JP2721106B2 - Surface modifier for inorganic material and its use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to surface modification of inorganic materials.
It relates to agents and their uses . For details, the present invention is a rubber molding material, the inorganic filler used in the plastic molding material and paints; parent surface of an inorganic material such as, paints, adhesives, pressure-sensitive adhesives, inorganic substrate for applying a sealing agent Oiling to improve the wetting and dispersibility of the inorganic material with respect to the organic medium constituting the rubber molding material, plastic molding material, paint, adhesive, sealing agent, etc., or at the interface between the organic medium and the inorganic material The present invention relates to a surface modifier for an inorganic material composed of a specific silicon-containing polymer in order to enhance the adhesiveness of the polymer and maintain its effect for a long period of time .

[0002] The present invention also relates to an inorganic element,
The present invention relates to a method for modifying the surface of an inorganic material, which is brought into contact with a material. This invention also molding the resin composition for other
It is related to the use of. About resin compositions for molding materials
More specifically, the resin composition for molding materials
Is electrical characteristics, heat resistance and flame retardancy is excellent, in particular, moldability, workability, Ri mechanical strength and excellent molding resin composition der its durability of the resulting molded product , electricity useful insulating material such equipment and electronic communication components, as the sealing material and / or flame retardant materials, in particular suitable as an IC encapsulation material.

[0003]

2. Description of the Related Art Conventionally, in rubber molding materials, plastic molding materials, paints, etc., weight increase, lightening, reinforcement, coloring, or sliding properties (slip properties), conductivity, piezoelectricity, magnetism, flame retardancy, concealment. Many fillers made of inorganic materials are used for the purpose of imparting properties such as resistance and rust prevention. Further, a paint or the like is applied to the surface of a substrate made of an inorganic material, and is used for various purposes.

[0004] For example, in the field of rubber molding materials and plastic molding materials, an IC encapsulant in which a large amount of fused silica or crystalline silica is blended to impart moisture resistance reliability and a low coefficient of linear expansion to an epoxy resin; Flame retardant materials containing a large amount of magnesium hydroxide, aluminum hydroxide, antimony trioxide, etc. to impart flame retardancy to ethylene-ethyl acrylate copolymer, polyvinyl chloride, epoxy resin, etc .; 2. Description of the Related Art There is known an electric insulating material or the like in which a large amount of fused silica, calcium carbonate, glass fiber, or the like is blended to impart electric insulating properties or moisture resistance to a phenol resin or the like.

[0005] In the field of paints, for example, aluminum, stainless steel,
(Meth) acrylic-urethane resin, (meth) acrylic-melamine resin, (meth) acrylic-silicone resin, (meth) acrylic-epoxy on inorganic substrates such as tin, tin, steel plate, concrete, mortar, slate, and glass Vehicles obtained by dissolving and dispersing resins such as resins, polyester-melamine resins, and alkyd resins in an organic solvent, as they are, or inorganic pigments such as titanium oxide, iron oxide, and carbon black, lead chromate, and zinc chromate And an inorganic filler such as a flame-retardant filler such as aluminum hydroxide and magnesium hydroxide.

[0006] These inorganic materials are poor in lipophilicity because their surfaces are covered with hydroxyl groups or adsorbed water. There is a problem that adhesion to a medium is poor. Therefore, a filler or substrate made of an inorganic material is subjected to surface treatment with a surface modifier such as a higher fatty acid; a surfactant; a silane-based, titanium-based or aluminum-based coupling agent; Attempts have been made to improve the properties and to add the above-mentioned surface modifier at the time of kneading when preparing a molding material or at the time of preparing a paint, and these have been put to practical use.

[0007]

However, the surface modifiers such as higher fatty acids, surfactants and various coupling agents have a surface modification effect of the inorganic material, that is, an affinity of the interface between the organic medium and the inorganic material. Insufficient. For example, a large amount of an inorganic filler needs to be added to the above-described electric insulating material, flame-retardant material, IC sealing material, and the like. Even when the above-described surface modifier is used, the viscosity at the time of kneading is high and the fluidity is high. There is a problem that the moldability and workability are deteriorated due to the badness, and that the defoaming at the time of molding becomes insufficient, so that pinholes and voids are generated in the molded body, and the mechanical strength is reduced. In particular, in the case of an IC encapsulant, if the fluidity of fused silica, crystalline silica, or the like deteriorates, there is a problem that a gold wire is deformed or cut during molding. In addition, in the paint, the dispersibility and sedimentation stability of the inorganic filler are poor, and the resulting coating film has roughness and color separation, and further, the adhesion between the coating film and the substrate and a decrease in the coating film strength are seen. There was a problem.

Therefore, the inventors have conducted various studies in order to solve the above problem. As a result, recently, the above-mentioned problems can be solved by using a specific silicon-containing polymer in a method for modifying the surface of an inorganic material, and a resin composition suitable for a plastic or rubber molding material. The inventors have already applied for a patent for a method for modifying the surface of an inorganic material and a resin composition using the silicon-containing polymer (see Japanese Patent Application No. 4-101470 for a method for modifying the surface of an inorganic material, For the resin composition, see Japanese Patent Application No. 4-333180.).

The above-mentioned specific silicon-containing polymer is mainly composed of a polymer having a hydrolyzable group, which is a bonding point with an inorganic material, bonded to a silicon atom, and the silicon atom has a role of improving affinity with an organic medium. It has a structure directly or indirectly bonded to a chain by a Si—O—C bond. However, according to subsequent studies by the inventors, molding materials, coating films, and the like manufactured using the silicon-containing polymer have fluidity during kneading, moldability, workability, mechanical strength, and coating films with substrates. Adhesion, roughness and color separation of the coating film are sufficiently improved, but when placed in a heated and humid atmosphere or in hot or cold water for a long time, the mechanical strength of the molded body decreases or In some cases, the adhesion between the organic medium and the inorganic material such as the adhesion of the coating film was reduced, and it was found that there was a problem in durability.

[0010] Therefore, since the present invention is to improve wetting of the inorganic material to the organic medium, the dispersion or adhesive or the like
To, strive sufficient modification of inorganic materials, a specific structure that can Rukoto to maintain this modification effect <br/> result long term silicon-Motopo
Table of inorganic material surface modifier
And Men'aratameshitsu method, molding material for resin composition using the surface modifying agent, dispersion, and it is an object to provide a composite material.

[0011]

In order to solve the above-mentioned problems of the prior art, the present inventors have proposed a method for further improving the wetting, dispersibility, adhesion, and durability of an inorganic material with respect to an organic medium, and a method for improving the electric conductivity. Investigation into resin compositions for molding materials that excel in moldability, workability, mechanical strength of the obtained molded body, and its durability without deteriorating basic properties such as mechanical properties, heat resistance, flame retardancy, etc. As a result, it has been found that the above problems can be solved by bringing a specific silicon-containing polymer (P) into contact with an inorganic material or using a resin composition containing the silicon-containing polymer (P). I it has led to the completion of this invention.

Therefore, the surface modifier of the inorganic material according to the present invention includes (meth) acrylic resin, polystyrene,
Polyvinyl acetate, polyolefin, polyvinyl chloride,
Vinylidene chloride, polyester resin, copolymerization of these
In the body and in resins that have been modified from some of these resins
The backbone of the al chosen polymer, directly or indirectly by Si-C bonds, at least one polysiloxane group
And have a number average molecular weight of 1,000 to 1,000.
In the range of 0,000, all a silicon-containing polymer is soluble in an organic solvent, except that all of the Si atoms of the previous SL in the polysiloxane group is whether polysiloxane bond binds to a main chain, R ¹ O group [R ¹ is an alkyl group which may be substituted hydrogen atom or a C number 1 to 5, R ¹
Are present in one molecule, a plurality of R ¹ may be the same or different from each other. And a silicon-containing polymer bonded only to

[0013] The surface modifier according to the present invention,
Silicon-containing polymers, or reactive silane-compound (A) below
At least one selected from the following and the following silane compound (B)
A solid catalyst insoluble in the system with at least one selected from the group consisting of:
Polymerizable polymer obtained by co-hydrolytic condensation in the presence of (C)
0.1% to 50% by weight of polysiloxane (D) and one unsaturated group
And copolymerizable with the polymerizable polysiloxane (D)
Monofunctional monomer (E) with 99.9-50 wt%
(However, the total amount of (D) and (E) is 100 wt%
). (A) a reactive silane compound represented by the following general formula
Stuff.

