JP2018138627A - Organic/inorganic composite composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic/inorganic composite composition improved in moldability and optical characteristics.SOLUTION: An organic/inorganic composite composition contains thermoplastic resin (A) and inorganic particles (B), and satisfies (1)-(3) requirements. (1) a melt viscosity when a shear rate is 1,000(1/s) is 10-1,000 Pa s. (2) when power approximating a relation between a melt viscosity and a shear rate and showing by Y=AX, a value of B is -2≤B<-0.1(X is a shear rate;Y is a melt viscosity; and A is a constant). (3) a number-based median size D50 of the inorganic particle (B) is 1nm<D50<20nm, and a relation between a number-based median size of the inorganic particle (B) and a volume content of the inorganic particle (B) is V≤0.65×D50+12.1 [V is a volume content of the inorganic particle (B), and D50 is a number-based median size of the inorganic particle (B)].SELECTED DRAWING: None

Description

  The present invention relates to an organic-inorganic composite composition.

  Thermoplastic resins are being used in a wide range of fields such as mechanical mechanism parts, electrical and electronic parts, and automobile parts, taking advantage of their excellent heat resistance and other properties. In recent years, the demand for improved properties of molded products has increased with technological advances, and there has been a demand for manufacturing technology for molded products having more complicated shapes while maintaining the properties. It has come to be desired. Therefore, various techniques have been studied for improving the fluidity and mechanical properties of thermoplastic resins.

  For example, Patent Document 1 discloses a resin composition in which 0.5 to 100 parts by weight of a liquid crystalline resin (B) is blended with 100 parts by weight of a thermoplastic resin (A) having a glass transition temperature of 120 ° C. or higher. Thus, a thermoplastic resin composition in which the melting viscosity of the liquid crystalline resin (B) at + 10 ° C. satisfies a specific relationship is disclosed.

Patent Document 2 discloses (A) an anisotropy having a melt viscosity of 100 to 300 Pa · s as measured by a capillary rheometer at 300 ° C. and a shear rate of 1000 sec ⁻¹ using a nozzle having an inner diameter of 1 mm and a length of 20 mm. With respect to 100 parts by weight of a resin composition consisting of 91 to 99% by weight of a thermoplastic resin that does not form a melt phase and (B) 1 to 9% by weight of a liquid crystalline polymer that can form an anisotropic melt phase, (C) Heat in which 0.001 to 2 parts by weight of one or two or more selected from the phosphorus oxoacid monoesters and diesters represented by the general formulas (I) and (II) are blended and (B) the liquid crystalline polymer is dispersed in particles a thermoplastic resin composition, (a) of the component (B), an inner diameter of 1 mm, a nozzle length 20 mm, 300 ° C., capillary at a shear rate of 1,000 sec ^-1 Reome The short side / long side ratio of the rectangular surface obtained by injection molding a thermoplastic resin composition having a melt viscosity ratio (Aη) / (Bη) of 3.2 to 4.0 is 0.5. An information recording medium component that is 3 to 1.0 and has a rectangular surface thickness of 0.3 to 3 mm is disclosed.

JP 2000-313812 A JP 2007-217628 A

  According to the technique described in the above patent document, the fluidity and mechanical properties of the thermoplastic resin composition are improved to some extent. However, for fine and ultra-thin products such as smartphone lenses, for which demand has been increasing dramatically recently, improvements in moldability, optical properties, etc. are necessary. With the technology described in the above patent document, It has been found that the improvement of these characteristics is insufficient.

  Accordingly, an object of the present invention is to provide an organic-inorganic composite composition having improved moldability and optical properties.

  The present inventors have conducted intensive research to solve the above problems. As a result, an organic-inorganic composite composition containing inorganic particles and a thermoplastic resin having a particle size in a specific range, the melt viscosity of the composition being in a specific range, and the particle size and composition of the inorganic particles The organic-inorganic composite composition satisfying a specific formula when the volume content in the specific range is within a specific range and the relationship between the shear rate and the melt viscosity of the composition approximates to a power is to solve the above problem. The headline and the present invention were completed.

