JP2005307190A - Thermoplastic resin composition and the method for producing the same, and molded article comprising thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition in which phosphorus atoms containing nanoparticles such as a phosphate having ultraviolet absorption, and pyrophosphate particles dispersed finely in a thermoplastic resin matrix, and having excellent light resistance, heat stability, mechanical strength, molding surface smoothness and transparency. <P>SOLUTION: The thermoplastic resin composition comprising (A) a thermoplastic resin, (B) a nanoparticle, which is an ultraviolet absorption particle, containing a phosphorus atom, or an ultraviolet absorption particle (C-1) containing the particle and a dispersing agent. Alternatively, the thermoplastic resin composition comprises (A) the thermoplastic resin, (B) the ultraviolet absorption particle comprising the pyrophosphate particle represented by the composition formula: Ce<SB>1-n</SB>Ti<SB>n</SB>P<SB>2</SB>O<SB>7</SB>, and/or the ultraviolet absorption particle (C-1) containing the pyrophosphate particle and the dispersing agent. Alternatively, the thermoplastic resin composition comprises (A) the thermoplastic resin, an ultraviolet absorption particle (C-2) comprising the phosphates and the dispersing agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition containing phosphates or pyrophosphate particles having excellent light resistance, thermal stability, mechanical strength, and transparency. The present invention further relates to a method for producing the thermoplastic resin composition and a molded body comprising the same.

  Conventionally, in order to improve the light resistance of a thermoplastic resin, an inorganic oxide ultraviolet absorber such as titanium oxide, cerium oxide, or zinc oxide is contained in the thermoplastic resin. However, these inorganic oxide ultraviolet absorbers themselves have a function as a photocatalyst or a thermal catalyst. Therefore, the thermoplastic resin composition containing these inorganic oxide ultraviolet absorbers has problems such as degradation of the resin due to photocatalytic activity during light irradiation, and degradation of the resin due to thermal catalytic activity during thermoplastic molding of the resin. Therefore, improvement is desired.

On the other hand, amorphous pyrophosphate having a composition of Ce _1-n Ti _n P ₂ O ₇ (where n is an arbitrary number of 0 to 1 representing a metal composition) changes the ultraviolet absorption ability (the ratio of Ce and Ti). Therefore, it is known that the ultraviolet absorption wavelength is variable (for example, see Non-Patent Document 1). The particle size distribution of the primary particles of the amorphous pyrophosphate is 15 to 30 nm. As the light absorptivity, although there is an absorption band on the short wavelength side in the light absorption curve in the visible light region, it is relatively excellent in transparency. Since the refractive index is small compared to titanium oxide and zinc oxide, which are general-purpose inorganic ultraviolet absorbers, high transparency can be maintained when dispersed in an organic medium, and refraction is achieved by changing the composition ratio of Ce and Ti. The rate can be varied in the range of about 1.6-2. In addition, amorphous pyrophosphate has many excellent features such as extremely low photocatalytic activity and thermal catalytic activity, and does not contain highly toxic elements, so it can be dispersed in organic media such as cosmetics that require sunscreen properties. It is expected to be used for applications that

  There is no known example of blending the above amorphous pyrophosphate with a resin for the purpose of improving the light resistance of a thermoplastic resin. The above amorphous pyrophosphate can only be isolated as agglomerated particles having a number average particle size of 50 nm or more in which primary particles having a particle size distribution of 15 to 30 nm are secondarily aggregated, Even when blended with a resin or the like, it is difficult to obtain a resin composition having excellent mechanical strength and transparency.

  Incidentally, certain types of phosphates (for example, pyrophosphates, titanium phosphates, zirconium phosphates, apatites, etc.) exhibit ultraviolet absorptivity. Since the photocatalytic activity or thermal catalytic activity of such phosphates is smaller than that of the inorganic oxide ultraviolet absorber, it is considered to improve the light resistance of the thermoplastic resin by using such phosphates as the ultraviolet absorber. It is done.

For example, as a known technique, a thermoplastic resin composition of hydroxyapatite fine particles is disclosed (Patent Document 1). However, according to the study by the present inventors, the method disclosed by this technique does not use a dispersant, so that the short diameter (diameter in the case of a fiber and thickness in the case of a flake) is several tens of nm. Since the hydroxyapatite fine particles cannot be sufficiently peptized (disaggregated) and dispersed, it is inevitable that the aggregated particles have a short diameter of several μm, and the toughness, transparency of the resin composition, In some cases, molding surface smoothness and the like were impaired.

  In addition, when inorganic particles selected from the group consisting of metal oxides and metal salts of oxygen acids (for example, phosphates) are mechanically pulverized in an organic solvent, an acidic compound such as an organic phosphoric acid is added to the organic solvent. A method for pulverizing inorganic particles characterized by coexisting as a dispersant is disclosed (Patent Document 2). However, this technique cannot finely disperse the crushed inorganic particles applied to the thermoplastic resin to obtain a thermoplastic resin composition having excellent mechanical strength, molded surface smoothness and transparency.

Nobuhito IMANAKA, 3 others, “Amorphous Celium-Titanium Solid Solution Phosphate as a Novel Family of Band Gap Tunable Sunscreen Materials ", Chemistry of Materials (USA), June 17, 2003, Vol. 15, No. 12, p. 2289-2291 International Publication 2002/033004 Pamphlet JP 2004-283822 A

  The present invention has been made in view of the above circumstances, and its purpose is to finely disperse phosphorus atom-containing nanoparticles such as pyrophosphate and phosphate particles having ultraviolet absorptivity in a thermoplastic resin matrix, The object is to provide a thermoplastic resin composition having excellent light resistance, thermal stability, mechanical strength, molding surface smoothness and transparency.

  Another object of the present invention is to provide a method for producing the above thermoplastic resin composition and a molded article comprising the same. Another object is to provide a novel dispersant used to make it possible to highly disperse ultraviolet-absorbing nanoparticles with a thermoplastic resin.

As a result of intensive studies, the present inventors have determined that the thermoplastic resin has a composition formula Ce _1-n Ti _n P ₂ O ₇ having an ultraviolet absorptivity (where n represents a metal composition and any number from 0 to 1). UV absorption particles comprising pyrophosphate particles or phosphate particles represented by) or UV absorbing particles containing the pyrophosphate particles or phosphate particles and a dispersant are included to absorb UV. It was found that a thermoplastic resin having high performance and excellent light resistance, thermal stability, mechanical strength, molding surface smoothness and transparency can be obtained. In the present invention, when the term “phosphate particles” is simply used, it means the concept of excluding the pyrophosphate particles.

  That is, the first gist of the present invention is that the thermoplastic resin (A), the ultraviolet absorbing particles and the nanoparticles (B) containing phosphorus atoms, or the ultraviolet absorbing particles containing the particles and a dispersing agent. A thermoplastic resin composition comprising (C-1).

The second aspect of the present invention, the thermoplastic resin (A), represented by the composition formula _{Ce 1-n Ti n P 2} O 7 ( where n is any number of 0 to 1. representing the metal composition) pyrophosphate A thermoplastic resin composition comprising ultraviolet absorbing particles (B) comprising acid salt particles and / or ultraviolet absorbing particles (C-2) containing the pyrophosphate particles and a dispersant. Exist.

  The third gist of the present invention is a method for producing the above thermoplastic resin composition, which is obtained by crushing particles that contain ultraviolet atoms and that contain phosphorus atoms in the presence of a dispersant. A method for producing a thermoplastic resin composition, comprising preparing particles and mixing the ultraviolet-absorbing particles with a raw material for producing a thermoplastic resin, a reaction mixture of the raw material for production, and / or the obtained thermoplastic resin. Exist.

  The fourth gist of the present invention is a method for producing the thermoplastic resin composition described above, which comprises a step of mixing ultraviolet absorbing particles and nanoparticles containing phosphorus atoms in a solution of the thermoplastic resin. It exists in the manufacturing method of the thermoplastic resin composition characterized by having.

  The fifth gist of the present invention resides in a molded body made of the thermoplastic resin composition having a thickness of 0.001 to 100 mm.

  The sixth gist of the present invention resides in aromatic phosphate esters represented by any one of the following general formulas (1) to (6).

In general formulas (1) to (6), m and n are independently a natural number of 2 or less, R ¹ is an alkyl group having 12 or less carbon atoms, an aryl group having 12 or less carbon atoms, or an alkoxy having 12 or less carbon atoms. any group or more than 12 aryloxy group having a carbon, R x ^(where x is a natural number of 2 to 5) each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 12 or less carbon atoms, R ⁶ is An alkyl group or an aryl group having 12 or less carbon atoms, R is a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms, L is a carbonyl group (-CO-), a sulfide bond (-S-), a sulfoxide bond (-SO -) and a sulfone bond (-SO ₂ - one of) represent respectively.

  The seventh gist of the present invention resides in the ultraviolet-absorbing particles surface-treated with any of the above-mentioned aromatic phosphates.

  In the thermoplastic resin composition of the present invention, instead of inorganic oxide ultraviolet absorbers such as titanium oxide, cerium oxide, and zinc oxide, which have been used to improve light resistance, phosphorus atoms having ultraviolet absorptivity are used. Since it contains nanoparticles (for example, phosphate particles, pyrophosphate particles, etc.), it has excellent light resistance, thermal stability, mechanical strength, molding surface smoothness and transparency.

Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents. The thermoplastic resin composition of the present invention comprises a thermoplastic resin and nanoparticles that are UV-absorbing particles and contain phosphorus atoms (for example, phosphate particles or a composition formula Ce _1-n Ti _n P ₂ O ₇ ( However, n contains the ultraviolet absorptive particle | grains containing the pyrophosphate particle | grains represented by the arbitrary number of 0 or more and 1 or less showing a metal composition.

(1) Thermoplastic resin:
The thermoplastic resin can be any one of injection molding, extrusion molding, and hot press molding, as long as it is a thermoplastic resin monomer unit (polymer repeating unit) chemical structure, terminal There are no particular restrictions on the chemical structure, molecular weight and branched structure of the group, and any thermoplastic resin can be used. The thermoplastic resin may contain a cross-linked polymer component as long as it retains its thermoplasticity (property that can be softened by heating), and two or more (chemical structure, molecular weight, branched structure, etc.) A mixture of thermoplastic resins).

Thermoplastic resins include acrylic resins, styrene resins, polypropylene resins, polyethylene resins, polycycloolefin resins, and other amorphous polyolefin resins, aromatic polycarbonate resins, polyarylate resins, polyester resins, polyamide resins, polyphenylene ether resins, poly Examples include arylene sulfide resin, polyacetal resin, cellulose acetate resin, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer resin, vinyl chloride resin, and fluorine resin, and preferably acrylic resin, styrene resin, polycycloolefin resin, aromatic Polycarbonate resin, polyarylate resin, polyester resin having a deflection temperature under load of 455 kPa according to ASTM standard D648 in the range of 50 to 130 ° C., and A polypropylene resin. When a thermoplastic resin having high transparency in the visible wavelength region is selected, a thermoplastic resin having a light transmittance of 80% or more, preferably 90% or more according to ASTM standard D1003 may be selected. Hereinafter, a suitably used thermoplastic resin will be described.

acrylic resin:
Examples of the acrylic resin include homopolymers or copolymers of acrylic acid derivatives such as acrylic acid or its esters, methacrylic acid or its esters, acrylamides, methacrylamides, acrylonitrile, methacrylonitrile and the like. Examples of the acrylic acid derivatives are described in, for example, “Plastic Materials Course” Vol. 16 published by Nikkan Kogyo Shimbun, and are typically methyl acrylate, ethyl acrylate, butyl acrylate, phenyl acrylate, methacrylic acid. Methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, norbornane methyl methacrylate, norbornene methyl methacrylate, adamantyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, phenyl methacrylate, acrylamide, methacrylamide, N-Iro Examples include propylacrylamide, N, N-dimethylacrylamide, acrylonitrile, methacrylonitrile and the like, and these monomers may be used in one kind of homopolymerization or in plural kinds of copolymerization.

  There is no restriction | limiting in particular in the manufacturing method of an acrylic resin, It can manufacture by radical polymerization and ionic polymerization by arbitrary polymerization methods, such as well-known block polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Typical acrylic resins include polymethyl methacrylate (PMMA), polycyclohexyl methacrylate (PCHM), polyethyl acrylate, methyl methacrylate-cyclohexyl methacrylate copolymer, and the like. A combination of more than one species may be used. From the viewpoint of light transmittance and mechanical properties, PMMA resin is particularly preferable.

  The molecular weight of the acrylic resin is not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is usually 10,000, such as the quality of PMMA resin described in the reagent catalog of Aldrich. It is preferable that the weight average molecular weight Mw is 20,000 to 800,000 from the viewpoints of mechanical properties and melt fluidity. The stereoregularity of the polymer can be random, isotactic, syndiotactic or the like, but is not particularly limited.

Styrene resin:
Examples of the styrene resin include a homopolymer of a styrene derivative and a copolymer resin of a styrene derivative as a main component and a vinyl compound copolymerizable therewith. Examples of the styrene derivative include aromatic vinyl compounds such as styrene, α-methylstyrene, p-chlorostyrene, p-methylstyrene, and vinylnaphthalene. A rubber component may coexist in the polymerization of the aromatic vinyl compound. Typical styrene resins include polystyrene (PS resin), poly (α-methylstyrene), styrene-acrylonitrile copolymer (SAN resin), styrene-methyl methacrylate copolymer (MS resin), and the like. These may be used alone or in combination of two or more. Among these, MS resin is very preferable as a matrix resin when used as a raw material for a diffusion plate used in a direct liquid crystal display such as a liquid crystal television.

  There is no restriction | limiting in particular as a manufacturing method of a styrene resin, It can manufacture by radical polymerization by arbitrary polymerization methods, such as well-known block polymerization, suspension polymerization, block-suspension polymerization, and emulsion polymerization. The molecular weight of the styrene resin is not particularly limited, but the weight average molecular weight Mw measured by GPC is usually 10,000 to 1,000,000, and the weight average molecular weight Mw is 20 from the viewpoint of mechanical properties and melt fluidity. It is preferable that it is 1,000,000-800,000. The stereoregularity of the polymer can be random, isotactic, syndiotactic or the like, but is not particularly limited.