[0014] [Wherein R ¹ is a hydrogen atom or a C 1-5
An alkyl group which may be substituted; R ² is a hydrogen atom or
Is a methyl group; R ³ is a divalent organic group;
The numbers R ¹ may be the same or different. ] (B) a silane compound represented by the following general formula.

Si (OR ¹ ) ₄ ... [In the general formula, R ¹ is the same as described above. Multiple in one molecule
The numbers R ¹ may be the same or different. ] This
The method for modifying the surface of an inorganic material according to
The modifier is brought into contact with the inorganic material. in this case,
The inorganic material can be inorganic particles, and furthermore,
If the inorganic material is an inorganic filler,
From 0.1 to 30% by weight of the silicon-containing polymer
It is preferred to contact the filler.

The molding resin composition according to the present invention, the above-described surface modifying agent and at least one tree fat and low without <br/> least one inorganic filler as essential components, wherein the inorganic filling
In the range of 20～90Wt% of the total amount of blending ratio between the resin and the surface modifier agent, and said surface modifier
Of 0.1 to 30% by weight of the inorganic filler
Range der of Ru. (In this specification, wt% represents weight%). In this case, the resin must be epoxy resin
And the inorganic filler is fused silica and / or crystalline
Preferably, silica is essential.

The inorganic filler dispersion according to the present invention
The inorganic filler with the surface modifier attached to the surface is an organic medium
It is dispersed inside. The inorganic filler according to the present invention
Filler dispersions also include the above surface modifiers, inorganic fillers, and organic fillers.
It is obtained by mixing with a medium. According to the present invention,
In the composite material, the surface modifier is attached to the inorganic particles.
It is.

In the above description, a polysiloxane group means that two or more Si atoms have a polysiloxane bond (Si—O—Si
A group linked by a bond) in a linear or branched manner. The number of Si atoms in the polysiloxane group is
Although not particularly limited, the effect of modifying the surface of the inorganic material is further improved, whereby the viscosity, fluidity, moldability, workability, and the obtained molded body of the resin composition or paint for a molding material described below are obtained. In order to further improve the mechanical strength and the coating strength of the polysiloxane group, the average is preferably 4 or more, more preferably 11 or more per polysiloxane group. In the case of a group having only one Si atom, the ionicity of the Si atom is weakened by the Si—C bond with the main chain, so that the R ¹ O group bonded to the Si atom is hydrolyzable and reacts with the inorganic material. Is reduced. The polysiloxane group is a silicon-containing polymer (P)
It is at least one per molecule, particularly preferably 1 to
There are three ranges. If more than three, when the inorganic material is an inorganic filler (T), the silicon-containing polymer (P) acts as a coagulant and the dispersibility may be reduced. When a plurality of polysiloxane groups are present in one molecule of the silicon-containing polymer (P), the plurality of polysiloxane groups may be the same or different.

As described above, the silicon-containing polymer (P) has a structure in which a polysiloxane group is directly or indirectly bonded to a main chain by a Si—C bond. In the direct bonding between the polysiloxane group and the polymer main chain, the Si atom in the polysiloxane group and the C atom in the polymer main chain are directly bonded by a single bond (Si-C bond). In the indirect bonding between the polysiloxane group and the polymer main chain, the Si atom in the polysiloxane group and the C atom in the branch branched from the polymer main chain are bonded by a single bond (Si-C bond). .

[0020] In indirect attachment of polysiloxane groups and the polymer backbone, described above, as the branches divided from the polymer backbone, for example, a divalent radical of following. However, it is not limited to these. -COOR ³ --R ³ --CONHR ^3- [R ³ is a divalent organic group. Specific examples of R ³ include, for example, a linear or branched alkylene group or a substituted alkylene group (eg, methylene, ethylene, propylene, butylene, hexylene, octylene, dodecylene, octadecylene, 2-methyltetramethylene, -Methyltetramethylene, etc.),
Phenylene group or substituted phenylene group, -CH ₂ CHR
^2- (OCH ₂ CHR ² ) _q- [q is an integer of 1 or more;
² is a hydrogen atom or a methyl group. And the like, the carbon chain in the alkylene group exemplified as above is interrupted by an oxygen atom at an arbitrary position, such as an oxyalkylene group. When a plurality of R ³ are present in one molecule, the plurality of R ³ may be the same or different from each other.

Since the bond between the main chain and the Si atom is a Si—C bond as described above, the covalent bond is increased as compared with the Si—O—C bond. It will be excellent in property. Polymer part of silicon-containing polymer (P)
As described above, (meth) acrylic resin, polystyrene
Ren, polyvinyl acetate, polyolefin, polyvinyl chloride
, Polyvinylidene chloride, polyester resin, these
In copolymers and resins with some of them modified
Silicon-containing polymer
The main chain of (P) is mainly composed of carbon. Sand
That is, the main chain bond is composed of only carbon atoms,
The moiety may be composed of atoms other than carbon atoms. carbon
The atoms other than the atom (C) include a nitrogen atom (N) and an oxygen atom
(O), a sulfur atom (S) or a phosphorus atom (P).
As can be seen from the type of resin used as the polymer,
Of the carbon atoms constituting the main chain of the base polymer (P)
The proportion is far above 70 mol%.

The presence of the main chain on the surface of the inorganic material improves the wettability and dispersibility of the inorganic material in organic media used for rubber molding materials, plastic molding materials, paints, etc. Reduce the viscosity of the resin composition to improve moldability and workability, improve the sedimentation stability of the inorganic filler in the paint, and obtain the mechanical strength of the molded product and coating film, and to inorganic substrates Of the coating film can be improved.

Inorganic filler (T) in an organic medium used for rubber molding materials, plastic molding materials, paints, etc.
In order to increase the dispersibility of the polymer, the silicon-containing polymer (P) preferably has a hydrophobic group. Although the reason is not clear, the Si—O—R ¹ group in the silicon-containing polymer (P) is hydrolyzed into a hydrophilic Si—OH group,
It is considered that the silicon-containing polymer (P) acts like a surfactant by balancing the OH groups and the hydrophobic groups. Examples of the hydrophobic group include an alkyl group having 6 or more C atoms (for example, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.) The above aryl groups (for example, phenyl group, tolyl group, xylyl group, etc.) and aralkyl groups having 7 or more C atoms (for example, benzyl group, phenethyl group, etc.) are directly in the main chain or organic groups having the hydrophobic group. It only has to be attached to the chain. The amount of these hydrophobic groups is
Although it depends on the type of the organic medium, it is preferably in the range of 1 to 100 on average per molecule of the silicon-containing polymer (P). If the amount of the hydrophobic group is too small, the dispersibility of the inorganic filler (T) in the organic medium may be reduced. If the amount of the hydrophobic group is too large, the phase of the organic medium and the silicon-containing polymer (P) may vary depending on the type of the organic medium. The solubility may be reduced, and the adhesiveness may be reduced.

[0024] The silicon-containing polymers (P), (meth) acrylate
Resin; polystyrene; polyvinyl acetate; polyethylene
Polyolefins such as polypropylene and polypropylene; polyvinyl chloride
Le; polyvinylidene chloride; polyethylene terephthalate
And polyester resins such as these;
The Si atom in the polysiloxane group is bonded to one or more carbon atoms of the main chain of the polymer selected from the partially modified resin directly or through the above-mentioned divalent group. It has the following structure.

The silicon-containing polymer (P) is a rubber molding material,
In order to increase the wettability, dispersibility, and adhesion of the inorganic material to an organic medium used for a plastic molding material, a paint, or the like, a material that is compatible with the organic medium is preferable. Therefore, it is preferable to use a silicon-containing polymer (P) having a value close to the solubility parameter of the organic medium used, and more preferably a polymer having a chemical structure similar to that of the organic medium.

The Si—OR ¹ group in the silicon-containing polymer (P) is a group that serves as a bonding portion between the silicon-containing polymer (P) and the inorganic material.
By bonding with an R ¹ group, wetting, dispersibility, adhesiveness, and the like of an inorganic material with an organic medium in a rubber molding material, a plastic molding material, a paint, and the like can be improved.