That is, the present invention is an organic-inorganic composite composition that includes the thermoplastic resin (A) and the inorganic particles (B) and satisfies the following (1) to (3):
(1) In the range of the melting point of the thermoplastic resin (A) from + 10 ° C. to + 30 ° C., the organic-inorganic composite composition has a melt viscosity of 10 Pa · s to 1000 Pa · s when the shear rate is 1000 (1 / s). (2) In the range from the melting point + 10 ° C. to + 30 ° C. of the thermoplastic resin (A), the relationship between the melt viscosity and the shear rate of the organic-inorganic composite composition is approximated to the power, and the following formula (I) The value of B when represented by − is not less than −2 and less than −0.1

  (3) The number-based median diameter of the inorganic particles (B) is more than 1 nm and less than 20 nm, the number-based median diameter of the inorganic particles (B) and the inorganic particles in the organic-inorganic composite composition ( The relationship with the volume content of B) satisfies the following formula (1).

  According to the present invention, an organic-inorganic composite composition having improved moldability and optical properties is provided.

  Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 ° C. or more and 25 ° C. or less) / relative humidity 40% RH or more and 60% RH or less. In the present specification, the organic-inorganic composite composition of the present invention is also simply referred to as “the composition of the present invention” or “composition”.

The present invention is an organic-inorganic composite composition comprising a thermoplastic resin (A) and inorganic particles (B) and satisfying the following (1) to (3):
(1) In the range of the melting point of the thermoplastic resin (A) from + 10 ° C. to + 30 ° C., the organic-inorganic composite composition has a melt viscosity of 10 Pa · s to 1000 Pa · s when the shear rate is 1000 (1 / s). (2) In the range from the melting point + 10 ° C. to + 30 ° C. of the thermoplastic resin (A), the relationship between the melt viscosity and the shear rate of the organic-inorganic composite composition is approximated to the power, and the following formula (I) The value of B when represented by − is not less than −2 and less than −0.1

  (3) The relationship between the number-based median diameter of the inorganic particles (B) and the volume content of the inorganic particles (B) in the organic-inorganic composite composition satisfies the following formula (1).

  The organic-inorganic composite composition of the present invention having such a configuration is excellent in moldability and optical characteristics.

[Requirements for (1) above]
The composition of the present invention has a melting viscosity of 10 Pa · s or more at a shear rate of 1000 (1 / s) of the organic-inorganic composite composition in the range of the melting point of the thermoplastic resin (A) + 10 ° C. to + 30 ° C. 1000 Pa · s or less. When the melt viscosity is less than 10 Pa · s, molding defects such as burrs occur when the composition of the present invention is molded. On the other hand, when the melt viscosity exceeds 1000 Pa · s, molding cannot be performed. The melt viscosity is preferably 50 Pa · s or more and 600 Pa · s or less.

  The melt viscosity at a shear rate of 1000 (1 / s) of the composition of the present invention can be measured by the method described in the examples.

[Requirements for (2) above]
The composition of the present invention approximates the relationship between the melt viscosity and the shear rate of the organic-inorganic composite composition in the range of the melting point of the thermoplastic resin (A) from + 10 ° C. to + 30 ° C. When represented, the value of B is -2 or more and less than -0.1.

  When molding (especially injection molding) a composition containing a thermoplastic resin, a wide range of shear rate is applied to the composition, and therefore it is preferable that the composition flows substantially uniformly in the same range. For this purpose, the composition is required to have a property that the melt viscosity hardly changes in a wide shear rate region. The composition of the present invention approximates the relationship between the melt viscosity of the organic-inorganic composite composition and the shear rate in the range from the melting point of the thermoplastic resin (A) + 10 ° C. to + 30 ° C. When represented, the value of B is -2 or more and less than -0.1. Therefore, regardless of what shear rate is applied, the composition of the present invention flows substantially uniformly in the same manner, and a highly accurate molded product can be obtained even in a thin and fine shape.

  When the value of B in the above formula (I) is less than −2, the melt viscosity of the composition at a low shear rate is too high, and molding (particularly injection molding) becomes impossible. On the other hand, if the value of B in the formula (I) is −0.1 or more, the effect of the present invention cannot be obtained. The value of B is preferably −1.5 or more and less than −0.1.

  The value of B in the above formula (I) is determined by measuring the melt viscosity of the composition of the present invention by the method described in the Examples, and plotting the logarithm of the melt viscosity (vertical axis) against the shear rate (horizontal axis). Thus, it can be calculated by obtaining a power approximation curve.

  The requirements (1) and (2) are controlled by the type and molecular weight of the thermoplastic resin (A), the type of inorganic particles (B), the particle diameter, the amount of inorganic particles (B) added, and the like. be able to.

