WO2021039529A1

WO2021039529A1 - Inorganic oxide particle dispersion, molding composition in which same is used, and molded article

Info

Publication number: WO2021039529A1
Application number: PCT/JP2020/031253
Authority: WO
Inventors: 亮介権藤; 酒井　隆行
Original assignee: 東洋インキＳｃホールディングス株式会社; トーヨーカラー株式会社
Priority date: 2019-08-23
Filing date: 2020-08-19
Publication date: 2021-03-04

Abstract

An inorganic oxide particle dispersion containing inorganic oxide particles, a dispersant, an alkoxysilane compound, and a plasticizer free of polymerizable unsaturated groups that has a boiling point of 200°C or higher, wherein the dispersant includes at least one selected from the group consisting of dispersants A represented by general formula A and dispersants B represented by general formula B.

Description

Inorganic oxide particle dispersion and molding composition using it, molded body

An embodiment of the present invention relates to an inorganic oxide particle dispersion, a composition for molding using the dispersion, and a molded product. More specifically, the present invention relates to an inorganic oxide particle dispersion having high heat resistance and high transparency, and a molded product containing the dispersion.

In the field of plastic moldings, films, and film laminates, organic compounds and inorganic oxides having the desired physical characteristics are combined by various methods in order to obtain mechanical and optical properties that cannot be achieved by the resin alone. The method of making it has been tried. For example, as optical characteristics, it is common to impart physical properties such as UV shielding, heat ray shielding, and refractive index adjustment, and conventionally, a method of applying a paint having optical characteristics to a film has been used. On the other hand, in recent years, with the miniaturization and thinning of electronic devices, it has become possible to reduce the coating thickness and the cost without the need for a coating process. Therefore, an inorganic oxide is added to the film itself. The method of adding is becoming a trend.

In many cases, it is necessary to maintain the transparency of the resin, so when adding an inorganic oxide, it is necessary to disperse it to the nano level. For example, in the application of laminating a polyvinyl butyral film between glass for the purpose of preventing glass from scattering, indium tin oxide, which is an infrared shielding agent, is dispersed to the nano level in the plasticizer used at the time of film molding. Techniques have been applied. In this method, a mixture of a highly volatile solvent and a plasticizer is used, and it has been a problem that the temperature and kneading conditions at the time of film molding affect the transparency. In addition, it has been difficult to disperse zirconia and titanium oxide used for the purpose of UV shielding and refractive index adjustment to the nano level by the dispersant used in this method.

In UV curable paints, it has been proposed to use an alkoxysilane compound in combination with a specific dispersant as a method for maintaining nano-level dispersion of zirconia in the paint. UV curable acrylate is used as a solvent in the paint by this method. Therefore, considering the use for film molding, it is difficult to use the paint component for general purposes from the viewpoint of deterioration of transparency at high temperature and compatibility with the resin and plasticizer used for molding, and the application is limited. There is a problem of being done.

Japanese Unexamined Patent Publication No. 2005-343723 Japanese Unexamined Patent Publication No. 2013-112707

Therefore, the present invention is applicable to various plastic materials, and an inorganic oxide particle dispersion having heat resistance and transparency against a high temperature at the time of molding, and a molded body containing the inorganic oxide particle dispersion. The purpose is to provide.

The present invention relates to the embodiments described below. However, the present invention is not limited to the embodiments described below, but includes various embodiments.
One embodiment is an inorganic oxide particle dispersion containing inorganic oxide particles, a dispersant, an alkoxysilane compound, and a plasticizer having a boiling point of 200 ° C. or higher and having no polymerizable unsaturated group. The present invention relates to an inorganic oxide particle dispersion containing at least one selected from the group consisting of a dispersant A represented by the following general formula A and a dispersant B represented by the following general formula B. ..

(R ¹ is an alkyl group having a branched structure or a linear structure, and represents an alkyl group having 10 to 18 carbon atoms. A represents an alkylene group having a linear structure having 2 to 3 carbon atoms. n ₁ is an integer of 5 to 20.)

(X ¹ represents a hydrogen atom or Y ^1. R ² is an alkyl group having a branched structure or a linear structure, and n _{2 represents an alkyl group having a main chain having 12 to 13 carbon atoms.} R ³ is an alkyl group having a branched structure or a linear structure, and represents an alkyl group having a main chain having 12 to 13 carbon atoms. N ₃ is an integer of 1 to 10. .)

Further, one embodiment relates to the inorganic oxide particle dispersion in which the inorganic oxide particles contain zirconium oxide particles.

Further, one embodiment relates to the above-mentioned inorganic oxide particle dispersion in which the above-mentioned plasticizer is at least one selected from the group consisting of polyethylene glycol-based ester, polypropylene glycol, and polypropylene glycol-based ester.