Amorphous polyolefin resin:
The amorphous polyolefin resin is a resin obtained by coordination polymerization, metathesis polymerization, radical polymerization or the like of hydrocarbons containing carbon-carbon multiple bonds. Specifically, double bonds of ring-opening metathesis polymers of hydrogenated polystyrene, poly (4-methyl-1-pentene), poly (3-methyl-1-butene), polytetracyclododecenes, norbornenes And cyclocycloolefin polymers obtained by hydrogenation, polycycloolefin resins such as ethylene and norbornene hydrocarbon copolymers, and copolymers based on these structures (for example, hydrophilicity by copolymerization of polar monomers) Examples thereof include controlled copolymers). Examples of commercially available amorphous polyolefin resins include “Arton” manufactured by JSR, “ZEONEX” and “ZEONOR” manufactured by ZEON, and “APEL” manufactured by Mitsui Chemicals. And polycycloolefin resins such as “Zeonex” and “Zeonor” manufactured by ZEON are preferable.

  Although there is no restriction | limiting in particular in the molecular weight of an amorphous polyolefin resin, The weight average molecular weight Mw measured by a gel permeation chromatography (GPC) is 10,000-1,000,000 normally, Mechanical property and melt fluidity | liquidity In view of the above, the weight average molecular weight Mw is preferably 15,000 to 700,000. Moreover, when using a polycycloolefin resin, it is preferable from the point of light resistance and thermal stability that there are as few residual double bonds as possible.

Aromatic polycarbonate resin:
An aromatic polycarbonate resin is produced by reacting one or more bisphenols that can contain polyhydric phenols having three or more valences as copolymerization components with carbonate esters such as bisalkyl carbonates, bisaryl carbonates, and phosgene. Even if aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid or a derivative thereof (for example, aromatic dicarboxylic acid diester) is used as a copolymerization component to make an aromatic polyester carbonate if necessary. Good. Examples of bisphenols include bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, and bisphenol Z (for abbreviations refer to the reagent catalog of Aldrich), among which bisphenol A and bisphenol Z Bisphenol A is preferred and particularly preferred. The aromatic polycarbonate resin may be used alone or in combination of plural kinds, or may be a copolymer of plural kinds of monomers.

  There are no particular restrictions on the method for producing the aromatic polycarbonate resin. For example, (a) an organic solvent that dissolves the polymer produced from an alkali metal salt of bisphenols and a carbonate derivative (for example, phosgene) that is active in nucleophilic attack. (E.g. methylene chloride) and an interfacial polymerization method in which polycondensation reaction is performed at the interface between alkaline water and (b) a bisphenol and a carbonic acid ester derivative active in the nucleophilic attack as a raw material in an organic base such as pyridine. Pyridine method for condensation reaction, (c) melt polymerization method for melt polycondensation using bisphenols and carbonate esters such as bisalkyl carbonate and bisaryl carbonate (preferably diphenyl carbonate) as raw materials, and (d) bisphenols and monoxide Any known method such as a method of manufacturing by reaction of carbon or carbon dioxide is adopted. Kill.

  There is no restriction | limiting in particular in the molecular weight of aromatic polycarbonate resin, The weight average molecular weight Mw measured by GPC (using a single molecular weight dispersion polystyrene as a standard sample) by a 40 degreeC chloroform solvent is 10,000-500,000 normally. From the viewpoint of mechanical properties and melt fluidity, the weight average molecular weight Mw is preferably 15,000 to 200,000, more preferably 20,000 to 100,000. The glass transition point is usually 120 to 190 ° C., preferably 130 to 180 ° C., more preferably 140 to 180 ° C. from the viewpoints of heat resistance and melt fluidity.

Polyarylate resin:
The polyarylate resin is an aromatic dicarboxylic acid (for example, terephthalic acid, isophthalic acid, etc.) or a derivative thereof (for example, aromatic dicarboxylic acid diesters, such as dimethyl terephthalate and dimethylisophthalate), and a total fragrance made from the bisphenols. It is a resin made of a group polyester. A preferred polyarylate resin is a polyester obtained by polycondensation of terephthalic acid and / or isophthalic acid and bisphenol A (which can be polymerized in the same manner as in the method for producing the aromatic polycarbonate resin). As a polyarylate resin available as a commercial product, U polymer manufactured by Unitika Ltd. is exemplified. The polyarylate resin may be used alone or in combination of two or more. In particular, the polyarylate resin has excellent compatibility with the aromatic polycarbonate resin and the polyester resin described later, or can be blended by transesterification, and can be blended with these resins.

  Although there is no restriction | limiting in particular in the molecular weight of polyarylate resin, The weight average molecular weight Mw measured by GPC (using a single molecular weight dispersion polystyrene as a standard sample) by a 40 degreeC chloroform solvent is 8,000-200,000 normally. From the viewpoint of mechanical properties and melt fluidity, it is preferably 10,000 to 100,000, more preferably 15,000 to 80,000.

Polyester resin:
The polyester resin includes an aromatic polyester resin having an aromatic ring in the molecular chain obtained by a condensation reaction of a dicarboxylic acid or an ester-forming derivative thereof and a diol, and a condensation of the dicarboxylic acid or an ester-forming derivative thereof and a diol. It can be divided into aliphatic polyester resins that do not have an aromatic ring in the molecular chain obtained by the reaction. Examples of aromatic polyesters include polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, polybutylene terephthalate (PBT) resin, poly 1,3-propylene terephthalate resin, and the like. Aliphatic polyester resins include polylactic acid resin, poly-4-hydroxybutyrate resin, copolymer resin of hydroxybutanoic acid and hydroxyvaleric acid, polybutylene succinate resin, polybutylene adipate resin, adipic acid and terephthalic acid. Copolyester resin of mixed dicarboxylic acid and 1,4-dihydroxybutane, polyester resin having biodegradability such as polycaprolactone, polyester resin of cyclohexanedimethanol and cyclohexanedicarboxylic acid (hereinafter sometimes abbreviated as “PCC”) Are). It is also possible to impart flexibility to the polyester resin by using polyether diols such as polytetramethylene glycol, polytrimethylene glycol, and polyethylene glycol as the diol.

  Regardless of whether the polyester resin is an aromatic polyester resin or an aliphatic polyester resin, it may be used alone or in combination of two or more kinds. Also, blending with the above-mentioned aromatic polycarbonate resin having excellent compatibility with the polyester resin is possible, and as a polyester resin blend material available as a commercial product, a compatible polymer alloy material of PCC resin and aromatic polycarbonate resin is available. And “Xylex” (registered trademark) manufactured by Nippon GE Plastics Co., Ltd. having a glass transition point of about 100 ° C. is exemplified. Although there is no restriction | limiting in particular in the molecular weight of a polyester resin, The intrinsic viscosity [(eta)] measured at 30 degreeC of the polyester solution which used the mixed solvent of 1: 1 weight ratio of phenol and tetrachloroethane, and was made into the density | concentration of 1 g / dL. Usually, 0.5 to 3.0 dL / g. When the intrinsic viscosity is smaller than this range, the toughness is extremely lowered. On the contrary, when the intrinsic viscosity is larger than this range, the melt viscosity is too large, which may hinder thermoplastic molding.

It is preferable that the deflection temperature under load at a load of 455 kPa (4.6 kgf / cm ² ) according to ASTM standard D648 of the polyester resin is 50 to 130 ° C. All the exemplified polyester resins (including the polyester resin blend material) satisfy the above-mentioned deflection temperature under load. When the polyester resin blend material is used in the present invention, the greater the proportion of aliphatic polyesters, the better the light resistance may be. This is because the content of aromatic rings such as benzene rings that absorb ultraviolet rays decreases. For the same reason, aliphatic polyesters may be superior to aromatic polyesters in terms of light resistance.

Polypropylene resin:
The polypropylene resin is a polymer obtained by addition polymerization using propylene as an essential monomer in the presence of a transition metal catalyst. The stereoregularity of polypropylene may be any stereoregular structure such as syndiotactic, isotactic, or atactic, and a plurality of these may be used in combination. The polypropylene resin may contain a branched structure. The terminal group may be a functional group containing an element other than carbon and hydrogen, such as a hydroxyl group and an amino group. Further, it may be a copolymerized copolymerization monomer such as ethylene or butadiene. The method for producing the polypropylene resin is not particularly limited. Moreover, there is no restriction | limiting in particular in the molecular weight of a polypropylene resin, A melt index is 0.1-50 normally, Preferably it is 0.5-30.

(2) Ultraviolet absorbing particles (B) and ultraviolet absorbing particles (C-1) and (C-2):
The ultraviolet-absorbing particles (B) and (C-1) and (C-2) in the present invention contain phosphorus atoms. The valence of the phosphorus atom is preferably pentavalent, and specifically the one containing a P═O bond is preferred. In addition, there are two types of primary particles constituting the ultraviolet absorbing particles (B) and (C) in the present invention. The first particles are pyrophosphate particles having a specific chemical composition having ultraviolet absorptivity, and the second particles are phosphate particles having ultraviolet absorptivity.

The pyrophosphate constituting the pyrophosphate particles used in the ultraviolet absorbing particles (B), (C-1), and (C-2) is Ce _1-n Ti _n P ₂ O ₇ (where n is a metal composition). Any number of 0 to 1 inclusive). Although there is no particular limitation on the method for producing pyrophosphate, for example, as described in Non-Patent Document 1, a mixed aqueous solution of cerium (IV) sulfate and titanium (IV) sulfate and a sodium pyrophosphate aqueous solution are mixed. Can be manufactured by a sedimentation method. The arbitrary number n representing the metal composition in the chemical composition formula can be controlled by the charging ratio of cerium (IV) and titanium (IV) used as raw materials, and the lower limit is colorlessness and thermal catalyst in the visible light wavelength region. From the viewpoint of reducing the activity, it is usually 0.2, more preferably 0.5, and n is preferably larger, but the upper limit is preferably 0.95.

  Examples of phosphate particles having ultraviolet absorptivity include layered phosphates such as titanium phosphate and zirconium phosphate, transition metal phosphates such as zinc phosphate and iron phosphate, and apatites such as hydroxyapatite and fluorapatite Etc. are exemplified. These phosphate particles are known as hydrothermal synthesis method, coprecipitation method in which raw materials are mixed and precipitated in an aqueous solution, flux method in which phosphate particles are formed in the phase using sodium chloride as a flux. It is manufactured by the method.

  The pyrophosphate particles and phosphate particles obtained by the above method are usually those in which primary particles (nanoparticles) of about 15 to 30 nm are loosely aggregated.

  The number average particle diameter of primary particles of pyrophosphate in the ultraviolet absorbing particles (B), (C-1) and (C-2) is 1 to 100 nm, and the mechanical strength and transparency of the thermoplastic resin composition From the viewpoint of property, the upper limit is preferably 70 nm, more preferably 50 nm.

  The ultraviolet absorbing particles (B) in the present invention are preferably the pyrophosphate particles or the phosphate particles having ultraviolet absorbing properties (hereinafter these two types of particles may be collectively referred to as “UV absorber particles”). Particles). These UV absorber particles are preferably dispersed in the thermoplastic resin in the form of primary particles that are not secondary agglomerated. In this case, the number average particle size of the ultraviolet absorbing particles (B) is basically The number average particle size of the primary particles of pyrophosphate is the same. The number average particle diameter can be measured by observation with a transmission electron microscope (TEM). In addition, when the UV absorber particles in the present invention are in the form of flakes having an aspect ratio of 5 or more obtained by dividing the major axis by the minor axis, the UV resistance of the thermoplastic resin composition may be improved due to the UV blocking effect. The flaky aspect ratio is preferably 10 or more, more preferably 15 or more.

  The ultraviolet absorbing particles (C-1) in the present invention are preferably composed of the phosphate particles and a dispersant. As the dispersant, a dispersant composed of inorganic particles for dispersing the UV absorber particles in the UV absorbing particles, and the surface of the UV absorber particles are coated, and the form of primary particles in the thermoplastic resin. And a dispersant composed of an organic compound for dispersing in a thermoplastic resin.

UV absorbing particles B, (C-1) and (C-2) is not particularly limited to the production method of, for _{example, Ce 1-n Ti n P} 2 O 7 as described in the manufacturing method of the pyrophosphate (although The secondary agglomerated particles composed of primary particles of pyrophosphate having a composition of 15 to 30 nm having a composition of n (any number of 0 to 1 representing a metal composition) are pulverized to a desired dispersed particle size by mechanical crushing ( When pulverizing into nanoparticles, pulverization is performed in the presence of a dispersant composed of inorganic particles and / or a dispersant composed of organic compounds (which may be used in any state of vapor, liquid or solution). A method is mentioned. This is a usable method even in the case of phosphate. The pulverization process by mechanical crushing can be performed by either a dry method or a wet method (performed by dispersing in a liquid). At this time, ultrasonic waves or microwaves may be irradiated as necessary, and thermoplasticity From the viewpoint of achieving good dispersibility in the resin, it is particularly preferable to perform pulverization by a wet method.

  The dispersant composed of inorganic particles (hereinafter sometimes referred to as “additional inorganic material”) is not particularly limited as long as it is an inorganic particle other than the UV absorber particles, but from the viewpoint of chemical stability and non-toxicity, Oxides such as silicon oxide, titanium oxide, zirconium oxide, cerium oxide, zinc oxide and iron oxide, and silicates such as zinc silicate are preferred, and silicon oxide and zirconium oxide are preferred from the viewpoint of low photocatalytic activity. Silicon oxide is particularly preferable. Specifically, colloidal silica (particle size: usually 5 to 25 nm) manufactured by Catalyst Kasei Kogyo Co., Ltd. or Nissan Chemical Industries, Ltd., fumed silica manufactured by Nippon Aerosil Co., Ltd., silica nanoparticles manufactured by CI Kasei Co., Ltd. (manufactured by flame method), etc. Examples thereof include silica and colloidal titania. Moreover, you may use metal alkoxides, such as alkoxysilane, as a raw material of an addition inorganic substance.