[Requirements for (3) above]
The composition of the present invention has a number-based median diameter of the inorganic particles (B) of more than 1 nm and less than 20 nm, the number-based median diameter of the inorganic particles (B), and the organic-inorganic composite composition. The relationship with the volume content of the inorganic particles (B) satisfies the above formula (1).

  In order to obtain a composition having excellent moldability and optical properties, it is difficult for only the thermoplastic resin (A) to satisfy these properties, and the addition of inorganic particles (B) is essential. At this time, as a result of intensive studies by the present inventors on the amount of inorganic particles (B) added, the particle diameter and volume content of the inorganic particles (B) satisfy specific requirements in order to obtain the above effects. It turned out to be necessary. Specifically, when the present inventors examined the relationship between the number-based median diameter of inorganic particles (B) and the volume content from the viewpoint of mechanical strength (reliability) and optical properties, the above formula It was found that an organic-inorganic composite composition having excellent moldability as well as optical characteristics can be obtained when the relationship (1) is satisfied.

  The number-based median diameter (D50) of the inorganic particles (B) is more than 1 nm and less than 20 nm. When D50 is 1 nm or less, secondary aggregation of inorganic particles occurs. On the other hand, when D50 is 20 nm or more, the transparency and total light transmittance of the composition are lowered, and the optical properties are deteriorated. The number-based median diameter (D50) of the inorganic particles (B) is preferably more than 1 nm and 15 nm or less, and more preferably 3 nm or more and 10 nm or less. The number-based median diameter (D50) of the inorganic particles (B) is the number-based median diameter of primary particles obtained by a dynamic light scattering method, and more specifically, measured by the method described in the examples. can do.

  In addition, the number-based median diameter (D50) of the inorganic particles (B) was measured by dissolving the inorganic particles with a dichloromethane solution and further diluting with methanol as a dynamic light scattering photometer (for example, manufactured by Otsuka Electronics Co., Ltd.). , DL-8000).

  Further, when the volume content of the inorganic particles (B) is outside the range of the above formula (1), that is, when V> 0.65 × (D50) +12.1, the volume content of the inorganic particles (B) is Too much reduces the mechanical strength of the composition.

  In addition, the lower limit value of the volume content of the inorganic particles (B) in the composition of the present invention is not particularly limited, but is preferably 0.1% by volume or more.

  The number-based median diameter and volume content of the inorganic particles (B) contained in the composition of the present invention can be measured by the method described in the examples.

  Hereinafter, the constituent components of the organic-inorganic composite composition of the present invention will be described in detail. The organic-inorganic composite composition of the present invention is also simply referred to as “composition”.

[Thermoplastic resin (A)]
The type of the thermoplastic resin (A) is not particularly limited, and for example, low density polyethylene, linear low density polyethylene, high density polyethylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, isotactic polypropylene, syndiotactic Α-olefin heavy such as tic polypropylene, hemiisotactic polypropylene, polybutene, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene Copolymer, block or random copolymer of ethylene-propylene, impact copolymer polypropylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate Polyolefin resins such as copolymers, ethylene-butyl acrylate copolymers, α-olefin copolymers such as ethylene-vinyl acetate copolymers, and polyolefin thermoplastic elastomers; polystyrene, high-impact polystyrene (HIPS), acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, methyl methacrylate-butadiene-styrene (MBS) resin, heat-resistant ABS resin, acrylonitrile-acrylate-styrene (AAS) resin, styrene-maleic anhydride (SMA) resin , Methacrylate-styrene (MS) resin, styrene-isoprene-styrene (SIS) resin, acrylonitrile-ethylenepropylene rubber-styrene (AES) resin, styrene-butadiene-butylene-styrene ( BBS) resins, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resins, and styrene-ethylene-butylene-styrene (SEBS) resins, hydrogenated double bonds of these butadiene or isoprene moieties, styrene-ethylene-propylene -Polystyrene resins such as hydrogenated resins such as styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, styrene-ethylene-ethylene-propylene-styrene (SEEPS) resin; polyvinyl chloride, polyvinylidene chloride, chlorination Polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride Halogen-containing resins such as vinyl-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer; petroleum resin, coumarone resin, Polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; polyalkylene terephthalate resins such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc. Aromatic polyester resins such as alkylene naphthalate resins, linear polyester resins such as polytetramethylene terephthalate, polyhydroxybutyrate, polycaprolac , Polyester resins such as polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly (2-oxetanone); polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide Resin, polycarbonate resin, polycarbonate / ABS resin, polyacetal resin, polyphenylene sulfide resin, polyurethane resin, fiber resin, polyimide resin, polysulfone resin, polyphenylene ether resin, polyether ketone resin, polyether ether ketone resin, cycloolefin polymer, A liquid crystal polymer etc. are mentioned. These thermoplastic resins can be used singly or in combination of two or more.