Further, one embodiment relates to the above-mentioned inorganic oxide particle dispersion in which the above-mentioned alkoxysilane compound has an epoxy skeleton.

Further, one embodiment relates to a molding composition containing the above-mentioned inorganic oxide particle dispersion and a molding resin.

Further, one embodiment relates to a molded body using the above-mentioned inorganic oxide particle dispersion.
The disclosure of the present application is related to and all of the subjects described in Japanese Patent Application No. 2019-152855 filed on August 23, 2019 and Japanese Patent Application No. 2020-120323 filed on July 14, 2020. Disclosures of are incorporated herein by reference.

INDUSTRIAL APPLICABILITY The present invention provides an inorganic oxide particle dispersion that is applicable to various plastic materials and has heat resistance and transparency against high temperatures during molding, and a molded body containing the inorganic oxide particle dispersion. be able to.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the embodiments described below, and includes various embodiments.
<Inorganic oxide particle dispersion>
The inorganic oxide particle dispersion contains inorganic oxide particles, a dispersant, an alkoxysilane compound, and a plasticizer having a boiling point of 200 ° C. or higher and having no polymerizable unsaturated group. , At least one selected from the group consisting of the dispersant A represented by the following general formula A and the dispersant B represented by the following general formula B. Hereinafter, usable materials and the like will be specifically described.

<Inorganic oxide particles>
As the inorganic oxide particles used in the inorganic oxide particle dispersion, an oxide of at least one element selected from a metal element and Si can be used. Inorganic oxide particles can be selected according to the physical characteristic values required for the molded body, the laminate, and the like. For example, zirconia (ZrO ₂ ), titania (TIO ₂ ), silica (SiO ₂ ), alumina (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ), copper oxide (CuO), zinc oxide (ZnO), Itria. (Y ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), molybdenum oxide (MoO ₃ ), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), lead oxide (PbO), bismuth oxide (Bi ₂ O ₃ ), ceria (CeO ₂ ), antimony oxide (Sb ₂ O ₅ , Sb ₂ O ₃ ) and the like. The inorganic oxide particles may be used alone or in combination of two or more.

The particle size of the inorganic oxide particles is preferably in the range of 15 to 50 nm on average from the viewpoint of transparency. Here, the average particle size is an arithmetic mean value of the particle size observed with a scanning electron microscope (SEM). More specifically, it is a value obtained by observing the powder of inorganic oxide particles at a magnification of 20000 times, selecting arbitrary 100 particles, and averaging the particle diameters of each. When the particle shape has a major axis and a minor axis, the average value of the lengths of the major axis and the minor axis is taken as the particle diameter of the particle.

Inorganic oxide particles can be appropriately selected according to the desired physical property values. For example, in the case of an application for adjusting the refractive index, it is preferable to use inorganic oxide particles selected from zirconium oxide, titanium oxide, and alumina. Zirconium oxide is preferable from the viewpoint of maintaining transparency during heat resistance. For UV shielding applications, it is preferable to use inorganic oxide particles selected from zinc oxide, titanium oxide, and cerium oxide. For antistatic applications, inorganic oxide particles selected from indium-doped tin oxide particles, antimony-doped tin oxide particles, phosphorus-doped tin oxide particles, fluorine-doped tin oxide particles, and tin oxide particles can be used. preferable. From the viewpoint of controlling the thermal expansion, it is preferable to use inorganic oxide particles such as silica and alumina. For heat ray shielding applications, it is preferred to use indium-doped tin oxide particles, antimony-doped tin oxide particles, and cesium-tungsten oxide particles. When a plurality of physical properties are required for a molded body, it is preferable to contain a plurality of inorganic oxide particles in one dispersion.

The amount of inorganic oxide particles added is not particularly limited. In one embodiment, from the viewpoint of dispersibility over time and handleability, the amount of inorganic oxide particles in 100% by mass of the inorganic oxide particle dispersion is preferably 10 to 40% by mass, more preferably 20. ~ 30% by mass.

<Dispersant A>
As the inorganic oxide particle dispersion, a dispersant A represented by the following general formula A can be used.

R ¹ is an alkyl group having a branched structure or a linear structure, and represents an alkyl group having 10 to 18 carbon atoms. A represents an alkylene group having a linear structure having 2 to 3 carbon atoms. n ₁ is an integer of 5 to 20. It is preferable that R ¹ has 12 to 18 carbon atoms.

<Dispersant B>
As the inorganic oxide particle dispersion, a dispersant B represented by the following general formula B can be used.

X ¹ represents a hydrogen atom or Y ¹ . R ² is an alkyl group having a branched structure or a linear structure, and represents an alkyl group having a main chain having 12 to 13 carbon atoms. n ₂ is an integer from 1 to 10. R ³ is an alkyl group having a branched structure or a linear structure, and represents an alkyl group having a main chain having 12 to 13 carbon atoms. n ₃ is an integer from 1 to 10.