  The form of the ultraviolet absorbing particles (C-1) and (C-2) when using a dispersant composed of inorganic particles is such that the primary particles of the UV absorber particles are not agglomerated and the inorganic particles In the case of combining and containing one UV absorber particle primary particle in one UV absorbing particle (C-1) or (C-2) (form a), The primary particles are combined with inorganic particles without secondary aggregation, and a single ultraviolet absorbing particle (C-1) or (C-2) contains a plurality of primary particles of the UV absorber particles. (Form b), the primary particles of the UV absorber particles may be combined with inorganic particles in a secondary aggregated state (form c), but the UV absorber particles may be UV-absorbing particles. Forms a and b dispersed with primary particles in (C-1) or (C-2) are preferred. There. In the forms a and b, various forms are conceivable depending on the size relationship and blending ratio between the inorganic particles and the UV absorber particles, and the UV absorber particles having a small particle size are formed on the surface of the large particle inorganic particles. A form in which the UV absorber particles having a small particle diameter are disposed in a gap between a matrix made of inorganic particles having a large particle diameter, and the UV absorber particles having the same particle diameter and the inorganic particles are uniform. The mixed form etc. are illustrated and any form may be sufficient. The inorganic particles do not necessarily have a homogeneous and continuous structure. For example, a discontinuous structure in which commercially available colloidal silica particles having a particle diameter of about 5 to 20 nm are accumulated as primary particles may be used. Such a fine structure can be confirmed by observation with a transmission electron microscope (TEM).

  The number average particle diameter of the ultraviolet absorbing particles (C-1) and (C-2) when inorganic particles are used as the dispersant is usually 0.01 to 50 μm in a state dispersed in the thermoplastic resin composition. In view of the mechanical strength and transparency of the thermoplastic resin composition, the upper limit is preferably 1 μm, more preferably 0.1 μm. The number average particle diameter can be measured by observation with a transmission electron microscope (TEM). The content of the inorganic particles in the ultraviolet absorbing particles (C-1) and (C-2) is usually 10 to 90% by weight.

The inorganic particles (additional inorganic material) not only disperse the UV absorber particles, but also have a function of appropriately changing the refractive index of the ultraviolet absorbing particles (C-1) and (C-2). For example, when the inorganic particles have a silicon oxide composition (preferably SiO ₂ and a refractive index of about 1.48 to 1.5), the pyrophosphate particles have a refractive index of 1.6 to 2.0. Therefore, the refractive index of the ultraviolet absorbing particles (C-1) and (C-2) can be adjusted in the range of about 1.5 to 2 according to the content of the inorganic particles. When polycycloolefin resin or aromatic polycarbonate resin, which is important as a transparent resin, is used as a thermoplastic resin, the refractive indexes thereof are about 1.53 and 1.59, respectively, at room temperature. The ultraviolet absorbing particles (C-1) in the thermoplastic resin composition are blended so that the refractive index of the ultraviolet absorbing particles (C-1) and (C-2) is close to the refractive index of the resin. And the light scattering by (C-2) is significantly reduced, and the transparency is greatly improved.

For such refractive index adjustment, an aromatic polycarbonate resin is used as the thermoplastic resin, the pyrophosphate particles having a refractive index of 1.8, and SiO ₂ (with a refractive index of 1.5) as the inorganic particles. The case where the ultraviolet absorbing particles (C-1) and (C-2) are mixed and dispersed will be described more specifically as an example. Assuming that the refractive index of the ultraviolet absorbing particles (C-1) and (C-2) is the sum of the refractive indexes of the constituent components multiplied by the respective volume fractions, the refractive index of the aromatic polycarbonate resin is 1. In order to match the refractive index of the ultraviolet absorbing particles (C-1) and (C-2) to 59, the content of the pyrophosphate particles in the ultraviolet absorbing particles should be about 30% by volume. become.

  The dispersant composed of the organic compound covers the surface of the pulverized particles generated in the pulverization step by mechanical crushing, and prevents or suppresses the pulverized particles from reaggregating. That is, aggregation of the primary particles of the UV absorber particles can be prevented, or the aggregated particle diameter can be reduced. In particular, it is preferable to use a dispersant in order to obtain UV-absorbing particles whose primary particles have a minor axis number average particle diameter of 1 to 100 nm. Since the surface of the UV absorber particles is hydrophilic, the dispersant is preferably an organic compound containing a hydrophilic functional group in the chemical structure. Examples of the dispersant include acidic organic compounds represented by the following general formula (7) or general formula (8).

However, in the general formula (7) or the general formula (8), R ¹ , R ² and R ³ are each independently an organic residue having 6 or more carbon atoms, A is P (═O) (OH) ₂ , SO ₃ Each represents an acidic group of H and COOH)

R ¹ , R ² and R ³ in the general formula (7) or the general formula (8) may be bonded to the acidic group A or the phosphorus atom with any element contained in the chemical structure. For example, in the general formula (7), when the acidic group A is P (═O) (OH) ₂ and R ¹ is a carbon atom and is bonded to the acidic group A, this molecule is a phosphonic acid and is also bonded by an oxygen atom. In this case, the molecule is a phosphate monoester. In the general formula (8), when both R ² and R ³ are carbon atoms and are bonded to the phosphorus atom of the P (═O) OH group, this molecule is phosphinic acid, and one of R ² and R ³ is carbon. When an atom is attached to the phosphorus atom of the P (═O) OH group, the other being an oxygen atom, the molecule is a phosphonic acid monoester, both R ² and R ³ are oxygen atoms and P (═O) When attached to the phosphorus atom of the OH group, this molecule is a phosphodiester.

R ¹ , R ² and R ³ in the general formula (7) or the general formula (8) each independently represent an organic residue having 6 or more carbon atoms, and are represented by such R ¹ , R ² and R ^3. Examples of the organic residue include the following monovalent organic residues or groups containing a divalent organic residue that links the monovalent organic residue and A or P (═O) OH.

As monovalent organic residues contained in R ¹ , R ² and R ³ , an n-hexyl group, a cyclohexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group and the like having 20 or less carbon atoms. Aliphatic hydrocarbon group, phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-hexylphenyl group, 4-dodecylphenyl group, naphthyl group, benzyl group, 4-methylbenzyl group , Hydrocarbon groups having 20 or less carbon atoms such as 4-dodecylbenzyl group, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy Group, n-hexyloxy group, cyclohexyloxy group, octyloxy group, benzyloxy group, etc. Aryloxy groups such as alkoxy groups of 8 or less, phenoxy group, 4-methylphenoxy group, 2-hydroxyethyl group, 2,3-dihydroxy-n-propyl group, 2,3,4-trihydroxy-n-butyl group , Hydrocarbon groups having a hydroxyl group such as 2,2,2-tris (hydroxymethyl) ethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, polyalkylene glycol residue represented by the following general formula (9) Among them, it is preferable to include a polyalkylene glycol residue represented by the following general formula (9).

  However, in General formula (9), R represents either a hydrogen atom, a C1-C7 hydrocarbon group, and a C2-C7 acyl group, m represents an integer of 1-4, and n is 1 Represents an integer of -10. )

As the divalent organic residue (linking group) that R ¹ , R ² and R ³ can contain, a methylene group having 1 to 20 carbon atoms and a methylene group having a side chain having 2 to 20 carbon atoms (the side chain is Usually a hydrocarbon group having 1 to 8 carbon atoms), 1,4-phenylene group, 1,3-phenylene group and the like, and even when a divalent organic residue is further linked through an oxygen atom or the like. Good.

Preferred dispersants are a compound represented by general formula (7) in which A is P (═O) (OH) ₂ and a compound represented by general formula (8). A compound that is P (═O) (OH) ₂ is particularly preferred. The reason for this is not clear, but when it is a phosphoric acid derivative that is a strong acid or has a P (═O) (OH) ₂ group that is a divalent acidic group, the two hydroxyl groups are the surfaces of the UV absorber particles. It is presumed that they are strongly bonded at two locations, or because they are divalent acidic groups, the bond formation rate with the surface of the UV absorber particles is high.

As specific examples of the dispersant, in the case of a compound in which A is P (═O) (OH) ₂ in the general formula (7), aliphatic phosphonic acids such as octylphosphonic acid and tetradecylphosphonic acid, phenylphosphonic acid, Aromatic phosphonic acids such as 4-methylphenylphosphonic acid, 4-octylphenylphosphonic acid and 4-dodecylphenylphosphonic acid, and a methylene group represented by the following general formula (10) as a linking group, Examples thereof include phosphonic acids bonded to the polyalkylene glycol residue of the general formula (9) through an atom, phosphoric acid monoalkyl esters such as phosphoric acid monooctyl ester and phosphoric acid monododecyl ester. In addition, a mixture of phosphoric acid monoesters and phosphoric acid diesters can be suitably used, for example, as a phosphate ester additive manufactured by Johoku Chemical Industry. For example, the product number “JP-506H” of Johoku Chemical Industry Co., Ltd., n-butyloxyethyl ester of phosphoric acid (a mixture of monoester and diester), and the like can be mentioned.

  However, in General formula (10), p represents the integer of 1-20.

  Phosphonic acids use an Arbuzov reaction in which a halide (eg, bromide) of a desired organic residue is mixed and heated with a phosphating agent such as tris (trimethylsilyl) phosphite or triethylphosphite to form a carbon-phosphorus bond. Can be synthesized. Phosphate esters include hydroxy compounds (alcohols and phenols) and acid chlorides of phosphoric acid (eg, phosphorus oxychloride, diethyl chlorophosphate, dimethyl chlorophosphate, diphenyl chlorophosphate, ethyl dichlorophosphate, phenyl dichlorophosphate) Etc.) in the presence of a suitable base (for example, nitrogen-containing compounds such as pyridine and triethylamine, inorganic bases such as potassium carbonate, magnesium oxide, sodium hydroxide, etc.).

  When using a resin unit containing a carbonyl group in a monomer unit such as an aromatic polycarbonate resin, a polyester resin, a polyarylate resin, or a polyamide resin as a thermoplastic resin, the carbonate bond, ester bond, amide bond, etc. of these resins An acidic compound having compatibility or exchange reactivity (an acidic organic compound represented by the general formula (7) or the general formula (8)) is a preferable dispersant. In particular, an acidic organic compound containing a carbonate bond or an ester bond in the molecular structure is more preferable in terms of exchange reactivity, and among them, an acidic organic compound containing an aromatic carbonate bond or an aromatic ester bond in the molecular structure is preferable. More preferable from the viewpoint of compatibility with engineering plastics and heat resistance, and aromatic phosphates represented by any one of the following general formulas (1) to (6) are exemplified as the most preferable compounds in such molecular design. The

In general formulas (1) to (6), m and n are independently a natural number of 2 or less, R ¹ is an alkyl group having 12 or less carbon atoms, an aryl group having 12 or less carbon atoms, or an alkoxy having 12 or less carbon atoms. any group or more than 12 aryloxy group having a carbon, R x ^(where x is a natural number of 2 to 5) each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 12 or less carbon atoms, R ⁶ is An alkyl group or an aryl group having 12 or less carbon atoms, R is a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms, L is a carbonyl group (-CO-), a sulfide bond (-S-), a sulfoxide bond (-SO -) and a sulfone bond (-SO ₂ - one of) represent respectively.

  Specific examples of the compound corresponding to the general formula (1) include phosphate ester of bisphenol A monophenyl carbonate, phosphate ester of bisphenyl carbonate of 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1 , 1-Tris (4-hydroxyphenyl) ethane bisbenzoate phosphate ester.

  Specific examples of the compound corresponding to the general formula (2) include phosphate ester of monophenyl carbonate of 4,4′-dihydroxydiphenylsulfone, phosphate ester of monobenzoate of 4,4′-dihydroxydiphenylsulfone, 4 4'-dihydroxybenzophenone monophenyl carbonate phosphate ester, 4,4'-dihydroxybenzophenone monobenzoate phosphate ester.

  Specific examples of the compound corresponding to the general formula (3) include phosphate ester of 4,4'-dihydroxybiphenyl monophenyl carbonate, phosphate ester of 4,4'-dihydroxybiphenyl monobenzoate.

  Specific examples of the compound corresponding to the general formula (4) include phosphate ester of bisphenol A monobenzyl ether and phosphate ester of bisbenzyl ether of 1,1,1-tris (4-hydroxyphenyl) ethane.

  Specific examples of the compound corresponding to the general formula (5) include a phosphoric ester of monobenzyl ether of 4,4'-dihydroxydiphenylsulfone.

  Specific examples of the compound corresponding to the general formula (6) include phosphate ester of monobenzyl ether of 4,4′-dihydroxybiphenyl.

  An example of the synthesis procedure of these aromatic phosphates will be described with reference to a case where bisphenol A (hereinafter sometimes abbreviated as BPA) is used as a raw material. First, BPA is dissolved in tetrahydrofuran or acetone, and phenyl chloroformate, benzoyl chloride, or benzyl bromide (formers of phenyl carbonate, benzoate ester, and benzyl ether, respectively) are added to the phenolic hydroxyl group. The reaction is carried out in the presence of 1 equivalent of a base such as potassium carbonate or triethylamine. At this time, for example, when an inorganic base such as potassium carbonate is used, an alkali metal scavenging assisting agent such as 18-crown-6 ether is used as necessary in order to improve the reactivity of the base in an organic solvent. A phase transfer catalyst such as a quaternary ammonium salt or quaternary phosphonium salt may be used in combination. The resulting mono-substituted product (that is, a BPA monocarbonate-substituted product, monoester-substituted product, or monoether-substituted product) is purified and isolated by silica gel column chromatography or recrystallization.

  Subsequently, diethyl chlorophosphate is used as a solvent and heated to about 50 to 100 ° C. with magnesium oxide (powder) as a base as necessary to convert the diethyl phosphate group to the other phenolic hydroxyl group of the BPA residue. Combine. Since this reaction usually proceeds in good yield, it is purified by column chromatography or the like as necessary. Finally, in a solvent such as methylene chloride, a small excess equivalent of trimethylsilyl iodide is allowed to act on the ethyl group of the diethyl phosphate group to selectively remove ethyl ester and purify by column chromatography or the like. A compound can be obtained. When the terminal group is an ether bond such as benzyl ether, it has high resistance to the cleavage condition of the phosphate ester bond, so deethylesterification can be carried out efficiently under reaction conditions using a strong base such as caustic alkali. It is.

When A is SO ₃ H in the general formula (10), it is a sulfonic acid dispersant, and examples thereof include those used for general-purpose sulfonic acid surfactants (acidic type) such as dodecylbenzenesulfonic acid and dodecylsulfonic acid. The Moreover, when A is COOH in General formula (7), it becomes a dispersing agent of carboxylic acids, and fatty acids such as lauric acid, stearic acid, and maleic acid are exemplified.