  Among these thermoplastic resins, at least one selected from the group consisting of polycarbonate resins, polyolefin resins, acrylic resins, polyester resins, and cycloolefin polymers is particularly preferable from the viewpoint of excellent optical properties.

  Further, from the viewpoint that a composition satisfying the above requirements (1) to (3) can be more easily obtained, the thermoplastic resin (A) in the range of the melting point of the thermoplastic resin (A) from + 10 ° C. to + 30 ° C. It is preferable that the value of b is −1 or more and less than 0 when the relationship between the melt viscosity and the shear rate is approximated to the power and represented by the following formula (II).

  As the thermoplastic resin (A), a commercially available product may be used, or a synthetic product synthesized by a conventionally known method may be used. Examples of commercially available products include, for example, Panlite (registered trademark) series manufactured by Teijin Limited, and Appel (registered trademark) series manufactured by Mitsui Chemicals.

[Inorganic particles (B)]
The kind in particular of inorganic particle (B) is not restrict | limited, A metal oxide, a metal sulfide, a metal selenide, a metal telluride, etc. are mentioned.

  Among these, metal oxides are preferable from the viewpoint of easily obtaining the effects of the present invention, and include Si, Al, Ti, Zn, Sn, Zr, Y, Ce, Ba, Sr, C, B, La, Gd, and Nb. It is preferably a metal oxide containing at least one element selected from the group consisting of Mg, Ca, and Ta.

  More specific examples of inorganic particles include, for example, zirconium oxide, yttria-added zirconium oxide, lead zirconate, strontium titanate, tin titanate, tin oxide, bismuth oxide, niobium oxide, tantalum oxide, potassium tantalate, oxidation Examples include tungsten, cerium oxide, lanthanum oxide, gallium oxide, silica, alumina, titanium oxide, zirconium oxide, barium titanate, and the like. The inorganic particles can be used alone or in combination of two or more.

  When the organic-inorganic composite composition is used for optical applications, the inorganic particles preferably have a high refractive index, and it is preferable to use inorganic particles having a refractive index of 1.8 or more. Specifically, the inorganic particles are titanium oxide, barium titanate (refractive index = about 2.4), zirconium oxide (refractive index = about 2.1), and cerium oxide (refractive index = about 2.2). It is preferable. Titanium oxide has two types of crystal structures, mainly rutile type (refractive index = about 2.7) and anatase type (refractive index = about 2.5), but anatase type titanium oxide has high photocatalytic activity, Rutile type titanium oxide is preferred because it is not very suitable for use in optical applications. Moreover, in order to reduce the photocatalytic activity of titanium oxide, titanium oxide particles whose surface is coated with silica or the like may be used.

  As described above, in the present invention, the relationship between the median diameter (D50) based on the number of inorganic particles and the volume content of the inorganic particles in the organic-inorganic composite composition satisfies the above formula (1). Next, the volume content of the inorganic particles is determined. The organic-inorganic composite composition of the present invention having such a volume content of inorganic particles can easily satisfy the requirements (1) to (2), and is excellent in moldability and optical properties. Become. That is, the present invention includes a thermoplastic resin (A) and inorganic particles (B), the number-based median diameter of the inorganic particles (B) is more than 1 nm and less than 20 nm, and the inorganic particles (B) The organic-inorganic composite composition in which the relationship between the number-based median diameter and the volume content of the inorganic particles (B) in the organic-inorganic composite composition satisfies the following formula (1) is also provided.

  Moreover, the composition of the present invention containing the inorganic particles (B) with the volume content as described above has reduced shrinkage during molding and improved releasability from the mold.