The average number of R ¹ O groups is preferably 5 to 400 per molecule of the silicon-containing polymer (P).
More preferably, the number is up to 300. If there is no R ¹ O group, there is no bonding point between the silicon-containing polymer (P) and the inorganic material, and the inorganic material does not exhibit wettability, dispersibility and adhesiveness to an organic medium. Is an inorganic filler (T), the silicon-containing polymer (P) acts as a coagulant, and the dispersibility and adhesiveness may decrease.

Here, R ¹ is a hydrogen atom or a C 1 to 1
5 is an optionally substituted alkyl group. C number 1
Specific examples of the alkyl group of 5 include, for example, methyl,
Examples include groups such as ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, pentyl, amyl and the like. Examples of the substituted alkyl group include, for example,
One or more hydrogen atoms of the alkyl group are, for example, an alkoxy group such as a methoxy group and an ethoxy group; an acyl group such as an acetyl group and a propionyl group;
Examples thereof include groups substituted with halogen such as bromine.
The C number does not include the C number in the substituent. When a plurality of R ¹ are present in one molecule, the plurality of R ¹ may be the same or different from each other. R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and most preferably a methyl group. This is because the rate of hydrolysis and condensation of the R ¹ O group is further increased.

The Si atoms in the polysiloxane group, in addition the direct or indirect attachment and polysiloxane bond to the polymer backbone (Si-O-Si bond), we are looking bond with R ¹ O group. In such a case, the ionicity of the Si atom is further increased, and as a result, the rate of hydrolysis and condensation of the R ¹ O group is increased, and the number of reaction points with the inorganic material is increased.

The number average molecular weight of the silicon-containing polymer (P) used in the present invention must be in the range of 1,000 to 1,000,000, and in the range of 2,000 to 200,000. Is preferred. When the molecular weight is small, the effect of surface modification is small as in the case of the silane coupling agent.
Conversely, when the molecular weight is large, it is difficult to dissolve or melt it in an organic solvent when contacting it with an inorganic material.

Silicon-containing polymer (P) used in the present invention
Must be soluble in an organic solvent. Thereby, the silicon-containing polymer (P) is dissolved in an organic solvent and brought into contact with the inorganic material, or when the thermoplastic resin and the inorganic material are melt-kneaded, the silicon-containing polymer (P) is directly added to make contact with the inorganic material. To improve the surface. The fact that the silicon-containing polymer (P) is soluble in an organic solvent means that
The silicon-containing polymer (P) does not have a highly crosslinked structure and exhibits thermoplasticity, and can be examined, for example, by a solubility test method in Examples described later. The silicon-containing polymer (P) may be soluble in at least one kind of organic solvent described later or a mixed solvent of two or more kinds.

Such organic solvents may be reactive or non-reactive. Specific examples include benzene,
Aromatic hydrocarbons such as toluene, xylene, styrene, α-methylstyrene; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono acetate Esters such as butyl ether, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and glycidyl methacrylate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as tetrahydrofuran, dioxane and di-n-butyl ether; isopropanol; Alcohols such as butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether Lumpur acids; methylene chloride, halogenated hydrocarbons such as chloroform; and the like.

The silicon-containing polymer (P) used in the present invention
Preferably has a structure containing at least one selected from an acidic functional group, a hydroxyl group, an amino group and an epoxy group. By having the above group, a reaction with an organic medium such as a resin (S) described below is promoted, and the mechanical strength of the obtained molded article or coating film is improved. In particular, when an epoxy resin is used as the resin (S), the silicon-containing polymer (P) having an epoxy group can reduce the viscosity at the time of kneading to prevent cutting and deformation of the gold wire at the time of molding, and also to reduce the mechanical property of the molded body. It is suitable for a resin composition for an IC sealing material due to its excellent mechanical strength.

The silicon-containing polymer (P) can be produced by the method for producing a silicon-containing polymer according to the present invention. However, the present invention is not limited to this, and the silicon-containing polymer (P)
Can also be produced, for example, by the following methods (i) to (iv). (I) After copolymerizing a reactive silane compound (A) described below and a monofunctional monomer (E), the obtained copolymer and a silane compound (B) described below and / or a hydrolyzed condensate thereof are treated with hydrochloric acid. And co-hydrolysis-condensation in the presence of a catalyst that dissolves in a system such as an inorganic or organic acid such as acetic acid or acetic acid, or a base such as ammonia or amine.

(Ii) After polymerizing the monofunctional monomer (E) in the presence of a silane compound having a chain transfer ability such as γ-mercaptopropyltrimethoxysilane, the obtained polymer is mixed with the silane compound (B) and And / or a method of co-hydrolyzing and condensing the hydrolyzed condensate in the presence of the above catalyst. (Iii) a silane compound having a chain transfer ability and a silane compound (B) are co-hydrolyzed and condensed in the presence of the above catalyst to obtain a polysiloxane compound, and then a monofunctional monomer in the presence of the polysiloxane compound ( A method of polymerizing E).

(Iv) The reactive silane compound (A) and the silane compound (B) are cohydrolyzed and condensed in the presence of the above-mentioned catalyst to obtain a reactive polysiloxane compound. A method of copolymerizing with a monofunctional monomer (E). However, when a silane compound having a chain transfer ability such as γ-mercaptopropyltrimethoxysilane is used in the methods shown in the above (i) to (iv), if an unreacted product remains, a molding as a final product Offensive odor is emitted from materials and paints. Also, when co-hydrolytic condensation,
When a catalyst that dissolves in a system such as an inorganic acid or an organic acid or ammonia or an amine is used, gelation may occur during co-hydrolytic condensation or polymerization, and the desired silicon-containing polymer (P) may not be obtained. , Obtained silicon-containing polymer (P)
May increase in viscosity over time to increase the molecular weight, and in some cases, the stability over time such as gelation may be poor. Further, a method of co-hydrolytic condensation after polymerization ((i),
In (ii)), a polysiloxane compound that does not bind to the polymer is generated, and the aggregation of the inorganic filler (T) is promoted to increase the viscosity of the resin composition for a molding material or the coating material, thereby improving the moldability,
Workability may decrease. Further, in any case, the remaining of the catalyst causes the physical properties of the final product (for example, electrical properties such as electrical insulation, mechanical strength of the molded product and durability of coating film strength, and coating film with the substrate). (E.g., durability such as adhesion) and the corrosion of the substrate may be accelerated.

On the other hand, the method for producing a silicon-containing polymer according to the present invention has few problems as described above. Therefore, the silicon-containing polymer (P) is most preferably produced by this production method. The reactive silane compound (A) used in the method for producing a silicon-containing polymer according to the present invention is represented by the general formula (1) or (2).
R ¹ , R ² and R ³ are the same as described above.

[0038] Specific examples of the general formula reactive silane compound represented by (A) is, .gamma.-methacryloxypropyl trimethoxysilane, .gamma.-methacryloxypropyl triethoxysilane, gamma - acryloxypropyltrimethoxysilane, main Takuri b is an ethoxy trimethoxy shea <br/> run-like. Examples of the reactive silane compound (A) represented by the general formula are vinyl trimethoxy silane, vinyl triethoxysilane down like.

Specific examples of the reactive silane compound (A) represented by the above general formula include 1-hexenyltrimethoxysilane, 1-octenyltrimethoxysilane, vinyloxypropyltrimethoxysilane, and 3-vinylphenyltrimethoxysilane. , 3- (vinylbenzylaminopropyl)
And trimethoxysilane. The reactive silane compound (A) represented by the above general formula (1)
May be used alone or in combination of two or more. These formulas reactive silane compound represented by the ~ (A) is, s, for t and u is 0, hydrolytic condensation rate is high, Ru readily available. In particular, those in which R ¹ is an alkyl group having 1 to 3 C atoms are preferable, and those in which a methyl group is particularly preferable, since the rate of hydrolysis and condensation is high and the generated R ¹ OH can be easily removed outside the system. .