  Examples of the organic compound containing a hydrophilic functional group in the chemical structure other than the acidic organic compound include esters and amides that are derivatives of the acidic organic compound represented by the general formula (7) or the general formula (8). Besides, tertiary amines such as trimethylamine, triethylamine, tributylamine, trihexylamine, trioctylamine, tridecylamine, triphenylamine, methyldiphenylamine, diethylphenylamine, tribenzylamine, etc. as amines, diethylamine, dibutylamine Secondary amines such as dihexylamine, dioctylamine, didecylamine, diphenylamine, dibenzylamine, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, phenylamine, benzyl Primary amines such as tromethamine and the like, further, a carboxylic acid derivative having a nitrilotriacetic acid and its esters and the amino group of the amide and the like.

  Among these, one alkyl group such as carboxylic acid amides having 6 to 20 carbon atoms such as hexanoic acid amide, lauric acid amide, stearic acid amide, dihexylamine, dioctylamine, didecylamine, diphenylamine, dibenzylamine, etc. Or secondary amines having 6 to 20 carbon atoms per aryl group, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, phenylamine, benzylamine, etc. ~ 20 primary amines are preferred.

  In addition, since there are hydroxyl groups represented by P—OH, Ce—OH and Ti—OH on the surface of the pyrophosphate particles and phosphate particles which are the UV absorber particles, an organic compound which can react with them. For example, metal alkoxides represented by the general formula (11) such as alkoxysilane are also effective dispersants. Since the metal alkoxide can react with the surface of an additional inorganic substance such as silicon oxide, it is particularly preferably used for the ultraviolet absorbing particles (C-1) and (C-2).

  In the general formula (11), M represents a metal atom (including boron and silicon), R represents an alkoxy group having 6 or less carbon atoms, Z represents a hydrogen atom, a hydroxyl group, or an alkyl group having 10 or less carbon atoms. Or it represents either an aryl group. M + n is a natural number equal to the valence number of the metal atom M, m represents a natural number, and n represents an integer of 0 or more.

  As the metal alkoxide represented by the general formula (11), alkoxysilane in which M is a silicon atom is preferable. Examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane (TEOS), tetra-n-propyloxysilane, tetraisopropyloxysilane, tetra-n-butoxysilane, and the like, methyltrimethoxysilane, and methyltriethoxysilane. Methyltri-n-propyloxysilane, ethyltriethoxysilane, cyclohexyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltri Monoalkyltrialkoxysilanes such as ethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, Triethoxysilane, naphthyltriethoxysilane, 4-chlorophenyltriethoxysilane, 4-cyanophenyltriethoxysilane, 4-aminophenyltriethoxysilane, 4-nitrophenyltriethoxysilane, 4-methylphenyltriethoxysilane, 4- Monoaryltrialkoxysilanes such as hydroxyphenyltriethoxysilane, phenoxytriethoxysilane, naphthyloxytriethoxysilane, 4-chlorophenyloxytriethoxysilane, 4-cyanophenyltrioxyethoxysilane, 4-aminophenyloxytriethoxysilane, Monoaryloxy such as 4-nitrophenyloxytriethoxysilane, 4-methylphenyloxytriethoxysilane, 4-hydroxyphenyloxytriethoxysilane Cihydroxyalkoxysilane, monohydroxytrimethoxysilane, monohydroxytriethoxysilane, monohydroxytrialkoxysilane such as monohydroxytri-n-propyloxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propyloxysilane, Dialkyl dialkoxy silanes such as methyl (ethyl) diethoxysilane, methyl (cyclohexyl) diethoxy silane, monoalkyl monoaryl dialkoxy silanes such as methyl (phenyl) diethoxy silane, diaryl dialkoxy silanes such as diphenyl diethoxy silane, Dihydroxydialkoxysilanes such as dihydroxydimethoxysilane and dihydroxydiethoxysilane, and monoalkylmonos such as methyl (hydroxy) dimethoxysilane Monoarylmonohydroxydialkoxysilanes such as hydroxy dialkoxysilane, phenyl (hydroxy) dimethoxysilane, trialkylmonoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, dimethyl (ethyl) ethoxysilane, dimethyl (cyclohexyl) ethoxysilane, Dialkyl monoaryl monoalkoxysilanes such as dimethyl (phenyl) ethoxysilane, monoalkyldiaryl monoalkoxysilanes such as methyl (diphenyl) ethoxysilane, trihydroxymonoalkoxysilanes such as trihydroxymethoxysilane and trihydroxyethoxysilane, tetramethoxysilane Oligomers of the alkoxysilane such as 2 to 5 mer of the above (for example, “MKC silicate” (registered trademark) manufactured by Mitsubishi Chemical Corporation) And the like.

  Examples of metal alkoxides in which M is other than a silicon atom include triethoxyboron, triethoxyaluminum, tetraethoxytitanium, tetra-n-butoxytitanium and the like. In the above metal alkoxide, methyltriethoxysilane, ethyltriethoxysilane, n-butyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3- Monoalkyltrialkoxysilanes such as glycidyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-acryloyloxypropyltriethoxysilane are preferred. A compound in which a metal element is bonded to a nitrogen atom such as hexamethyldisilazane can also be used as a dispersant. Two or more of the above dispersants may be used in combination with any composition.

  As a method for obtaining a thermoplastic resin composition in which UV absorber particles are dispersed in a thermoplastic resin matrix with a small dispersed particle size using the above-described dispersant, UV absorber particles whose surfaces are coated with the dispersant are used. It is preferable to prepare a dispersion (hereinafter sometimes referred to as “dispersion liquid”) in a solvent (preferably an organic solvent) and then mix it with a thermoplastic resin by the method described below.

  Specifically, (i) a method of melt-kneading the UV absorber particle dispersion with the thermoplastic resin; (ii) mixing the UV absorber particle dispersion with the raw material monomer (monomer) of the thermoplastic resin; A method of proceeding the polymerization reaction; (iii) a method in which the liquid monomer of the thermoplastic resin itself is used as a solvent for the UV absorber particle dispersion, and then a polymerization reaction is performed; (iv) the UV absorber particle dispersion is used for the thermoplastic resin. Examples of the solution mixing method include mixing with a solution and then removing the solvent component.

  From the viewpoint of dispersibility and productivity in a thermoplastic resin, a solution mixing method and melt kneading are preferable. In the solution mixing method, the concentration of the UV-absorbing particles in the resin composition particularly exceeds 10% by weight. In this case, it is preferable because extreme deterioration of productivity due to an increase in viscosity during production (for example, it becomes difficult to transfer and extract the resin composition by piping) can be avoided. By adopting such a method, it is possible to obtain a thermoplastic resin composition in which UV absorber particles are dispersed with a small dispersed particle diameter which has not been conventionally obtained.

  The amount of the dispersant composed of the organic compound is usually 0.1 to 100 times the weight of the UV absorber particles, and the upper limit is preferably 70 times the weight from the viewpoint of effectively using the dispersant. More preferably, it is 50 times weight, while the lower limit is preferably 0.5 times weight, more preferably 1 time weight from the viewpoint of dispersion effect. In order to effectively use the dispersant, excess dispersant may be collected and reused after mechanical crushing. Although there is no particular limitation on the method of such recovery, for example, a method in which the produced UV-absorbing particles are precipitated by gravity or centrifugation and then separated as a supernatant, Size-exclusion chromatography (SEC), silica gel column chromatography, gel Examples thereof include a chromatographic method such as filtration and a separation method using a membrane having fine pores such as an ultrafiltration method.

  When the dispersion process such as pulverization or peptization of the UV absorber particles is performed by a wet method, it is preferably performed in a highly polar organic solvent having excellent solvation ability. Examples of the organic solvent include alcohols having 4 or less carbon atoms such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, and t-butyl alcohol, polyvalent glycols such as ethylene glycol and glycerin, acetone, and methyl ethyl ketone. , Ketones having 6 or less carbon atoms such as cyclohexanone, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, aliphatic linear ethers such as diethyl ether, methyl cellosolve and ethyl cellosolve, nitriles such as acetonitrile and acrylonitrile, methyl acetate and acetic acid Esters of lower fatty acids such as ethyl, cyclic esters such as ε-caprolactone, nitrogen-containing aromatic compounds such as pyridine, N, N-dimethylacetamide, N, N-dimethylformamide (DMF), N Aprotic amide solvents such as methylpyrrolidone (NMP), sulfoxides such as dimethyl sulfoxide (DMSO) are exemplified. These high polar organic solvents may be used in combination of two or more, or may be used by mixing with a low polar organic solvent such as toluene or hexane, and water may be added as necessary.

  Since the above organic solvent needs to be removed by distillation or evaporation in a later step (for example, a mixing step with a thermoplastic resin), methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, t -A relatively low-boiling organic solvent having a boiling point of 150 ° C or lower, such as butyl alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, pyridine, etc. is preferred, and among them, lower alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol and tetrahydrofuran are more preferred. Ethanol and tetrahydrofuran are particularly preferred in terms of solubility and low toxicity.

  As the mechanical crushing device used in the granulation process, conventionally known devices can be used, for example, rolling or vibration mills such as bead mills, rod mills, centrifugal mills, planetary mills, impact mills that collide particle dispersions, and stirring mills. (Arm type, disk type, etc.), roller mill, inner piece type (for example, “Ang Mill” manufactured by Hosokawa Micron Corporation), and the like are exemplified. Among these, a bead mill, a planetary mill, and an impact mill are preferable, and a bead mill is particularly preferable. Specific examples of the mechanical crushing apparatus include “Ultra Apex Mill” (Ultra Apex Mill, registered trademark) manufactured by Kotobuki Giken Kogyo.

(3) Thermoplastic resin composition:
In the thermoplastic resin composition of the present invention, the thermoplastic resin is a nanoparticle (for example, phosphate particles or Ce _1-n Ti _n P ₂ O ₇ (for example, phosphate-absorbing particles or phosphorous atoms). n is an arbitrary number of 0 or more and 1 or less representing a metal composition), and the above ultraviolet absorbing particles containing pyrophosphate particles represented by a composition are dispersed. The content of the UV-absorbing particles is usually 0.01 to 90% by weight, and the lower limit is the light resistance and inorganic thin film of the thermoplastic resin composition (for example, hard coat, UV-absorbing coat, antireflection coat, etc.) From the viewpoint of adhesion, the upper limit is preferably 0.05% by weight, more preferably 0.1% by weight, and the upper limit is the mechanical strength of the thermoplastic resin composition (particularly toughness represented by bending displacement). ) And transparency, it is preferably 70% by weight, more preferably 60% by weight. In particular, when the content of the UV-absorbing particles is 5% by weight or more, the effect of improving dimensional stability such as a reduction in molding shrinkage rate and linear expansion coefficient becomes remarkable.

  By the way, in the present invention, the thermoplastic resin (A) and the ultraviolet-absorbing particles, the nanoparticles (B) containing phosphorus atoms, or the ultraviolet-absorbing particles (C-1) containing the particles and a dispersant. The effect of the present invention is that the organic component in the dry residue of the insoluble component when the resin composition is dissolved in a solvent capable of dissolving the thermoplastic resin is a specific ratio. It is preferable for more performance.

  This condition means that the ultraviolet absorbing particles that are the main component of the insoluble component chemically bond an organic component (for example, the dispersant or the thermoplastic resin) to the surface thereof.

  Due to the chemical bond of the organic component to the particle surface, the ultraviolet absorbing particles exhibit very excellent dispersibility and interface wettability in the thermoplastic resin composition.

  The method for quantifying the organic component in the dry residue of the insoluble component is as follows. That is, first, the given thermoplastic resin composition is sufficiently dissolved in a good solvent for the thermoplastic resin forming the thermoplastic resin composition to sufficiently dissolve the thermoplastic resin matrix component. This dissolution is usually performed by selective extraction using thorough soxhlet extraction using a Soxhlet continuous extraction apparatus, or by dissolving at a maximum temperature of about 100 ° C. in order to avoid thermal decomposition, and then precipitating insoluble components (for example, static Use gravity by placing or centrifuge.) Use precipitation method to separate from supernatant solution, or a combination of both. In any dissolution method, the dissolution operation is repeated until no organic component is substantially detected in the solution obtained by the dissolution operation. The weight loss of 20 ± 5 mg of the insoluble component thus obtained after vacuum drying at an upper limit temperature of about 100 ° C. is ashed for 1 hour at 600 ° C. in an air stream, and then measured. This heat loss measurement is performed with a commercially available TG-DTA (thermogravimetric analysis) apparatus. The weight ratio of the heat loss is defined as the weight ratio of the organic component in the dry residue of the insoluble component, and in the present invention, this value is 5 to 80% by weight. If the upper limit of this weight ratio is exceeded, the fluidity (that is, moldability) of the thermoplastic resin composition in the molten state or in the solution state is extremely deteriorated, so it is preferably 70% by weight, more preferably 60% by weight. . On the other hand, when the lower limit of the weight ratio is not reached, the dispersibility of the ultraviolet absorbing particles in the thermoplastic resin composition is deteriorated and the molding surface smoothness and transparency are deteriorated. Is 20% by weight.

  Any of the thermoplastic resin compositions of the present invention preferably contains an organic ultraviolet absorber having an absorption spectrum maximum at a wavelength of 200 to 400 nm in order to improve its light resistance. Examples of the organic ultraviolet absorber include known benzotriazole ultraviolet absorbers, liquid ultraviolet absorbers, triazine ultraviolet absorbers, and benzophenone ultraviolet absorbers. It is also preferable to contain a hindered amine light stabilizer (HALS, having a radical scavenging function).

  As the hindered amine light stabilizer, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester (for example, “TINUVIN123S” manufactured by Ciba Specialty Chemicals), Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate (“TINUVIN 144” manufactured by the same company) ), Decanedioic acid bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester (manufactured by “TINUVIN765”), etc., among others, bis (1,2,2,6,6-pentamethyl) -4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalo Over door (manufactured by the same company "TINUVIN144") it is particularly preferred.

  The effect of the organic ultraviolet absorber and the hindered amine light stabilizer is presumed to be due to a synergistic effect with the ultraviolet absorbing particles, but the mechanism is not clear. Although there is no restriction | limiting in particular in content of an organic ultraviolet absorber and a hindered amine type light stabilizer, Usually, it is 10-10,000 ppm on the basis of the weight of a thermoplastic resin composition. When there is too much content, the deterioration of the thermal stability of a thermoplastic resin composition, the increase in bleed-out, the fall of the adhesiveness of the molded object surface mentioned later and an inorganic thin film may become remarkable. The upper limit of the content is preferably 5000 ppm, more preferably 1000 ppm. On the other hand, when there is too little said content, the effect which improves light resistance may fall. The lower limit of the content is preferably 50 ppm, more preferably 100 ppm.