As the dispersant A, for example, "Kao Akipo RLM-100" manufactured by Kao Corporation, "NIKKOL AKYPO RLM 100" manufactured by Nikko Chemicals Co., Ltd., "NIKKOL ECT-7", and "Viewlight LCA" manufactured by Sanyo Chemicals Inc. -H "and the like.

The amount of the dispersant added is not particularly limited. In one embodiment, it is preferable to use the dispersant in an amount of 10 to 50% by mass based on 100% by mass of the inorganic oxide particles. By using the dispersant in the above range, it is easy to disperse various inorganic oxide particles well in the plasticizer. In addition, the dispersibility of the inorganic oxide particles is unlikely to decrease even during kneading with the molding resin. If necessary, only one type of dispersant A and dispersant B may be used alone or in combination.

<Alkoxysilane compound>
Alkoxysilane compound is a general term for compounds in which an alkoxyl group is bonded to silicon. Apart from the alkoxyl group, it further contains an alkyl group or a vinyl group, or an alkyl group having a functional group such as a vinyl group, a glycidyl group, a methacryl group, a styryl group, an acrylic group, an amino group, an isocyanate group, and a carboxyl group. May be good.

Examples of the alkoxysilane compound include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane. Phenyltrimethoxysilane, diphenyltrimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 6-vinilohexylmethyldiethoxysilane, 2-( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltri Ethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acry Loxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-isocyanoxidetriethoxysilane, 3-trimethoxy Examples thereof include silylpropyl succinic acid anhydride.
Among the above, from the viewpoint of transparency and heat resistance of the dispersion, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxy An alkoxysilane compound having an epoxy skeleton such as silane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane is preferable.

The amount of the alkoxysilane compound added is not particularly limited. In one embodiment, the alkoxysilane compound is preferably used in an amount of 5 to 60% by mass, more preferably 10 to 50% by mass, based on 100% by mass of the inorganic oxide particles. By using the alkoxysilane compound in the above range, it becomes easy to disperse various inorganic oxide particles well in the plasticizer. As a result, high heat resistance can be obtained as the dispersion, and the dispersibility of the inorganic oxide particles is less likely to decrease even when kneading with the molding resin. Further, from the viewpoint of heat resistance, in one embodiment, it is preferable to perform heat treatment at 50 to 200 ° C. and chemically surface-treat the inorganic oxide particles with the alkoxysilane compound. If necessary, the alkoxysilane compound is preferably used alone or in combination of two or more.

Examples of alkoxysilane compounds include KBM series and KBE series manufactured by Shinetsu Silicone Co., Ltd., WACKER SILICATE series and GENIOSIL series manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and DOWNSIL series and XIAMETER series manufactured by DOWN Toray Co., Ltd. Can be mentioned.

<Plasticizer>
In the process of producing the molding resin, a solvent containing no polymerizable unsaturated group that softens or partially dissolves the molding resin can be used as the plasticizer. Plasticizers include, for example, phthalates, adipic acid esters, phosphate esters, trimellitic acid esters, propylene glycol, propylene glycol esters, ethylene glycol, ethylene glycol esters, vegetable oils, epoxidized vegetable oils, and Examples thereof include aliphatic hydrocarbons such as paraffin, and high boiling point cyclic compounds such as valerolactone and caprolactone. These plasticizers may be used alone or in combination of two or more.

Since a general molding resin is softened and molded at a high temperature of 100 ° C. or higher, a plasticizer having a boiling point of 200 ° C. or higher can be used as the plasticizer. When the boiling point is 200 ° C. or higher, the dispersibility of the inorganic oxide particle dispersion is maintained and good transparency can be exhibited when kneading with the molding resin. Further, since bubbles and the like are not generated in the molded body, the mechanical property value can be improved. When a plasticizer having a boiling point of less than 200 ° C. is used, it is preferably 10% by mass or less in the inorganic oxide particle dispersion. When the amount is adjusted in this way, the dispersibility of the inorganic oxide particle dispersion is maintained when kneading with the molding resin, and it becomes easy to develop good transparency.

Since the dispersibility of the inorganic oxide particle dispersion can be improved and it can be applied to various resins, it is preferable to use polyethylene glycol-based ester, polypropylene glycol, and polypropylene glycol ester-based plasticizer. In particular, triethylene glycol-di-ethylhexanoate (boiling point: 219 ° C.), triethylene glycol bis (2-ethylhexanoate) (boiling point: 344 ° C.), triethylene glycol-di-ethylhexanoate di (boiling point: 349 ° C.) Polyethylene glycol-based esters such as 2-butoxyethoxyethyl) adipate (boiling point: 230 ° C.) and tetraethylene glycol-di-2-ethylhexanoate (boiling point: 499 ° C.) can be used to improve the transparency of the inorganic oxide particle dispersion. It is preferable from the viewpoint of heat resistance.

