, a plasma display, or a projector. Specifically, an IR cut filter, a retardation film, a polarizing plate protective film, a film for a liquid crystal cell substrate, a liquid crystal display element substrate, a touch panel substrate, or a raw film thereof can be used. These films may be used by laminating an antireflection film, an antiglare film, a hard coat layer, an antifouling layer, a transparent conductive film or the like as a post process by a dry method or a wet method.

  The method for producing the optical film of the present invention is not particularly limited as long as it is obtained by molding the resin composition of the present invention into a film, and a known molding method can be adopted. For example, extrusion molding methods such as T-die method and inflation method; blow molding method; calendar molding method; injection molding method;

[Production Example 1] Production of alicyclic structure-containing polymer having no polar group In a nitrogen atmosphere, 500 parts by mass of dehydrated cyclohexane, 0.82 parts by mass of 1-hexene, 0.15 parts by mass of dibutyl ether and triisobutylaluminum 0.30 part by mass was placed in a reactor, mixed at room temperature, and then maintained at 45 ° C. while maintaining tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (tetracyclododecene, hereinafter abbreviated as “TCD”) 80 parts by mass, 7,8-benzotricyclo [4.3.0.1 ^2,5 ] deca 120 parts by mass of -3-ene (methanotetrahydrofluorene, hereinafter abbreviated as “MTF”) and 80 parts by mass of tungsten hexachloride (0.7 mass% toluene solution) were continuously added over 2 hours. Polymerized. A polymerization reaction solution containing a ring-opening polymer was prepared by adding 1.06 parts by mass of butyl glycidyl ether and 0.52 parts by mass of isopropyl alcohol to inactivate the polymerization catalyst to stop the polymerization reaction. Obtained.

  Next, 270 parts by mass of cyclohexane is added to 100 parts by mass of the polymerization reaction solution containing the obtained ring-opening polymer, and further 5 parts by mass of a nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) is added as a hydrogenation catalyst. The reaction solution containing 20% by mass of TCD / MTF ring-opening copolymer hydride was obtained by pressurizing to 5 MPa, heating to 200 ° C. with stirring, and reacting for 4 hours. After the resulting reaction solution was filtered to remove the hydrogenation catalyst, an antioxidant (manufactured by Ciba Specialty Chemicals, Irganox 1010) was added to 100 parts by mass of the hydrogenated TCD / MTF ring-opening copolymer. It added and dissolved in the reaction solution obtained by filtration so that it might become 0.1 mass part.

  Subsequently, a TCD / MTF ring-opening copolymer hydride was extruded in a molten state while removing cyclohexane and other volatile components at 270 ° C. and 1 kPa or less using a cylindrical concentration dryer (manufactured by Hitachi, Ltd.). Were extruded into strands, cooled, and pelletized to produce pellets. The thus-produced hydride of TCD / MTF ring-opening copolymer, which is an example of an alicyclic structure-containing polymer having no polar group, has a weight average molecular weight of 34,000 and a hydrogenation rate of 99. 0.9% and the glass transition point was 160 ° C.

[Production Example 2] Production of polymer containing polar group-containing alicyclic structure Under nitrogen atmosphere, dehydrated cyclohexane (500 parts by mass), 1-hexene (0.82 parts by mass), dibutyl ether (0.15 parts by mass) and triisobutylaluminum (0) .30 parts by mass in a reactor, mixed at room temperature, and then kept at 45 ° C. while maintaining 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter abbreviated as “ETCD”) 100 parts by mass and 40 parts by mass of tungsten hexachloride (0.7 mass% toluene solution) were continuously added over 2 hours. And polymerized. A polymerization reaction solution containing a ring-opening polymer was prepared by adding 1.06 parts by mass of butyl glycidyl ether and 0.52 parts by mass of isopropyl alcohol to inactivate the polymerization catalyst to stop the polymerization reaction. Obtained.

  Next, 270 parts by mass of cyclohexane is added to 100 parts by mass of the polymerization reaction solution containing the obtained ring-opening polymer, and further 5 parts by mass of a nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) is added as a hydrogenation catalyst. The reaction solution containing 20% by mass of ETCD ring-opening polymer hydride was obtained by pressurizing to 5 MPa, heating to 200 ° C. with stirring, and reacting for 4 hours. After the resulting reaction solution was filtered to remove the hydrogenation catalyst, an antioxidant (Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added in an amount of 0.1 to 100 parts by mass of the ETCD ring-opening polymer hydride. It added and dissolved in the reaction solution obtained by filtration so that it might become a mass part.

