KR20120030037A - Resin composition and process for producing same - Google Patents

Abstract

Resin (A) and particles (B1) having an average particle diameter of 100 nm to 50 µm and an average particle diameter of 1 to 300 nm (wherein the average particle diameter of the particles (B1)> average particles of inorganic fine particles (B2)). The resin composition containing the composite particle | grains (B) comprised from the inorganic fine particle (B2) of diameter). Thereby, while providing the resin composition which can disperse | distribute the particle | grains contained in it satisfactorily and can provide the molded object with low linear expansion rate.

Description

Resin composition and its manufacturing method {RESIN COMPOSITION AND PROCESS FOR PRODUCING SAME}

TECHNICAL FIELD This invention relates to a resin composition and its manufacturing method. When it demonstrates further in detail, it is related with the resin composition to which the composite particle by which the inorganic particle adheres is a particle surface mix | blended, and its manufacturing method.

In recent years, the method of adding fillers, such as particle | grains, to resin is examined variously for the purpose of the improvement of the physical property of a resin molding.

For example, Patent Document 1 discloses a method of adding calcium carbonate and / or magnesium carbonate to an aliphatic polyester resin to improve mechanical strength, and the like.

Moreover, addition of particle | grains etc. as a filler in a resin composition is performed in order to obtain the resin molded object with high linear stability by making linear expansion coefficient small.

In this case, the larger the amount of particles or the like added, the smaller the linear expansion coefficient of the molded body can be. However, if the amount of the particles or the like added to the resin is increased, the particles aggregate in the composition, resulting in a decrease in physical properties of the resulting resin molded body. Since there existed, the addition amount was restrict | limited and it could not be said that the linear expansion rate was fully reduced and obtained to the target level.

Therefore, attempts have been made to increase the amount of the particles added in the resin by adding a dispersant to the resin composition or treating the particles to be blended with a surface treatment agent to improve the dispersibility of the particles.

However, in this case, depending on the dispersing agent and surface treatment agent to be used, the reactivity with resin may become a problem.

In addition, deterioration of physical properties such as heat resistance, linear expansion coefficient, flexural strength, tensile strength, and electrical conductivity of the resin molded article obtained by adding a dispersant or using surface-treated particles, deterioration of chemical properties such as chemical resistance and water resistance, and transparency There was a problem that the reduction (coloring) of the particles was caused, and that the particles became expensive due to the surface treatment.

From these problems, the method of improving the dispersibility of particle | grains in resin is calculated | required by methods other than the process by a dispersing agent and a surface treating agent.

Japanese Patent Application Laid-Open No. 4-146952

This invention is made | formed in view of such a situation, and an object of this invention is to provide the resin composition which can disperse | distribute favorably, and can provide the molded object with low linear expansion rate, and its manufacturing method.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, while discovering that the composite particle | grains which consist of predetermined particle | grains and the inorganic fine particles adhering to this surface disperse | distribute favorably in resin, The molded object obtained from the blended resin composition was found to have a low coefficient of linear expansion, thereby completing the present invention.

That is, the present invention,

1.Resin (A) and particles (B1) having an average particle diameter of 100 nm to 50 µm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface thereof, provided that the average particle diameter of the particles (B1)> A resin composition comprising a composite particle (B) composed of an average particle diameter of the inorganic fine particles (B2),

2. Resin composition of 1 whose said particle | grains (B1) are inorganic particle,

3. 1 or 2 resin composition whose said particle | grains (B1) are flaky particle,

4. Resin composition of any one of 1-3 whose said composite particle (B) is surface-treated with organic compound,

5. Resin composition in any one of 1-4 whose difference of the refractive index of said resin (A) and said particle | grain (B1) is less than 0.1,

6. Resin (A) and particles (B1) having an average particle diameter of 100 nm to 50 µm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface thereof, provided that the average particle diameter of the particles (B1)> The composite particle | grain (B) comprised from the average particle diameter of inorganic fine particle (B2), and Resin (A) are mixed, The manufacturing method of the resin composition characterized by the above-mentioned.