<Composition for molding>
The molding composition contains an inorganic oxide particle dispersion and a molding resin. By using the molding composition, it is possible to easily obtain a molded body having excellent dispersion stability, high transparency, and high heat resistance.

<Molding resin>
Any resin that softens by heating and can be molded into a predetermined shape by extrusion, pressing, or the like can be used as a molding resin. For example, polycarbonate, polyethylene terephthalate, polypropylene, polyethylene, polyacrylic, polyvinyl chloride, polystyrene, copolymer of acrylonitrile-butadiene-styrene, copolymer of acrylonitrile-styrene, polybutylene terephthalate, polyamide, polyether ketone, polyvinyl acetal. , Polyvinyl butyral, polyester, polyvinylidene fluoride and the like, and can be selected according to the desired physical properties.

<Dispersion method>
In order to prepare the inorganic oxide particle dispersion, a disperser generally used for the purpose of achieving high transparency can be used. Examples thereof include dispersers such as dispersers, homomixers, planetary mixers, ball mills, sand mills, attritors, pearl mills, wet jet mills, and roll mills. As the disperser, one type may be used alone, or a plurality of types may be used in combination.

<Kneading method>
In order to produce a molded body, a general kneader capable of kneading the inorganic oxide particle dispersion and the molding resin for the purpose of uniformly dispersing the inorganic oxide particles in the molding resin is used. be able to. For example, a roll mill such as a two-roll or three-roll mill, a pressure kneader, a Banvari mixer, a twin-screw extruder, a kneader such as a single-screw extruder can be mentioned. One type of kneader may be used alone, or a plurality of types may be used in combination.

<Molding method>
A general molding machine can be used for the purpose of molding the kneaded product of the inorganic oxide particle dispersion and the molding resin into a desired shape. Molding such as extrusion molding, blow molding, and press molding can be performed to a desired shape using a mold or the like. At the time of molding, heating, cooling, and pressure can be adjusted according to the purpose.

<Laminate>
A laminate can be obtained by using a molded product composed of an inorganic oxide particle dispersion and a molding resin as a base material or a bonding medium. By stacking multiple types of layers, it is possible to unify various functions as a laminate. As the laminating method, a general method can be applied. For example, a method of applying paint on a molded body as a base material, a method of laminating various materials using a molded body as a medium by a hot press or the like, a method of using an adhesive or an adhesive or the like, and other materials on the molded body. There is a method of pasting together.

<Dispersed particle size>
In the inorganic oxide particle dispersion, the finer the dispersed particle size, the smaller the light scattering in the visible light region. Therefore, from the viewpoint of transparency of the molded body and the laminate, the dispersed particle size is preferably in the range of 1 to 100 nm, more preferably in the range of 1 to 70 nm, and preferably in the range of 1 to 50 nm. More preferred. Here, the "dispersed particle size" is a particle that becomes 50% when the volume ratio of the particles is integrated from the fine particle size distribution in the volume particle size distribution using a dynamic light scattering type particle size distribution meter. The diameter.

<Transparency>
Transparency is judged from the turbidity of the inorganic oxide particle dispersion and the molded product containing the inorganic oxide particle dispersion. The closer the turbidity is to 0, the higher the transparency.
The transparency of the inorganic oxide particle dispersion was diluted with a plasticizer so that the inorganic oxide particle dispersion was 0.05% by mass, and measured using a cell having an optical path length of 1 cm with the plasticizer as a reference. Judge from the turbidity of the time. In one embodiment, the turbidity is preferably 1 to 3%, more preferably 1% or less.
The transparency of the molded body is judged from the turbidity of the molded body containing the inorganic oxide particle dispersion. The turbidity of the molded body is preferably 1 to 3%, more preferably 1% or less, based on the molded body having the same film thickness composed of only the molding resin and the plasticizer used.

<Heat resistance>
The heat resistance is close to 0, judging from the absolute values of the changes in the dispersed particle size and turbidity before and after heating when the inorganic oxide particle dispersion and the molded product containing the inorganic oxide particle dispersion are heated. The higher the heat resistance.
Regarding the heat resistance of the inorganic oxide particle dispersion, the change in the dispersed particle size is preferably 10 nm or less, and more preferably 5 nm or less. The change in turbidity is preferably 0.4% or less, and preferably 0.1% or less. With respect to the molded product containing the inorganic oxide particle dispersion, the change in turbidity is preferably 0.4% or less, and more preferably 0.1% or less.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In the examples and comparative examples, “parts” and “%” mean parts by mass and% by mass, respectively, unless otherwise specified.

