JP4516779B2 - Metal oxide surface-treated particles, method for producing the same, and method for producing a resin composition - Google Patents

Description

The present invention, the surface metal oxide surface treated treated with a silane coupling agent particles and a method for producing the same, and a method of the metal oxide surface treated particles child producing the resin composition obtained by blending a thermosetting resin The present invention also relates to a method for producing a varnish in which the metal oxide surface-treated particles are dispersed in the varnish .

A thermosetting resin such as an epoxy resin is often used as a sealing material for electronic components such as semiconductor devices. For example, in flip chip mounting, a liquid epoxy resin-based sealing material (underfill material) is filled in a gap between a semiconductor element and a substrate. The sealing material is required to have adhesiveness, moisture resistance, heat cycle resistance, and the like in order to ensure various reliability of the semiconductor element. For this reason, for example, an epoxy resin composition in which metal oxide particles such as silica are blended with an epoxy resin as a matrix has been developed. Moreover, the trial which improves the moldability of an epoxy resin composition etc. is proposed by processing the surface of the metal oxide particle to mix | blend with a silane coupling agent (for example, refer patent document 1, 2).
JP 2001-189407 A JP 2002-114837 A

  As described above, in the flip chip mounting, it is necessary to allow the sealing material to enter a very small gap between the semiconductor element and the substrate. Therefore, high fluidity is required for the sealing material. However, when the metal oxide particles surface-treated with the silane coupling agent are dispersed in the resin, the metal oxide particles are likely to aggregate in the resin. For this reason, the viscosity of a resin composition becomes high and fluidity | liquidity will fall. Further, depending on the surface state of the metal oxide particles, the affinity with the resin is low, and cracks are likely to occur at the interface between the resin and the metal oxide particles. For this reason, the adhesiveness and durability as a sealing material also become a problem.

The present invention has been made in view of such a situation, and provides a metal oxide surface-treated particle having good affinity with a resin and a method for producing the same , which hardly aggregates when blended in a resin. Let it be an issue. Another object of the present invention is to provide a method for producing a resin composition having high fluidity and good adhesion and durability after curing by using the metal oxide surface-treated particles.

  As a result of intensive research on the above problems, the present inventor can improve both the dispersibility in the resin and the affinity with the resin by bringing the surface of the metal oxide particles into a predetermined state. I have come to the knowledge that I can do it.

  For example, there are OH groups (silanol: Si—OH) on the surface of the silica particles. Since silanol is hydrophilic, when silica particles are blended with a resin, the silica particles and the resin are not easily adapted. Further, even if the silica particles are subjected to surface treatment, if silanol remains on the particle surface, the affinity with the resin is low. For this reason, cracks are likely to occur at the interface between the silica particles and the resin after curing. On the other hand, if the surface treatment of the silica particles is performed using a large amount of silane coupling agent, all of the silanol can be reacted and eliminated. However, excessive silane coupling agent adheres to the particle surface. Thus, the silane coupling agent is condensed to form a polymer layer insoluble in the organic solvent. Since the strength of this polymer layer is low, cracks are likely to occur in the polymer layer after curing. Moreover, when a polymer layer is formed on the surface, the silica particles tend to aggregate. For this reason, the viscosity of a resin composition becomes high and fluidity | liquidity falls.

In contrast, the metal oxide surface-treated particles of the present invention are metal oxide surface-treated particles in which the surface of the metal oxide particles is treated with a silane coupling agent,
The surface treatment layer formed on the surface of the metal oxide particles is
A reaction insolubilized layer formed by a reaction between substantially all OH groups present on the surface of the metal oxide particles before the treatment and the silane coupling agent, and insoluble in an organic solvent;
A solubilized layer formed on the surface of the reaction insolubilized layer and soluble in an organic solvent;
It is characterized by including.
Further, the method for producing metal oxide surface-treated particles of the present invention is a method for producing metal oxide surface-treated particles, wherein the surface of the metal oxide particles is surface-treated with a silane coupling agent,
The vaporized silane coupling agent is brought into contact with the surface of the metal oxide particles, and the silane coupling agent is reacted with the OH groups present on the surface of the metal oxide particles, so that the reaction insolubilized layer is insoluble in an organic solvent. It has the process of forming .
And the surface of the said metal oxide surface treatment particle manufactured can have a solubilization layer which consists of the said silane coupling agent and has not reacted with the said OH group.
Furthermore, it is particularly desirable that the surface of the metal oxide surface-treated particles to be produced does not have a solubilized layer made of the silane coupling agent and not reacting with the OH group.