7. Resin (A) and particles (B1) having an average particle diameter of 100 nm to 50 μm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface thereof, provided that the average particle diameter of the particles (B1)> The composite particle | grain (B) comprised from the average particle diameter of inorganic fine particle (B2), and resin (A) are mixed, and the said composite particle (B) is disperse | distributed to resin (A), The dispersion method of the particle | grains characterized by the above-mentioned. ,

8. Dispersion method of 7 in which said composite particle (B) is surface-treated with organic compound,

9. A method of dispersing particles in which particles are blended with a resin or a resin composition and the particles are dispersed in the resin or resin composition, wherein the particles adhere to particles (B1) having an average particle diameter of 100 nm to 50 µm and the surface. Particles characterized by using a composite particle (B) composed of inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm (average particle diameter of particles (B1)> average particle diameter of inorganic fine particles (B2)). Dispersion method,

10. A method for producing a resin composition in which particles are blended with a resin or a resin composition, and the particles are dispersed in the resin or the resin composition, wherein the particles are particles (B1) having an average particle diameter of 100 nm to 50 μm and the surface thereof. It is characterized by using a composite particle (B) composed of an inorganic fine particle (B2) having an average particle diameter of 1 to 300 nm (wherein the average particle diameter of the particle (B1)> average particle diameter of the inorganic fine particle (B2)). The manufacturing method of the resin composition to make,

11. An expansion suppression method for reducing the linear expansion coefficient of a resin molded product obtained by blending particles with a resin or a resin composition, wherein the particles (B1) having an average particle diameter of 100 nm to 50 µm and the average particle diameter attached to the surface are used as the particles. Expansion particle suppression method characterized by using a composite particle (B) composed of 1 to 300 nm inorganic fine particles (B2) (average particle diameter of the particles (B1)> average particle diameter of the inorganic fine particles (B2)).

To provide.

The composite particles (B) contained in the resin composition of the present invention are composed of particles (B1) having an average particle diameter of 100 nm to 50 µm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface, and thus, inorganic The fine particles B2 act as spacers of the particles B1.

As a result, aggregation of the particles (B1) is suppressed as compared with the case of using the particles (B1) alone, so that more composite particles (B) are more easily available to the resin (A) even without adding a dispersant or performing a surface treatment. Can be highly dispersed.

As a result, adverse effects on the physical properties of the surface treatment agent, dispersant, and the like, which have been a problem in the past, do not cause a decrease in heat resistance and transparency, deterioration of the coefficient of linear expansion, and the like. A resin molded article can be obtained.

In addition, the composite particles (B) are easily dispersed as described above, and can be blended in an amount equivalent to that of the surface treatment even without the surface treatment, so that a higher-performance resin molded body can be obtained. do.

Moreover, the molded object obtained from the resin composition of this invention has a low linear expansion coefficient compared with the resin molded object which mix | blended the conventional filler in the same quantity, and it is hard to thermally expand.

The reason for this is that in the resin composition of the present invention, the resin (A) enters between the inorganic fine particles (B2) constituting the composite particle (B), that is, the composite particles (B) locally seal the resin. It is assumed to be.

In addition, since the composite particles (B) have an increased surface area compared with the particles (B1), the effect of the particles exhibiting in a resin molded body such as suppressing the linear expansion coefficient, the flame retardant effect, and the catalytic effect can be enhanced. Moreover, since it can disperse | distribute highly even without surface treatment, when the surface treatment is not performed, the effect which a particle exhibits in these resin moldings is not impaired.

Moreover, when a large amount of composite particle (B) is added to a resin composition by using the flaky particle for particle | grain (B1), making the refractive index of resin (A) and particle | grains (B1) the same, or making the difference of refractive index small. In addition, the resin molding which has high transparency is obtained.

In this case, the inorganic fine particles (B2) constituting the composite particle (B) have a resin molded article having a high transparency regardless of the refractive index of the inorganic fine particles (B2) because the average particle diameter is a size equal to or less than the wavelength of the visible light region. You can get it.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The resin composition according to the present invention comprises a resin (A) and particles (B1) having an average particle diameter of 100 nm to 50 µm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface (except for particles (B1)). It includes composite particles (B) composed of the average particle diameter of >> average particle diameter of the inorganic fine particles (B2).

In addition, in this invention, the average particle diameter and the thickness of particle | grains are the measured value by a particle size distribution meter (MICROTRACHRA 9320-X100, Nikki Corporation make).