The silane compound (B) used in the present invention
Are those represented by the general formula, specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, alkoxysilane compounds such as di <br/> methoxy diethoxy silane
Etc. , each of which is used alone or 2
It is used in combination with more than one species. Silane compounds represented by the general formula (B) are the p = 0, hydrolytic condensation rate is high, Ru readily available. In particular, the rate of hydrolysis and condensation is high, and the generated R ¹ OH can be easily removed out of the system.
R ¹ is preferably an alkyl group having 1 to 3 C atoms,
Those which are methyl groups are particularly preferred.

The reactive silane compound (A) and the silane compound (B) may be used in an arbitrary ratio. When used in the resin composition, at least one type of reactive silane compound (A) selected from the general formulas and at least one type of silane compound (B) represented by the general formula are used. , (A) and (B) with respect to the total amount of (A) is 0.1 to 30 mol%, preferably 1 to 20 mol%, and (B) is 99.9 to 7 mol%.
0 mol%, preferably in the range of 99 to 80 mol%. When (A) is more than 30 mol%, a large number of polymerizable double bond groups are introduced into the polymerizable polysiloxane (D), so that the polymerizable polysiloxane (D) and a monofunctional monomer (described later) are used. When copolymerization with E) occurs, gelation tends to occur. When (A) is less than 0.1 mol%, a polymerizable double bond group is not introduced into the polymerizable polysiloxane. In some cases, this is not preferable. The amount of the double bond group in the polymerizable polysiloxane (D) is preferably 1
~ 4 ranges.

The solid catalyst (C) which is insoluble in the system used in the present invention is used to improve the stability over time of the obtained silicon-containing polymer (P) and not to deteriorate the physical properties of the final product. The catalyst component is not particularly limited as long as it is insoluble in any of (A) and (B), water, the reaction product and the solvent. Specific examples of such a solid catalyst (C) are listed below. (C-1) Cation exchange resin : Amberlite 15, Amberlite 200C, Amberlyst 15 (all manufactured by Rohm and Haas);
Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (all manufactured by Dow Chemical Company);
Levatit SPC-108, Levatit SPC-118
(The above is manufactured by Bayer AG); Diaion RCP-150
H (manufactured by Mitsubishi Kasei Corporation); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite-464 (all manufactured by Sumitomo Chemical Co., Ltd.); Nafion-H (manufactured by DuPont) and the like. (C-2) Anion exchange resin : Amberlite IRA-400, Amberlite IRA
-45 (all manufactured by Rohm and Haas). (C-3) a group containing a protonic acid group is bonded to the surface
Inorganic solids : Zr (O ₃ PCH ₂ CH ₂ SO ₃ H) ₂ , Th (O ₃ P
CH ₂ CH ₂ COOH) _{2 and the} like. (C-4) Polyorganosiloxane containing a protonic acid group
San : a polyorganosiloxane having a sulfonic acid group. (C-5) Heteropoly acid : Cobalt tungstic acid, phosphomolybdic acid and the like. (C-6) Isopoly acid : Niobic acid, tantalum acid, molybdic acid and the like. (C-7) Single metal oxide : alumina, chromia, zirconia, CaO, MgO and the like. (C-8) Composite metal oxide : silica-alumina, silica-magnesia, silica-zirconia, zeolites and the like. (C-9) Clay mineral : acid clay, activated clay, montmorillonite, kaolinite and the like. (C-10) Metal sulfate : LiSO ₄ , MgSO _{4 and the} like. (C-11) Metal phosphate : zirconia phosphate, lanthanum phosphate and the like. (C-12) Metal nitrate : LiNO ₃ , Mn (NO ₃ ) _{2 and the} like. (C-13) a group containing an amino group bonded to the surface
Inorganic solids : Solids obtained by reacting aminopropyltriethoxysilane on silica gel. (C-14) Polyorganosiloxa containing amino group
Down: an amino-modified silicone resin.

The co-hydrolytic condensation reaction of compound (A) with compound (B) is carried out using at least one of these catalysts. These catalysts can be placed in a fixed bed and the reaction can be carried out in a flowing manner, or can be carried out in a batch manner. The amount of the catalyst used is not particularly limited, but is preferably 0.1 to 20% by weight based on the total amount of (A) and (B).

The amount of water added during the hydrolytic condensation is not particularly limited, but the resulting polymerizable polysiloxane (D)
Water is preferably used in an amount of 70 to 140 mol%, more preferably 90 to 140 mol%, based on the total number of moles of (A) and (B), since it affects storage stability of the polymer and further suppresses gelation during the polymerization. It is good to use in the range of 120 mol%. When the amount of water is more than 140 mol%, the storage stability of the polymerizable polysiloxane (D) may deteriorate, or gelation may occur when subjected to copolymerization with the monofunctional monomer (E). is there. On the other hand, when the amount of water is less than 70 mol%, the unreacted compounds (A) and (B) increase and the molecular weight of the polymerizable polysiloxane (D) does not increase,
The yield may be reduced. Also, the amount of water
When the amount is 70 mol% or more with respect to the total number of moles of (A) and (B), the average number of Si atoms in the polymerizable polysiloxane (D) tends to be 11 or more, so that the polymer is finally obtained. The number of Si atoms in the polysiloxane group of the silicon-containing polymer (P) is likely to be 11 or more on average per polysiloxane group.

The hydrolysis reaction of the compounds (A) and (B)
The reaction can be carried out by a method generally used in the related art, without solvent, or in a solvent in which (A), (B) and water are soluble and these compounds are inert. As the solvent, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane can be used. Preferably, the boiling point is 100 ° C. or lower. This is because the solvent can be easily removed by an operation such as distillation. The reaction temperature and time vary depending on the type of the raw material, but it is usually preferably from room temperature to 150 ° C, preferably from 50 to 100 ° C, for a period of 10 minutes to 5 hours. It is not preferable to carry out the reaction at a high temperature or for a long time because polymerization of the double bond group (A) occurs. The pressure during the reaction is preferably in the range of 1 × 10 ^{−3 to} 7600 Torr.

R ¹ OH by-produced by the hydrolytic condensation reaction
Is preferably removed from the system during or after the hydrolysis condensation reaction. When a solvent is used, it is preferable that the solvent is also removed from the system. The reason for this is that if R ¹ OH or a solvent remains in addition to the polymerizable polysiloxane (D), the silicon-containing polymer (P) obtained at the time of copolymerization with the monofunctional monomer (E) will not be used in the system. In the case where the silicon-containing polymer (P) having a desired molecular weight cannot be obtained or the obtained silicon-containing polymer (P) is used in a paint and an isocyanate compound is used as a curing agent, the isocyanate compound And the residual R ¹ OH react with each other to cause insufficient curing. The total amount of R ¹ OH and the solvent remaining in the product after the hydrolytic condensation is 20% by weight or less, preferably 10% by weight, based on the total amount including the polymerizable polysiloxane (D).
It is better to do the following.

The method for removing R ¹ OH and the solvent outside the system is as follows.
Distillation is preferred, and the temperature, time and pressure are preferably set within the ranges described above. In this reaction system, a polymerization inhibitor may be added. This is effective to prevent the double bond group of the compound (A) from being polymerized, and specific examples thereof include hydroquinone and hydroquinone monomethyl ether.

The polymerizable polysiloxane (D) thus obtained is, for example, a number average molecular weight of 400 to 10
000 (in terms of polystyrene), preferably 1,200
In the range of ２０20,000, the main skeleton is composed of a polysiloxane bond (Si—O—Si), and an organic group having a double bond and an R ¹ O group are directly bonded to Si of the main skeleton. Things.

The monofunctional monomer (E) used in the present invention is a compound having one polymerizable unsaturated group, for example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid; acrylic esters Unsaturated carboxylic esters such as methacrylic esters, crotonic esters, itaconic esters, maleic esters, fumaric esters; acrylamides; methacrylamides; allyl compounds; vinyl ethers; vinyl esters At least one compound selected from styrenes, vinyl nitriles, and the like.

When the polymerizable polysiloxane (D) and the monofunctional monomer (E) are copolymerized, the ratio of (D) and (E) is based on the total amount of (D) and (E). (D) 0.1
-50 wt%, (E) 99.9-50 wt%, preferably
(D) is in the range of 5 to 35 wt%, and (E) is in the range of 95 to 65 wt%. When the content of (D) is less than 0.1% by weight, the amount of the silicon-containing polymer having a polysiloxane group in the silicon-containing polymer (P) may be reduced. Or the stability of the obtained silicon-containing polymer with time may be deteriorated.