  A surface treatment layer including at least the reaction insolubilized layer of the reaction insolubilized layer and the solubilized layer is formed on the surface of the metal oxide particles. That is, in the metal oxide surface-treated particles of the present invention, only the reaction insolubilized layer is formed on the surface of the metal oxide particles, and both the reaction insolubilized layer and the solubilized layer are formed. There are two modes. In FIG. 1, the cross-sectional model figure of the metal oxide surface treatment particle | grains of this invention is shown. In FIG. 1, (a) shows an embodiment in which the surface treatment layer consists only of a reaction insolubilized layer, and (b) shows an embodiment in which the surface treatment layer comprises a reaction insolubilized layer and a solubilized layer. As shown in FIG. 1 (a), the metal oxide surface-treated particles 1 are composed of metal oxide particles 2 and a surface-treated layer 3. The surface treatment layer 3 includes a reaction insolubilized layer 4. The reaction insolubilized layer 4 is formed on the surface of the metal oxide particles 2. Further, as shown in FIG. 1B, the metal oxide surface-treated particles 1 are composed of metal oxide particles 2 and a surface-treated layer 3. The surface treatment layer 3 includes a reaction insolubilized layer 4 and a solubilized layer 5. The reaction insolubilized layer 4 is formed on the surface of the metal oxide particles 2. The solubilized layer 5 is formed on the surface of the reaction insolubilized layer 4.

  The reaction insolubilized layer is formed by reacting all OH groups present on the surface of the metal oxide particles with the silane coupling agent before the surface treatment. In addition to the disappearance of the hydrophilic OH group by the reaction, the formed reaction insolubilized layer is easily adapted to the resin. Therefore, for example, in a mode in which the surface treatment layer is composed only of the reaction insolubilized layer, the affinity with the resin is high, and cracks hardly occur at the interface with the resin even after curing. In addition, aggregation in the resin hardly occurs.

  The solubilized layer is formed on the surface of the reaction insolubilized layer. The solubilized layer is formed from a silane coupling agent that has not been used for the reaction with the OH groups on the surface of the metal oxide particles. Unlike the polymer layer, the solubilized layer is soluble in an organic solvent. That is, the solubilized layer is removed by washing with an organic solvent. The solubilized layer diffuses and disperses in the resin. Therefore, even if the solubilized layer is formed, the affinity with the resin is not inhibited. For this reason, even after curing, cracks hardly occur at the interface with the resin, and aggregation in the resin hardly occurs. Thus, the metal oxide surface-treated particles of the present invention are excellent in dispersibility in the resin and affinity with the resin.

Metal oxide surface treated particles to be produced by the production method of the present invention, as described below, it exhibits an excellent effect as incorporated into a resin or varnish. That is, the method for producing a resin composition of the present invention is characterized in that the metal oxide powder of the present invention is blended with a thermoplastic or thermosetting resin. The method for producing a varnish composition of the present invention is characterized in that the metal oxide powder of the present invention is blended with a woven cloth impregnating varnish or a film forming varnish.

In the method for producing the resin composition and varnish composition of the present invention (hereinafter appropriately referred to as “resin composition etc.”) , the metal oxide surface-treated particles produced by the production method of the present invention are blended. The For this reason, in the resin composition etc. manufactured with the manufacturing method of the resin composition etc. of this invention, aggregation of metal oxide surface treatment particle | grains is suppressed and the raise of a viscosity is also small. Therefore, the fluidity of the resin composition produced by the production method of the present invention is high. In addition, since the affinity between the resin or varnish and the metal oxide surface-treated particles is good, the adhesion between them is high, and the metal oxide surface-treated particles are difficult to fall off from the resin or varnish after curing.

Thus, the resin composition produced by the production method of the present invention is suitable as a sealing material for electronic parts such as semiconductor devices. Moreover, according to the varnish composition of the present invention, it is possible to produce a prepreg for a multilayer wiring board, an insulating film and the like having a small thermal expansion coefficient and high reliability.

The surface treatment layer of the metal oxide surface treatment particles produced by the production method of the present invention has a reaction insolubilized layer. Since the hydrophilic OH group is eliminated by the reaction with the silane coupling agent, the metal oxide surface-treated particles of the present invention have good affinity with the resin. Moreover, even when it has a solubilization layer in addition to the reaction insolubilization layer, since the solubilization layer diffuses and disperses in the resin, the affinity with the resin is not inhibited. Moreover, since the metal oxide surface-treated particles produced by the production method of the present invention do not have a polymer layer, they are difficult to aggregate in the resin.

In the resin composition produced by the method of the present invention, since the metal oxide surface-treated particles hardly aggregate in the resin or varnish, the increase in viscosity is small and the fluidity is high. In addition, since the affinity between the resin or varnish and the metal oxide surface-treated particles is good, the adhesion between the two is high, and the metal oxide surface-treated particles are difficult to drop off from the resin or varnish after curing.

Hereinafter, the metal oxide surface-treated particles of the present invention, the production method thereof, and the production method of the resin composition and the like will be described in detail based on the embodiments.

< Method for producing metal oxide surface-treated particles>
The metal oxide surface-treated particles produced by the method of the present invention are metal oxide surface-treated particles in which the surface of the metal oxide particles is treated with a silane coupling agent, and are formed on the surface of the metal oxide particles. The surface-treated layer formed by reaction of all OH groups present on the surface of the metal oxide particles before the treatment with the silane coupling agent, and a reaction-insolubilized layer insoluble in an organic solvent, and the reaction Of the solubilized layer formed on the surface of the insolubilized layer and soluble in the organic solvent, at least the reaction insolubilized layer is included.