  The thermoplastic resin composition of the present invention is a heat stabilizer, a release agent, a plasticizer, a lubricant, a flame retardant, a pigment, a dye, various fillers (for example, glass fiber, glass beads, Inorganic fillers such as glass flakes, clay minerals, talc and kaolin, carbon materials such as carbon fibers, carbon whiskers, carbon nanotubes and graphite, metal fillers such as metal fibers, metal flakes and metal powders, resin beads such as cross-linked acrylic resins) In addition, known resin additives such as impact resistance imparting agents such as rubber and elastomer may be added. When an aromatic polycarbonate resin is used as the thermoplastic resin, it is desirable to add about 1-1000 ppm of an aromatic phosphite heat stabilizer. These resin additives may be used in combination as necessary.

  Although there is no restriction | limiting in particular in the manufacturing method of the thermoplastic resin composition of this invention, For example, it uses a twin-screw extruder etc., and melt-kneads an ultraviolet-absorbing particle or its dispersion liquid (slurry may be sufficient), and a thermoplastic resin. A method of mixing ultraviolet absorbent particles or a dispersion thereof (which may be a slurry) and a raw material monomer of a thermoplastic resin, followed by a polymerization reaction, a raw material monomer of a thermoplastic resin (for example, methyl methacrylate, styrene, etc.) Examples include a method in which a liquid monomer is used as a solvent for ultraviolet absorbing particles or a dispersion thereof (or a slurry) and then a polymerization reaction is performed, and the solution mixing method.

(4) Molded body comprising thermoplastic resin composition:
As explained above, nanoparticles that are UV-absorbing particles and contain phosphorus atoms (for example, the pyrophosphate particles and the phosphate particles) have very low thermal catalytic activity as well as photocatalytic activity. The thermoplastic resin composition of the present invention is superior in light resistance and thermal stability (heat decomposability) compared to conventional resin compositions in which general-purpose ultraviolet absorbing inorganic substances (titanium oxide, zinc oxide, cerium oxide, etc.) are dispersed. ). Furthermore, since the ultraviolet-absorbing particles are finely dispersed compared to conventional ones, the mechanical strength (particularly toughness represented by bending displacement) is excellent. Moreover, it also has adhesiveness with inorganic thin films (for example, a hard coat, an ultraviolet absorption coat, an antireflection coat, etc.). Further, incidental effects include improvement in dimensional stability such as reduction in molding shrinkage rate and linear expansion coefficient, stabilization of dimensions and mechanical properties due to reduction in water absorption, and improvement in flame retardancy. Therefore, the thermoplastic resin composition of the present invention can be used for molded articles for various purposes. In particular, when the thermoplastic resin is a transparent resin, it exhibits excellent transparency. Therefore, it is suitable for applications exposed to strong light including ultraviolet rays, for example, optical members (lenses, diffusion plates, etc.) for display / projection devices, automotive outer plate members (windows, bumpers, etc.), and outdoor building materials. Used for.

  The molded body of the present invention is obtained by molding the thermoplastic resin composition of the present invention, and the thickness thereof is 0.001 to 100 mm, preferably 0.01 to 50 mm. As a molding method, a known thermoplastic resin molding method such as injection molding, extrusion molding, press molding, injection press molding, or vacuum press molding can be employed. Moreover, a well-known solution shaping | molding method can also be used and a thin film and a sheet-like molded object can be obtained by various film forming methods, such as dip coating, die coating, bar coating, spray coating, and spin coating. The thermoplastic molding temperature of the molded article of the present invention is usually 150 to 370 ° C., and preferably 170 to 340 ° C., more preferably 200 to 320 ° C. from the viewpoint of molding fluidity and prevention of thermal deterioration due to excessively high temperature. It is.

  Molding by the various film forming methods can also be performed using a mixed solution of the thermoplastic resin and the ultraviolet absorbing particles in the solution mixing method. In the case of such a thin film or sheet-like molded product, a molded product such as a plate made of an arbitrary material can be used as the substrate. Examples of the material of the substrate include resin, metal, ceramics, glass, wood, paper and the like. As a particularly preferred form of use, the resin composition (for example, polypropylene resin, polyamide resin, aromatic polycarbonate resin, polyester resin, etc.) is coated on the surface of the thermoplastic resin composition of the present invention to form a light resistance. In addition, it is possible to exemplify a molded product obtained by laminating an inorganic thin film to be described later as a hard coat layer.

  When the thermoplastic resin composition contains a crystalline thermoplastic resin material such as a polypropylene resin or an aromatic polyester resin / aromatic polycarbonate resin blend material, or a rubber component such as an ABS resin or a rubber toughened polyamide resin The molded body is particularly useful as an automobile outer plate (for example, a bumper or a fender) having improved light resistance.

  For example, when the molded product of the present invention requires transparency, the light transmittance at a wavelength of 430 nm measured in the thickness direction is usually 80% or more, preferably 85% or more. In particular, when used as an optical member of an optical device such as a display or a liquid crystal projector, or when surface hardness or wear resistance is required such as an exterior member of an automobile, antireflection, improvement of light extraction efficiency, surface hardness and It is preferable to have an inorganic thin film on the surface of the molded body from the viewpoints of improvement of wear resistance (hard coat), conductivity, antistatic property and the like. Due to the effect of the inorganic particles contained in the thermoplastic resin composition of the present invention, there is a preferable effect that the adhesion of the inorganic thin film is improved. As the material of such an inorganic thin film, silica is most commonly used, and as a high refractive index material, titania (titanium oxide), a composite oxide of titanium and lanthanum, zinc oxide, zirconia (zirconium oxide), etc. are exemplified. Examples of the refractive index material include magnesium fluoride and mesoporous silica. Such an inorganic thin film is usually attached to the entire surface of the molded body, but may be attached to only one surface of the molded body as necessary. Moreover, you may attach the inorganic thin film which has a some function. Although it changes with functions to provide as thickness of an inorganic thin film, it is 0.05-10 micrometers normally, Preferably it is 0.1-5 micrometers, More preferably, it is 0.2-3 micrometers.

  When the molded article of the present invention is applied to optical members such as lenses (multi-lenses, convex lenses, concave lenses, etc.), prisms, diffusion plates, diffusion sheets, etc., an inorganic thin film can be attached as an antireflection coating (AR coating). It may be preferable in terms of transmittance. As the AR coating, conventionally known coatings can be used, in which silica layers and titania layers are alternately laminated, silica layers and titania / lanthanum composite oxide layers are alternately laminated, silica titania layers and titania layers. Examples include a two-layer laminate including a high refractive index layer made of a lanthanum composite oxide and a low refractive index layer made of magnesium fluoride.

  The inorganic thin film is usually formed by a known vacuum process such as vapor deposition or sputtering. Although it can be formed by a coating process using a liquid raw material, it is preferably formed by a vacuum process from the viewpoints of hardness, denseness, conductivity, homogeneity, and the like.

  The molded article of the present invention is particularly useful as an optical member such as a lens or prism used in applications that make use of its transparency and light resistance, for example, applications that transmit light including ultraviolet rays. When the molded article of the present invention is used as a lens, the thickness of the thickest part of the lens is usually 0.1 to 100 mm, preferably 0.5 to 50 mm, more preferably 1 to 30 mm. If the thickness is too large, dimensional changes due to molding shrinkage and temperature / humidity changes after molding may become extremely large and molding residual distortion may become extremely large.If the thickness is too small, the focal length of the lens can be taken sufficiently. There may be no mechanical strength. The diameter of the lens is usually 0.1 to 1000 mm, preferably 0.5 to 500 mm, more preferably 1 to 200 mm. If the lens diameter is too large, dimensional changes due to molding shrinkage and temperature / humidity changes after molding may become extremely large or molding residual distortion may become extremely large. If the lens diameter is too small, the focal point of the lens The distance may not be sufficient or the mechanical strength may be insufficient. Since the curvature of the lens can be reduced as the refractive index of the thermoplastic resin composition increases, thermoplasticity containing a resin having a refractive index of 1.58 or more at room temperature as a matrix, such as aromatic polycarbonate resin or polyarylate resin. It is preferable to mold as a lens using the resin composition.

  The molded article of the present invention is also useful as a sheet-like molded article because it has excellent resistance to exposure to sunlight and mechanical strength such as impact resistance to withstand crashes such as pebbles and folds. As the thermoplastic resin used for the sheet-like molded body, an aromatic polycarbonate resin is preferable from the viewpoint of excellent mechanical strength. The thickness of a sheet-like molded object is about 0.1-50 mm normally, Preferably it is 0.5-40 mm from a mechanical strength or a lightweight viewpoint, More preferably, it is 1-30 mm. The sheet-like molded body can be suitably used for roofs of parking lots and bicycle parking lots, transparent soundproof walls of roads, windshield windows for automobiles, airplanes, and the like. Since such a sheet-shaped molded body is a molded body that is usually much larger than the above-mentioned lens, it is preferably produced by known extrusion molding.

  The tensile elongation at break according to ASTM standard D638 of a molded article comprising the thermoplastic resin composition of the present invention is usually 1 to 200%, preferably 5 to 200%. In addition, the molding shrinkage at a thickness of 3 mm in the flow direction at the time of injection molding is usually 0.01 to 2%, preferably 0.01 to 1.5%. Furthermore, the linear expansion coefficient according to ASTM standard D696 is usually 40 to 100 ppm / ° C., preferably 40 to 80 ppm / ° C.

  Since the pyrophosphate particles contained in the thermoplastic resin composition of the present invention are excellent in harmlessness to the human body, they are used in bottles and bags, molded food products that require UV shielding (for example, PET bottles, gas barrier films) , Food storage containers, etc.) and medical packaging applications (infusion packages, etc.).

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples, unless the summary is exceeded. Examples 1 to 8 below relate to the sixth gist of the present invention, Examples 9 to 20 and Comparative Examples 1 to 10 relate to the second gist of the present invention, and Examples 21 to 26 and Comparative Example 11 are This relates to the third aspect of the present invention.
In addition, the heat loss measurement of the solvent-insoluble component of the resin composition was performed by using a TG-DTA320 manufactured by Seiko Instruments Inc. in a platinum pan in the air from room temperature (about 23 ° C.) to 600 ° C. at a rate of 10 ° C./min. The measurement was carried out for 1 hour. Moreover, the following number average measurement of various particle sizes was performed by observation with H-9000NA (100 kV) which is a transmission electron microscope manufactured by Hitachi, Ltd.

Synthesis Example 1 (Synthesis of 10- [2- (2-methoxyethoxy) ethoxy] ethoxydecylphosphonic acid):
10- [2- (2-methoxyethoxy) ethoxy] ethoxydecylphosphonic acid (hereinafter abbreviated as MTEG-PA) represented by the following formula (12) was synthesized.

  After adding 741.6 mg of oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) to the flask and substituting the inside of the flask with argon, triethylene glycol monomethyl ether (hereinafter abbreviated as MTEG, Tokyo) at 0 ° C. under an argon stream. 1.27 g (produced by Kasei Co., Ltd.) and distilled dimethylformamide (10 mL) were added and mixed, followed by stirring at room temperature for 30 minutes. The flask was placed in a cold water bath, and 9 mL of 1,10-dibromodecane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with stirring, followed by stirring at room temperature for 3.5 hours and further standing overnight at room temperature. 3 mL of methanol was added to the reaction mixture, stirred at room temperature for 30 minutes, and then concentrated under reduced pressure. 100 mL of methylene chloride was added to the reaction mixture after concentration, and the organic layer was separated, washed with water, dried over magnesium sulfate, filtered and concentrated, and vacuum dried at room temperature to obtain a crude product.

  The obtained crude product was purified using silica gel chromatography of n-hexane-ethyl acetate system to obtain purified 1-bromo-10- [2- (2-methoxyethoxy) ethoxy] ethoxydecane. 382.4 mg of 1-bromo-10- [2- (2-methoxyethoxy) ethoxy] ethoxydecane was added to the flask, the inside of the container was replaced with argon, and then tris (trimethylsilyl) phosphite (Tokyo) (Made by Kasei Co., Ltd.) 1.05 g was added and mixed. After stirring at 120 ° C. for 13.5 hours, the mixture was cooled to 85 ° C. with stirring, and excess tris (trimethylsilyl) phosphite was removed under reduced pressure. When no decrease in the amount of the mixture was observed, the mixture was cooled to room temperature.

  After returning the inside of the container to normal pressure with argon, tetrahydrofuran / water = 5/1 (volume ratio, 3.2 mL) was added, followed by stirring at room temperature for 3 hours and further stirring under reduced pressure for 1 hour. Chloroform was added to the remaining reaction mixture for extraction, the extract was passed through a silica gel column (silica gel amount 0.09 g), and the column was washed with chloroform. The extract and the washing solution passed through the column were combined and concentrated under reduced pressure. Ethanol was added to the residue to dissolve, and the solution was concentrated again under reduced pressure. The residue was dissolved by adding ethyl acetate, and then concentrated again under reduced pressure and vacuum dried at room temperature to obtain 351.6 mg of product.

The resulting product was identified by IR ^{spectrum, 2750cm -1, 2363cm -1,} phosphonic acid structure to 1199cm ^-1 and 1018 cm ^-1, ether structure derived MTEG to 1107cm ^-1, and 2928cm ^-1 and 2856cm ^{- 1} , absorption bands attributed to alkylphosphonic acid and MTEG-derived hydrocarbon structures were observed. Furthermore, in ¹ H-NMR measurement (solvent: CDCl ₃ ), δ1.16-1.84 (multiplet, 18 protons, phosphonic acid aliphatic chain), δ3.35 (singlet, 3 protons, methyl group), δ3. 42 (triplet, 2 protons, J = 6.6 Hz, phosphonic acid side methylene group adjacent to the ether bond), δ3.50-3.70 (multiplet, 12 protons), δ8.86 (broad singlet, 2 protons, Signals and integral values of phosphonic acid-derived hydroxyl groups) were observed, which were reasonable signals and integral values consistent with the expected structure. Therefore, it was concluded that purified MTEG-PA was obtained.