  Subsequently, using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), the ETCD ring-opening polymer hydride was melted from the extruder in a strand state while removing cyclohexane and other volatile components at 270 ° C. and 1 kPa or less. And cooled, and pelletized to produce pellets. The weight average molecular weight of the ETCD ring-opening polymer hydride which is an example of the alicyclic structure-containing polymer having no polar group thus produced is 40,000, the hydrogenation rate is 99.9%, The glass transition point was 138 ° C.

10 parts by weight of maleic anhydride, 3 parts by weight of dicumyl peroxide and 230 parts by weight of tert-butylbenzene were mixed with 100 parts by weight of the ETCD ring-opening polymer hydride thus obtained, and 135 ° C. in an autoclave. The mixture was reacted for 6 hours, and then precipitated by adding it in a large amount of isopropyl alcohol, followed by filtration to obtain a resin. This resin was dried at 100 ° C. and 0.1 kPa or less for 48 hours to obtain 105 parts by mass of a maleic anhydride-modified ETCD ring-opening polymer hydride, which is an example of an alicyclic structure-containing polymer having a polar group. This maleic anhydride-modified ETCD ring-opening polymer hydride had a weight average molecular weight of 65,000, a glass transition point of 135 ° C., and a maleic anhydride modification amount measured by ¹ H-NMR of 0.45 mmol / g.

[Production Example 3] Production of organically treated montmorillonite 100 parts by mass of montmorillonite (layered silicate, average major axis 0.1 μm) was uniformly dispersed in 1,000 parts by mass of distilled water at 60 ° C. to prepare a montmorillonite dispersion. Next, while stirring this montmorillonite dispersion, a solution prepared by dissolving 20 parts by mass of dimethyl distearyl ammonium chloride in 300 parts by mass of distilled water was slowly added, and stirring was continued at 60 ° C. for 3 hours, followed by filtration. The solid was separated. The solid was added to 500 parts by mass of distilled water at 60 ° C. and dispersed again, and then filtered again to separate the solid. After repeating this dispersion and filtration three times, moisture was removed by freeze drying to produce an organically treated montmorillonite.

[Example 1]
40 parts by mass of an alicyclic structure-containing polymer having no polar group produced by Production Example 1, 5 parts by mass of an alicyclic structure-containing polymer having a polar group produced by Production Example 2, and a phthalocyanine-based organic functional agent In a suspension obtained by dispersing 0.5 parts by mass of a pigment (trade name: IR-12, manufactured by Nippon Shokubai Co., Ltd.) in an amount of 0.5 parts by mass of an organically treated montmorillonite produced in Production Example 3 in 450 parts by mass of toluene. In addition, using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), while excluding toluene at 270 ° C. and 1 kPa or less, it was extruded into a strand from the extruder in a molten state, cooled, pelletized, and alicyclic Structure-containing polymer composition 1 was produced.

[Example 2]
A pellet-shaped alicyclic ring in the same manner as in Example 1 except that the organic functional agent in Example 1 was changed to 0.5% by mass of the light stabilizer hindered amine compound (trade name: Tinuvin 622-LD, manufactured by Ciba-Gaiky). Structure-containing polymer composition 2 was produced.

[Comparative Example 1]
A pellet-shaped alicyclic structure-containing polymer composition 3 was produced in the same manner as in Example 1 except that the organically treated montmorillonite was not used in Example 1.

[Comparative Example 2]
A pellet-like alicyclic structure-containing polymer composition 4 was produced in the same manner as in Example 2 except that the organically treated montmorillonite was not used in Example 2.

[Comparative Example 3]
In a small twin-screw extruder, 40 parts by mass of the alicyclic structure-containing polymer produced by Production Example 1 and having no polar group, 5 parts by mass of the alicyclic structure-containing polymer produced by Production Example 2 and As an organic functional agent, 0.5 parts by mass of a phthalocyanine dye (trade name: IR-12, manufactured by Nippon Shokubai Co., Ltd.) and 0.5 parts by mass of the organically treated montmorillonite produced by Production Example 3 are fed at a set temperature of 200 ° C. The extruded strand was pelletized with a pelletizer to produce pellet-shaped alicyclic structure-containing polymer composition 5.

[Comparative Example 4]
In the same manner as in Comparative Example 3 except that 0.5 parts by mass of a hindered amine compound (trade name: Tinuvin 622-LD, manufactured by Ciba Gaiky), which is a light stabilizer, was used as the organic functional agent in Comparative Example 3, A ring structure-containing polymer composition 6 was produced.

Physical property evaluation test of resin composition (1)
The pellets of the alicyclic structure-containing polymer compositions 1 to 6 obtained in Examples 1 and 2 and Comparative Examples 1 to 4 were each hot-pressed to prepare molded bodies having a thickness of 1 mm. Using the obtained molded body, the haze value was measured using an automatic digital haze meter (UDH-20D, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JISK7136. Further, the dispersion state of the organically treated montmorillonite was observed with a transmission electron microscope. The measurement results of the haze value and the results are summarized in Table 1.
In the column of the organic functional agent in Table 1, A is a phthalocyanine-based dye (trade name: IR-12, manufactured by Nippon Shokubai Co., Ltd.), and B is a hindered amine-based compound (trade name: Tinuvin 622-LD, manufactured by Ciba-Gaiky). Represent.