Examples of the metal oxide particles include single metal oxide particles such as silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), and SiO ₂ —Al _2. Composite oxide particles such as O ₃ , SiO ₂ —TiO ₂ , and SiO ₂ —ZrO ₂ may be used. Among them, it is possible to adopt metal oxide particles mainly composed of silica, considering that it is the cheapest, is strong and chemically stable against corrosion by acids and alkalis, and has a low dielectric constant. desirable. In the present specification, metal oxide particles containing silica as a main component are referred to as “silica particles”.

  The method for producing metal oxide particles is not particularly limited. For example, it can be manufactured by burning metal, such as VMC (Vaperized Metal Combution) method. With the VMC method, a chemical flame is formed by a burner in an atmosphere containing oxygen, and an amount of metal powder that forms the target metal oxide particles is introduced into the chemical flame so that a dust cloud is formed, In this method, metal oxide particles are obtained by deflagration. The VMC method uses the principle of dust explosion. According to the VMC method, a large amount of metal oxide particles can be obtained instantaneously. The obtained particles have a substantially spherical shape. For example, when obtaining silica particles, silicon powder may be charged, and when obtaining alumina particles, aluminum powder may be charged. It is possible to adjust the particle diameter of the metal oxide particles obtained by adjusting the particle diameter of the powder to be input, the input amount, the flame temperature, and the like. Moreover, you may manufacture by crushing the crushed metal oxide or crushing the metal oxide. Thus, one or more kinds selected from combustion metal oxide particles obtained by burning metal, molten metal oxide particles obtained by melting crushed metal oxide, and crushed metal oxide particles obtained by crushing metal oxide May be metal oxide particles.

  As the silane coupling agent, various known silane coupling agents may be used. For example, the silane coupling agent shown in the following Table 1 is mentioned. In Table 1, “reaction insolubilized layer formation amount” will be described later. Among these, it is desirable to use epoxy silane, methacryl silane, or amino silane. By blending the metal oxide surface-treated particles thus treated with the resin, a resin composition having better physical properties after curing can be obtained.

The metal oxide surface-treated particles of the present invention are produced by treating the surface of metal oxide particles with a silane coupling agent. The surface treatment with the silane coupling agent is performed by contacting the vaporized silane coupling agent. For example, a powder to be treated made of metal oxide particles may be accommodated in a treatment container and reacted with a silane coupling agent vaporized while stirring the powder to be treated. By this reaction, a surface treatment layer is formed on the surface of the metal oxide particles. The surface treatment layer includes an aspect in which only the reaction insolubilized layer is formed and an aspect in which both the reaction insolubilized layer and the solubilized layer are formed depending on the surface treatment conditions. From the viewpoint of reducing the amount of the silane coupling agent to be used, it is desirable that the surface treatment layer has only a reaction insolubilized layer.

Hereinafter, the identification method of the metal oxide surface treatment particle | grains of this invention is demonstrated. For example, after the sample to be specified is washed with an organic solvent, the presence or absence of OH groups on the surface of the metal oxide particles may be confirmed by infrared spectroscopic analysis. For example, when the sample is a silica powder composed of silica particles surface-treated with a silane coupling agent, if no silanol absorption near 3740 cm ⁻¹ is detected in the infrared absorption spectrum, silanol is not present on the silica particle surface. It can be judged that there is no, that is, at least a reaction insolubilized layer is formed. On the other hand, when silanol absorption is detected, unreacted silanol remains on the surface of the silica particles. Therefore, in this case, it is determined that the sample is not composed of the metal oxide surface-treated particles of the present invention.

In the case where silanol absorption is not detected in the infrared absorption spectrum, only the reaction insolubilized layer is formed, and further the solubilized layer is formed (for example, a polymer layer is formed by condensation of an excess silane coupling agent). A mode ) . Therefore, the sample after washing with an organic solvent is heated at a temperature of 800 ° C., and the weight loss before and after heating is measured. When heated at 800 ° C., the silane coupling agent volatilizes. Therefore, the amount of silane coupling agent adhering to the surface of the silica particles can be known by measuring the amount of weight loss before and after heating. The heating time is, and for 1 hour.

The amount of the silane coupling agent that reacts with all the OH groups present on the surface of the silica particles, in other words, the amount of the silane coupling agent that forms the reaction insolubilized layer can be determined by calculation. Table 1 shows the amount of reaction insolubilized layer formed per 1 m ^{2 of} silica particle surface area calculated for various silane coupling agents. When the solubilized layer is formed, the solubilized layer is removed by washing the sample with an organic solvent in advance. On the other hand, the polymer layer is not removed by washing with an organic solvent. From this, the amount of weight reduction before and after heating at 800 ° C. is measured and compared with the amount of reaction insolubilized layer formed in Table 1 to determine whether or not a polymer layer is formed on the surface of the silica particles. That is, when the amount of weight reduction per 1 m ² of silica particle surface area before and after heating is within the range of the reaction insolubilized layer formation amount of the corresponding silane coupling agent in Table 1, the sample is subjected to the metal oxidation of the present invention. It is determined to consist of object surface-treated particles. On the other hand, when the same weight reduction amount is outside the range of the reaction insolubilized layer formation amount of the corresponding silane coupling agent, the silica particles have a polymer layer, and the sample is subjected to the metal oxide surface treatment of the present invention. It is determined that it does not consist of particles. When the surface treatment is performed with a plurality of silane coupling agents, the reaction insolubilized layer formation amount of the silane coupling agent shown in Table 1 is multiplied by the weight fraction of the used silane coupling agent, The sum may be determined as the reaction insolubilized layer formation amount.

