TW202244095A - Hollow particle and method for manufacturing the same, and resin composition including the hollow particle and method for manufacturing the same wherein the hollow particle is capable of decreasing the dielectric coefficient, the dielectric loss tangent, and the thermal expansion coefficient of various electronic materials - Google Patents

Abstract

The present invention provides an organic hollow particle capable of decreasing the dielectric coefficient, decreasing the dielectric loss tangent, and decreasing the thermal expansion coefficient of various electronic materials, and a resin composition including the same. The hollow particle of the present invention is equipped with a shell formed by a polymer having a urea bond and/or a urethane bond, and a hollow portion surrounded by the shell, the polymer having a urea bond and/or a urethane bond is obtained by reacting an isocyanate compound having multiple isocyanate groups, and an active hydrogen compound having multiple amino groups or hydroxyl groups and/or water; the isocyanate compound is polymeric MDI, or the active hydrogen compound is acrylic polyol. The hollow particle of the present invention can be produced by the following method, in an emulsion obtained by mixing "an oil-based mixture obtained by mixing the isocyanate compound and a hydrophobic solvent" and "a water-based mixture obtained by mixing the active hydrogen compound and/or water," reacting the isocyanate compound and the active hydrogen compound and/or water.

Description

Hollow particle and its manufacturing method, and resin composition containing the hollow particle and its manufacturing method

The present invention relates to a hollow particle and its manufacturing method, as well as a resin composition containing the hollow particle and its manufacturing method. More specifically, the present invention relates to a low dielectric constant substrate, build-up substrate, sealing material, prepreg, etc. used in electronic equipment corresponding to high-frequency communication systems, etc. Resin composition with low dielectric loss tangent and low thermal expansion coefficient and its manufacturing method, and hollow particles used in the resin composition and its manufacturing method.

Thermosetting resins containing epoxy resins, polyimide resins, maleimide resins, phenol resins, etc., or polyethylene resins, acrylic resins, polycarbonate resins, polyarylate resins, Resin compositions of thermoplastic resins such as fluororesins are widely used as materials for electronic circuit boards, build-up boards, sealing materials, prepregs, etc. of electronic devices. In order to correspond to high-frequency communication systems, more excellent low dielectric properties are required, and various resin compositions have been developed in recent years.

In Patent Document 1, an electrical insulating resin composition is described, which contains a thermosetting resin and organic particles. The organic particles are composed of polymers or copolymers of crosslinkable monomers, and/or crosslinkable monomers and It is composed of a copolymer of monofunctional monomers, and the surface of the above-mentioned particles is masked. Vinyl monomers are used as crosslinkable monomers and monofunctional monomers. The electrical insulating resin composition has a low dielectric coefficient and is suitable for making multilayer printed wiring boards.

In Patent Document 2, a low-dielectric resin composition is described, which is a low-dielectric resin composition containing hollow particles composed of a shell and a hollow part and a thermosetting resin, and uses "98% by mass of the whole shell" The above are made of silicon dioxide, have an average porosity of 30-80% by volume, and an average particle diameter of 0.1-20 μm" as hollow particles. With the low-dielectric resin composition, the dielectric coefficient, dielectric loss tangent, and thermal expansion rate can all be reduced. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-8750 [Patent Document 2] Japanese Unexamined Patent Publication No. 2008-31409

[Problem to be Solved by the Invention]

However, the resin composition described in Patent Document 1 cannot fully exhibit the low dielectric properties required especially in fifth-generation (5G) and later high-frequency communication systems whose operating frequency is several to several tens of gigahertz (GHz). " question. For example, if compared with Comparative Example 1 of Patent Document 1, the ethylene-based organic hollow particles of Example 1 of Patent Document 1 (composed of divinylbenzene polymer, hollow rate 60%, styrene alone The decrease rate of the dielectric coefficient of the resin composition is only about 9% (the dielectric coefficient of Example 1 in Patent Document 1/the dielectric coefficient of Comparative Example 1=3.12/3.43=0.91) . With this drop rate, it is difficult to correspond to high-frequency communication systems after 5G.