1. 1. Raw material <Inorganic oxide particles>
The inorganic oxide particles used in Examples and Comparative Examples are listed below.
PCS-60 (Zirconium oxide, average particle size 15 nm, manufactured by Nippon Denko Co., Ltd.)
STR-100A-LP (titanium oxide, average particle size 50 nm, manufactured by Sakai Chemical Industry Co., Ltd.)
E-ITO (tin-doped indium oxide, average particle size 30 nm, Mitsubishi Materials Electronics Chemical Co., Ltd.)

<Dispersant>
The dispersants used in Examples and Comparative Examples are listed below.
NIKKOL AKYPO RLM 100 (polyoxyethylene lauryl ether acetic acid, n ₁ = 10, dispersant A, manufactured by Nikko Chemicals Co., Ltd.)
NIKKOL ECT-7 (polyoxyethylene tridecyl ether acetic acid, n ₁ = 7, dispersant A, manufactured by Nikko Chemicals Co., Ltd.)
Beaulite LCA-25NH (Polyoxyethylene lauryl ether acetic acid, n ₁ = 3, manufactured by Sanyo Chemical Industries, Ltd.)
Prysurf A219B (Polyoxyethylene lauryl ether phosphate, manufactured by Daiichi Kogyo Co., Ltd.)
Prysurf AL (polyoxyethylene styrenated phenyl ether phosphate, manufactured by Daiichi Kogyo Co., Ltd.)
High Tenor LA-10 (Polyoxyethylene Lauryl Ether Ammonium Sulfate, manufactured by Daiichi Kogyo Co., Ltd.)
Neodecanoic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)

<Method for producing dispersant 1>
400 parts of toluene, 213.3 parts of isotridecanol ethylene oxide 10 mol adduct, 50.7 parts of monochloroacetate, sodium hydroxide in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer. Was charged in 17.3 parts, replaced with nitrogen gas, and then heated at 80 ° C. for 3 hours and stirred. 39.0 parts of 98% sulfuric acid was added to this mixture to obtain a white suspension. Then, the white suspension was thoroughly washed with purified water, and the solvent was distilled off under reduced pressure to obtain a dispersant 1 as a dispersant A. The dispersant 1 has a structure in which R ¹ is a branched alkyl group having 13 carbon atoms and n ₁ is 10.

<Method for producing dispersant 2>
400 parts of toluene, 286.7 parts of 15 mol of isotridecanol ethylene oxide adduct, 50.7 parts of monochloroacetate, sodium hydroxide in a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer. Was charged in 17.3 parts, replaced with nitrogen gas, and then heated at 80 ° C. for 3 hours and stirred. 39.0 parts of 98% sulfuric acid was added to this mixture to obtain a white suspension. Then, the white suspension was thoroughly washed with purified water, and the solvent was distilled off under reduced pressure to obtain a dispersant 2 as a dispersant A. The dispersant 2 has a structure in which R ¹ is a branched alkyl group having 13 carbon atoms and n ₁ is 15.

<Method for producing dispersant 3>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 400 parts of toluene, 236.8 parts of an adduct of 10 mol of isostearyl alcohol ethylene oxide, 50.7 parts of sodium monochloroacetate, and sodium hydroxide. After charging 17.3 parts and replacing with nitrogen gas, the mixture was heated at 80 ° C. for 3 hours and stirred. 39.0 parts of 98% sulfuric acid was added to this mixture to obtain a white suspension. Then, the white suspension was thoroughly washed with purified water, and the solvent was distilled off under reduced pressure to obtain a dispersant 3 as a dispersant A. The dispersant 3 has a structure in which R ¹ is a branched alkyl group having 18 carbon atoms and n ₁ is 10.

<Method for producing dispersant 4>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 400 parts of toluene, 199.4 parts of an adduct of 10 mol of isodecanol ethylene oxide, 50.7 parts of sodium monochloroacetate, and sodium hydroxide. After charging 17.3 parts and replacing with nitrogen gas, the mixture was heated at 80 ° C. for 3 hours and stirred. 39.0 parts of 98% sulfuric acid was added to this mixture to obtain a white suspension. Then, the white suspension was thoroughly washed with purified water, and the solvent was distilled off under reduced pressure to obtain a dispersant 4 as a dispersant A. The dispersant 4 has a structure in which R ¹ is a branched alkyl group having 10 carbon atoms and n ₁ is 10.

<Method for producing dispersant 5>
400 parts of toluene, 218.5 parts of 1-tetradecanol ethylene oxide 10 mol adduct, 50.7 parts of sodium monochloroacetate, hydroxide in a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer. After 17.3 parts of sodium was charged and replaced with nitrogen gas, the mixture was heated at 80 ° C. for 3 hours and stirred. 39.0 parts of 98% sulfuric acid was added to this mixture to obtain a white suspension. Then, the white suspension was thoroughly washed with purified water, and the solvent was distilled off under reduced pressure to obtain a dispersant 5 as a dispersant A. The dispersant 5 has a structure in which R ¹ is a linear alkyl group having 14 carbon atoms and n ₁ is 10.