< Metal oxide surface treatment particles >
The metal oxide surface-treated particles of the present embodiment are metal oxide surface-treated particles in which the surface of the metal oxide particles is treated with a silane coupling agent. A surface treatment layer is formed on the surface of the metal oxide particles. The surface treatment layer is formed by the reaction of all OH groups present on the surface of the metal oxide particles before the treatment and the silane coupling agent, and is formed on the surface of the reaction insolubilization layer insoluble in the organic solvent and the surface of the reaction insolubilization layer. And a solubilized layer soluble in an organic solvent. Since the reaction insolubilized layer and the solubilized layer are as described above, further explanation is omitted.
< Method for producing resin composition, etc.>
By blending the metal oxide surface-treated particles produced by the production method of the present invention, it is possible to constitute a resin composition having high fluidity and good adhesion and durability after curing. Metal oxide particles not subjected to surface treatment may be mixed as necessary (hereinafter, the metal oxide surface-treated particles and other metal oxide particles are collectively referred to as “metal oxide powder”). ).

(1) The manufacturing method of the resin composition of this invention mix | blends the metal oxide surface treatment particle | grains manufactured with the manufacturing method of the said invention to the thermoplastic or thermosetting resin. Here, the kind of resin is not particularly limited, and examples of the thermosetting resin include an epoxy resin, a silicon resin, a phenol resin, a melamine resin, a urea resin, and an unsaturated polyester resin. Examples of the thermoplastic resin include fluorine resin, polyimide, polyamide resin (polyamideimide, polyetherimide, etc.), polyester (polybutylene terephthalate, polyethylene terephthalate, wholly aromatic polyester, etc.), polysulfone resin, polycarbonate, and the like.

For example, when using the resin composition manufactured by the manufacturing method of this invention as sealing materials, such as a semiconductor device, it is good to employ | adopt an epoxy resin. As the epoxy resin, monomers, oligomers and polymers having two or more epoxy groups in one molecule are suitable. For example, biphenyl type epoxy resin, stilbene type epoxy resin, bisphenol type epoxy resin, triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, naphthol type epoxy resin, triazine core containing An epoxy resin etc. are mentioned. One of these may be used alone, or a plurality may be used in combination.

  The blending ratio of the metal oxide powder is not particularly limited. For example, from the viewpoint of reducing the thermal expansion coefficient and the water absorption rate, the blending ratio of the metal oxide powder is preferably 70% by weight or more when the entire resin composition is 100% by weight. More preferably, it is 85% by weight or more. Further, the metal oxide powder may be composed of one kind of the metal oxide surface-treated particles of the present invention, or may be composed of a mixture of two or more kinds of the metal oxide surface-treated particles of the present invention. . Moreover, you may comprise the metal oxide surface treatment particle | grains of this invention, and particles, such as another metal oxide, mixing.

  The particle diameter of the metal oxide surface-treated particles of the present invention constituting the metal oxide powder is not particularly limited. For example, when considering using the resin composition of the present invention as a sealing material for a semiconductor device or the like, it is desirable that the average particle diameter of the metal oxide powder be 0.05 μm or more and 20 μm or less. Further, when used as a sealing material or a substrate, it is desirable that the number of coarse particles having a large particle diameter is small. In this case, coarse particles of 45 μm, 20 μm, 5 μm, 3 μm or more may be removed depending on each application. By doing so, even when a very small gap such as a semiconductor circuit is filled, it is difficult to cause a problem. Thus, when considering reducing coarse particles, a metal oxide powder having an average particle diameter of 2 μm or less may be used. Further, by blending coarse particles and particles having a small particle diameter and performing close packing, a larger amount of particles can be blended in the resin.

Moreover, in the manufacturing method of the resin composition of this invention, the aspect containing a hardening | curing agent and a curing catalyst in addition to the said resin and metal oxide powder is desirable. As the curing agent, a known curing agent may be used. For example, amine curing agents such as aliphatic polyamine, polyamide polyamine, alicyclic polyamine, aromatic polyamine, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl Examples thereof include anhydride-based curing agents such as hexahydrophthalic anhydride, and phenol-based curing agents such as o-cresol, p-cresol, t-butylphenol, and cumylphenol. As the curing catalyst, a known curing catalyst may be used, and examples thereof include tertiary amines, quaternary ammonium salts, imizodal compounds, boron compounds, and organometallic complex salts. Furthermore, as necessary, various additives such as colorants such as carbon black and bengara, mold release agents such as natural wax and synthetic wax, low stress additives such as silicone oil, ion supplement, flame retardant and rubber. May be blended.