On the other hand, the "hollow particles whose entire shell is approximately 98% by mass of inorganic silica" described in Patent Document 2 generally have poor affinity with organic resins and are dispersed uniformly in the resin. There are issues. In addition, in the stirring step for dispersion, cracks or cracks are likely to occur in the silica in the shell of the hollow particles, and there is also a possibility that the hollow structure cannot be maintained.

Therefore, it is hoped to develop a low-dielectric characteristic required in high-frequency communication systems after 5G, good affinity with organic resins, and cracks or cracks in the shell are not likely to occur during the stirring step, and can maintain hollowness Constructed hollow particles of organic matter.

Therefore, an object of the present invention is to provide an organic hollow particle and a resin composition containing the same, which can lower the dielectric constant, lower the dielectric loss tangent, and lower the coefficient of thermal expansion of various electronic materials. [Technical means to solve the problem]

The present invention is a method for producing hollow particles, which is a method for producing hollow particles having a shell formed of a polymer having a urea bond and/or an urethane bond (urethane bond), and the above-mentioned The shell portion surrounds the hollow portion; the manufacturing method has the following steps: (a) Mixing an isocyanate compound having a plurality of isocyanate groups and a hydrophobic solvent to obtain an oily mixed solution; (b) mixing an active hydrogen compound having a plurality of amine groups or hydroxyl groups and/or water to obtain a water-based mixed solution; (c) mixing the above water-based mixed liquid and the above-mentioned oil-based mixed liquid to obtain an emulsion in which the above-mentioned oil-based mixed liquid is dispersed in the above-mentioned water-based mixed liquid; and (d) reacting the above-mentioned isocyanate compound with the above-mentioned active hydrogen compound and/or the above-mentioned water in the above-mentioned emulsion to form a polymer having urea bonds and/or urethane bonds; The above-mentioned isocyanate compound is polymeric MDI (polymeric MDI). Alternatively, the present invention is a method for producing hollow particles, which is a method for producing hollow particles having a shell portion formed of a polymer having a urea bond and/or an urethane bond, and the shell portion Surrounding the hollow portion; the manufacturing method has the following steps: (a) Mixing an isocyanate compound having a plurality of isocyanate groups and a hydrophobic solvent to obtain an oily mixed liquid; (b) mixing an active hydrogen compound having a plurality of amine groups or hydroxyl groups and/or water to obtain a water-based mixed solution; (c) mixing the above water-based mixed liquid and the above-mentioned oil-based mixed liquid to obtain an emulsion in which the above-mentioned oil-based mixed liquid is dispersed in the above-mentioned water-based mixed liquid; and (d) reacting the above-mentioned isocyanate compound with the above-mentioned active hydrogen compound and/or the above-mentioned water in the above-mentioned emulsion to form a polymer having urea bonds and/or urethane bonds; The above-mentioned active hydrogen compound is an acrylic polyhydric alcohol.

The present invention is a hollow particle comprising a shell formed by a polymer having a urea bond and/or an urethane bond, and a hollow portion surrounded by the shell, the polymer having a urea bond and/or urethane bond The material is obtained by reacting an isocyanate compound with multiple isocyanate groups, an active hydrogen compound with multiple amine groups or hydroxyl groups and/or water; the above-mentioned isocyanate compound is polymeric MDI. Alternatively, the present invention is a hollow particle comprising a shell formed by a polymer having a urea bond and/or an urethane bond, and a hollow portion surrounded by the shell, and the shell having a urea bond and/or an urethane bond The polymer is obtained by reacting an isocyanate compound having a plurality of isocyanate groups, an active hydrogen compound having a plurality of amine groups or hydroxyl groups and/or water; the above active hydrogen compound is an acrylic polyol.

The present invention is a manufacturing method of a resin composition, which has the following steps: Hollow particles are obtained by the above method; and The above-mentioned hollow particles are mixed with a resin component.

The present invention is a resin composition containing a resin component and the above-mentioned hollow particles. [Effect of Invention]

According to the present invention, it is possible to provide organic hollow particles capable of lowering the dielectric constant, lowering the dielectric loss tangent, and lowering the coefficient of thermal expansion of various electronic materials, and a resin composition containing the same.