  As described above, the inorganic particles preferably have a high refractive index, specifically, the refractive index is preferably 1.8 or more, more preferably 1.9 or more, and 2.0 or more. Is more preferable. By using such inorganic particles, a resin composition having a high refractive index can be obtained. Further, the higher the refractive index of the inorganic particles, the better, but it is usually 3.0 or less. The preferable range of the refractive index of the inorganic particles is preferably 1.8 or more and 3.0 or less, more preferably 1.9 or more and 3.0 or less, considering the balance with the Abbe number. The refractive index of the inorganic particles can be calculated, for example, by measuring the refractive index difference between the inorganic particle dispersions having different concentrations.

  The Abbe number of the inorganic particles is preferably 20 or more from the viewpoint of improving optical properties. The upper limit of the Abbe number of the inorganic particles is not particularly limited, but is preferably 80 or less.

  The Abbe number of the inorganic particles can be measured by the method described in the examples.

  The inorganic particles can be produced using known methods described in JP2011-213505A, JP2012-180241A, and the like.

  Moreover, a commercial item may be used for an inorganic particle, and a solvent dispersion may be sufficient in this case. Examples of such commercially available products include SZR-W, SZR-CW, SZR-M, SZR-K (zirconium oxide dispersion, manufactured by Sakai Chemical Industry Co., Ltd.); Tynock (registered trademark) RA-6, NRA-10M ( And titanium oxide dispersion (manufactured by Taki Chemical Co., Ltd.).

  The composition according to the present invention optionally comprises an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a colorant, a bluing agent, a flame retardant, a flame retardant aid, a release agent, It may contain additives such as plasticizers, impact resistance improvers, reinforcing agents, dispersants, antistatic agents, foaming agents, antibacterial agents, other resins, and elastomers.

[Method for producing organic-inorganic composite composition]
The production method of the composition of the present invention is not particularly limited, but a method of producing by melting and kneading a thermoplastic resin, inorganic particles, and, if necessary, an additive is preferable. Examples of the apparatus that can be used for melt kneading include a closed kneading apparatus such as a lab plast mill, a Brabender, a Banbury mixer, a kneader, a roll, and the like, or a batch kneading apparatus. Further, a continuous melt kneader such as a single screw extruder or a twin screw extruder can be used.

  The thermoplastic resin and the inorganic particles may be added and kneaded all at once, or may be added in stages and kneaded. In this case, in a melt-kneading apparatus such as an extruder, it is possible to add the components to be added step by step from the middle of the cylinder. Further, after kneading in advance, components not added with components other than the thermoplastic resin (for example, inorganic particles, the above-mentioned additives, etc.) may be added and further melt-kneaded. At this time, these components may be added in a lump and kneaded, or may be added in stages and kneaded. The method of adding in a divided manner or the method of adding one component in several times can be adopted, the method of adding one component at a time and the method of adding different components in stages can also be adopted, or a method combining them Good.

  The inorganic particles can be added in powder form or in an aggregated state. Or it is also possible to add in the state disperse | distributed in the liquid. In the case of adding in a dispersed state in the liquid, it is preferable to add the agglomerated particles dispersed in the primary particles in advance. Further, devolatilization is preferably performed after kneading.

  The organic-inorganic composite composition of the present invention obtained as described above can have a high refractive index. Specifically, the refractive index of the organic-inorganic composite composition of the present invention is preferably 1.60 or more and 2.00 or less. The refractive index can be measured by the method described in the examples.

[Molded products, optical components]
One embodiment of the present invention relates to a molded article comprising the organic-inorganic composite composition. Another embodiment of the present invention relates to an optical component comprising the organic-inorganic composite composition described above. The shape of the molded product is not particularly limited, and may be any shape such as a lens shape (spherical lens, aspheric lens, Fresnel lens, etc.), film shape, sheet shape, plate shape, rod shape, fiber shape, prism shape, and the like. It's okay. In the production of molded products, for example, injection molding, compression molding, extrusion molding, transfer molding method, blow molding method, press molding method, injection press molding, coating method (spin coating method, roll coating method, curtain coating method, dip coating, etc. Although known molding methods such as a coating method and a casting molding method can be used, the composition of the present invention is particularly suitable for injection molding. When molding by injection molding, for example, the resin temperature is 200 ° C. or more and 300 ° C. or less, the mold temperature is 50 ° C. or more and 150 ° C. or less, and the injection speed (screw speed) is 10 mm / sec or more and 100 mm / sec or less. It is.