<Method for producing dispersant 6>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst were charged, and nitrogen was charged. After replacement with gas, the mixture was heated at 120 ° C. for 4 hours and stirred. After confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added to this mixture and reacted at 120 ° C. for 2 hours to obtain a dispersant 6 having the structure of the dispersant B. .. The dispersant 6 has a structure in which R ² is a linear alkyl group having 12 carbon atoms, n ₂ is 7, R ³ is a linear alkyl group having 12 carbon atoms, and n ₃ is 7. ..

<Method for producing dispersant 7>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 31.3 parts of 1-dodecanol, 143.7 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst, and nitrogen. After replacement with gas, the mixture was heated at 120 ° C. for 4 hours and stirred. After confirming that 98% had reacted by solid content measurement, 32.2 parts of trimellitic anhydride was added to this mixture and reacted at 130 ° C. for 4 hours to obtain a dispersant 7 having the structure of the dispersant B. .. The dispersant 7 has a structure in which X ¹ is a hydrogen atom, R ³ is a linear alkyl group having 12 carbon atoms, and n ₃ is 7.

<Method for producing dispersant 8>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 31.3 parts of 1-dodecanol, 143.7 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst, and nitrogen. After replacement with gas, the mixture was heated at 120 ° C. for 4 hours and stirred. After confirming that 98% had reacted by solid content measurement, 16.4 parts of maleic anhydride was added to this mixture, and the mixture was reacted at 130 ° C. for 4 hours to obtain a dispersant 8.

<Method for producing dispersant 9>
400 parts of toluene, 264.9 parts of 2-decyl-1-tetradecanol ethylene oxide 10 mol adduct, 50.7 parts of sodium monochloroacetate in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer. 17.3 parts of sodium hydroxide was charged, replaced with nitrogen gas, and then heated at 80 ° C. for 3 hours and stirred. 39.0 parts of 98% sulfuric acid was added to this mixture to obtain a white suspension. Then, the white suspension was thoroughly washed with purified water, and the solvent was distilled off under reduced pressure to obtain a dispersant 9.

<Alkoxysilane compound>
KBM-403 (3-glycidoxypropyltrimethoxysilane, Shinetsu Silicone Co., Ltd.)
KBM-303 (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Shinetsu Silicone Co., Ltd.)
KBM-13 (Methyltrimethoxysilane, Shinetsu Silicone Co., Ltd.)
KBM-22 (dimethyldimethoxysilane, Shinetsu Silicone Co., Ltd.)
KBM-3033 (n-propyltrimethoxysilane, Shinetsu Silicone Co., Ltd.)
KBM-103 (Phenyltrimethoxysilane, Shinetsu Silicone Co., Ltd.)
KBM-1003 (Vinyltrimethoxysilane, Shinetsu Silicone Co., Ltd.)

<Plasticizer>
PEG # 200 (polyethylene glycol, boiling point: 250 ° C, manufactured by NOF CORPORATION)
Tripropylene glycol (boiling point: 273 ° C or higher, manufactured by Asahi Glass Co., Ltd.)
Proviprest 1783 (triethylene glycol bis (2-ethylhexanoate), boiling point: 344 ° C, manufactured by Proviron)
Nonion L-2 (polyethylene glycol monolaurate, boiling point: 300 ° C or higher, manufactured by NOF CORPORATION)
Vinysizer 90 (di2-ethylhexyl phthalate, boiling point: 403 ° C, manufactured by Kao Corporation)
Exepearl M-OL (methyl oleate, boiling point: 218 ° C, manufactured by Kao Corporation)
BFG (boiling point 170 ° C, propylene glycol monobutyl ether, manufactured by Nippon Embroidery Co., Ltd.)
Butycel acetate (boiling point 192 ° C, ethylene glycol monobutyl ether acetate, manufactured by KH Neochem Co., Ltd.)
FA-BZA (boiling point 210 ° C, benzyl acrylate, manufactured by Hitachi Kasei Co., Ltd.)

<Molding resin>
Elitel UE-9200 (polyester resin, manufactured by Unitika Ltd.)

2. 2. Inorganic oxide particle dispersion (Examples 1 to 32, Comparative Examples 1 to 11)
<Preparation of inorganic oxide particle dispersion>
According to the compounding compositions shown in Tables 1 and 2, the mixture was stirred and mixed so as to be uniform, and then dispersed in a sand mill for 5 hours using zirconia beads having a diameter of 0.1 mm. Then, the mixture was allowed to stand at 50 ° C. for 3 hours and filtered through a filter having a pore size of 1 μm to obtain an inorganic oxide particle dispersion. In Table 1, numbers without unit notation represent parts, and blanks indicate that they are not mixed.