As a method for producing the resin composition of the present invention, a metal oxide powder, a curing agent, and the like are blended into a resin, mixed at room temperature with a mixer, etc., then melt-kneaded with a hot roll, a kneader, etc., and crushed after cooling. As a specific example, the manufacturing method can be given. By this resin composition, when sealing the electronic components such as semiconductor devices, transfer molding, compression molding may be molded cured by a method such as injection molding.

(2) The manufacturing method of the varnish composition of this invention mix | blends the metal oxide powder of the said this invention with the varnish for textile cloth impregnation or the varnish for film formation.

  Resins such as epoxy resins, BT (bismaleimide / triazine) resins, and polyamideimides are usually used for woven cloth impregnating varnishes and film forming varnishes. As the solvent, ketone, aromatic hydrogen sulfide, DGMM (diethylene glycol monomethyl ether) or the like is used. In both varnishes, the mixing ratio of the metal oxide powder, the particle diameter of the metal oxide surface-treated particles, the curing agent, the curing catalyst, and various additives may be in accordance with the above resin composition.

It has been described an embodiment method for producing such metal oxide surface treated particles and a method for producing the same, and the resin composition of the present invention. However, the onset Ming is not intended to be limited to the disclosed embodiments without departing from the scope and spirit of the present invention, modifications that those skilled in the art can perform, can be carried out in various forms subjected to improvements etc. .

  Based on the said embodiment, the metal oxide powder which consists of the metal oxide surface treatment particle | grains of this invention was manufactured. About the manufactured metal oxide powder, the weight loss amount before and behind 800 degreeC heating was measured, and the infrared absorption spectrum was measured by FT-IR (Fourier transform infrared spectroscopy analyzer). Moreover, the manufactured metal oxide powder was mix | blended with resin, the resin composition was manufactured, the viscosity measurement and the evaluation of the aggregation state were performed. Further, the produced resin composition was cured, and the fracture surface was observed with a scanning electron microscope (SEM). Hereinafter, it demonstrates in order.

<Manufacture of metal oxide powder>
(1) Example 1
The surface treatment of the metal oxide particles was performed using the surface treatment apparatus shown in FIG. As shown in FIG. 2, the surface treatment apparatus 6 includes a treatment container 7, a ribbon stirring blade 8, and a treatment agent evaporator 9. The processing container 7 contains a powder 10 to be processed made of metal oxide particles. The ribbon stirring blade 8 is disposed at the center of the processing container 7. The processing agent evaporator 9 is installed at one end on the inner upper side of the processing container 7. In FIG. 2, the processing agent evaporator 9 includes a cylindrical metal container 90, a heater 91, and glass wool 92 as shown by enlarging a circle A. The heater 91 is wound around the outer periphery of the metal container 90. Glass wool 92 is filled into a metal container 90.

First, a silica powder (manufactured by Admatechs Co., Ltd .: Admafine SE2200-) having an average particle diameter of 0.5 μm and a specific surface area of 4.5 m ² / g produced by the VMC method as the powder to be treated 10 is placed in the treatment container 7. 20 kg of SQ) was stored. Further, 200 g of epoxy silane (“γ-glycidoxypropyltrimethoxysilane” in Table 1 above, manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403) as a silane coupling agent was impregnated into glass wool 92. . Next, the processing vessel 7 was sealed, and the metal vessel 90 was heated by the heater 91 while rotating the ribbon stirring blade 8 at a rotation speed of 80 rpm, and the temperature of the metal vessel 90 was set to 150 to 200 ° C. By maintaining this state for 48 hours, the surface treatment of the silica powder was performed. The obtained powder was used as the powder of Example 1.

(2) Example 2
In the surface treatment of Example 1 above, the powder to be treated was silica powder having an average particle size of 0.2 μm and a specific surface area of 17 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SC1500-SQ), and a silane coupling agent. The surface treatment of the silica powder was carried out in the same manner as in Example 1 except that the amount of was 400 g and the treatment time was 72 hours. The obtained powder was used as the powder of Example 2.

(3) Example 3
In the surface treatment of Example 1, the powder to be treated was a silica powder having an average particle size of 1.0 μm and a specific surface area of 4.5 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SC4500-SQ). In the same manner as in Example 1, the surface treatment of the silica powder was performed. The obtained powder was used as the powder of Example 3.

(4) Example 4
In the surface treatment of Example 1 described above, the powder to be treated was a silica powder having an average particle size of 1.5 μm and a specific surface area of 4.5 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SC5500-SQ). In the same manner as in Example 1, the surface treatment of the silica powder was performed. The obtained powder was used as the powder of Example 4.

(5) Example 5
In the surface treatment of Example 1, the powder to be treated was silica powder having an average particle size of 2.0 μm and a specific surface area of 2.0 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SC6500-SQ), and a silane cup The silica powder was surface treated in the same manner as in Example 1 except that the amount of the ring agent was 100 g. The obtained powder was used as the powder of Example 5.