  By adopting the above method as a molding method for obtaining a molded product, it can be processed into a three-dimensional molded product, a sheet, a container pipe, etc., making use of its excellent fluidity and having a thin part. A molded product (for example, a resin lens) can be obtained efficiently. When molding by an injection molding method, it is preferable to pelletize the composition by extrusion molding in the previous stage. For pelletization, for example, a single-screw extruder, a twin-screw extruder, a tri-screw extruder, a kneader-type kneader equipped with a “unimelt” type screw can be used.

  After the obtained pellets are sufficiently dried, a molded product (particularly an optical component) having a desired shape can be obtained by using it for injection molding, for example.

  The organic-inorganic composite composition of the present invention obtained as described above is particularly excellent in optical properties. The haze value of a molded product obtained by molding the organic-inorganic composite composition of the present invention to a thickness of 0.5 mm is preferably less than 3, and more preferably 2 or less. In addition, the yellowness (YI) of a molded product obtained by molding the organic-inorganic composite composition of the present invention to a thickness of 0.5 mm is preferably 5 or less, and more preferably 3 or less. Furthermore, the total light transmittance of a molded product obtained by molding the organic-inorganic composite composition of the present invention to a thickness of 0.5 mm is preferably 70% or more, more preferably 80% or more, and 90% or more. Preferably there is.

  In addition, the 0.5 mm-thick molded product was obtained by the method described in the Examples, and the haze value, yellowness (YI), and total light transmittance of the obtained molded product were described in the Examples. It can be measured by the method.

  The above optical components include displays (for example, smartphone displays, liquid crystal displays, and plasma displays), photographing devices (for example, cameras and videos), optical pickups, projectors, optical fiber communication devices (for example, optical amplifiers), automobiles, and the like. It can be suitably used as an optical component that transmits light (passive optical component) in a headlamp for an automobile. Examples of such a passive optical component include a lens, a film, an optical waveguide, a prism, a prism sheet, a panel, an optical disk, an LED sealing agent, and the like. Such an optical component may have various functional layers such as an antireflection layer, a light absorption layer, a hard coat layer, and an antiglare layer as necessary.

  Hereinafter, the present invention will be described using examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

Example 1
In a separable flask equipped with a stirrer and a thermometer, 100.0 parts by mass of zirconium oxide / methanol / acetic acid dispersion (manufactured by Sakai Chemical Industry Co., Ltd., SZR-M, solid content 30% by mass) and benzoic acid 2 as a surface modifier 0.000 part by mass was added and stirred at 35 ° C. for 5 hours. The obtained liquid was further dispersed in dichloromethane to prepare a zirconium oxide fine particle dichloromethane dispersion having a solid content of 10% by mass.

  A polycarbonate resin (manufactured by Teijin Ltd., Panlite (registered trademark) AD5503, Tg = 130 ° C.) was used as the thermoplastic resin, and the thermoplastic resin was dissolved in dichloromethane so that the solid content was 10% by mass. To the product (A), the zirconium oxide fine particle dichloromethane dispersion (solid content: 10% by mass) (B) obtained above was added dropwise over 1 hour in an amount of 1/2 mass ratio to (A). After stirring for 1 hour, it was cast on a polyimide film substrate, dried at room temperature (25 ° C.) for 30 minutes, and then further dried on a hot plate at 80 ° C. for 1 hour. And crushed.

  The pulverized film was melt-kneaded at a resin temperature of 270 ° C. with a 30 mm twin screw extruder and pelletized to obtain the desired organic-inorganic composite composition.

  When extruding from the extruder, care should be taken so that air does not enter the kneaded product and oxidize conditions, and the target organic-inorganic composite composition is prepared while removing volatile components from the vent by decompression. Went.

  Next, using the obtained organic-inorganic composite composition (pellet), using an injection molding machine (manufactured by FANUC CORPORATION, ROBOSHOTS-2000i30A), the resin temperature is 270 ° C., the mold temperature is 80 ° C., and the screw speed is Molding was performed at 30 mm / sec and an injection pressure of 100 MPa to obtain a rectangular molded product (side gate) having a length of 10 mm, a width of 5 mm, and a thickness of 0.2 to 0.5 mm.

  In the polycarbonate resin used, b in the formula (II) was −0.83.

  Moreover, the refractive index of zirconium oxide was about 2.1, and the Abbe number was 36.