In this invention, although the average particle diameter of particle | grains (B1) can be about 100 nm-100 micrometers, considering the transparency, the linear expansion coefficient, etc. of the resin molding obtained, it is preferable to set it as about 100 nm-50 micrometers as mentioned above, 200 nm-50 micrometers are more preferable, 200 nm-20 micrometers are still more preferable, 300 nm-10 micrometers are especially preferable.

There is no restriction | limiting in particular as a material of particle | grains (B1), Although an inorganic particle or organic particle | grains may be sufficient, an inorganic particle is suitable in consideration of heat resistance, linear expansion coefficient, etc. of the resin molding obtained.

Examples of the inorganic particles include metal silicates such as calcium silicate, barium silicate, magnesium silicate, zinc silicate, aluminum silicate and copper silicate, metal phosphates such as calcium phosphate, barium phosphate and magnesium phosphate, calcium sulfate, barium sulfate and sulfuric acid. Metal sulfates such as magnesium, silicon oxide (silica), magnesium oxide, aluminum oxide, zinc oxide, iron oxide, titanium oxide, cobalt oxide, nickel oxide, manganese oxide, antimony oxide, tin oxide, calcium oxide, potassium oxide, silicon oxide, Metal oxides such as chromium oxide, iron hydroxide, nickel hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, chromium hydroxide, potassium hydroxide, metal hydroxides such as zinc hydroxide, metal nitrides such as silicon nitride, aluminum nitride, boron nitride, zinc carbonate, aluminum carbonate Metal fluorides such as boron fluoride, wollastonite, metal carbonates such as cobalt carbonate, nickel carbonate, calcium carbonate and basic copper carbonate, Silicate minerals such as notle, talc, mica, hydrotalcite, potassium titanate, calcium titanate, and the like; graphite particles such as carbon and graphite; metal powders such as iron, copper, gold and silver; These can be used individually by 1 type or in combination of 2 or more types. What is necessary is just to select these optimally according to the function etc. which are given to a resin composition.

Among these, in consideration of imparting suitable functionality required for the resin composition of the present invention, silicon oxide (silica), magnesium oxide, aluminum oxide, zinc oxide, iron oxide, titanium oxide, cobalt oxide, nickel oxide, manganese oxide, and oxidation Metal oxides such as antimony, tin oxide, calcium oxide, potassium oxide, silicon oxide, chromium oxide, iron hydroxide, nickel hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, metal hydroxides such as chromium hydroxide, potassium hydroxide, zinc hydroxide, silicon nitride, nitride It is preferable to use metal nitrides such as aluminum and boron nitride, metal fluorides such as boron fluoride, silicate minerals such as wollastonite and zonoelite, talc, mica, hydrotalcite, potassium titanate, calcium titanate and glass, and the like. In particular, in order to lower the thermal expansion rate of the resin composition and to impart flame retardancy, it is usually industrially. Metal hydroxides, silicon oxides and glass, which are used, are suitable, in particular metal hydroxides and silicon oxides.

On the other hand, as the organic particles, various conventionally known polymer particles can be used, and for example, urethane resin, urea resin, melamine resin, acrylic resin, epoxy resin, styrene resin, silicone resin, fluorine resin, and vinyl type The particle | grains which consist of resin, an olefin resin, ester resin, an amide resin, imide resin, carbodiimide resin, alkyd resin, or these copolymers are mentioned.

The shape of the particles (B1) is arbitrary, such as spherical, elliptic, needle, plate, flaky, pulverized, irregularities, and the like, and when obtaining a transparent resin composition (molded product), it is optimal depending on the application, such as using flaky particles. What is necessary is just to select the shape of.

In addition, flaky particle is a thin plate-like particle like a scale, The plane shape is not specifically limited, such as circular, elliptical, square, indefinite form.

When particle | grains (B1) are flaky, it is preferable at the point of suppressing transparency and the thermal expansion coefficient of the resin molded object obtained that it is 1 nm-10 micrometers. More preferably, 2 nm-5 micrometers, especially 3 nm-3 micrometers are suitable. The aspect ratio (average particle diameter / thickness) of the flaky particles is preferably 2 to 50 in terms of transparency and suppression of thermal expansion rate. More preferably, 3-30, especially 5-20 are suitable.