As a method for copolymerizing the polymerizable polysiloxane (D) and the monofunctional monomer (E), a conventionally known method can be adopted. In the presence of a radical initiator, bulk polymerization, solution polymerization, suspension polymerization, Any method such as polymerization and emulsion polymerization may be used. However, in a method other than solution polymerization, a polymer having a highly cross-linked structure is obtained, which is insoluble in an organic solvent, or because it does not melt,
The surface modification of the inorganic material becomes insufficient, and the effect of the resin composition for a molding material is hardly exhibited because the dispersibility of the inorganic filler (T) cannot be improved. Therefore, it is preferable to perform solution polymerization.

As the radical polymerization initiator, for example,
Conventionally known compounds can be used and are not particularly limited, but are preferably at least one compound selected from azo compounds, peroxides and the like. The amount of the above-mentioned radical polymerization initiator is not particularly limited. It is preferable to use 0.5 to 7% by weight, more preferably 1 to 4% by weight, based on the total amount of (D) and (E).

The organic solvent used for the solution polymerization is not particularly limited as long as the polymerizable polysiloxane (D) and the monofunctional monomer (E) can be dissolved. Group hydrocarbons, ethers,
Alcohols, halogenated hydrocarbons and the like,
Either one may be used alone, or a mixed solvent of two or more solvents may be used.

The temperature at the time of copolymerization can be appropriately selected depending on the polymerization method and the radical polymerization initiator to be used. Range. At the time of copolymerization, a chain transfer agent, a molecular weight regulator, a surfactant and the like may be appropriately used. The time for performing the polymerization is, for example, 1 to 12
Time.

The inorganic material treated by the surface modification method of the present invention is not particularly limited.
Oxides, hydroxides, sulfides, carbides, nitrides, sulfates, carbonates, phosphates and ferrocyanides of one or more metals selected from the groups Ia to Va, Ib to VIIb and VIII Carbon; and at least one metal selected from the group consisting of one or more metal elements selected from Group IIIa, Ib to IIb and Group VIII of the periodic table. Specific shapes of inorganic materials include granular, spherical, hollow, fibrous,
Inorganic fillers (T) in the form of scales, plates (or flakes), etc .; inorganic substrates; and the like, but are not limited thereto. The following are more specific examples.

-Inorganic filler (T)-(oxide): titanium dioxide, zinc oxide, ferric oxide, chromium oxide, cuprous oxide, cupric oxide, antimony trioxide,
Antimony pentoxide, silicon dioxide, alumina, tin oxide,
Potassium titanate, magnesium oxide, cobalt blue (CoO.nAl ₂ O ₃ ), cobalt green (CoO
.NZnO), titanium green (TiO ₂ .CoO.N)
iO.ZnO), titanium yellow (TiO ₂ .NiO.
Sb ₂ O ₃ ), iron black (Fe ₃ O ₄ ), talc [Mg ₃ S
i ₄ O ₁₀ (OH) ₂ ], lead red (Pb ₃ O ₄ ), lead oxide, basic lead chromate (PbCrO ₄ .PbO), calcium leadate, zinc chromate, clay, barium ferrite, mica, Glass etc.

(Hydroxide): aluminum hydroxide, magnesium hydroxide, hydrous silicic acid, yellow iron oxide (α-FeOO)
H) etc. (Sulfide): zinc sulfide, cadmium yellow (Cd
S), cadmium red [Cd (S, Se)] and the like. (Carbide): silicon carbide and the like.

(Nitride): silicon nitride or the like. (Sulfate): barium sulfate, lead sulfate, strontium sulfate, etc. (Carbonate): calcium carbonate, basic magnesium carbonate [4MgCO ₃ .Mg (OH) ₂ .4H ₂ O] and the like. (Phosphate): zinc phosphate, potassium zinc phosphate, cobalt purple [Co ₃ (PO ₄ ) ₂ ] and the like.

(Ferocyanide): Navy blue (Fe ₃ K ₃₎
Fe (CN) _{6 3),} cyanides such as lead. (Carbon): carbon black, graphite and the like. (Metal): Al, Zn, Ni, Cu, Fe, Ag, Au
etc. -Inorganic substrate-Glass plate, steel plate, alumina plate, aluminum nitride plate, S
iC plate, Al plate, galvanized plate, tin plate, mortar plate, cement plate, concrete plate, quartz plate, steel plate treated with zinc phosphate, etc.

The surface modification method of the present invention is performed, for example, in the following manner, but is not limited thereto. The case where the inorganic material is an inorganic filler (T) and the case where the inorganic material is an inorganic substrate will be described as examples. First, when the inorganic material is an inorganic filler (T), the surface of the inorganic material is modified either before or during the mixing of the inorganic filler (T) with the organic medium.

When the surface modification is performed before mixing with the organic medium, for example, the inorganic filler (T) is immersed in a solution obtained by dissolving the silicon-containing polymer (P) in an organic solvent, and thereafter,
A method of drying by heating; a method of spraying a solution obtained by dissolving the silicon-containing polymer (P) in an organic solvent onto a well-stirred inorganic filler (T), followed by drying; Dispersed to obtain a slurry,
A method of adding the silicon-containing polymer (P) or a solution obtained by dissolving the silicon-containing polymer (P) in an organic solvent to the slurry while stirring the slurry, followed by drying; and heating the inorganic filler (T) in advance at a high temperature. Under the high temperature, the silicon-containing polymer (P) is added to the high-temperature inorganic filler (T).
A silicon-containing polymer (P) is brought into contact with an inorganic filler (T) by, for example, spraying a solution prepared by dissolving the polymer in an organic solvent;
A method of mixing the composite material with an organic medium after obtaining a composite material adhered to the substrate; or adding an inorganic filler (T) to a solution obtained by dissolving the silicon-containing polymer (P) in an organic solvent. Then, a method of preparing a paint by adding a vehicle of the paint to the slurry and mixing the slurry is adopted.

In the case where surface modification is performed when mixing with an organic medium, for example, when the resin (S) and the inorganic filler (T) described below are melt-kneaded, a silicon-containing polymer (P) is added and extruded. A method of performing molding or injection molding; adding a silicon-containing polymer (P) to a monomer or oligomer before polymerization for synthesizing the resin (S) and dissolving it; adding an inorganic filler (T) thereto; After slurrying,
A method of performing cast polymerization or the like; a method of adding and dissolving a silicon-containing polymer (P) to a vehicle of a paint, adding an inorganic filler (T) thereto, and mixing and slurrying; In these methods, the surface of the inorganic filler (T) is modified by bonding the silicon-containing polymer (P) to the surface of the inorganic filler (T) at the time of melt-kneading or preparing a slurry.

Inorganic filler (T) and silicon-containing polymer (P)
Is preferably used in a proportion of 0.1 to 30 wt%, more preferably 0.5 to 10 wt%, with respect to the inorganic filler (T). preferable. When the proportion of the silicon-containing polymer (P) is small, the amount of the silicon-containing polymer (P) bonded to the inorganic filler (T) is small, and thus the dispersibility and adhesion of the inorganic filler (T) in an organic medium may be reduced. If the amount is too large, the silicon-containing polymer (P) remaining without being bonded to the surface of the inorganic filler (T) is present, and consequently the adhesiveness may be reduced.

As the solution obtained by dissolving the silicon-containing polymer (P) in an organic solvent, for example, the concentration of the silicon-containing polymer (P) is preferably 30% by weight or less, preferably 10% by weight or less.
More preferably, it is not more than wt%. If the concentration is too high, the viscosity of the solution may increase, and the treatment efficiency of the surface of the inorganic filler (T) may deteriorate. As described above, the surface-modified inorganic filler (T) is added at the time of melt-kneading the resin (S), or the surface-modifying agent is added at the time of melt-kneading the resin (S).
When the surface of the inorganic filler (T) is modified by doing so, the dispersibility of the inorganic filler (T) in the resin (S) is improved, and the fluidity of the compound during extrusion molding or injection molding is increased. In addition, the filling of the inorganic filler (T) is increased and workability is improved. In addition, since the adhesion at the interface between the resin (S) and the inorganic filler (T) is improved, the strength of the finally obtained plastic product or rubber product is increased. In the case of performing the melt kneading, the temperature for the melt kneading is preferably a temperature equal to or higher than the melting point of the resin (S) and the silicon-containing polymer (P) and lower than the decomposition temperature.