  From Table 1, it can be seen that in the examples, the organic functional agent is supported on montmorillonite which is an inorganic filler. When the montmorillonite, which is an inorganic filler, is dispersed in an alicyclic structure-containing polymer resin having a length of 100 nm and a thickness of 2 nm (Examples 1 and 2), a molded product having a small haze value (1%). was gotten. On the other hand, when an inorganic filler is not used (Comparative Examples 1 and 2), or when montmorillonite as a filler is dispersed in an alicyclic structure-containing polymer resin with a length of 600 nm and a thickness of 10 nm (comparison) In Examples 3 and 4, a molded product having a large haze value (13 to 20%) and poor transparency was obtained.

Physical property evaluation test of resin composition (2)
Using an injection molding machine (SG-75, manufactured by Sumitomo Heavy Industries, Ltd.), pellets of the alicyclic structure-containing polymer compositions 1 to 6 obtained in Examples 1 and 2 and Comparative Examples 1 to 4 have a resin temperature of 300. An optical lens having an outer diameter of 7.4 mmΦ, a lens surface thickness of 2.7 mm, and a peripheral portion thickness of 3.0 mm was obtained by injection molding at a temperature of 0 ° C., a mold temperature of 130 ° C., and a pressure of 50 kg / cm ² . This lens was evaluated for optical distortion due to birefringence.
Optical distortion due to birefringence in a portion having a radius of 3 mm or less from the center of the molded product was placed between polarizing plates on which a crossed Nicol was placed on a white light source, and visually observed from above and evaluated. The case where the whole was black to gray and no color was applied and the optical distortion was sufficiently small was evaluated as ◯, and the case where there was a colored striped pattern or a leak of dotted transmission light and the optical distortion was large was evaluated as x. The evaluation results are summarized in Table 2.

  From Table 2, birefringence is obtained by using a resin composition (Examples 1 and 2) in which montmorillonite as a filler is dispersed in an alicyclic structure-containing polymer resin with a length of 100 nm and a thickness of 2 nm. An optical lens with less optical distortion was obtained. In contrast, a resin in which a filler is not used (Comparative Examples 1 and 2), or a montmorillonite as a filler is dispersed in an alicyclic structure-containing polymer resin with a length of 600 nm and a thickness of 10 nm. When the composition (Comparative Examples 3 and 4) was used, an optical lens having a colored stripe pattern or spot-like transmitted light leakage and large optical distortion was obtained.

[Example 3]
The molded body obtained in Example 1 was evaluated for transparency in the visible light region and near infrared absorption ability (spectral absorption spectrum measurement at a wavelength of 200 to 1000 nm). The spectral absorption spectrum measurement results are shown in FIG. As shown in FIG. 1, a molded article having flat and excellent absorption in the visible region from a wavelength of 400 nm to 600 nm and a steep absorption at a wavelength of 700 nm or more was obtained.

Further, the molded article obtained in Example 2, using a fade meter, change in hue after 200 hours irradiation in the ultraviolet irradiance 2 mJ / m ² ultraviolet long life carbon arc lamp (.DELTA.YI) a color difference meter (manufactured by Suga Test Machine). It had excellent weather resistance at ΔYI = 2 before and after irradiation.

It is a figure which shows the spectral absorption spectrum measurement result in the wavelength 200nm to 1000nm of the molded object obtained in Example 1. FIG.

Claims (8)

  A resin and an inorganic filler dispersed in the resin, the inorganic filler carrying an organic functional agent, and having a haze value of 10% or less at an optical path length of 1 mm of the resin composition molded body. A resin composition characterized.   The resin composition according to claim 1, wherein the inorganic filler is an inorganic layered compound having a length of 500 nm or less or inorganic fine particles having a number average particle diameter of 20 nm or less.   The resin composition according to claim 1, wherein the organic functional agent is a light absorber or a light stabilizer.   The resin composition according to any one of claims 1 to 3, wherein the organic functional agent is covalently bonded, ionic bonded, coordinated bonded, or hydrogen bonded to the inorganic filler.   The resin composition according to any one of claims 1 to 4, wherein the resin is an alicyclic structure-containing polymer.   The resin composition according to claim 1, wherein the resin is an alicyclic structure-containing polymer having a polar group.   An optical material comprising the resin composition according to claim 1. The optical film formed by shape | molding the resin composition in any one of Claims 1-6 in a film form.

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