The inorganic fine particles (B2) are particles that adhere to the surface of the particles (B1), and their average particle diameter is smaller than that of the particles (B1), specifically 1 to 300 nm. More preferably, 1-200 nm, especially 1-100 nm are preferable.

Thus, since the average particle diameter of an inorganic fine particle (B2) is smaller than the wavelength of visible light, even when obtaining a transparent resin composition, it does not affect transparency.

As the inorganic fine particles, for example, silica, talc, mica, glass, borosilicate glass, synthetic hydrotalcite, potassium titanate, wollastonite, zonoelite, magnesium oxide, magnesium hydroxide, aluminum hydroxide, titanium oxide, ferrite, fluoride Graphite particles such as boron, carbon, graphite, metal powders such as cobalt oxide, potassium hydroxide, calcium hydroxide, nickel hydroxide, chromium hydroxide, aluminum nitride, boron nitride, iron, copper, gold, silver, and the like. When () is an inorganic particle, the same material as this or a different material may be sufficient.

In particular, it is preferable to use silica from the point that industrial ease of acquisition and reduction of the linear expansion coefficient of the resin molding obtained are aimed at.

The shape of the inorganic fine particles (B2) is not particularly limited, and spherical, elliptic, needle, plate, flaky, pulverized, uneven particles and the like can be appropriately selected.

The method of adhering the inorganic fine particles (B2) to the surface of the particles (B1) is not particularly limited, (1) the method of surface-treating the particles (B1), and chemically bonded to the inorganic fine particles (B2), (2) Surface treatment of the inorganic fine particles (B2) and chemical bonding to the surface of the particles (B1), (3) precipitation and growth of the inorganic fine particles (B2) on the surface of the particles (B1), (4) particles (B1) And a method of mixing and stirring the inorganic fine particles (B2) and (5) a method of mixing and stirring the particles (B1), the inorganic fine particles (B2) and the silane coupling agent.

In this case, since the use ratio of the particle B1 and the inorganic fine particle (B2) is changed depending on the average particle diameter, material, etc. of each particle to be used, it cannot be specified uniformly, but the resin (A) of the composite particle (B) In consideration of improving the dispersibility in the inside and reducing the coefficient of linear expansion of the resulting resin molded body, in the range of the average particle diameter of the particles (B1) and the inorganic fine particles (B2) described above, B1) :( B2) = 1: 1-10000: 1 It can be set. In addition, unattached particle | grains can be easily isolate | separated into composite particle | grains (B) by methods, such as washing with a solvent.

As described above, the composite particles (B) used in the present invention are excellent in dispersibility to the resin (A) alone, and have a higher ratio than the conventional particles without adding a dispersant or surface treatment of the particles. Although it can mix | blend in resin (A) and can use, you may process the surface with an organic compound for the purpose of further improving dispersibility of a layer, or improving affinity with resin (A).

By surface-treating and improving dispersibility, more composite particle | grains (B) can be mix | blended with resin (A). Moreover, the improvement of the physical strength of the molded object obtained as a result of making the resin (A) and a composite particle (B) adhere firmly by improving affinity with resin (A) can also be expected. When obtaining a transparent resin molded object, since adhesiveness of particle | grains and resin improves, a space | gap does not generate | occur | produce, and transparency also improves.

In addition, the surface treatment of the composite particle (B) means the surface treatment performed after affixing particle | grain B1 and an inorganic fine particle (B2), and is performed to particle | grain B1 and / or inorganic fine particle (B2) before their attachment. It is different from the processing.

Examples of the organic compound used for the surface treatment include fatty acids, fatty acid amides, fatty acid salts, fatty acid esters, aliphatic alcohols, silane coupling agents, titanium coupling agents, silicone polymers, phosphate esters, and the like. If it does not damage, it will not specifically limit.

In addition, the polymer layer may be formed by performing graft polymerization or the like on the surface of the composite particle (B).

Moreover, it is preferable that the organic compound couple | bonds with composite particle | grains (B) by chemical bonds, such as a covalent bond. As a method of chemically bonding an organic compound and a composite particle (B), for example, the method of making the organic compound which has a functional group and the reactive functional group on the surface of a composite particle (B) react, and it couple | bonds, or Unexamined-Japanese-Patent No. 2005-179576. As in the publications described in the publications of WO2006 / 137430 pamphlet, a method of forming an organic compound layer (polymer layer) on the composite particles (B) by graft polymerization, and the like can be given.