Synthesis Example 2 (Preparation of Ce _0.1 Ti _0.9 P ₂ O ₇ Nanoparticle Dispersion):
In accordance with the method described in Non-Patent Document 1, 100 ml of a mixed aqueous solution of cerium (IV) sulfate and titanium (IV) sulfate (cerium sulfate concentration 0.001N, titanium sulfate concentration 0.009N) and sodium pyrophosphate aqueous solution (pyrophosphate) Aggregated particles of Ce _0.1 Ti _0.9 P ₂ O ₇ having a minor axis number average primary particle size of about 20 nm were synthesized by a coprecipitation method in which 100 ml of sodium concentration 0.01 N) was mixed with water. Was sufficiently washed to remove by-product sodium sulfate. As a dispersant, an ethanol solution in which MTEG-PA obtained in Synthesis Example 1 having a weight of about 10 times the dry weight of the aggregated particles was dissolved was used, and the aggregated particles were redispersed in the ethanol solution. Mechanical crushing was performed using “Ultra Apex Mill” (registered trademark, zirconia beads having a particle diameter of 50 μm) manufactured by Kotobuki Giken Kogyo Co., Ltd. The primary particles of Ce _0.1 Ti _0.9 P ₂ O _{7 in} the ethanol dispersion thus obtained had a number average dispersed particle size of less than 50 nm.

<Synthesis Example of Aromatic Phosphate Esters>
Example 1 (Synthesis of phosphate ester of bisphenol A monophenyl carbonate):
The reaction scheme is shown below (common to Example 1 and Example 2).

  Bisphenol A (22.8 g, 1 equivalent) and pyridine (7.9 g) were dissolved in tetrahydrofuran (220 mL), ice-cooled, and tetrahydrofuran solution (80 mL) containing phenyl chloroformate (15.7 g, 1 equivalent) with stirring. ) Was added dropwise and stirring was continued at room temperature for 5 hours. Tetrahydrofuran was distilled off under reduced pressure, dissolved in methylene chloride, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. This concentrated residue was fractionated and purified by silica gel column chromatography (using Wako Gel C300 manufactured by Wako Pure Chemical Industries, Ltd.) to isolate bisphenol A monophenyl carbonate (compound A in Reaction Scheme 1, hereinafter abbreviated as BPA-MPC). . BPA-MPC (8.0 g), magnesium oxide (manufactured by Aldrich, purity 99.99% product: 7.2 g) and diethyl chlorophosphate (20 g) were mixed in a 200 mL eggplant flask whose inside was replaced with nitrogen gas. The temperature was gradually raised to 70 ° C. while stirring. The reaction started with foaming along the way.

  When the disappearance of BPA-MPC as a raw material was confirmed by UV irradiation of silica gel thin layer chromatography (hereinafter abbreviated as TLC, manufactured by Merck), it was concentrated under reduced pressure, and fractionated and purified by silica gel column chromatography as described above. Was phosphate ester-bonded diethyl phosphate (Compound B in Reaction Scheme 1, hereinafter abbreviated as BPA-MPC-Et2P). This structure was confirmed in the proton NMR spectrum because the protons of the aromatic ring and methyl group derived from the BPA-MPC residue and the ethyl group were observed with reasonable integral values. BPA-MPC-Et2P (5.0 g) thus obtained was dissolved in methylene chloride (40 mL), cooled with ice, and trimethylsilyl iodide (manufactured by Aldrich: 5.0 g) was added dropwise with stirring. After 30 minutes, the temperature was returned to room temperature. When the disappearance of BPA-MPC-Et2P as a raw material was confirmed by TLC, the solution was concentrated under reduced pressure.

  The concentrated residue was fractionally purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate system to ethyl acetate / methanol system, and finally a small amount of acetic acid was added thereto), and BPA-MPC- The target compound (compound C in reaction scheme 1, hereinafter abbreviated as BPA-MPC-PA) from which two ethyl esters were selectively deethylated was isolated from Et2P. This structure was confirmed by observing the protons of the aromatic ring and methyl group derived from the BPA-MPC residue with a reasonable integral value in the proton NMR spectrum, and the disappearance of the ethyl group proton.

Example 2 (Synthesis of bis (4-hydroxyphenyl) sulfone monophenyl carbonate phosphate ester):
In Example 13, which will be described later, bis (4-hydroxyphenyl) sulfone was used in place of bisphenol A, and the others were reacted at the same stoichiometric ratio, and the same purification operation was performed. The structure of the intermediate compound was confirmed in the same manner, and reasonable proton NMR spectrum results were obtained. Finally, the target compound (Compound D in Reaction Scheme 1, hereinafter abbreviated as BPS-MPC-PA) was isolated. In the confirmation of this structure, as in Example 1, each aromatic ring proton derived from the starting material was observed, and the protons derived from the two ethyl ester groups of the precursor (compound E in Reaction Scheme 1) disappeared. It confirmed from that.

Example 3 (Synthesis of phosphate ester of 4,4′-dihydroxybiphenyl monophenyl carbonate):
The reaction scheme is shown below.

  In Example 13, which will be described later, 4,4'-dihydroxybiphenyl was used in place of bisphenol A, and the others were reacted at the same stoichiometric ratio and subjected to the same purification operation. The structure of the intermediate compound was confirmed in the same manner, and reasonable proton NMR spectrum results were obtained. Finally, the target compound (Compound I in Reaction Scheme 2, hereinafter abbreviated as BPh-MPC-PA) was isolated. In the confirmation of this structure, each aromatic ring proton derived from the starting material was observed as in Example 1, and the protons derived from the two ethyl ester groups of the precursor (compound H in Reaction Scheme 2) disappeared. I confirmed it.

Example 4 (Synthesis of phosphate ester of trisphenol bisphenyl carbonate):
The reaction scheme is shown below (common to Example 4 and Example 5).

  In Example 1, 1,1,1-tris (4-hydroxybiphenyl) ethane (1 equivalent) was used instead of bisphenol A, and 2 equivalents of phenyl chloroformate were used for the same reaction and purification. In the first silica gel column chromatography, a monophenyl carbonate form was also isolated as a by-product. Others were reacted at the same stoichiometric ratio, and the same purification operation was performed. The structure of the intermediate compound was confirmed in the same manner, and reasonable proton NMR spectrum results were obtained. Finally, the target compound (Compound L in Reaction Scheme 3, hereinafter abbreviated as TP-BPC-PA) was isolated. In the confirmation of this structure, as in Example 1, each aromatic ring proton derived from the starting material was observed, and the protons derived from the two ethyl ester groups of the precursor (compound K in Reaction Scheme 3) disappeared. I confirmed it.

Example 5 (Synthesis of phosphate ester of trisphenol bisbenzoate ester):
In Example 4, the same reaction and purification were performed using benzoyl chloride instead of phenyl chloroformate. In the first silica gel column chromatography, a monobenzoate ester was also isolated as a by-product. Others were reacted at the same stoichiometric ratio, and the same purification operation was performed. The structure of the intermediate compound was confirmed in the same manner, and reasonable proton NMR spectrum results were obtained. Finally, the target compound (Compound O in Reaction Scheme 3, hereinafter abbreviated as TP-BBz-PA) was isolated. In the confirmation of this structure, as in Example 1, each aromatic ring proton derived from the starting material was observed, and the protons derived from the two ethyl ester groups of the precursor (compound N in Reaction Scheme 3) disappeared. It confirmed from that.

Example 6 (Synthesis of phosphate ester of trisphenol bisbenzyl ether):
In Example 4, benzyl bromide was used in place of phenyl chloroformate, and benzyl etherification was performed using potassium carbonate (4.5 equivalents ground in a mortar) and 18-crown-6 ether (0.4 equivalents) as the base. The same purification as in Example 1 was performed. In the first silica gel column chromatography, a monobenzyl ether was also isolated as a by-product. Others were reacted at the same stoichiometric ratio, and the same purification operation was performed. The structure of the intermediate compound was confirmed in the same manner, and reasonable proton NMR spectrum results were obtained. Finally, the target compound (Compound R in Reaction Scheme 3, hereinafter abbreviated as TP-BBE-PA) was isolated. Confirmation of this structure is similar to Example 1, in which each aromatic ring proton and benzylic proton derived from the starting material are observed, and derived from the two ethyl ester groups of the precursor (compound Q in Reaction Scheme 3). This was confirmed by the disappearance of protons.

Example 7 (Synthesis of phosphate ester of monobenzyl ether of bis (4-hydroxyphenyl) sulfone):
The reaction scheme is shown below.

  In Example 6, 1 equivalent of bis (4-hydroxyphenyl) sulfone was used instead of 1,1,1-tris (4-hydroxybiphenyl) ethane, 1 equivalent of benzyl bromide, 2.25 equivalents of potassium carbonate, 18 -Crown-6 ether was synthesized and purified in the same manner except that 0.2 equivalent was used. The structure of the intermediate compound was confirmed in the same manner, and reasonable proton NMR spectrum results were obtained. Finally, the target compound (Compound U in Reaction Scheme 4, hereinafter abbreviated as BPS-MBE-PA) was isolated. Confirmation of this structure is similar to Example 1, in which each aromatic ring proton and benzylic proton derived from the starting material are observed, and derived from the two ethyl ester groups of the precursor (compound T in Reaction Scheme 4). This was confirmed by the disappearance of protons.

Example 8 (Synthesis of phosphate ester of monobenzyl ether of bis (4-hydroxyphenyl) biphenyl):
The reaction scheme is shown below.

  In Example 7, the same synthesis and purification operations were performed except that bis (4-hydroxyphenyl) biphenyl was used instead of bis (4-hydroxyphenyl) sulfone. The structure of the intermediate compound was confirmed in the same manner, and reasonable proton NMR spectrum results were obtained. Finally, the target compound (Compound X in Reaction Scheme 5, hereinafter abbreviated as BPh-MBE-PA) was isolated. Confirmation of this structure is similar to Example 1, in which each aromatic ring proton and benzylic proton derived from the starting material are observed, and also derived from the two ethyl ester groups of the precursor (compound W in Reaction Scheme 5). This was confirmed by the disappearance of protons.

Example 9 (Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles-containing polycarbonate resin composition):
In Synthesis Example 2 such that the content of Ce _0.1 Ti _0.9 P ₂ O ₇ is 1% by weight in a pellet of polycarbonate resin (“NOVALEX 7025A” (registered trademark) manufactured by Mitsubishi Engineering Plastics). The obtained dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles was mixed, melt-kneaded at 260 ° C. using a “KZW15-30MG” twin-screw kneading extruder manufactured by Technobel, and polycarbonate resin. A composition was obtained.

Example 10: (Preparation by melt polymerization of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles-containing polycarbonate resin composition):
In the dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles obtained in Synthesis Example 2, bisphenol A and diphenyl carbonate are each dissolved in an amount 8 times the weight of the nanoparticles, and then heated to add ethanol. Distillation was removed under atmospheric pressure, and the temperature was raised to 270 ° C. while gradually reducing the pressure to proceed the polycondensation reaction between bisphenol A and diphenyl carbonate. An aqueous cesium carbonate solution was added as a polymerization catalyst. The content of nanoparticles in the obtained polycarbonate resin composition was about 10% by weight.

Comparative Example 1 (Polycarbonate resin composition containing titanium oxide particles):
In Example 9, instead of a dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles, a toluene dispersion of titanium oxide nanoparticles (average particle size 35 nm) manufactured by CI Kasei Co., Ltd. was used, and titanium oxide nanoparticles were used. A polycarbonate resin composition was obtained in the same manner as in Example 1 except that the addition amount was adjusted so that the content of 1 was 1% by weight.

In Example 9, Example 10, and Comparative Example 1, a 2 mm thick flat plate injection molded product was prepared, and the obtained molded product was visually evaluated for transparency. As a result, the visual transparency of the polycarbonate resin compositions obtained in Example 9 and Example 10 was superior to that of Comparative Example 1. This is thought to be because Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles have a smaller refractive index difference from the polycarbonate resin than titanium oxide. Further, the 2 mm-thick flat plate injection molded product prepared in Example 9, Example 10 and Comparative Example 1 may be referred to as a 130 W ultra-high pressure mercury lamp (hereinafter referred to as UHP lamp). The mercury lamps were observed for the progress of yellowing and white turbidity when irradiated with the mercury lamp. As a result, the molded products obtained in Example 9 and Example 10 had almost no change, but the molded product obtained in Comparative Example 1 progressed yellowing rapidly and was cloudy. This is considered that the photodecomposition reaction of the resin progressed at the interface with the polycarbonate resin due to the photocatalytic activity of the dispersed titanium oxide powder. It can be seen that the polycarbonate resin composition containing Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles has better light resistance.

Example 11 (Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles-containing PMMA resin composition):
The dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles obtained in Synthesis Example 2 and methyl methacrylate were mixed, and ethanol was distilled off by distillation. To the mixture (99.5 parts by weight) prepared by adding methyl methacrylate as appropriate and adjusting the weight ratio of methyl methacrylate to Ce _0.1 Ti _0.9 P ₂ O ₇ to be 95: 5, Initiator N, N-azobisisobutyronitrile (0.5 parts by weight) was added, poured into a flat plate under a nitrogen gas atmosphere, heated to 70 ° C. for radical polymerization, and PMMA resin A 2 mm thick flat plate-shaped product of the composition was prepared.

Comparative Example 2 (PMMA resin composition containing titanium oxide particles):
In Example 11, instead of a dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles, a toluene dispersion of titanium oxide nanoparticles (average particle size: 35 nm) manufactured by CI Kasei Co., Ltd. was used, and methyl methacrylate was used. A 2 mm thick plate-like molded product of the PMMA resin composition was prepared by performing the same operation as in Example 11 except that the addition amount was adjusted so that the weight ratio of titanium oxide nanoparticles to titanium oxide nanoparticles was 95: 5.

When the visual transparency of the 2 mm thick flat plate-shaped molded article of the PMMA resin composition prepared in Example 11 and Comparative Example 2 was compared, the transparency of the molded article prepared in Example 11 was superior. This is considered to be because Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles have a smaller refractive index difference from the PMMA resin than titanium oxide. Further, when the flat plate injection molded product having a thickness of 2 mm prepared in Example 11 and Comparative Example 2 is irradiated with a UHP lamp in the same manner as in Example 1, the yellowing of the molded product progresses and the white turbidity progresses. Observed about. As a result, the molded product obtained in Example 11 had almost no change, but the molded product obtained in Comparative Example 2 had a fast yellowing process and was clouded. This is considered that the photodecomposition reaction of the resin progressed at the interface with the PMMA resin due to the photocatalytic activity of the dispersed titanium oxide powder. Therefore, it can be seen that the PMMA resin composition containing Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles has better light resistance.