＜Hollow particle and its manufacturing method＞ The hollow particle of the present invention is an organic hollow particle, and has a shell formed of a polymer having a urea bond and/or an urethane bond, and a hollow surrounded by the shell. By blending such hollow particles into various electronic materials, it is possible to achieve low dielectric coefficient, low dielectric loss tangent, and low thermal expansion coefficient.

The urea bond is represented by -NH-CO-NH-, such as represented by the following formula (1), which can be obtained by a compound having an isocyanate group (-NCO) and an amine group (-NH ₂ ). formed by the reaction of the compound. Moreover, a urea bond can be formed by reaction of the compound which has an isocyanate group (-NCO) and water ( _H2O ) as represented by following formula (2), for example. The urethane bond (also called urethane bond) is represented by -NH-COO-, such as represented by the following formula (3), which can be obtained by a compound having an isocyanate group (-NCO), It is formed by the reaction with a compound having a hydroxyl group (-OH).

The polymer having urea bonds and/or urethane bonds can be formed by reacting an isocyanate compound having multiple isocyanate groups, an active hydrogen compound having multiple amine groups or hydroxyl groups, and/or water. More specifically, polyurea, a polymer having urea bonds, is formed by reacting an isocyanate compound having a plurality of isocyanate groups with an active hydrogen compound having a plurality of amine groups and/or water. Polyurethane (polyurethane), a polymer with urethane bonds, is formed by reacting an isocyanate compound with multiple isocyanate groups and an active hydrogen compound with multiple hydroxyl groups. By reacting an isocyanate compound having a plurality of isocyanate groups, an active hydrogen compound having a plurality of amine groups and/or water, and an active hydrogen compound having a plurality of hydroxyl groups, a compound having a urea bond and an urethane bond is formed. The polymer is polyureaurethane. By reacting an isocyanate compound with multiple isocyanate groups with an active hydrogen compound with both amine groups and hydroxyl groups (it can also further cause an isocyanate compound with multiple isocyanate groups to react with water) , and form a polymer with urea bonds and urethane bonds, that is, polyurea urethane.

It does not specifically limit as an isocyanate compound which has a plurality of isocyanate groups, For example, a well-known polyfunctional isocyanate compound can be used. Specific examples of isocyanate compounds having a plurality of isocyanate groups include hexamethylene diisocyanate (HMDI), isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylene diisocyanate, and methylene diisocyanate. Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymerized MDI, modified diphenylmethane diisocyanate (carbodiimide modification, prepolymer modification, etc.), o-toluidine diisocyanate, naphthyl Diisocyanate, xylylene diisocyanate, lysine diisocyanate, etc. The isocyanate compound which has several isocyanate groups can be used individually by 1 type, or can use it in combination of 2 or more types. Among these, polymeric MDI is preferred.

It does not specifically limit as an active hydrogen compound which has a plurality of amine groups, For example, a well-known polyamine compound can be used. Specific examples of active hydrogen compounds having a plurality of amine groups include ethylenediamine, propylenediamine, pentamethylenediamine, isophoronediamine, xylylenediamine, diphenylmethanediamine, hydrogenated Bifunctional polyamines such as diphenylmethanediamine and hydrazine; trifunctional or higher polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and polyamide polyamine; etc. The active hydrogen compound having a plurality of amine groups may be used alone or in combination of two or more.

It does not specifically limit as an active hydrogen compound which has several hydroxyl groups, For example, a well-known polyol compound can be used. Specific examples of active hydrogen compounds having a plurality of hydroxyl groups include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, polysiloxane Department of polyols, etc. The active hydrogen compound which has several hydroxyl groups can be used individually by 1 type, or can use it in combination of 2 or more types. Among these, acrylic polyols are preferable.

It does not specifically limit as an active hydrogen compound which has both an amino group and a hydroxyl group, For example, a well-known alkanolamine compound can be used. Specific examples of active hydrogen compounds having both amine groups and hydroxyl groups include monoalkanolamines such as methanolamine, ethanolamine, and propanolamine; dimethylolethylamine, diethanolmethylamine, and dipropanolethylamine; , Dibutanolmethylamine and other dialkanolamines; etc. The active hydrogen compound which has both an amino group and a hydroxyl group can be used individually by 1 type, or can use it in combination of 2 or more types.