It does not specifically limit as resin (A) used for the resin composition of this invention, Urethane type resin, Urea type resin, Melamine type resin, Acrylic resin, Epoxy type resin, Styrene type resin, Silicone type resin, Fluorine type resin, Polycarbonate type Resins, vinyl-based resins, olefin-based resins, ester-based resins, amide-based resins, imide-based resins, carbodiimide-based resins, alkyd-based resins, copolymers thereof, and the like. What is necessary is just to select suitably.

When obtaining a transparent resin molded object, it is preferable to make the refractive index of resin (A) and particle | grains B1 the same, or to make small the difference of refractive index.

In particular, when the refractive index difference is 0.1 or less, preferably 0.07 or less, and more preferably 0.05 or less, a resin molded article having high transparency can be obtained even when a large amount of the composite particles (B) is added to the resin (A). .

The resin composition of this invention can mix and obtain said composite particle (B) and resin (A), and can disperse | distribute composite particle (B) in resin (A).

In this case, although the mixing ratio of both is arbitrary as long as it can shape | mold a molded object, 25-5000 mass parts of composite particles (B) are preferable with respect to 100 mass parts of resin (A), and 40-3500 mass More preferably, 100-2000 mass parts are more preferable.

By setting it as the compounding ratio of this range, the effect of mix | blending composite particle | grains (B), such as a fall effect of a linear expansion rate, is fully exhibited without causing a fall of mechanical strength etc. in the obtained molded object.

Moreover, you may add other additives, such as a flame retardant, a low elasticity agent, an adhesive imparting agent, a diluent, an antifoamer, a coupling agent, to the resin composition of this invention in the range which does not impair the objective of this invention.

The method of mix | blending a composite particle (B) with resin (A) is arbitrary, You may add a composite particle (B) to resin (A), or may add resin (A) to composite particle (B). In that case, the said arbitrary additive may be added at any stage.

The mixing and dispersing method of resin (A) and composite particle (B) is arbitrary, and the conventionally well-known various methods which can prepare a uniform resin composition can be used.

As a specific example, the mixing-dispersion method with a stirring type disperser, the bead mill, the mixing-dispersion method with a ball mill, the mixing-dispersion method with a three-roll mill, the mixing-dispersion method with a rotating and revolving mixer, etc. are mentioned.

In addition, you may add an organic solvent as needed at the time of mixing and dispersion | distribution. As such an organic solvent, methyl ethyl ketone, N, N- dimethylformamide, etc. are mentioned, for example, It is not limited to these.

By molding the resin composition prepared as described above, a resin molded article having a low linear expansion rate can be obtained in which the composite particles (B) are highly dispersed therein. That is, adding a composite particle (B) to resin (A) or a resin composition can also be called a method of suppressing the linear expansion rate of the resin molding obtained.

In this case, the molding method is not particularly limited, and various conventionally known molding methods can be used. As the specific example, blow molding, injection molding, extrusion molding, compression molding, etc. are mentioned, You may apply | coat the said resin composition, and may form a film | membrane.

The obtained molded object or film can be suitably used as an optical material, an electronic material, a building material, an electrode material, a pharmaceutical cosmetic material, an automobile part, a medical product, or the like.

(Example)

Hereinafter, although this invention is demonstrated further more concretely by giving a synthesis example, an Example, and a comparative example, this invention is not limited to the following Example. In addition, evaluation of a raw material, a resin composition, and a resin molded object was performed by the following method.

[1] coefficients of linear expansion

Measured by thermal analysis. Specifically, from the molded products obtained in the Examples and Comparative Examples, a thermal analysis device (TMA8310, manufactured by Rigaku Co., Ltd.) was used for a test piece having a width of 5 mm, a length of 15 mm, and a thickness of 150 µm, and a load of 98 mN and a temperature increase. The range of 30-200 degreeC was measured at the speed of 10 degreeC / min.

[2] transparency (haze)

In accordance with JIS K 7136, it measured using the haze meter (NDH-500 Nihon Denshoku Kogyo Co., Ltd. product).