Example 12 (Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticle-containing polycycloolefin resin composition):
A pellet of polycycloolefin resin (“Zeonor 1600” (registered trademark, high heat resistance grade) manufactured by Zeon Co., Ltd.) was synthesized so that the Ce _0.1 Ti _0.9 P ₂ O ₇ content was 0.1% by weight. The dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles obtained in Example 2 was mixed and melt kneaded at 260 ° C. using a “KZW15-30MG” twin-screw kneading extruder manufactured by Technobel. A polycycloolefin resin composition was obtained.

Comparative Example 3 (Polycycloolefin resin composition containing titanium oxide particles):
In Example 12, instead of a dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles, a toluene dispersion of titanium oxide nanoparticles (average particle size: 35 nm) manufactured by CI Kasei Co., Ltd. was used, and titanium oxide nanoparticles were used. A polycycloolefin resin composition was obtained by performing the same operation as in Example 12 except that the amount added was adjusted so that the content of was 0.1 wt%.

In Example 12 and Comparative Example 3, a flat injection molded product having a thickness of 2 mm was prepared, and the obtained molded product was visually evaluated for transparency. As a result, the visual transparency of the polycycloolefin resin composition obtained in Example 12 was superior to that of Comparative Example 3. This is considered to be because Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles have a smaller refractive index difference from the polycycloolefin resin than titanium oxide. Further, when the flat plate injection molded product having a thickness of 2 mm prepared in Example 12 and Comparative Example 3 is irradiated with a UHP lamp in the same manner as in Example 1, the yellowing of the molded product proceeds and the white turbidity progresses. Was observed. As a result, the molded product obtained in Example 12 had almost no change, but the molded product obtained in Comparative Example 3 had a fast yellowing process and was clouded. This is considered that the photodecomposition reaction of the resin progressed at the interface with the polycycloolefin resin due to the photocatalytic activity of the dispersed titanium oxide powder. It can be seen that the polycycloolefin resin resin composition containing Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles has better light resistance.

Example 13 (Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles-containing polystyrene resin composition):
A dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles obtained in Synthesis Example 2 and styrene were mixed, and ethanol was distilled off by distillation. To the mixture (99.5 parts by weight) prepared by adding styrene appropriately, the weight ratio of styrene to Ce _0.1 Ti _0.9 P ₂ O ₇ was 99.7: 0.3. Initiator N, N-azobisisobutyronitrile (0.5 parts by weight) was added, poured into a flat plate under a nitrogen gas atmosphere, heated to 80 ° C. for radical polymerization, and polystyrene resin. A 2 mm thick flat plate-shaped product of the composition was prepared.

Comparative Example 4 (Polystyrene resin composition containing titanium oxide particles):
In Example 13, instead of a dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles, a toluene dispersion of titanium oxide nanoparticles (average particle size 35 nm) manufactured by CI Kasei Co., Ltd. was used and oxidized with styrene. A 2 mm thick flat plate molded product of polystyrene resin composition was prepared by performing the same operation as in Example 13 except that the addition amount was adjusted so that the weight ratio with respect to titanium nanoparticles was 99.7: 0.3. did.

When the visual transparency of the 2 mm-thick flat plate molded product of the polystyrene resin composition prepared in Example 13 and Comparative Example 4 was compared, the transparency of the molded product prepared in Example 13 was superior. This is presumably because Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles have a smaller refractive index difference from polystyrene resin than titanium oxide. Further, when the flat plate injection molded product having a thickness of 2 mm prepared in Example 13 and Comparative Example 4 is irradiated with a UHP lamp in the same manner as in Example 1, the yellowing of the molded product progresses and the white turbidity progresses. Observed about. As a result, there was almost no change in the molded product obtained in Example 13, but the molded product obtained in Comparative Example 4 had a fast yellowing and white turbidity. This is considered that the photodecomposition reaction of the resin progressed at the interface with the polystyrene resin due to the photocatalytic activity of the dispersed titanium oxide powder. Therefore, it can be seen that the polystyrene resin composition containing Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles has better light resistance.

Example 14 (Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticle-containing polyarylate resin composition):
In Synthesis Example 2 such that the content of Ce _0.1 Ti _0.9 P ₂ O ₇ is 1 wt% in pellets of polyarylate resin (“U Polymer U-100” (registered trademark) manufactured by Unitika). The obtained Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticle dispersion was mixed, melt-kneaded at 290 ° C. using a “KZW15-30MG” twin-screw kneading extruder manufactured by Technobel, and polyarylate. A resin composition was obtained.

Comparative Example 5 (polyarylate resin composition containing titanium oxide particles):
In Example 14, instead of a dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles, a titanium dispersion of titanium oxide nanoparticles (average particle size: 35 nm) manufactured by CI Kasei Co., Ltd. was used. A polyarylate resin composition was obtained in the same manner as in Example 14 except that the addition amount was adjusted so that the content of 1 was 1% by weight.

In Example 14 and Comparative Example 5, a flat injection molded product having a thickness of 2 mm was prepared, and the obtained molded product was visually evaluated for transparency. As a result, the visual transparency of the polyarylate resin composition obtained in Example 14 was superior to that of Comparative Example 5. This is considered to be because Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles have a smaller refractive index difference from the polyarylate resin than titanium oxide. Further, when the flat plate injection molded product having a thickness of 2 mm prepared in Example 14 and Comparative Example 5 is irradiated with a UHP lamp in the same manner as in Example 1, the yellowing of the molded product proceeds and the white turbidity progresses. Observed about. As a result, there was almost no change in the molded product obtained in Example 14, but the molded product obtained in Comparative Example 5 had a fast yellowing process and was clouded. This is considered that the photodecomposition reaction of the resin progressed at the interface with the polyarylate resin due to the photocatalytic activity of the dispersed titanium oxide powder. It can be seen that the polyarylate resin resin composition containing Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles has better light resistance.

Example 15 (Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticle-containing PET resin composition):
Ce _0.1 Ti _0.9 P ₂ O ₇ content is contained in pellets of polyethylene terephthalate (PET) resin (inherent viscosity [η] = 0.64 (dL / g)) produced using antimony trioxide as a polymerization catalyst. The dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles obtained in Synthesis Example 2 was mixed so as to be 2% by weight, and a “KZW15-30MG” twin-screw kneading extruder manufactured by Technobel was used. Used and melt-kneaded at 285 ° C. to obtain a PET resin composition.

Comparative Example 6 (Titanium oxide particle-containing PET resin composition):
In Example 7, instead of a dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles, a toluene dispersion of titanium oxide nanoparticles (average particle size: 35 nm) manufactured by CI Kasei Co., Ltd. was used, and titanium oxide nanoparticles were used. A PET resin composition was obtained in the same manner as in Example 7, except that the addition amount was adjusted so that the content of was 2% by weight.

In Example 15 and Comparative Example 6, a plate-like injection molded product having a thickness of 2 mm was prepared, and the obtained molded product was visually evaluated for transparency. As a result, the visual transparency of the PET resin composition obtained in Example 15 was superior to that of Comparative Example 6. This is considered to be because Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles have a smaller refractive index difference from the PET resin than titanium oxide. Further, when the flat plate injection molded product having a thickness of 2 mm prepared in Example 15 and Comparative Example 6 is irradiated with a UHP lamp in the same manner as in Example 1, the yellowing of the molded product progresses and the white turbidity progresses. Was observed. As a result, there was almost no change in the molded product obtained in Example 15, but the molded product obtained in Comparative Example 6 progressed yellowing rapidly and was cloudy. This is considered that the photodecomposition reaction of the resin progressed at the interface with the PET resin due to the photocatalytic activity of the dispersed titanium oxide powder. It can be seen that the PET resin resin composition containing Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles has better light resistance.

Example 16 (Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles-containing polypropylene resin composition):
The content of Ce _0.1 Ti _0.9 P ₂ O ₇ is 50% by weight in pellets of polypropylene resin (“NOVATEC PP” (registered trademark, ASTM standard D1238 melt index = 1.9) manufactured by Nippon Polypro Co., Ltd.) Thus, the dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles obtained in Synthesis Example 2 was mixed and 230 ° C. using a “KZW15-30MG” twin-screw kneading extruder manufactured by Technobel. The high-concentration polypropylene resin composition was excellent in dispersibility of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles during dilution kneading. Useful as a batch.

Example 17 (Diluted molded product of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles-containing polypropylene resin composition):
The polypropylene resin composition (10 parts by weight) obtained in Example 16 and the Novatec PP (90 parts by weight) used in Example 16 were dry blended and a “KZW15-30MG” twin-screw kneading extruder manufactured by Technobel was used. Then, it was injection-molded at 230 ° C. and made into a dumbbell-shaped molded piece (thickness 1/8 inch) for tensile test of ASTM standard D638.

Comparative Example 7 (Titanium oxide particle-containing polypropylene resin composition):
In Example 16, instead of a dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles, a toluene dispersion of titanium oxide nanoparticles (average particle size: 35 nm) manufactured by CI Kasei Co., Ltd. was used, and titanium oxide nanoparticles were used. A polypropylene resin composition was obtained in the same manner as in Example 16 except that the addition amount was adjusted so that the content of was 5% by weight. A polypropylene resin composition obtained by using a “KZW15-30MG” twin-screw kneading extruder manufactured by Technobell was injection molded at 230 ° C., and a dumbbell-shaped molded piece (1/8 inch in thickness) for ASTM standard D638. ) Created.

The tensile test pieces in Example 17 and Comparative Example 7 were observed for the progress of yellowing of the molded product when irradiated with a UHP lamp in the same manner as in Example 1. As a result, the molded product obtained in Example 17 hardly changed, but the molded product obtained in Comparative Example 7 progressed yellowing rapidly. In addition, the photocatalytic activity of the dispersed titanium oxide powder caused the photodecomposition reaction of the resin to proceed at the interface with the polypropylene resin, thereby reducing the toughness (tensile elongation at break) of the resin composition. It can be seen that the polypropylene resin resin composition containing Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles has better light resistance.

Example 18 (Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticle-containing polycarbonate / polyester blend resin composition):
The pellet content of polycarbonate / polyester blend resin (“Xylex X7200MR (registered trademark)” manufactured by GE Plastics, Japan) is such that the Ce _0.1 Ti _0.9 P ₂ O ₇ content is 1% by weight. The dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles obtained in Synthesis Example 2 was mixed and melted at 250 ° C. using a “KZW15-30MG” twin-screw kneading extruder manufactured by Technobel. The mixture was kneaded to obtain a polycarbonate / polyester blend resin composition.

Comparative Example 8 (polycarbonate / polyester blend resin composition containing titanium oxide particles):
In Example 18, instead of the dispersion of Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles, a toluene dispersion of titanium oxide nanoparticles (average particle size: 35 nm) manufactured by CI Kasei Co., Ltd. was used, and the titanium oxide nanoparticles were used. A polycarbonate / polyester blend resin composition was obtained in the same manner as in Example 18 except that the addition amount was adjusted so that the content of was 1% by weight.

In Example 18 and Comparative Example 8, a flat injection molded product having a thickness of 2 mm was prepared, and the obtained molded product was visually evaluated for transparency. As a result, the visual transparency of the PET resin composition obtained in Example 18 was superior to that of Comparative Example 8. This is presumably because Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles have a smaller refractive index difference from the polycarbonate / polyester blend resin than titanium oxide. Further, when the flat plate injection molded product having a thickness of 2 mm prepared in Example 18 and Comparative Example 8 is irradiated with a UHP lamp in the same manner as in Example 1, the yellowing of the molded product progresses and the white turbidity progresses. Was observed. As a result, the molded product obtained in Example 10 had almost no change, but the molded product obtained in Comparative Example 8 had a fast yellowing progress and was cloudy. This is considered that the photodecomposition reaction of the resin progressed at the interface with the PET resin due to the photocatalytic activity of the dispersed titanium oxide powder. It can be seen that the polycarbonate / polyester blend resin composition containing Ce _0.1 Ti _0.9 P ₂ O ₇ nanoparticles has better light resistance.

Example 19 (flat plate molded product of polycarbonate resin composition):
The polycarbonate resin composition produced in Example 9 was injection-molded onto a 2 mm thick flat plate, and an antireflection coat (thickness: about 1 μm) in which silicon oxide (silica) and titanium oxide were deposited on each side was formed.

Comparative Example 9 (Plate molded body of polycarbonate resin):
Novalex 7025A, which is a PC resin used in Example 9, was injection-molded on a 2 mm thick flat plate, and an antireflection coating (thickness of about 1 μm) in which silicon oxide (silica) and titanium oxide were deposited on each side was provided.

Example 20 (Plate molding of polyarylate resin composition):
The polyarylate resin composition produced in Example 6 was injection-molded into a 2 mm thick flat plate, and an antireflection coat (thickness: about 1 μm) in which silicon oxide (silica) and titanium oxide were deposited on each side was formed.

Comparative Example 10 (polyarylate resin flat plate molded body):
Anti-reflective coating in which polyarylate resin ("U polymer U-100" (registered trademark) manufactured by Unitika Co., Ltd.) used in Example 14 was injection-molded onto a 2 mm thick flat plate, and silicon oxide (silica) and titanium oxide were vapor deposited. (Thickness of about 1 μm) was formed on both sides.

  The antireflection coating surface of the flat molded body obtained in Examples 19 and 20 and Comparative Examples 9 and 10 was irradiated with a UHP lamp in the same manner as in Example 9 (the temperature of the flat molded body was about 100). ° C). In the flat molded article of the polycarbonate resin of Comparative Example 9, cracks occurred in the antireflection coating earlier than the flat molded article of the polycarbonate resin composition of Example 19. Similarly, in the flat molded body of the polyarylate resin of Comparative Example 10, cracks occurred in the antireflection coating earlier than the flat molded body of the polyarylate resin composition of Example 20.

<Polycarbonate resin resin composition (containing HAp particles) prepared by solution mixing method and molded article thereof>
Example 21 (when aromatic phosphate ester is used as a dispersant for HAp particles):
(1) Synthesis of dispersion:
Synthesis of Hydroxyapatite Particle Dispersion (Synthesis Example 3):
K. Sonoda, et al. , Solid State Ionics, Vol. 151, 321-327 (2002), hydroxyapatite particles (hereinafter abbreviated as HAp particles) were synthesized. That is, dodecane (400 mL) in which pentaethylene glycol dodecyl ether (5 g) was dissolved was heated to 70 ° C., and a 2.5 mol / L calcium hydroxide aqueous suspension (100 mL) was added for 1 hour with vigorous stirring. And stirring was continued for another hour. Next, while continuing vigorous stirring at 70 ° C., a 1.5 mol / L potassium dihydrogen phosphate (KH ₂ PO ₄ ) aqueous solution (100 mL) was added dropwise over 1 hour, and the reaction was continued for another 24 hours. . The particulate product was centrifuged, washed several times with a large amount of water, then several times with ethanol, and dried in a hot air oven at 60 ° C.