In the present invention, it is particularly preferable to prepare an emulsion of "an oil phase in which an active hydrogen compound having a plurality of amine groups or hydroxyl groups is used as an aqueous phase and an isocyanate compound having a plurality of isocyanate groups is dispersed therein", and In the vicinity of the interface between the water phase and the oil phase, the isocyanate compound, the active hydrogen compound and/or water are reacted. By such a method, hollow particles having a shell portion composed of a polymer having a urea bond and/or an urethane bond, and a hollow portion surrounded by the shell portion can be formed. More specifically, it is preferable to form hollow particles as follows.

First, an isocyanate compound having a plurality of isocyanate groups and a hydrophobic solvent are mixed to obtain an oil-based liquid mixture (step (a)). The hydrophobic solvent is not particularly limited, and a solvent having low reactivity with isocyanate compounds and low solubility in water can be used. Specific examples of hydrophobic solvents include aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons such as heptane and hexane; hydrocarbons; esters such as ethyl acetate; etc. The hydrophobic solvent may be used individually by 1 type, or may use it in combination of 2 or more types. Among these, aliphatic hydrocarbons are preferred, and toluene and/or xylene are more preferred. The concentration of the isocyanate compound in the oil-based mixed solution is preferably from 5 to 65% by weight, more preferably from 20 to 60% by weight.

On the other hand, an active hydrogen compound having a plurality of amine groups or hydroxyl groups and/or water is mixed to obtain an aqueous mixed solution (step (b)). That is, the active hydrogen compound having a plurality of amine groups or hydroxyl groups is preferably partially or completely dissolved in water. Furthermore, water is a solvent component for dissolving an active hydrogen compound, and also serves as a substrate for reacting with an isocyanate compound having a plurality of isocyanate groups.

Next, the oil-based mixed liquid obtained in step (a) and the water-based mixed liquid obtained in step (b) are mixed to obtain an emulsion in which the oil-based mixed liquid is dispersed in the water-based mixed liquid (step (c)). For the mixing of water-based mixed liquid and oil-based mixed liquid, for example, a homogeneous emulsifier can be used. The rotation speed and rotation time of the homo-emulsifier can be appropriately adjusted so as to form "droplets of the oil-based mixed liquid having a desired size dispersed in the aqueous mixed liquid". The blending ratio of the water-based mixed liquid and the oil-based mixed liquid is preferably 5-60 parts by weight, more preferably 15-40 parts by weight, of the oil-based mixed liquid relative to 100 parts by weight of the water-based mixed liquid.

In step (c), an emulsifier (surfactant) may be used. It does not specifically limit as an emulsifier, For example, well-known nonionic surfactant, anionic surfactant, cationic surfactant, zwitterionic surfactant can be used. Moreover, a high molecular type surfactant can also be used as an emulsifier. Specific examples of the polymeric surfactant include polyvinyl alcohol-based surfactants, casein-based surfactants, carboxymethylcellulose-based surfactants, acrylic-based surfactants, and the like. Furthermore, when an active hydrogen compound having a plurality of amine groups or hydroxyl groups has a surface active function, it can also be used as a surfactant.

Next, in the emulsion obtained in the step (c), the isocyanate compound is reacted with the active hydrogen compound and/or water to form a polymer having urea bonds and/or urethane bonds (step (d)). By the step (d), the isocyanate compound can be reacted with the active hydrogen compound and/or water in the vicinity of the droplet surface of the oil-based mixed liquid dispersed in the aqueous mixed liquid (near the interface between the aqueous mixed liquid and the oil-based mixed liquid) , therefore, it is possible to form particles having a shell portion composed of a polymer having urea bonds and/or urethane bonds. The reaction can be carried out at room temperature, or the emulsion can be heated.

Furthermore, a hydrophobic solvent exists inside the particles obtained through the reaction of the step (d). Therefore, it is preferable to remove and dry the hydrophobic solvent after completion of the reaction. Thereby, hollow particles having a shell formed of a polymer having a urea bond and/or an urethane bond, and a hollow surrounded by the shell can be obtained. Furthermore, since air is considered to exist in the hollow part, by blending the hollow particles into the resin component, it is possible to lower the dielectric constant, lower the dielectric loss tangent, and lower the coefficient of thermal expansion.