[3] transparency (transmittance)

In accordance with JIS K 7361-1, it measured using the haze meter (NDH-500 Nippon Denshoku Kogyo Co., Ltd. product).

[4] formability tests

Except having made the thickness of the test piece about 150 micrometers, the molded object was evaluated by the following reference | standard based on the evaluation method of JISK7104 (feel, visual observation).

○: smooth surface of the cured product

(Triangle | delta): Unevenness | corrugation exists in a part of surface of hardened | cured material

X: Unevenness exists in the whole surface of hardened | cured material

[5] flame retardant tests

Based on UL94V "vertical flame retardancy test method (combustion standard of plastic material)", the combustion test was evaluated with the thickness of the test piece as 150 micrometers. The result was evaluated by four criteria of V-0, V-1, V-2, and combustion according to the criterion.

[6] particle diameters and thicknesses

The average particle diameter and the thickness of the particles were measured using a particle size distribution meter (MICROTRACHRA 9320-X100, manufactured by Nikkiso Corporation).

[7] refractive indices

It measured by the refractive index meter (model 2010 prism coupler, Seki Techron Co., Ltd. product).

[8] hardness

It measured based on JISK6911.

[9] shrinkage rate

About the test piece of width 5mm, length 15mm, and thickness of 150 micrometers, the shrinkage rate at the time of heat processing at 100 degreeC for 200 second was measured.

[10] flexural strength

It measured based on JISK6911.

Synthesis Example 1

In a 500 mL eggplant flask, 10 g of spherical silica (manufactured by Nippon Aerosol Co., Ltd.) having an average particle diameter of 20 nm was well dispersed in 100.0 g of methyl ethyl ketone (manufactured by Sanyo Casein Co., Ltd.). Subsequently, 0.3 g of tetraethoxysilane (silane coupling agent, Chiso Co., Ltd. product) was added, and it stirred at 70 degreeC for 3 hours. After completion of the reaction, in order to remove the unreacted monomer, the reaction solvent and the silica particles were separated by a centrifuge. The obtained silica particles were again dispersed in 100 g of methyl ethyl ketone.

Subsequently, 100 g of magnesium hydroxide (Kisuma 5: Kyowa Kagaku Co., Ltd.) having an average particle diameter of 700 nm, a thickness of 100 nm, and a refractive index of 1.56 was well dispersed in 150 g of dimethylformamide (manufactured by Aldrich Japan Co., Ltd.), and the silica The particle dispersion solution was added, and further stirred at 70 ° C for 3 hours to chemically bond silica particles to magnesium hydroxide. The obtained dispersion solution was separated into particles and a solvent by a centrifugal separator, and the particles were collected. After wash | cleaning the collected particle | grains 3 times, it was observed with the scanning electron microscope (FE-SEMS-4800: Hitachi High-Tech Co., Ltd.) that the silica particle couple | bonded with magnesium hydroxide. This confirmed that the silica particles were chemically bonded to magnesium hydroxide.

Synthesis Example 2

30 g of magnesium hydroxide particles obtained in Synthesis Example 1 were dispersed in 50 g of methyl ethyl ketone, 1 g of an epoxy silane (silane coupling agent, manufactured by Chiso Co., Ltd.) was added, and the mixture was stirred at 70 ° C. for 3 hours. After completion of the reaction, in order to remove the unreacted monomer, the reaction solvent and magnesium hydroxide particles were separated by a centrifugal separator, and the particles were collected.

Synthesis Example 3

30 g of magnesium hydroxide particles obtained in Synthesis Example 1 were dispersed in 50 g of methyl ethyl ketone, 1 g of vinylsilane (silane coupling agent, Chiso Co., Ltd. product) was added, and stirred at 70 ° C. for 3 hours. After completion of the reaction, in order to remove the unreacted monomer, the reaction solvent and magnesium hydroxide particles were separated by a centrifugal separator, and the particles were collected.

Synthesis Example 4

30 g of magnesium hydroxide particles (Kisuma 5: Kyowa Kagaku Co., Ltd.) were dispersed in 50 g of methyl ethyl ketone, 1 g of epoxy silane (silane coupling agent, Tosoh Co., Ltd.) was added, and the mixture was stirred at 70 ° C. for 3 hours. . After completion of the reaction, in order to remove the unreacted monomer, the reaction solvent and magnesium hydroxide particles were separated by a centrifugal separator, and the particles were collected.