(6) Example 6
In the surface treatment of Example 1 above, the powder to be treated was silica powder having an average particle size of 0.5 μm and a specific surface area of 5.5 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SC2500-SQ). The silica powder was subjected to a surface treatment in the same manner as in Example 1 except that the amount of the ring agent was changed to 104 g. The obtained powder was used as the powder of Example 6.

(7) Example 7
In the surface treatment of Example 1 above, the powder to be treated was silica powder having an average particle size of 0.5 μm and a specific surface area of 5.5 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SC2500-SQ). As a ring agent, 100 g of epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403) and 100 g of phenyl silane (“Phenyltrimethoxysilane” in Table 1 above, Shin-Etsu Chemical Co., Ltd .: KBM-103) The silica powder was subjected to a surface treatment in the same manner as in Example 1 except that and were used. The obtained powder was used as the powder of Example 7.

(8) Example 8
In the surface treatment of Example 1 above, the powder to be treated was silica powder having an average particle size of 0.5 μm and a specific surface area of 5.5 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SC2500-SQ). Except for using 200 g of acrylic silane (“γ-acryloxypropyltrimethoxysilane” in Table 1 above, manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103) as the ring agent, the same as in Example 1, The surface treatment of the silica powder was performed. The obtained powder was used as the powder of Example 8.

(9) Example 9
In the surface treatment of Example 1 above, the powder to be treated was silica powder having an average particle size of 0.5 μm and a specific surface area of 5.5 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SC2500-SQ). The surface of the silica powder in the same manner as in Example 1 except that 100 g of vinylsilane (“vinyltrimethoxysilane” in Table 1 above, manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-1003) was used as the ring agent. Processed. The obtained powder was used as the powder of Example 9.

(10) Comparative Example 1
The surface treatment of the metal oxide particles was performed using a mixer. First, an average particle diameter of 0.5 μm and a specific surface area of 5.5 m ² / manufactured by a VMC method as a powder to be processed in a mixer (manufactured by Taiheiyo Kiko Co., Ltd .: Proshear mixer WB-75 type, the same shall apply hereinafter). 20 kg of silica powder (manufactured by Admatechs Co., Ltd .: Admafine SO-C2) was accommodated. Next, the mixture was stirred for 15 minutes at a rotation speed of 30 rpm while spraying 200 g of epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403) as a silane coupling agent. The obtained powder was used as the powder of Comparative Example 1.

(11) Comparative Example 2
In the surface treatment of Comparative Example 1 above, except that the powder to be treated was silica powder having an average particle diameter of 0.2 μm and a specific surface area of 17 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SO-C1). In the same manner as in Example 1, the surface treatment of the silica powder was performed. The obtained powder was used as the powder of Comparative Example 2.

(12) Comparative Example 3
In the surface treatment of Comparative Example 1, except that the powder to be treated was silica powder having an average particle size of 1.0 μm and a specific surface area of 4.5 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SO-C3). In the same manner as in Comparative Example 1, the surface treatment of the silica powder was performed. The obtained powder was used as the powder of Comparative Example 3.

(13) Comparative Example 4
In the surface treatment of Comparative Example 1, the powder to be treated was a silica powder having an average particle diameter of 1.5 μm and a specific surface area of 4.5 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SO-C5). In the same manner as in Comparative Example 1, the surface treatment of the silica powder was performed. The obtained powder was used as the powder of Comparative Example 4.

(14) Comparative Example 5
In the surface treatment of Comparative Example 1, the powder to be treated was silica powder having an average particle size of 2.0 μm and a specific surface area of 2.0 m ² / g (manufactured by Admatechs Co., Ltd .: Admafine SO-C6). The silica powder was surface-treated in the same manner as in Comparative Example 1 except that the amount of the ring agent was 100 g. The obtained powder was used as the powder of Comparative Example 5.

(15) Comparative Example 6
In the surface treatment of Comparative Example 1, silica powder was surface treated in the same manner as Comparative Example 1 except that the amount of the silane coupling agent was changed to 104 g. The obtained powder was used as the powder of Comparative Example 6.

(16) Comparative Example 7
In the surface treatment of Comparative Example 1, 100 g of epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403) and 100 g of phenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-103) are used as silane coupling agents. The silica powder was surface treated in the same manner as in Comparative Example 1 except that the mixed solution was used. The obtained powder was used as the powder of Comparative Example 7.

(17) Comparative Example 8
In the surface treatment of Comparative Example 1, silica powder surface treatment was performed in the same manner as in Comparative Example 1, except that 200 g of acrylic silane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103) was used as the silane coupling agent. Went. The obtained powder was used as the powder of Comparative Example 8.

(18) Comparative Example 9
In the surface treatment of Comparative Example 1, the silica powder was surface treated in the same manner as in Comparative Example 1, except that 100 g of vinylsilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-1003) was used as the silane coupling agent. went. The obtained powder was used as the powder of Comparative Example 9.

<Evaluation of metal oxide powder>
(1) Evaluation method (a) Infrared absorption spectrum measured by FT-IR Each of the produced powders was washed with isopropyl alcohol (IPA) and dried. Then, the infrared absorption spectrum of 4000～2500Cm ^-1 undiluted measured by diffuse reflection method was examined for silanol absorption around 3740cm ^-1.