The average particle size (median particle size) of the hollow particles is preferably from 0.05 to 50 μm, more preferably from 0.1 to 30 μm, and still more preferably from 0.5 to 10 μm. In addition, the average particle diameter (median diameter) of a hollow particle can be measured using the laser diffraction/scattering type particle size distribution measuring apparatus, for example.

The hollow rate of the hollow particles is preferably from 10 to 90%, more preferably from 20 to 80%, and still more preferably from 30 to 70%. Furthermore, the hollowness ratio of the hollow particle can be calculated by the following calculation formula by measuring the inner diameter and outer diameter of the hollow particle with a scanning electron microscope. Hollow ratio (%) = (inner diameter of hollow particles/outer diameter of hollow particles) ³ × 100 In addition, the hollow ratio of hollow particles can also be obtained by using the same material as particles without hollow parts (dense particles) ) is calculated by comparing the settling properties.

The hollow particles of the present invention can achieve low dielectric coefficient, low dielectric loss tangent, and low coefficient of thermal expansion.

＜Resin composition and its production method＞ The resin composition of the present invention is a resin composition for electronic circuit boards, build-up boards, sealing materials, prepregs, etc. of electronic devices, and contains resin components and hollow particles of the present invention. In this way, by blending the hollow particles of the present invention into the resin component, various electronic materials can be reduced in dielectric coefficient, dielectric loss tangent, and thermal expansion. Specific examples of the resin component include thermosetting resins such as epoxy resins, polyimide resins, maleimide resins, and phenol resins; polyethylene resins, acrylic resins, polycarbonate resins, polyester resins, etc. Thermoplastic resins such as arylate resins and fluororesins; etc. Among them, a thermosetting resin is preferable, and an epoxy resin is more preferable. Furthermore, when using an epoxy resin as a resin component, it is preferable to mix hardening agents, such as amines, acid anhydrides, and imidazoles, or a catalyst suitably.

The resin composition of the present invention can be obtained by mixing the above-mentioned hollow particles and the resin component. The blending ratio may be appropriately adjusted so as to have desired dielectric properties, but it is preferably blended so that the content of hollow particles becomes 1 to 50% by weight, more preferably 5% by weight. ~30% by weight. When the resin component is a thermosetting resin, it is preferably cured at room temperature or by heating after mixing.

The resin composition of the present invention has low dielectric coefficient, low dielectric loss tangent, and low thermal expansion coefficient, so it is suitable for use in electronic circuit substrates, build-up substrates, sealing materials, prepregs, etc. of electronic equipment. [Example]

＜Manufacture of hollow particle 1＞ Prepare a reaction device equipped with a stirrer, a 2-liter reaction vessel, a condenser tube for solvent removal, a stirring blade, a thermometer, and an oil bath. Prepare an oil-based mixture consisting of 180 g of polymerized MDI with an NCO content of 31% (manufactured by Tosoh Corporation, trade name: Millionate MR-200) and 180 g of toluene. Prepare a water-based mixture consisting of 1,170 g of deionized water and 90 g of acrylic polymer surfactant (20% aqueous solution). Furthermore, the solid content of the acrylic polymer surfactant is composed of 35% methacrylic acid, 45% methyl methacrylate, 9% hydroxyethyl methacrylate, nonylphenoxy polyethylene methacrylate Sodium salt of copolymer consisting of 11% of oxyester (addition 45 moles).

In a 2-liter container, put the above-mentioned water-based mixed solution, and then add the above-mentioned oil-based mixed solution, and at the same time emulsify with a homogeneous emulsifier (cylinder outer diameter: 25 mm) at an emulsifying speed of 18,000 rpm for 2 minutes to obtain Milky white liquid. Move the obtained milky white liquid to the above-mentioned reaction device, and stir it. At the same time, the temperature of the liquid is slowly heated from room temperature to 70°C with an oil bath for about 2 hours, so as to promote the formation of isocyanate groups and water, and isocyanate groups and water. The reaction of the hydroxyl groups in the acrylic polymer surfactant forms a polymer shell having urea bonds and urethane bonds, and becomes an aqueous dispersion of particles containing toluene inside. Slowly heat the aqueous dispersion to remove toluene and water azeotropically at about 70°C or higher, and then raise the liquid temperature to 100°C for about 2 hours to remove the toluene component, thereby completing the formation of urea bonds and urethane bonds reaction.