<Evaluation of inorganic oxide particle dispersion>
The dispersed particle size, transparency, and heat resistance of the inorganic oxide particle dispersions prepared in Examples 1 to 32 and Comparative Examples 1 to 11 were evaluated by the following methods, respectively. The results are shown in Table 3.

(Dispersed particle size)
The dispersed particle size of the inorganic oxide particle dispersion is determined by using a dynamic light scattering type particle size distribution meter (Microtrac UPA, manufactured by Nikkiso Co., Ltd.) in the volume particle size distribution, from the finer particle size to the volume ratio of the particles. The particle size of 50% was measured as the dispersed particle size. The sample used for the measurement was prepared by adding an inorganic oxide particle dispersion to the plasticizer used at the time of preparing the dispersion in an arbitrary amount that can be measured, and dispersing it with a bath-type ultrasonic device. did. The finer the dispersed particle size, the more preferable it is from the viewpoint of transparency, and the evaluation was made according to the following criteria.
A: 60 nm or less (extremely good)
B: Over 60 nm, 70 nm or less (good)
C: Over 70 nm (defective)

(Transparency 1)
For the sample for evaluating the transparency of the inorganic oxide particle dispersion, 0.5 part of the inorganic oxide particle dispersion was added to 29.5 parts of the plasticizer used when preparing the inorganic oxide particle dispersion, and bath-type ultrasonic waves were used. It was dispersed and prepared by the device. The obtained evaluation sample was placed in a quartz cell having an optical path length of 1 cm in an arbitrary amount that can be measured, and used when preparing an inorganic oxide particle dispersion using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). The turbidity of the above evaluation sample was measured using the plasticizer as a reference (as the zero point of haze). The closer the turbidity is to 0, the more preferable. Transparency was judged based on the following criteria.
A: 1% or less (extremely good)
B: 1% over, 3% or less (good)
C: Over 3% (defective)

(Heat resistance 1)
For the heat resistance 1 of the inorganic oxide particle dispersion, the dispersed particle size of the sample obtained by allowing the inorganic oxide particle dispersion to stand at 200 ° C. for 1 hour was measured. Then, the absolute value of the value obtained by subtracting the value of the dispersed particle size after standing (sample) from the value of the dispersed particle size of the inorganic oxide particle dispersion before standing is obtained and evaluated as the amount of change in the dispersed particle size. did. The smaller the amount of change in the dispersed particle size, the more preferable. The heat resistance was evaluated according to the following criteria from the amount of change in the dispersed particle size.
A: 5 nm or less (extremely good)
B: Exceeding 5 nm and 10 nm or less (good)
C: Exceeding 10 nm (defective)

(Heat resistance 2)
For the heat resistance 2 of the inorganic oxide particle dispersion, 0.5 part of the inorganic oxide particle dispersion left at 200 ° C. for 1 hour was added to 29.5 parts of the plasticizer used when preparing the inorganic oxide particle dispersion. Then, a sample was prepared by dispersion treatment with a bath type ultrasonic device. The turbidity of the obtained sample was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) with reference to the plasticizer used when preparing the inorganic oxide particle dispersion. The turbidity of the sample left at 200 ° C. for 1 hour was calculated as an absolute value obtained by subtracting the turbidity value of the sample before standing, and evaluated as the rate of change in turbidity. The smaller the rate of change in turbidity, the more preferable. The heat resistance was evaluated according to the following criteria from the rate of change in turbidity.
A: 0.1% or less (extremely good)
B: Exceeds 0.1%, 0.4% or less (good)
C: Over 0.4% (defective)

As shown in Table 3, Examples 1 to 32 had good dispersion particle size, transparency, and heat resistance as dispersions. In particular, with respect to Examples 1, 4 to 32, the dispersed particle size and transparency are extremely good, and further, in Examples 1, 4 to 6, 8 to 10, 12, 18, 24 to 26, and 29 to 32. The heat resistance was also extremely good.

3. 3. Molded body (Examples 33 to 64, Comparative Examples 12 to 22)
<Manufacturing and evaluation of molded body>
Molds were prepared using the inorganic oxide particle dispersions prepared in Examples 1 to 32 and Comparative Examples 1 to 11, respectively, and the transparency and heat resistance of the molded bodies were evaluated by the following methods. The evaluation results are shown in Table 4.
(Transparency 2)
A mixture containing 3.3 parts of the inorganic oxide particle dispersion, 90 parts of Elitel UE-9200 (molding resin), and 6.7 parts of Proviblast 1783 was kneaded at 130 ° C. for 3 minutes using two rolls. .. The kneaded product obtained by kneading was press-molded at 130 ° C. for 5 minutes using a press molding machine to obtain a molded product (A) having a thickness of 0.8 mm. On the other hand, 90 parts by mass of the molding resin and 10 parts by mass of Proviblast 1783 (plasticizer) are kneaded and press-molded by the same method to obtain a molded body (B) consisting of only the molding resin and the plasticizer. Obtained.
The total light transmittance of each of the obtained molded bodies was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). The value of the total light transmittance is preferably close to 100.
Further, the total light transmittance of the molded body (A) formed by kneading the inorganic oxide particle dispersion is based on the value of the total light transmittance of the molded body (B) composed of only the molding resin and the plasticizer. The rate of change was calculated from the value. Transparency was evaluated from the obtained rate of change according to the following criteria. The results are shown in Table 4.
A: 1% or less (extremely good)
B: 1% over, 3% or less (good)
C: Over 3% (defective)