(Example 2)
A rectangular molded product was obtained in the same manner as in Example 1 except that 100.0 parts by mass of the cerium oxide methanol acetic acid dispersion was used instead of the zirconium oxide methanol acetic acid dispersion as the dispersion containing the inorganic particles. It was.

  The refractive index of cerium oxide was about 2.2, and the Abbe number was about 50.

(Example 3)
As a thermoplastic resin, a polyolefin resin (manufactured by Mitsui Chemicals, Apel (registered trademark) APL5014CL, cycloolefin polymer, Tg = 100 ° C.) was used in the same manner as in Example 2 instead of the polycarbonate resin. A rectangular molded product was obtained.

  In the polyolefin resin used, b in the above formula (II) was −0.11.

(Example 4)
As a dispersion containing inorganic particles, a rectangular shaped product was obtained in the same manner as in Example 3 except that 100.0 parts by mass of barium titanate methanol acetic acid dispersion was used instead of zirconium oxide methanol acetic acid dispersion. Obtained. The refractive index of barium titanate was about 2.4, and the Abbe number was about 50.

(Comparative Example 1)
Organic-inorganic composite composition in the same manner as in Example 1 except that the amount of zirconium oxide fine particle dichloromethane dispersion (solid content 10% by mass) (B) was changed to an amount of 2% by mass with respect to (A). I got a thing. Using this composition, injection molding was attempted in the same manner as in Example 1, but ejection became impossible and a molded product could not be obtained. Total light transmittance, haze value, refractive index, Abbe number, and YI Could not be evaluated.

(Comparative Example 2)
A composition was obtained in the same manner as in Example 2 except that the amount of the cerium oxide methanol acetic acid dispersion used was changed to a 2/3 mass ratio with respect to (A). Using this composition, injection molding was attempted in the same manner as in Example 1, but ejection became impossible and a molded product could not be obtained. Total light transmittance, haze value, refractive index, Abbe number, and YI Could not be evaluated.

(Comparative Example 3)
A composition was obtained in the same manner as in Example 3 except that the amount of the cerium oxide methanol acetic acid dispersion used was changed to a 2/3 mass ratio with respect to (A). When this composition was used for injection molding in the same manner as in Example 1, a molded product was obtained, but spots were formed on the molded product, and the refractive index, Abbe number, and YI were evaluated. I could not.

(Comparative Example 4)
A rectangular molded product was obtained in the same manner as in Example 3 except that the inorganic particles were not used.

(Comparative Example 5)
A rectangular molded product was obtained in the same manner as in Example 1 except that polyester resin was used as the thermoplastic resin and inorganic particles were not used.

<Evaluation method>
(Melt viscosity)
Using a rheometer MCR302 (manufactured by Anton Paar), the relationship between the melting point of the thermoplastic resin at + 20 ° C. and the melt viscosity was measured. From this measurement result, power approximation was performed to obtain B in the above formula (I).

(Median diameter based on the number of inorganic particles in the organic-inorganic composite resin composition)
Using a focused ion beam apparatus (FIB), the obtained molded product was sliced to about 100 nm and observed and measured with a transmission electron microscope.

(Volume content of inorganic particles)
First, the composition of the thermoplastic resin and the inorganic particles was determined by ICP emission spectroscopy (high frequency inductively coupled plasma emission spectroscopy), FT-IR (measurement of thermoplastic resin), X-ray diffraction (XRD) (inorganic particles). Measurement), energy dispersive X-ray analysis (measuring inorganic particles), and the like. Next, the specific gravity of each material and the specific gravity of the composition were measured using SD-200L manufactured by M & K Corporation, and the volume content was calculated.

(Injection moldability)
The state of the molded product obtained after injection molding was visually observed and evaluated according to the following criteria. ○ is practical:
○: A desired shape was secured. Δ: Injection molding was possible, but the shape was defective. ×: Injection molding was not possible.

(Measurement of total light transmittance and haze value)
The total light transmittance and haze value of the 0.5 mm thick molded product obtained above were measured using a haze meter “NDH5000” manufactured by Nippon Denshoku Industries Co., Ltd.

(Measurement of refractive index and Abbe number)
The refractive index of the 0.5 mm-thick molded product obtained above was measured using “DM-M4” manufactured by Atago Co., Ltd.