Synthesis Example 5

30 g of magnesium hydroxide particles (Kisuma 5: Kyowa Kagaku Co., Ltd.) were dispersed in 50 g of methyl ethyl ketone, 1 g of vinyl silane (silane coupling agent, Tosoh Co., Ltd.) was added and stirred at 70 ° C. for 3 hours. did. After completion of the reaction, in order to remove the unreacted monomer, the reaction solvent and magnesium hydroxide particles were separated by a centrifugal separator, and the particles were collected.

[Synthesis Example 6]

10 g of spherical silica (manufactured by Nippon Aerosol Co., Ltd.) having an average particle diameter of 20 nm is dispersed in 100 g of methyl ethyl ketone, and 0.3 g of epoxy silane (silane coupling agent, manufactured by Tosso Co., Ltd.) is added thereto at 70 ° C. It stirred for 3 hours. After completion of the reaction, in order to remove the unreacted monomer, the reaction solvent and the silica particles were separated by a centrifugal separator, and the particles were collected.

Example 1

150 to 300 particles obtained in Synthesis Example 1 in 100 parts by mass of an epoxy resin (Principal: Pelox ME-540 CLEAR, Curing agent: Pelcure HV-540 compounding ratio 100: 60 Pelnox Co., Ltd., refractive index: 1.55, the same) A mass part and 30 mass parts of methyl ethyl ketones were added, and it stirred with the rotating and revolving mixer (Awa Torrenta Co., Ltd. make, same as below) so that particle | grains may be disperse | distributed uniformly, and obtained the resin composition.

The obtained resin composition was heated and hardened at 150 degreeC for 16 hours, and the transparent resin molded object was obtained. The size and thickness of the test piece were produced according to each evaluation method.

[Example 2]

A resin composition and a transparent resin molded product were obtained in the same manner as in Example 1 except that the particles obtained in Synthesis Example 2 were used.

Example 3

43 to 150 parts by mass of the particles of Synthesis Example 1 and 1500 parts by mass of dimethylformamide are added to 100 parts by mass of the urethane resin (F-42R, manufactured by Nisshinbo Chemical Co., Ltd., the same), so that the particles are uniformly dispersed. It stirred with the rotating and revolving mixer, and obtained the resin composition.

The obtained resin composition was heated and dried at 80 degreeC for 2 hours, and the resin molded object was obtained. The size and thickness of the test piece were produced according to each evaluation method.

Example 4

A resin composition and a resin molded body were obtained in the same manner as in Example 3 except that the particles obtained in Synthesis Example 3 were used.

Comparative Example 1

A resin composition and a resin molded product were obtained in the same manner as in Example 1 except that the particles of Synthesis Example 1 were changed to magnesium hydroxide (Kisuma 5: Kyowa Kagaku Co., Ltd.).

Comparative Example 2

Except having changed the particle | grains of the synthesis example 2 into the particle | grains of the synthesis example 4, it carried out similarly to Example 2, and obtained the resin composition and the resin molded object.

Comparative Example 3

A resin composition and a resin molded product were obtained in the same manner as in Example 3 except that the particles of Synthesis Example 1 were changed to magnesium hydroxide (Kisuma 5: Kyowa Kagaku Co., Ltd.).

[Comparative Example 4]

Except having changed the particle | grains of the synthesis example 3 into the particle | grains of the synthesis example 5, it carried out similarly to Example 4, and obtained the resin composition and the resin molded object.

[Comparative Example 5]

Using only epoxy resin, molding and curing were carried out in the same manner as in Example 1 to obtain a resin molded body.

[Comparative Example 6]

Using only a urethane resin, molding and curing were carried out in the same manner as in Example 3 to obtain a resin molded body.

Comparative Example 7

Magnesium hydroxide (Kisuma 5: Kyowa Kagaku Co., Ltd.) and spherical silica (Nippon Aerosil Co., Ltd.) having a particle diameter of 20 nm are 50: 1 (mass ratio). A resin composition and a resin molded body were obtained in the same manner as in Example 1 except that the mixture was changed to a mixture.