The slurry obtained by cooling to room temperature with a solid content of 19.0% was poured into a pan to a depth of about 2 cm, and the water was evaporated at 70°C for 24 hours to obtain a white lump, which was then pulverized by a pulverizer. Hollow particles in the form of white powder 1.

The average particle diameter (frequency 50% median particle diameter) of the obtained hollow particles 1 was measured using a laser diffraction/scattering type particle size distribution measuring device (manufactured by Horiba, trade name: LA-960), and the result was 2.52 μm.

＜Manufacture of Hollow Particles 2＞ The addition amount of the acrylic polymer surfactant (20% solid content aqueous solution) was set to 45 g, and the rotation speed of the homogeneous emulsifier was changed to 10,000 rpm. In the same way as the hollow particle 1 The hollow particle 2 was obtained as a white powder. The average particle diameter of the obtained hollow particles 2 was 5.01 μm.

<Example 1> Make a mold frame with a thickness of 1 mm x width 30 mm x length 100 mm with a release sheet attached on the inside. The resin composition blended according to Table 1 was poured into the above mold frame and leveled to a thickness of about 1 mm. After that, after 3 hours at room temperature, and then 2 hours at 150°C to harden, the obtained resin plate was taken out from the mold frame, and processed into a sample piece with a size of 0.9 mm thick x 3 mm wide x 80 mm long . The dielectric coefficient and dielectric loss tangent of the obtained sample pieces were measured by the cavity resonator method (frequency: 10 GHz, room temperature). The results are shown in Table 1. Also, the thermal expansion coefficient of the obtained sample piece was measured by the TMA method using a thermomechanical analyzer (manufactured by NETZSCH, trade name: TMA402F1 Hyperion). Table 1 shows the results.

The cut surface of the sample piece of the resin composition of Example 1 was photographed by a scanning electron microscope (SEM). As shown in Fig. 1, it is observed that there are countless hollow particles 1 with a particle diameter of about 2-3 μm in the epoxy resin. Also, in FIG. 2 , observing the cut hollow particle 1, it can be confirmed that the hollow particle 1 has a large hollow structure.

Here, the hollow ratio of the hollow particle 1 can be defined as follows. Hollow particle 1 hollow rate (%) = (hollow particle 1 inner diameter/hollow particle 1 outer diameter) ³ × 100 If the cut hollow particle 1 inner diameter (shell inner diameter) and The outer diameters (shell outer diameters) are 2.37 μm and 2.89 μm, respectively. When these measured values are substituted into the formula of said hollow ratio, the result is as follows. Hollow Particle 1 Hollow Rate (%)=(2.37/2.89) ³ ×100=55 Based on the above, it is known that the hollow particle 1 has a hollow rate of about 55%.

<Example 2> 14.2 g of hollow particle 2 was blended instead of hollow particle 1, 28.3 g of hardener B and 0.8 g of hardener C were blended instead of hardener A, and a sample piece was prepared in the same manner as in Example 1. . The dielectric coefficient, dielectric loss tangent, and thermal expansion coefficient of the obtained sample pieces are shown in Table 1. In addition, the cross-section of the sample piece of the resin composition of Example 2 was photographed by a scanning electron microscope (SEM), and it was found that the hollowness of the hollow particles 2 was about 56%.

<Example 3> 2.0 g of hollow particles 1 were dispersed in 8.0 g of epoxy diluent. After heating 50.0 g of epoxy resin B to about 120°C and melting it, 0.2 g of hardener C was added to 10.0 g of the above dispersion liquid and mixed. The mixed solution was poured into the same mold frame as in Example 1, and after hardening at 120° C. for 1 hour, a sample piece was produced in the same manner as in Example 1. The dielectric coefficient and dielectric loss tangent of the obtained sample pieces are shown in Table 1.