(B) Measurement of weight loss before and after heating at 800 ° C. 6 g of the produced powder was used as a sample. Each sample and 24 g of IPA were placed in a centrifuge tube and irradiated with 500 W ultrasonic waves for 1 minute. Thereafter, solid-liquid separation was performed by centrifugation, and the supernatant was removed. Further, 24 g of IPA was added, and the solid content was suspended by stirring and irradiated with 500 W ultrasonic waves for 1 minute. Thereafter, solid-liquid separation was performed by centrifugation, and the supernatant was removed. Further, 24 g of IPA was added, and the solid content was suspended by stirring and irradiated with 500 W ultrasonic waves for 1 minute. Thereafter, solid-liquid separation was performed by centrifugation, and the supernatant was removed. The solid content was dried at 120 ° C. for 3 hours, and then the weight was measured. The weight at this time was defined as the weight before heating. And the dried solid content was heated at 800 degreeC for 1 hour, and measured the weight again after that. The weight at this time was defined as the weight after heating. The difference between the weight before heating and the weight after heating was defined as the weight reduction amount, and the ratio of the heat reduction amount to the weight before heating was determined.

(C) Aggregation evaluation 18 g of each powder produced, 13.33 g of a liquid epoxy resin (manufactured by Tohto Kasei Co., Ltd .: ZX-1059, the same shall apply hereinafter), and 2PHZ (2-phenyl-4, 0.67 g of 5-dihydroxymethylimidazole) was mixed for 1 minute with a planetary mixer (revolution speed: 2000 rpm, rotation speed: 800 rpm) to obtain a mixture. Each mixture was diluted with 500 ml of MEK (methyl ethyl ketone) and passed through a 20 μm sieve. The sieve residue was collected and dried at 110 ° C. for 2 hours. The sieve residue after drying was weighed to obtain the amount of aggregation.

(D) Viscosity measurement 36 g of each produced powder, 26.67 g of liquid epoxy resin, and 2PHZ1.33 g of a latent curing catalyst were mixed for 4.5 minutes with a planetary mixer (same as above), and the mixture was mixed. Obtained. Each mixture was dispersed with three rolls and aged at 80 ° C. for 1 hour to obtain a varnish for viscosity measurement. The viscosity at 25 ° C. of this varnish for measuring viscosity was measured with an E-type viscometer.

(E) SEM observation The varnish for viscosity measurement produced in the above (d) was put into a varnish mold and cured by heating at 120 ° C. for 4 hours and 150 ° C. for 1 hour to obtain a cured product. The cured product was broken and the fractured surface was observed with an SEM.

(2) Results Table 2 shows the ratio of the amount of heat reduction with respect to the weight before heating (weight reduction rate), the amount of weight reduction per 1 m ^{2 of} silica particle surface area, the presence or absence of silanol absorption, and the amount of aggregation. As an example of the infrared absorption spectrum, the infrared absorption spectra of the powder of Example 6 and the powder of Comparative Example 6 are shown in FIG.

As shown in Table 2, in the powders of Examples 1 to 9, the weight reduction amount per 1 m ^{2 of} the silica particle surface area was within the range of the reaction insolubilized layer formation amount shown in Table 1 above. Moreover, silanol absorption was not detected in the measured infrared absorption spectrum. That is, as shown in FIG. 3A, in the powder of Example 6, silanol absorption around 3740 cm ⁻¹ is not detected. On the other hand, as shown in FIG. 3B, in the powder of Comparative Example 6, silanol absorption was detected in the vicinity of 3740 cm ⁻¹ . From these results, it can be said that the powders of Examples 1 to 9 consist of the metal oxide surface-treated particles of the present invention.

  In addition, in the powders of Comparative Examples 1 to 9, the amount of aggregation was 0.80 g or more, whereas in the powders of Examples 1 to 9, the amount of aggregation was 0.08 to 0.21 g, which was very small. . From this, it can be seen that the metal oxide powder comprising the metal oxide surface-treated particles of the present invention hardly aggregates in the resin.

  Furthermore, as an example of the viscosity measurement result using each varnish for viscosity measurement, the varnish containing the powder of Example 1 (varnish of Example 1) and the varnish containing the powder of Comparative Example 1 (varnish of Comparative Example 1) The viscosity measurement results of) are shown in FIG. As shown in FIG. 4, the viscosity of the varnish of Example 1 was lower than that of the varnish of Comparative Example 1. Thus, in the varnish of Example 1, since the metal oxide powder hardly aggregates, an increase in viscosity is suppressed.

  FIG. 5A shows an SEM photograph of the cured varnish of Example 1, and FIG. 5B shows an SEM photograph of the cured varnish of Comparative Example 1. As shown to Fig.5 (a), the torn surface of the varnish hardened | cured material of Example 1 is smooth. From this, it can be seen that the adhesion between the contained particles and the resin is high, and the particles are difficult to drop off from the resin. On the other hand, as shown in FIG.5 (b), both a particle | grain and the crater-like hole from which particle | grains fell are observed in the fracture surface of the varnish hardened | cured material of the comparative example 1. FIG. In other words, the cured varnish of Comparative Example 1 is broken at the interface between the particles and the resin because the adhesion between the contained particles and the resin is poor.