  Further, the obtained powder was fired in an air at 650 ° C. for 1 hour in an electric furnace to burn off organic components. The crystal structure of the HAp particles thus obtained was confirmed from the X-ray scattering spectrum. The HAp particles and 30% by weight of TP-BPC-PA (synthesized in Example 4) were dispersed in tetrahydrofuran so that the concentration of HAp particles was 2% by weight, and the Ultra used in Synthesis Example 2 was used. Mechanical crushing was performed using an apex mill. The number average particle size of the primary particles of the HAp particles in the tetrahydrofuran dispersion thus obtained was 45 nm for the minor axis and 120 nm for the major axis.

(2) Production of resin composition:
As a dispersion of phosphate particles, the tetrahydrofuran dispersion of HAp surface-treated with TP-BPC-PA obtained in Synthesis Example 3 was used, and this was mixed with a polycarbonate resin ("NOVAREX 7030A" manufactured by Mitsubishi Engineering Plastics) ( (Registered Trademark)) was mixed with a 9% by weight methylene chloride solution of pellets so that the weight ratio of HAp to polycarbonate resin was 2:98 and concentrated under reduced pressure. The obtained solid content was melt-kneaded at 280 ° C. under reduced pressure using a lab plast mill manufactured by Shimadzu Corporation (model: 10C100, equipped with a segment mixer having an internal volume of 60 mL) to obtain a polycarbonate resin composition. This resin composition was hot press molded at 250 ° C. into a 1 mm thick flat plate.

  On the other hand, this resin composition was dissolved in a sufficient amount of methylene chloride, a white insoluble component was precipitated by centrifugation, and the supernatant was separated and removed by decantation. The operation of dispersing the precipitate again in methylene chloride and then carrying out the same centrifugation and removing the supernatant by decantation was repeated three times in total. When the final precipitate was subjected to the thermal loss (TG-DTA) measurement using 20 mg of the powder vacuum-dried at 120 ° C. for 12 hours or more as a sample, the thermal loss was 60% by weight of the powder.

Example 22 (when aliphatic phosphate is used as a dispersant for HAp particles):
(1) Synthesis of dispersion:

Synthesis of Hydroxyapatite Particle Dispersion (Synthesis Example 4):
In Example 21, instead of TP-BPC-PA which is a surface treatment agent, JP-506H which is an aliphatic phosphate ester manufactured by Johoku Chemical Industry Co., Ltd. (the structural formula is (C ₄ H ₉ OC ₂ H ₄ O)) _n P (O) (OH) _{3 -n} ; butoxyethyl acid phosphate (n = 1, 2) was used in the same manner except that 30% by weight of the HAp particles were used. The number average of primary particles of HAp particles in the tetrahydrofuran dispersion thus obtained was equivalent to Example 21.

(2) Production of resin composition:
In Example 21, the same procedure was followed except for using the tetrahydrofuran dispersion of HAp surface-treated with JP-506H obtained in Synthesis Example 4 as the dispersion of phosphate particles. A thick plate compact was obtained. The thermal loss analysis of the methylene chloride insoluble component of this resin composition was conducted in the same manner as in Example 21. As a result, the thermal loss was 35% by weight.

<Resin composition (containing PZr particles) prepared by a solution mixing method and molded body thereof (including formation of inorganic thin film)>
Example 23 (when an aromatic phosphate is used as a dispersing agent for PZr particles):
(1) Synthesis of dispersion:

Synthesis of dispersion of zirconium phosphate particles (Synthesis Example 5):
At room temperature with stirring to dissolve the phosphate (12 g) in hydrochloric acid (100 mL) of 2N concentration, dissolution 16g of zirconium chloride oxide octahydrate to (ZrOCl ₂ · _{8H 2} O) in 2 normal concentration of hydrochloric acid (50 mL) Was added dropwise. The purified white fine particles were allowed to stand at room temperature overnight and centrifuged. The operation of suspending and stirring the white fine particles in water, washing and centrifuging was repeated 4 times, and it was confirmed by adding silver nitrate aqueous solution that no white precipitate was formed by adding aqueous silver nitrate solution to the supernatant liquid. . The total amount of white fine particles thus obtained (considered as amorphous zirconium phosphate) was stirred and dispersed in a 10 mol / L phosphoric acid aqueous solution (320 mL) for a total of 62 hours, and the white fine particles were centrifuged. did.
Further, the operation of suspending the white fine particles in water, washing and centrifuging was repeated and purified. The white powder thus obtained was confirmed to be α-zirconium phosphate particles (hereinafter abbreviated as PZr particles) having an interlayer distance of 0.75 nm from the X-ray scattering spectrum.

  After drying the PZr particles in a hot air oven at 60 ° C., 30% of the weight of TP-BPC-PA (synthesized in Example 4) is mixed, and mechanical crushing is performed in the same manner as in Synthesis Example 3. Thus, a tetrahydrofuran dispersion was obtained. The average number of primary particles of PZr particles in the tetrahydrofuran dispersion thus obtained was 20 nm for the minor axis and 200 nm for the major axis.

(2) Production of resin composition:
In Example 21, as a dispersion of phosphate particles, the tetrahydrofuran dispersion of PZr surface-treated with TP-BPC-PA obtained in Synthesis Example 5 was used, and PZr and polycarbonate resin (Novalex 7030A) were mixed. The liquid mixture prepared so that a weight ratio might be set to 30:70 was obtained. The solid content obtained by concentrating this mixed solution was molded into a 1 mm-thick flat plate in the same manner as in Example 21, and the same test was conducted. Insoluble components were separated and purified in the same manner as in Example 21, and then dried in vacuo. The heat loss was measured in the same manner as in Example 21 and was 25% by weight.

Example 24 (when ester-type aromatic phosphate is used as a dispersant for PZr particles):
(1) Synthesis of dispersion:

Synthesis of dispersion of PZr particles (Synthesis Example 6):
A tetrahydrofuran dispersion was obtained in the same manner as in Synthesis Example 5 except that the ester type TP-BBz-PA synthesized in Example 5 was used instead of TP-BPC-PA. The average number of primary particles of PZr particles in the tetrahydrofuran dispersion thus obtained was 20 nm for the minor axis and 200 nm for the major axis.

(2) Production of resin composition:
In Example 23, the PZr tetrahydrofuran dispersion surface-treated with TP-BBz-PA obtained in Synthesis Example 6 was used as a dispersion of phosphate particles, and the weight ratio of PZr to polycarbonate resin was 5:95. The resin composition and its 1 mm-thick flat plate molded body were obtained by performing the same operations as in Example 21 except that the formulation was prepared as described above. When the heat loss of the methylene chloride insoluble component of the resin composition was measured in the same manner as in Example 21, it was 40% by weight of the insoluble component.

Example 25 (when an ether type aromatic phosphate ester is used as a dispersant for PZr particles):
(1) Synthesis of dispersion:

Synthesis of dispersion of PZr particles (Synthesis Example 7):
A tetrahydrofuran dispersion was obtained in the same manner as in Synthesis Example 5 except that the ether type BPh-MBE-PA synthesized in Example 8 was used instead of TP-BPC-PA. The primary particles of the PZr particles in the tetrahydrofuran dispersion thus obtained were layered, and the number average was 20 nm for the minor axis and 200 nm for the major axis.

(2) Production of resin composition:
In Example 23, the PZr tetrahydrofuran dispersion surface-treated with BPh-MBE-PA obtained in Synthesis Example 7 was used as the phosphate particle dispersion, and the weight ratio of PZr to polycarbonate resin was 1:99. The resin composition and its 1 mm-thick flat plate molded body were obtained by performing the same operations except that the components were prepared as described above. When the heat loss of the methylene chloride insoluble component of this resin composition was measured in the same manner as in Example 23, it was 20% by weight of the insoluble component.

<Resin composition (containing PTi particles) prepared by a solution mixing method and its molded body>
Example 26 (Lamination of PTi / polycarbonate resin composition and polycarbonate resin sheet by solution mixing method):
(1) Synthesis of dispersion:

Synthesis of dispersion of PTi particles (Synthesis Example 8):
In Synthesis Example 5, the same operation was performed except that titanium tetrachloride (9.4 g) was used instead of zirconium chloride octahydrate. However, titanium tetrachloride was added dropwise as it was without diluting, while cooling the reaction solution with ice (to generate heat). The obtained white fine particles were confirmed to be α-titanium phosphate particles (hereinafter abbreviated as PTi particles) having an interlayer distance of 0.76 nm from the X-ray scattering spectrum. After drying the PTi particles in a hot air oven at 60 ° C., 30% of the weight of TP-BPC-PA (synthesized in Example 4) is mixed, and mechanical crushing is performed in the same manner as in Synthesis Example 3. Thus, a tetrahydrofuran dispersion was obtained. The number average of primary particles of PTi particles in the tetrahydrofuran dispersion thus obtained was 20 nm for the minor axis and 200 nm for the major axis.

(2) Production of resin composition:
In Example 23, using a dispersion of PTi surface-treated with TP-BPC-PA obtained in Synthesis Example 8 as a dispersion of phosphate particles, the weight ratio of PTi to polycarbonate resin was 50:50. A resin composition and a 1 mm-thick flat plate molded body were obtained by performing the same operation except that the composition was as follows. When the heat loss of the methylene chloride insoluble component of this resin composition was measured in the same manner as in Example 23, it was 15% by weight of the insoluble component.

Comparative Example 11:
In Example 21, the toluene dispersion of the titanium oxide nanoparticles (average particle size 35 nm) used in Comparative Example 1 was used instead of the HAp particles, and the added amount of TP-BPC-PA as a dispersant (weight of the titanium oxide nanoparticles) And the weight ratio of titanium oxide nanoparticles to polycarbonate resin (2:98), and the same operations as in Example 21 were carried out to obtain a resin composition and its 1 mm thick flat plate molded body. The heat loss analysis of the methylene chloride insoluble component of this resin composition was conducted in the same manner as in Example 21. As a result, the heat loss was 7% by weight.

  The properties of the 5 mm examples of Examples 21 to 26 and the 1 mm thick flat plate molded body of Comparative Example 11 were compared. When bent by hand, the molded body of Example 21 was harder to break than the molded body of Example 22, and was excellent in toughness. All of the molded articles of these five examples had transparency, but the molded article of Comparative Example 11 was cloudy. This is presumably because the difference between the refractive index of the dispersed inorganic particles and the refractive index of the polycarbonate resin is larger in the case of the titanium oxide nanoparticles of Comparative Example 11.

  In the same manner as in Example 9, the progress of the yellowing of the molded product when the UHP lamp was irradiated was observed. As a result, there was almost no change in the molded bodies of the five examples of Examples 21 to 26, but the yellowing of the molded body of Comparative Example 11 was observed. Therefore, when phosphate particles are dispersed using a phosphate ester dispersant, light resistance is better than when conventional metal oxide ultraviolet absorbers such as titanium oxide are similarly dispersed. I understand.

Claims (14)

  It is characterized by comprising a thermoplastic resin (A) and ultraviolet-absorbing particles, nanoparticles (B) containing phosphorus atoms, or ultraviolet-absorbing particles (C-1) containing the particles and a dispersant. A thermoplastic resin composition. A thermoplastic resin (A), formula _{Ce 1-n Ti n P 2} O 7 ( where n is any number of 0 to 1. representing the metal composition) UV absorbing particles consisting of pyrophosphate particles represented by A thermoplastic resin composition comprising (B) and / or ultraviolet absorbing particles (C-2) containing pyrophosphate particles and a dispersant.   The thermoplastic resin composition according to claim 1, wherein the nanoparticles (B) containing phosphorus atoms are phosphates.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the number average particle diameter of the primary particles of the ultraviolet absorbing particles (B) is 1 to 100 nm.   The thermoplastic resin composition according to any one of claims 1 to 4, wherein the number average particle diameter of primary particles of pyrophosphate particles or phosphate particles in the ultraviolet absorbing particles is 1 to 100 nm.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the primary particles of the ultraviolet absorbing particles have a number average particle size of 0.01 to 50 µm.   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the content of the ultraviolet-absorbing particles is 0.01 to 90% by weight with respect to the entire thermoplastic resin composition.   The thermoplastic resin composition according to any one of claims 1 to 7, wherein the dispersant is an aromatic phosphate ester.   It is a manufacturing method of the thermoplastic resin composition in any one of Claims 1-8, Comprising: The nanoparticle obtained by crushing the particle | grains which are an ultraviolet absorptive particle and contain a phosphorus atom in presence of a dispersing agent. A method for producing a thermoplastic resin composition, comprising preparing particles and mixing the ultraviolet-absorbing particles with a raw material for producing a thermoplastic resin, a reaction mixture of the raw material for production, and / or the obtained thermoplastic resin.   It is a manufacturing method of the thermoplastic resin composition in any one of Claims 1-8, Comprising: The process of mixing the nanoparticle which is an ultraviolet-absorbing particle and contains a phosphorus atom in the solution of a thermoplastic resin. A method for producing a thermoplastic resin composition, comprising:   The molded article made of the thermoplastic resin composition according to any one of claims 1 to 8, which has a thickness of 0.001 to 100 mm.   The molded body according to claim 11, which has an inorganic thin film on the surface of the molded body. Aromatic phosphate esters represented by any one of the following general formulas (1) to (6).

In general formulas (1) to (6), m and n are independently a natural number of 2 or less, R ¹ is an alkyl group having 12 or less carbon atoms, an aryl group having 12 or less carbon atoms, or an alkoxy having 12 or less carbon atoms. any group or more than 12 aryloxy group having a carbon, R x ^(where x is a natural number of 2 to 5) each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 12 or less carbon atoms, R ⁶ is An alkyl group or an aryl group having 12 or less carbon atoms, R is a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms, L is a carbonyl group (-CO-), a sulfide bond (-S-), a sulfoxide bond (-SO -) and a sulfone bond (-SO ₂ - one of) represent respectively.   Ultraviolet absorbing particles surface-treated with any of the aromatic phosphate esters according to claim 13.