<Example 4> After heating 50.0 g of epoxy resin C to about 100° C. and melting it, 10.0 g of hollow particles 2 and 0.2 g of hardener C were added and mixed. The mixed solution was poured into the same mold frame as in Example 1, and after curing at 100° C. for 1 hour and at 150° C. for 2 hours, a sample piece was produced in the same manner as in Example 1. The dielectric coefficient and dielectric loss tangent of the obtained sample pieces are shown in Table 1.

＜Comparative example 1＞ A sample piece was produced in the same manner as in Example 1 except that the hollow particles 1 were not blended. The dielectric coefficient, dielectric loss tangent, and thermal expansion coefficient of the obtained sample pieces are shown in Table 1.

＜Comparative example 2＞ A sample piece was produced in the same manner as in Example 2 except that the hollow particles 2 were not blended. The dielectric coefficient, dielectric loss tangent, and thermal expansion coefficient of the obtained sample pieces are shown in Table 1.

＜Comparative example 3＞ A sample piece was produced in the same manner as in Example 3 except that the hollow particle 1 was not blended. The dielectric coefficient and dielectric loss tangent of the obtained sample pieces are shown in Table 1.

＜Comparative example 4＞ A sample piece was produced in the same manner as in Example 4 except that the hollow particles 2 were not blended. The dielectric coefficient and dielectric loss tangent of the obtained sample pieces are shown in Table 1.

[Table 1] Example comparative example 1 2 3 4 1 2 3 4 blending g Epoxy resin A 50.0 50.0 50.0 50.0 Epoxy resin B 50.0 50.0 Epoxy resin C 50.0 50.0 epoxy thinner 8.0 8.0 Hardener A 15.0 15.0 Hardener B 28.3 28.3 Hardener C 0.8 0.2 0.2 0.8 0.2 0.2 Hollow particle 1 11.4 2.0 Hollow particle 2 14.2 10.0 total 76.4 93.3 60.2 60.2 65.0 79.1 58.2 50.2 characteristic Permittivity 2.01 2.43 2.74 2.65 2.53 2.79 2.85 3.05 Relative Comparative Example Reduction Rate twenty one% 13% 4% 13% Dielectric loss tangent 0.020 0.019 0.029 0.025 0.025 0.022 0.030 0.029 Relative Comparative Example Reduction Rate 20% 14% 3% 14% Thermal expansion coefficient 59 58 94 92 Relative Comparative Example Reduction Rate 37% 37% Epoxy resin A: manufactured by Mitsubishi Chemical, trade name: jER 828 epoxy resin B: manufactured by Nippon Kayaku, trade name: WHR-991S epoxy resin C: manufactured by Mitsubishi Chemical, trade name: jER YX-7700 epoxy thinner : Yokkaichi Gosei, brand name: EPOGOSEY HD (D) Hardener A (amine): Mitani Paint, brand name: BOUJINTEX #8000 Hardener B (anhydride): Mitsubishi Chemical, brand name: jER YH306 Hardener C (imidazoles): 2-Eth-4-methimidazole, manufactured by Tokyo Chemical Industry

According to the above results, it can be seen that the dielectric coefficient, dielectric loss tangent, and thermal expansion coefficient of the resin composition obtained in the example can be greatly reduced compared with the resin composition obtained in the corresponding comparative example.

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[ Fig. 1 ] is a photograph of a cut section of a sample piece of the resin composition of Example 1 taken with a scanning electron microscope (SEM). It was confirmed that innumerable hollow particles with a particle diameter of about 2 to 3 μm exist in the epoxy resin. [Fig. 2] is an enlarged photograph of the cut hollow particle in Fig. 1. It was confirmed that a large hollow structure exists inside the hollow particles.