As described above, the surface-modified inorganic filler (T) is added to a monomer or oligomer before polymerization for synthesizing the resin (S), or the inorganic filler (T) is used when preparing a slurry. ), The viscosity of the slurry is reduced (the viscosity of the monomer-containing liquid is reduced as compared with the case where a conventional surface-modified filler is added), and the dispersibility of the inorganic filler (T) is reduced. This increases the slurry filling and the workability. Furthermore, as a result of improving the adhesiveness of the interface between the generated resin (S) and the filler, the strength of the obtained plastic product or rubber product increases. When the silicon-containing polymer (P) has, for example, a reactive group such as an epoxy group, a hydroxyl group, an amino group, or an acidic functional group, the resin (S) and the silicon-containing polymer (P) bond during the polymerization process. And
Adhesion is further improved.

As described above, when the surface-modified inorganic filler (T) is dispersed in the vehicle of the paint, or when the inorganic filler (T) is surface-modified at the time of preparing the paint, the inorganic filler (T) can be added to the vehicle. Since the dispersibility of the inorganic filler (T) and the wetting of the vehicle with the inorganic filler (T) are improved, the inorganic filler (T) is less likely to settle in the vehicle, and the storage stability of the paint is improved. For this reason, in the obtained coating film, color separation and surface roughness are suppressed. In addition, since the adhesion at the interface between the vehicle and the inorganic filler (T) increases, the strength of the coating film improves.

Examples of the vehicle resin of the above coating material include (meth) acrylic resin, (meth) acrylic-styrene resin, alkyd resin, alkyd-modified (meth) acrylic resin, (meth) acrylic-urethane resin, and (meth) acrylic resin. Acrylic-melamine resin, (meth) acryl-epoxy resin, (meth) acryl-silicone resin, polyester-melamine resin, and the like are used.

When the inorganic material is an inorganic substrate, the surface of the inorganic substrate is modified by bringing a liquid containing the silicon-containing polymer (P) into contact with the inorganic substrate. As the liquid containing the silicon-containing polymer (P) used for surface modification of the inorganic substrate, a liquid obtained by adding the silicon-containing polymer (P) to a product such as a paint, an adhesive, an adhesive, a sealing agent,
A solution obtained by dissolving the silicon-containing polymer (P) in an organic solvent can be used as a primer. After applying a liquid containing the silicon-containing polymer (P) to the inorganic substrate, the surface is modified by heating and drying. The coating method may be any of, for example, dipping, roll coater, bar coater, spin coater, brush coating, spraying, etc., and is not particularly limited. The concentration of the silicon-containing polymer (P) in the liquid is not particularly limited, but is preferably 0.1% by weight or more. If the concentration is lower than this, since the amount of the silicon-containing polymer (P) bonded to the inorganic substrate is small, the wettability of the organic medium used for paints, adhesives, pressure-sensitive adhesives, sealing agents, etc. on the inorganic substrate is low, Further, the adhesion between the organic medium and the inorganic substrate may be low. In particular, a method of coating a coating composition containing a vehicle and a silicon-containing polymer (P) as essential components on an inorganic substrate is preferable because the process is simple and sufficient adhesion between the substrate and the coating film is obtained. . At this time, the silicon-containing polymer (P) is added to the vehicle resin in an amount of 0.0
It is preferable to use it in the range of 5 to 20% by weight. If the silicon-containing polymer (P) is used outside of this range, the adhesion of the coating film to the substrate may decrease.

According to these methods, the surface of the inorganic substrate is modified by bonding the silicon-containing polymer (P) to the surface of the inorganic substrate, and the polymer is contained in a paint, an adhesive, an adhesive, a sealing agent, and the like. This improves the wetting of the organic medium with the inorganic substrate and the adhesion between the organic medium and the inorganic substrate. When the contacting of the inorganic material silicon-containing polymers (P), in order to promote the hydrolysis of Si-OR ¹ group in a molecule of the silicon-containing polymer (P), water may be added to the organic solvent . When using a solvent that does not dissolve water,
It is preferable to use a solvent that dissolves water in combination.
When water is added, R ¹ O of the silicon-containing polymer (P) is added.
It is preferable to add 100 mol or less of water to 1 mol of the group. If the proportion of water is too large, the silicon-containing polymer (P) may precipitate. When the surface of the inorganic material is modified by the above-described method, the final product, such as a molded product or a coating film, does not decrease its mechanical strength or adhesion to the substrate even in a long-term high-humidity atmosphere or in hot and cold water, It will be excellent in durability.

Next, the resin composition for a molding material according to the present invention will be described. The resin (S) used as an essential component of the resin composition for a molding material serves as a matrix constituting an insulating material, a sealing material, a flame-retardant material, and the like, and the type thereof is not particularly limited. One or two or more selected from thermoplastic resins, thermosetting resins and rubbers. As the thermoplastic resin, for example, polyamide (6-nylon, 66-nylon, 12
-Nylon, etc.), polyimide, polyurethane, polyolefin (polyethylene, polypropylene, etc.), polyester (PET, PBT, PEN, etc.), polyvinyl chloride,
Polyvinylidene chloride, polyvinyl acetate, polystyrene,
(Meth) acrylic resin, ABS resin, silicone resin,
Fluororesins, copolymers thereof, partially modified polymers and the like can be mentioned. As the thermosetting resin, for example,
Examples include phenol resins (phenol / formalin resins, cresol / formalin resins, etc.), epoxy resins, amino resins (urea resins, melamine resins, guanamine resins, etc.), and copolymers and partially modified polymers thereof. Examples of the rubber include isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorine rubber, urethane rubber, and copolymers thereof. And partially modified polymers.

The resin (S) which is particularly preferable as an electric insulating material includes polystyrene, polyolefin, polyvinyl chloride, polyimide, ABS resin, phenol resin, and epoxy resin which are well-balanced in electric insulation, moisture resistance, mechanical properties and the like. And copolymers of these and partially modified polymers. Preferred resins (S) as flame-retardant materials include polyolefin, polyvinyl chloride, (meth) acrylic resin, epoxy resin, phenolic resin, unsaturated polyester, and styrene, which are well-balanced in flame retardancy and mechanical properties. Butadiene rubber, ethylene-vinyl acetate rubber, ethylene-acrylic rubber, and copolymers and partially modified polymers thereof.

As the resin (S) which is preferable as the sealing material, an epoxy resin balanced in electrical insulation, moisture resistance, adhesion, mechanical properties and the like can be mentioned. More specifically, glycidylamine type epoxy resin can be used. Epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A epoxy resin, alicyclic epoxy resin, bisphenol F epoxy resin,
Resin type epoxy resin, tetrahydroxyphenylethane type epoxy resin, polyalcohol type epoxy resin, polyglycol type epoxy resin, glycerin triether type epoxy resin, polyolefin type epoxy resin, etc. )
It is preferable to use a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A type epoxy resin, and / or a partially modified epoxy resin having high moisture resistance as essential components. In addition, for use as an IC sealing material, it is preferable to use the above-described rubber or silicone resin in combination to alleviate the internal thermal stress.

The inorganic filler (T) used as an essential component of the resin composition for a molding material of the present invention is not particularly limited, and includes those already mentioned, and includes insulating materials, sealing materials, flame-retardant materials And the like to impart functions such as electrical insulation, heat resistance, flame retardancy, heat conductivity, dimensional stability, cosmetics, and mechanical strength. Inorganic filler (T), which is particularly preferable as an electrical insulating material, includes fused silica, crystalline silica, aluminum oxide, calcium carbonate, glass fiber, and the like, which can impart properties such as electrical insulation, thermal conductivity, and mechanical strength to the material. It is chopped fiber, milled fiber and glass powder obtained by chopping glass fiber. Further, preferred inorganic fillers (T) as flame-retardant materials are aluminum hydroxide, magnesium hydroxide, antimony trioxide, antimony pentoxide, and zinc borate, which can impart flame retardancy to the material. Preferred inorganic fillers (T) as sealing materials include fused silica, crystalline silica, aluminum oxide, calcium carbonate, talc, mica, and glass that can impart properties such as electrical insulation, thermal conductivity, and mechanical strength to the material. Inorganic filler (T), which is a fiber and is particularly preferable as an IC sealing material, is a fused silica having excellent thermal conductivity and / or
Alternatively, crystalline silica is preferably used as an essential component.