The Abbe number of the 0.5 mm-thick molded product and inorganic particles obtained above is “DM-M4” manufactured by Atago Co., Ltd., and the refractive index at three wavelengths (C-line, D-line, and F-line). And was calculated from the obtained refractive index value by the following formula:
Abbe number = (nD-1) / (nF-nC)
nC: Refractive index measured at C line (wavelength 656 nm)
nD: Refractive index measured at the D-line (wavelength 589 nm)
nF: Refractive index (wavelength 486 nm) measured with F-line.

(Measurement of YI)
The YI of the 0.5 mm-thick molded product obtained above was measured using a haze meter “NDH5000W” manufactured by Nippon Denshoku Industries Co., Ltd.

  The compositions and evaluation results of Examples and Comparative Examples are shown in Table 1 below. Note that “-” in the evaluation result column indicates that the evaluation could not be performed.

  As is clear from Table 1 above, it can be seen that the organic-inorganic composite compositions of the examples are excellent in moldability and optical properties. On the other hand, the organic-inorganic composite compositions of Comparative Examples 1 to 3 were deteriorated in injection moldability. In Comparative Examples 4 and 5 using only the thermoplastic resin, the refractive index decreased. Furthermore, in Comparative Example 5, the Abbe number decreased.

Claims (12)

An organic-inorganic composite composition containing the thermoplastic resin (A) and the inorganic particles (B) and satisfying the following (1) to (3):
(1) In the range of the melting point of the thermoplastic resin (A) from + 10 ° C. to + 30 ° C., the organic-inorganic composite composition has a melt viscosity of 10 Pa · s to 1000 Pa · s when the shear rate is 1000 (1 / s). (2) In the range from the melting point + 10 ° C. to + 30 ° C. of the thermoplastic resin (A), the relationship between the melt viscosity and the shear rate of the organic-inorganic composite composition is approximated to the power, and the following formula (I) The value of B when represented by − is not less than −2 and less than −0.1
(3) The number-based median diameter of the inorganic particles (B) is more than 1 nm and less than 20 nm, the number-based median diameter of the inorganic particles (B) and the inorganic particles in the organic-inorganic composite composition ( The relationship with the volume content of B) satisfies the following formula (1).
  The organic-inorganic composite composition according to claim 1, wherein the inorganic particles (B) have a refractive index of 1.8 or more and 3.0 or less and an Abbe number of 20 or more.   The inorganic particles (B) are selected from the group consisting of Si, Al, Ti, Zn, Sn, Zr, Y, Ce, Ba, Sr, C, B, La, Gd, Nb, Mg, Ca, and Ta. The organic-inorganic composite composition according to claim 1, which is a metal oxide containing at least one element.   The said thermoplastic resin (A) contains at least 1 sort (s) selected from the group which consists of a polycarbonate resin, polyolefin resin, an acrylic resin, a polyester resin, and a cycloolefin polymer, The any one of Claims 1-3. Organic-inorganic composite composition. In the range of the melting point of the thermoplastic resin (A) from + 10 ° C. to + 30 ° C., the relationship between the melt viscosity of the thermoplastic resin (A) and the shear rate is approximated by a power and expressed by the following formula (II) The organic-inorganic composite composition according to any one of claims 1 to 4, wherein a value of b is -1 or more and less than 0.
  The organic-inorganic composite composition according to any one of claims 1 to 5, wherein a molded product molded to a thickness of 0.5 mm has a haze value of less than 3.   The organic-inorganic composite composition according to any one of claims 1 to 6, wherein the yellowness (YI) of a molded product molded to a thickness of 0.5 mm is 5 or less.   The organic-inorganic composite composition according to any one of claims 1 to 7, wherein the molded product molded to a thickness of 0.5 mm has a total light transmittance of 70% or more.   The organic-inorganic composite composition according to any one of claims 1 to 8, wherein the refractive index is 1.60 or more and 2.00 or less.   The molded article containing the organic inorganic composite composition of any one of Claims 1-9.   The optical component containing the organic inorganic composite composition of any one of Claims 1-9. An organic-inorganic composite composition comprising a thermoplastic resin (A) and inorganic particles (B),
The number-based median diameter of the inorganic particles (B) is more than 1 nm and less than 20 nm, the number-based median diameter of the inorganic particles (B) and the inorganic particles (B) in the organic-inorganic composite composition An organic-inorganic composite composition whose relationship with the volume content satisfies the following formula (1).