(Heat resistance 3)
A mixture containing 3.3 parts of the inorganic oxide particle dispersion, 90 parts of Elitel UE-9200 (molding resin), and 6.7 parts of Proviblast 1783 was kneaded at 170 ° C. for 3 minutes using two rolls. .. The kneaded product obtained by kneading was press-molded at 170 ° C. for 5 minutes with a press molding machine to obtain a molded product (A) having a thickness of 0.8 mm. On the other hand, 90 parts by mass of the molding resin and 10 parts by mass of Proviblast 1783 (plasticizer) were kneaded and press-molded by the same method to obtain a molded body (B) consisting of only the molding resin and the plasticizer.
Using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), the obtained molded body is dispersed with inorganic oxide particles based on the molded body (B) consisting of only a molding resin and a plasticizer for turbidity. The value of the molded body (A) in which the body was kneaded was measured, and the absolute value of the value obtained by subtracting the value of the molded body and the turbidity under the press molding conditions used for the evaluation of transparency 1 was evaluated as the rate of change. The smaller the rate of change in turbidity, the more preferable. The heat resistance was evaluated according to the following criteria from the value of the rate of change in turbidity.
A: 0.1% or less (extremely good)
B: Exceeds 0.1%, 0.4% or less (good)
C: Over 0.4% (defective)

As shown in Table 4, the transparency and heat resistance of Examples 33 to 64 were good as molded bodies. In particular, with respect to Examples 33 and 36 to 64, the transparency was also extremely good. Further, in Examples 33, 36 to 42, 44, 50 to 51, 56 to 58 and 61 to 64, the heat resistance was also extremely good.

As described above, according to the present invention, the inorganic oxide particles capable of imparting functions such as refractive index adjustment, UV shielding, and heat ray shielding by using a specific dispersant, alkoxysilane compound, and plasticizing agent can be produced at a high level. It is possible to provide an inorganic oxide particle dispersion that can be dispersed to a dispersion level that can be made transparent and can maintain the dispersion level even under high temperature conditions. Further, since the inorganic oxide particle dispersion according to the present invention has high compatibility with the molding resin and can maintain the transparency as a molded body, UV shielding, infrared shielding, refractive index adjustment, antistatic property adjustment, heat resistance It is possible to achieve the imparting of properties by a simple process that does not use a coating process or a laminating process, and it can be applied to a wide range of plastic molding applications.

Claims

An inorganic oxide particle dispersion containing inorganic oxide particles, a dispersant, an alkoxysilane compound, and a plasticizer having a boiling point of 200 ° C. or higher and having no polymerizable unsaturated group, wherein the dispersant is as follows. An inorganic oxide particle dispersion containing at least one selected from the group consisting of a dispersant A represented by the general formula A and a dispersant B represented by the following general formula B.

(R 1 is an alkyl group having a branched structure or a linear structure, and represents an alkyl group having 10 to 18 carbon atoms. A represents an alkylene group having a linear structure having 2 to 3 carbon atoms. n 1 is an integer of 5 to 20.)

(X 1 represents a hydrogen atom or Y 1. R 2 is an alkyl group having a branched structure or a linear structure, and n 2 represents an alkyl group having a main chain having 12 to 13 carbon atoms. R 3 is an alkyl group having a branched structure or a linear structure, and represents an alkyl group having a main chain having 12 to 13 carbon atoms. N 3 is an integer of 1 to 10. .)
The inorganic oxide particle dispersion according to claim 1, wherein the inorganic oxide particles contain zirconium oxide particles.
The inorganic oxide particle dispersion according to claim 1 or 2, wherein the plasticizer contains at least one selected from the group consisting of polyethylene glycol-based esters, polypropylene glycols, and polypropylene glycol-based esters.
The inorganic oxide particle dispersion according to any one of claims 1 to 3, wherein the alkoxysilane compound has an epoxy skeleton.
A molding composition containing the inorganic oxide particle dispersion according to any one of claims 1 to 4 and a molding resin.
A molded product using the inorganic oxide particle dispersion according to any one of claims 1 to 4.