The proportions of the resin (S), the inorganic filler (T) and the silicon-containing polymer (P), which are essential components of the resin composition for a molding material of the present invention, are such that (T) is (S) and (T). 20) to 90% by weight, preferably 40 to 80% by weight, based on the total amount of
%, And (P) is 0.1 to 30 with respect to (T).
wt%, preferably 0.5 to 10 wt%. (T) is 20wt with respect to the total amount of (S) and (T)
%, The desired properties, for example, electrical properties, heat resistance, flame retardancy, etc., decrease. On the other hand, (T) is 90
If the content exceeds wt%, the amount of the inorganic filler (T) is too large, so that workability and moldability are deteriorated, and pinholes and voids are liable to be generated in a finally obtained molded body, and mechanical strength is also reduced. . When (P) is less than 0.1 wt% with respect to (T), for example, the effect of reducing the viscosity during kneading is reduced, so that the moldability and workability are reduced, and a large amount of the inorganic filler (T) is used. It is difficult to use. On the other hand, (P) is 30
If the content exceeds wt%, desired properties such as electrical properties, heat resistance, flame retardancy and the like are reduced.

In particular, for use as an IC sealing material, (T) is in the range of 50 to 90% by weight based on the total amount of (S) and (T).
Is preferably in the range of 0.5 to 6% by weight based on (T).
When (T) is less than 50 wt% with respect to the total amount of (S) and (T), the moisture resistance reliability of the IC chip, heat conduction and relaxation of thermal stress are reduced. And workability and formability decrease.

As described above, the resin composition for a molding material of the present invention comprises (S), (T) and (P) as essential components. Additives such as an accelerator, a colorant, a release agent, a coupling agent, a silicone compound, a reactive diluent, a plasticizer, a stabilizer, and a flame-retardant auxiliary can be used. The curing agent may be necessary when using a thermosetting resin as the resin (S). For example, when an epoxy resin is used as the resin (S), a polyamide, an aliphatic polyamine, a cycloaliphatic polyamine, Novolak curing agents such as aromatic polyamines or partially modified amines, acid anhydrides, dicyandiamides, imidazoles, amine imides, hydrazides, phenol novolaks, cresol novolaks, and the like. One or more are used. When a phenol resin is used as the resin (S), urotropin, formal and the like can be mentioned, and one or more of these may be used. The amount used is an appropriate amount based on the resin (S).

The curing accelerator has a function of accelerating the curing when a thermosetting resin is used as the resin (S), and is used for adjusting the curability of the finally obtained composition. . When an epoxy resin is used as the resin (S), for example, imidazoles or a salt thereof,
Tertiary amines or salts thereof, triazoles or salts thereof, organometallic complex salts, organic acid metal salts, quaternary ammonium salts, phosphines, phosphonium salts, diazobicycloalkenes or salts thereof, and the like. One type or two or more types may be used. In addition, resin (S)
When a phenol resin or an amino resin is used, for example, an acid (an organic acid such as oxalic acid or p-toluenesulfonic acid, a mineral acid such as hydrochloric acid) or an alkali (ammonia, sodium hydroxide, barium hydroxide, triethylamine, etc.) )
A catalyst may be mentioned, and one or more of these may be used.

As a coloring agent, an organic pigment or a dye can be used. Release agents include natural or synthetic paraffins, higher fatty acids or metal salts thereof, higher fatty acid amides, bis fatty acid amides, ester waxes such as carnauba wax,
Silicone and the like can be mentioned. The adhesion between the resin (S) and the inorganic filler (T) is sufficiently improved by the silicon-containing polymer (P). May be.

The silicone compound and silicone fine particles are
In particular, it may be used to improve low stress in IC sealing material applications. The reactive diluent is for further improving the workability when kneading the composition, for example,
When an epoxy resin is used as the resin (S), for example, aliphatic or aromatic mono- or diglycidyl ethers, and when a (meth) acrylic resin, polystyrene, unsaturated polyester, or the like is used as the resin (S), radical And polymerizable monomers.

The plasticizer is used to further improve the processability of the composition, and includes, for example, phosphates, phthalates, aliphatic- or dibasic esters,
Examples thereof include dihydric alcohol esters, oxyacid esters, and polyglycols. Particularly, when an epoxy resin is used as the resin (S), polyglycols are preferable.

The stabilizer suppresses the decomposition of the resin (S), and examples thereof include lead stearate and zinc stearate. Examples of the flame retardant aid include organic phosphorus compounds such as phosphate esters, phosphite esters, acidic phosphate esters, and phosphonium salts. These additives can be used in an appropriate amount with respect to the resin composition for a molding material.

The method for producing the resin composition for a molding material of the present invention and molding the same is not particularly limited. In general, for example, each component selected in a predetermined mixing ratio is obtained by: After sufficiently mixing uniformly using a mixing device such as a roll, a kneader, or a mixer, molding is performed. Molding methods include, for example, extrusion molding, injection molding, casting,
Compression molding, low-pressure transfer molding and the like can be mentioned. In particular, low pressure transfer molding is most commonly used as an IC sealing material. The molding temperature is, for example, from room temperature to 250
C., preferably in the range of 50 to 200C.

[0083]

The surface comprising the specific silicon-containing polymer (P)
When the modifier is brought into contact with the inorganic material, the silicon-containing polymer (P) binds to the inorganic material and modifies the surface, and the wettability, dispersibility, adhesion and durability of the inorganic material with various organic media are improved. improves. For example, when the inorganic material is an inorganic filler (T), the dispersibility of the inorganic filler (T) in various organic media and the adhesion between the organic medium and the inorganic filler (T) in plastics and rubbers are improved. Thus, the strength of the finally obtained product and its durability are increased. In the paint, the dispersibility of the inorganic filler (T) is improved, and the sedimentation stability is increased. Even in the finally obtained coating film, there is no color separation or roughness, and the strength and durability of the coating film are improved. In addition, when the inorganic material is an inorganic substrate, the wettability, adhesion (adhesion), and durability of the inorganic substrate with the paint, adhesive, pressure-sensitive adhesive, and sealing agent are improved. In the silicon-containing polymer (P) molecule, the direct or indirect bond (Si-C bond) between the Si atom in the polysiloxane group and the main chain is not easily hydrolyzed.
The above-mentioned improvement effect is maintained for a long period of time even if the inorganic material whose surface has been modified by contact with water is placed in a heated and humid atmosphere or in hot and cold water for a long time.

The above resin (S) and inorganic filler (T)
When a resin composition for a molding material is constituted by blending a surface modifying agent comprising a silicon-containing polymer (P) with the resin, the viscosity of the composition is reduced, workability and moldability are improved, and inorganic Higher filling of the filler (T) becomes possible, the sedimentation stability of the inorganic filler (T) during molding is improved, and the mechanical strength of the finally obtained product (molded product) is increased. In addition, the strength is maintained for a long time, and the durability is improved .

[0085]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples.
“%” And “parts” indicate “wt%” or “parts by weight” unless otherwise specified. First, a silicon-containing polymer was produced by the following method.

Example P-1 12.4 g of γ-methacryloxypropyltrimethoxysilane as a reactive silane compound (A) was placed in a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser.
05 mol), 144.4 g (0.95 mol) of tetramethoxysilane as silane compound (B), 100 g of methanol as solvent, 18 g (1 mol) of water, solid catalyst (C)
As Amberlyst 15 (Rohm and Haas
5 g of a cation exchange resin (manufactured by Japan Co., Ltd.) was added, and the mixture was stirred and reacted under reflux of methanol (65 ° C.) for 2 hours. After cooling the reaction mixture to room temperature, a distillation column is provided in place of a cooling tube, a cooling tube connected to the distillation column, and an outlet are provided. ) Was maintained at the same temperature until disappeared. In addition, 2
The reaction was further continued at a pressure of 00 mmHg at a temperature of 90 ° C. until the distilling liquid was exhausted. After cooling to room temperature again, Amberlyst 15 was separated by filtration to obtain a polymerizable polysiloxane (D-1) having a number average molecular weight of 1800.