Thus, the metal oxide surface-treated particles of the present invention and the metal oxide surface-treated particles produced by the method of the present invention are unlikely to aggregate in the resin. Therefore, an increase in the viscosity of the resin composition is suppressed. Moreover, since it is excellent in adhesiveness with resin, it is hard to fall off from resin after hardening.

It is a cross-sectional model figure of the metal oxide surface treatment particle | grains of this invention, (a) shows the aspect which a surface treatment layer consists only of a reaction insolubilization layer, (b) is a surface treatment layer solubilized with a reaction insolubilization layer. The aspect which consists of a layer is shown. It is the schematic of the surface treatment apparatus which performs the surface treatment of a metal oxide particle. (A) is the infrared absorption spectrum of the powder of Example 6, and (b) is the infrared absorption spectrum of the powder of Comparative Example 6. The viscosity measurement result of the varnish of Example 1 and the varnish of the comparative example 1 is shown. (A) is a SEM photograph of the cured varnish of Example 1, and (b) is a SEM photograph of the cured varnish of Comparative Example 1.

Explanation of symbols

1: Metal oxide surface treatment particles 2: Metal oxide particles 3: Surface treatment layer 4: Reaction insolubilization layer 5: Solubilization layer 6: Surface treatment device 7: Treatment vessel 8: Ribbon stirring blade 9: Treatment agent evaporator 90 : Metal container 91: Heater 92: Glass wool 10: Powder to be treated

Claims (12)

Metal oxide surface-treated particles in which the surface of the metal oxide particles is treated with a silane coupling agent,
The surface treatment layer formed on the surface of the metal oxide particles is
A reaction insolubilized layer formed by a reaction between substantially all OH groups present on the surface of the metal oxide particles before the treatment and the silane coupling agent, and insoluble in an organic solvent;
A solubilized layer formed on the surface of the reaction insolubilized layer and soluble in an organic solvent;
Metal oxide surface treated particles, which comprises a.   A method for producing metal oxide surface-treated particles, wherein the surface of the metal oxide particles is surface-treated with a silane coupling agent,
  The vaporized silane coupling agent is brought into contact with the surface of the metal oxide particles, and the silane coupling agent is reacted with the OH groups present on the surface of the metal oxide particles, so that the reaction insolubilized layer is insoluble in an organic solvent. A process for producing metal oxide surface-treated particles, comprising the step of forming a metal oxide.   The production of the metal oxide surface-treated particles according to claim 2, wherein the surface of the metal oxide surface-treated particles to be produced does not have a solubilized layer made of the silane coupling agent and not reacting with the OH group. Method.   The method for producing metal oxide surface-treated particles according to claim 2, wherein the surface of the metal oxide surface-treated particles to be produced has a solubilized layer made of the silane coupling agent and not reacting with the OH group. .   The method for producing metal oxide surface-treated particles according to any one of claims 2 to 4, wherein the metal oxide particles have silica as a main component.   The silane coupling agent is any one of those shown in Table 1 below,
  The manufactured metal oxide surface-treated particles were washed with an organic solvent, and then analyzed by infrared spectroscopic analysis at 3740 cm. ^-1 In Table 1, the amount of reaction insolubilized layer formed determined as the amount of weight loss before and after heating when no nearby silanol absorption is detected and heating at a temperature of 800 ° C. for 1 hour is defined for the silane coupling agent in Table 1. The method for producing metal oxide surface-treated particles according to claim 5, which falls within the specified range.

  The silane coupling agent is two or more selected from those shown in Table 2 below,
  The manufactured metal oxide surface-treated particles were washed with an organic solvent, and then analyzed by infrared spectroscopic analysis at 3740 cm. ^-1 Absorption of nearby silanol is not detected, and the amount of reaction insolubilized layer formed as the weight loss before and after heating when heated at 800 ° C. for 1 hour is the weight of the two or more silane coupling agents. The manufacturing method of the metal oxide surface treatment particle | grains of Claim 5 which becomes in the range calculated from the said Table 2 according to the rate.

  A step of producing metal oxide surface-treated particles by the production method according to any one of claims 2 to 7,
  And a step of dispersing the metal oxide surface-treated particles in a thermoplastic or thermosetting resin.   The method for producing a resin composition according to claim 8, wherein the resin includes an epoxy resin.   Furthermore, the manufacturing method of the resin composition of Claim 8 or 9 containing a hardening | curing agent and a hardening catalyst.   The method for producing a resin composition according to any one of claims 8 to 10, wherein the metal oxide surface-treated particles are blended in an amount of 70% by weight or more based on 100% by weight of the entire resin composition.   A step of producing metal oxide surface-treated particles by the production method according to any one of claims 2 to 7,
  And a step of dispersing the metal oxide surface-treated particles in a woven cloth impregnating varnish or a film forming varnish.

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