Claims (21)

A method for producing hollow particles, which is a method for producing hollow particles having a shell formed of a polymer having a urea bond and/or a urethane bond (urethane bond), and being surrounded by the shell A hollow portion; the manufacturing method has the following steps: (a) Mixing an isocyanate compound having a plurality of isocyanate groups and a hydrophobic solvent to obtain an oily mixed liquid; (b) mixing an active hydrogen compound having a plurality of amine groups or hydroxyl groups and/or water to obtain a water-based mixed solution; (c) mixing the above water-based mixed liquid and the above-mentioned oil-based mixed liquid to obtain an emulsion in which the above-mentioned oil-based mixed liquid is dispersed in the above-mentioned water-based mixed liquid; and (d) reacting the above-mentioned isocyanate compound with the above-mentioned active hydrogen compound and/or the above-mentioned water in the above-mentioned emulsion to form a polymer having urea bonds and/or urethane bonds; The above-mentioned isocyanate compound is polymeric MDI (polymeric MDI). The method for producing hollow particles as claimed in claim 1, wherein the above-mentioned active hydrogen compound is an acrylic polyol. A method for producing hollow particles, which is a method for producing hollow particles having a shell formed of a polymer having a urea bond and/or an urethane bond, and a hollow surrounded by the shell; The manufacturing method has the following steps: (a) Mixing an isocyanate compound having a plurality of isocyanate groups and a hydrophobic solvent to obtain an oily mixed liquid; (b) mixing an active hydrogen compound having a plurality of amine groups or hydroxyl groups and/or water to obtain a water-based mixed solution; (c) mixing the above water-based mixed liquid and the above-mentioned oil-based mixed liquid to obtain an emulsion in which the above-mentioned oil-based mixed liquid is dispersed in the above-mentioned water-based mixed liquid; and (d) reacting the above-mentioned isocyanate compound with the above-mentioned active hydrogen compound and/or the above-mentioned water in the above-mentioned emulsion to form a polymer having urea bonds and/or urethane bonds; The above-mentioned active hydrogen compound is an acrylic polyhydric alcohol. The method for producing hollow particles according to claim 1 or 3, wherein the above-mentioned hydrophobic solvent is an aromatic hydrocarbon. The method for producing hollow particles according to claim 4, wherein the above-mentioned aromatic hydrocarbon is toluene and/or xylene. The manufacturing method of hollow particles according to claim 1 or 3, which uses an emulsifier in the above step (c). The method for producing hollow particles as claimed in claim 1 or 3, wherein the average particle size (median particle size) of the above-mentioned hollow particles is 0.05-50 μm. The manufacturing method of hollow particles as claimed in claim 1 or 3, wherein the hollow ratio of the above-mentioned hollow particles is 10-90%. A method for producing a resin composition comprising the following steps: Hollow particles are obtained by the method of claim 1 or 3; and The above-mentioned hollow particles are mixed with a resin component. The method for producing a resin composition according to claim 9, wherein the content of the hollow particles is 1 to 50% by weight. The method for producing a resin composition according to claim 9, wherein the above-mentioned resin component is a thermosetting resin. The method for producing a resin composition according to claim 11, wherein the thermosetting resin is an epoxy resin. A hollow particle, which has a shell formed by a polymer having a urea bond and/or an urethane bond, and a hollow portion surrounded by the shell, the polymer having a urea bond and/or an urethane bond is obtained by Obtained by the reaction of an isocyanate compound with multiple isocyanate groups, an active hydrogen compound with multiple amine groups or hydroxyl groups and/or water; The above-mentioned isocyanate compound is polymerized MDI. The hollow particle according to claim 13, wherein the active hydrogen compound is an acrylic polyol. A hollow particle, which has a shell formed by a polymer having a urea bond and/or an urethane bond, and a hollow portion surrounded by the shell, the polymer having a urea bond and/or an urethane bond is obtained by Obtained by the reaction of an isocyanate compound with multiple isocyanate groups, an active hydrogen compound with multiple amine groups or hydroxyl groups and/or water; The above-mentioned active hydrogen compound is an acrylic polyhydric alcohol. For example, the hollow particles in claim 13 or 15 have an average particle size (median particle size) of 0.05-50 μm. For example, the hollow particles in claim item 13 or 15, the hollow rate is 10-90%. A resin composition, which contains a resin component and hollow particles in claim 13 or 15. The resin composition according to claim 18, wherein the content of the hollow particles is 1 to 50% by weight. The resin composition according to claim 18, wherein the resin component is a thermosetting resin. The resin composition according to claim 20, wherein the thermosetting resin is an epoxy resin.

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