Comparative Example 8

The resin composition and the resin molded body were carried out in the same manner as in Example 1 except that the particles obtained in Synthesis Example 4 were mixed so that the particles obtained in Synthesis Example 4 and the particles obtained in Synthesis Example 6 were 50: 1 (mass ratio). Got.

Various evaluation tests were done about the resin composition and resin molding obtained by each said Example and the comparative example. The results are shown in Tables 1 and 2.

As shown in Tables 1 and 2, it can be seen that in Examples 1 to 4, the particles can be highly charged as compared with the comparative examples.

Moreover, when Example 1, 2 and Comparative Examples 1 and 2 are compared with the same addition amount, it turns out that the molded object obtained in Examples 1 and 2 has a small linear expansion coefficient, it is difficult to expand, and it is excellent in strength.

In addition, when Examples 3 and 4 and Comparative Examples 3 and 4 are compared with each other in the same amounts, the molded bodies obtained in Examples 3 and 4 had a small coefficient of linear expansion and were difficult to expand, and also showed excellent dimensional stability during molding. Can be.

In addition, as can be seen by comparing Example 1 with Comparative Examples 7, 8, when only magnesium hydroxide and spherical silica were mixed instead of composite particles, the filling amount of the particles did not improve, and the strength of the resulting molded article also improved. It can be seen that the linear expansion coefficient did not decrease.

Claims (11)

Resin (A) and particles (B1) having an average particle diameter of 100 nm to 50 µm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface (however, the average particle diameter of the particles (B1)> inorganic fine particles). The composite composition (B) comprised from (average particle diameter of (B2)) is contained, The resin composition characterized by the above-mentioned. The resin composition according to claim 1, wherein the particles (B1) are inorganic particles. The resin composition according to claim 1 or 2, wherein the particles (B1) are flaky particles. The said composite particle (B) is surface-treated with the organic compound, The resin composition of any one of Claims 1-3 characterized by the above-mentioned. The resin composition according to any one of claims 1 to 4, wherein a difference in refractive index between the resin (A) and the particles (B1) is within 0.1. Resin (A) and particles (B1) having an average particle diameter of 100 nm to 50 µm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface (however, the average particle diameter of the particles (B1)> inorganic fine particles). The composite particle | grain (B) comprised from the average particle diameter of (B2), and resin (A) are mixed, The manufacturing method of the resin composition characterized by the above-mentioned. Resin (A) and particles (B1) having an average particle diameter of 100 nm to 50 µm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface (however, the average particle diameter of the particles (B1)> inorganic fine particles). The composite particle | grain (B) comprised of the average particle diameter of (B2), and resin (A) are mixed, and the said composite particle (B) is disperse | distributed to resin (A), The dispersion | distribution method of the particle | grains characterized by the above-mentioned. The dispersion method according to claim 7, wherein the composite particles (B) are surface treated with an organic compound. As a dispersion method of the particle | grains which mix | blend particle | grains with resin or a resin composition, and disperse | distribute this particle | grain in the said resin or resin composition,
As the particles, particles (B1) having an average particle diameter of 100 nm to 50 µm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface (wherein, the average particle diameter of the particles (B1)> inorganic fine particles (B2)). The composite particle | grains (B) which consist of (average particle diameter of) are used, The dispersion method of the particle | grains characterized by the above-mentioned. As a manufacturing method of the resin composition which mix | blended particle | grains with resin or a resin composition, and disperse | distributed these particle | grains in the said resin or resin composition,
As the particles, particles (B1) having an average particle diameter of 100 nm to 50 µm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface (wherein, the average particle diameter of the particles (B1)> inorganic fine particles (B2)). The composite particle | grain (B) comprised from the average particle diameter of is used, The manufacturing method of the resin composition characterized by the above-mentioned. As an expansion suppression method which mixes particle | grains with resin or a resin composition, and reduces the linear expansion rate of the resin molding obtained,
As the particles, particles (B1) having an average particle diameter of 100 nm to 50 µm and inorganic fine particles (B2) having an average particle diameter of 1 to 300 nm attached to the surface (wherein, the average particle diameter of the particles (B1)> inorganic fine particles (B2)). The composite particle | grains (B) which consist of (average particle diameter) of the expansion suppression method characterized by the above-mentioned.