The polymerizable polysiloxane (D-1) has an S
The elemental analysis value of i was 26%, and the average number of Si atoms in (D-1) was 17. The conversions of γ-methacryloxypropyltrimethoxysilane and tetramethoxysilane were 99 wt% and 98 wt%, respectively, and the amount of methanol remaining in the polymerizable polysiloxane (D-1) was 2.2.
wt%, γ-methacryloxypropyltrimethoxysilane and tetramethoxysilane were not detected. The obtained polymerizable polysiloxane (D-1) was stable in a sealed state at room temperature for one year or more.

Then, 200 g of toluene as an organic solvent was put into a 1-liter glass reactor equipped with a stirrer, a dropping port, a thermometer, a cooling pipe and an N ₂ gas inlet, and toluene was introduced while introducing N ₂ gas. The temperature was adjusted to ± 2 ° C. Then, a solution in which 20 g of polymerizable polysiloxane (D-1), 85 g of butyl acrylate, 85 g of styrene, and 10 g of glycidyl methacrylate were mixed with 6 g of 2,2'-azobisisobutyronitrile as a radical polymerization initiator with stirring. Was dropped from the dropping port over 2 hours. After stirring for 1 hour at the same temperature after dropping,
1,1'-bis (t-butylperoxy) -3,3,5
0.4 g of trimethylcyclohexane every 30 minutes
It was added twice, and further heated for 2 hours to carry out copolymerization to obtain a solution (solid content: 49%) in which the silicon-containing polymer (P-1) was dissolved in toluene. Then, toluene was distilled off under reduced pressure by an evaporator to remove the silicon-containing polymer (P-1) (solid content: 97%).
%). The polymer (P-1) was examined for number average molecular weight, confirmation of polysiloxane groups, number of R ¹ O groups, and solubility in organic solvents. The results of the analysis are shown in Table 1.

Reference Example P-2- Vinyltrimethoxysilane as a reactive silane compound (A) was placed in a 300 ml four-necked flask equipped with a stirrer, a thermometer, a distillation column, a condenser connected thereto and an outlet. 1
4.8 g (0.1 mol), 122.4 g (0.9 mol) of methyltrimethoxysilane as the silane compound (B),
100 g of methanol and 13.5 g of water (0.7
5 mol), Amberlite IRA as solid catalyst (C)
0.2 g of -45 (an anion exchange resin manufactured by Rohm and Haas Japan) is added, and the mixture is heated to 80 ° C under normal pressure.
The temperature was raised over time and maintained at the same temperature until there was no more liquid flowing out. After cooling the reaction mixture to room temperature, Amberlite IRA-45 was filtered off and the number average molecular weight was 18,000.
Was obtained as a polymerizable polysiloxane (D-2).

The S of the polymerizable polysiloxane (D-2)
From the result of elemental analysis of i, the average number of Si atoms in (D-2) was 165. The conversion of vinyltrimethoxysilane and methyltrimethoxysilane was 74 wt.
% And 73 wt%. Polymerizable polysiloxane (D
-2) each of methanol, vinyltrimethoxysilane and methyltrimethoxysilane remaining in 20 wt.
%, 1.8 wt% and 13 wt%. The obtained polymerizable polysiloxane (D-2) was stable in a sealed state at room temperature for one year or more.

Next, in Example P-1, 90 g of polymerizable polysiloxane (D-2) was used instead of polymerizable polysiloxane (D-1), and methyl methacrylate was used instead of butyl acrylate, styrene and glycidyl methacrylate. Example P- except that 50 g and 60 g of 2-ethylhexyl acrylate were used.
1, the silicon-containing polymer (P-2) (solid content 9
8%). Table 1 shows the analysis results of the obtained polymer (P-2).

Example P-3- In Example P-1, γ-acryloxypropyltriethoxysilane 6 instead of γ-methacryloxypropyltrimethoxysilane was used as the reactive silane compound (A).
Using 9 g (0.25 mol), the amount of tetramethoxysilane as the silane compound (B) was changed to 114 g (0.75 mol), and the amount of water was changed to 19.8 g (1.1 mol). Example P-1 except that 10 g of zeolite was used instead of Amberlyst 15 as the solid catalyst (C).
In the same manner as in the above, a polymerizable polysiloxane (D-3) having a number average molecular weight of 4,300 was obtained.

The polymerizable polysiloxane (D-3) has an S
From the result of elemental analysis of i, the average number of Si atoms in (D-3) was 38. The conversions of γ-acryloxypropyltrimethoxysilane and tetramethoxysilane were 99% by weight and 99% by weight, respectively. Γ-acryloxypropyltrimethoxysilane and tetramethoxysilane remaining in the polymerizable polysiloxane (D-3) were not detected, and methanol was 14% by weight and ethanol was 3.9% by weight.
Met. The obtained polymerizable polysiloxane (D-3) was stable in a sealed state at room temperature for one year or more.

Next, in Example P-1, 40 g of polymerizable polysiloxane (D-3) was used in place of polymerizable polysiloxane (D-1), and 70 g of ethyl acrylate and acrylic resin were used in place of butyl acrylate and glycidyl methacrylate. A silicon-containing polymer (P-3) (solid content: 97%) was obtained in the same manner as in Example P-1, except that 5 g of the acid was used. Table 1 shows the analysis results of the obtained polymer (P-3).

Reference Example P-4- In Reference Example P-2, 74.4 g (0.30 g) of γ-methacryloxypropyltrimethoxysilane was used as the reactive silane compound (A) instead of vinyltrimethoxysilane.
Mol), and dimethyldiethoxysilane 2 instead of methyltrimethoxysilane as the silane compound (B).
Using 9.6 g (0.20 mol) and 160 g (0.50 mol) of tetrabutoxysilane, the amount of water was 23.4 g.
(1.3 mol), and a polymerizable compound having a number average molecular weight of 7100 was obtained in the same manner as in Reference Example P-2 except that 1 g of Amberlyst 15 was used instead of Amberlite IRA-45 as the solid catalyst (C). Polysiloxane (D-4) was obtained.

The polymerizable polysiloxane (D-4) has an S
From the result of elemental analysis of i, the average number of Si atoms in (D-4) was 75. The conversion rates of γ-methacryloxypropyltrimethoxysilane, dimethyldiethoxysilane and tetrabutoxysilane were 100 wt% and 100 wt%, respectively.
% And 100 wt%. Γ-methacryloxypropyltrimethoxysilane, dimethyldiethoxysilane, and tetrabutoxysilane remaining in the polymerizable polysiloxane (D-4) were not detected. there were. The obtained polymerizable polysiloxane (D-4) was stable in a sealed state at room temperature for one year or more.

Next, in Example P-1, 20 g of polymerizable polysiloxane (D-4) was used instead of polymerizable polysiloxane (D-1), and butyl acrylate 85
g, styrene 85 g and glycidyl methacrylate 1
A silicon-containing polymer (P-4) (solid content 98%) was obtained in the same manner as in Example P-1, except that 90 g of butyl acrylate and 90 g of styrene were used instead of 0 g. Table 1 shows the analysis results of the obtained polymer (P-4).

Example P-5 In Example P-1, 3-vinylphenyltrimethoxysilane 11.2 was used instead of γ-methacryloxypropyltrimethoxysilane as the reactive silane compound (A).
A polymerizable polysiloxane (D-5) having a number average molecular weight of 1400 was obtained in the same manner as in Example P-1 except that g (0.05 mol) was used.

The S of the polymerizable polysiloxane (D-5)
From the result of elemental analysis of i, the average number of Si atoms in (D-5) was 13 atoms. The conversion of 3-vinylphenyltrimethoxysilane and tetramethoxysilane was 98% each.
wt% and 94 wt%. 3-vinylphenyltrimethoxysilane, tetramethoxysilane and methanol remaining in the polymerizable polysiloxane (D-5) were 0.2 wt%, 0.5 wt% and 0.3 wt%, respectively.
The obtained polymerizable polysiloxane (D-5) was stable at room temperature for one year or more in a sealed state.

Next, in Example P-1, 2 g of polymerizable polysiloxane (D-5) was used instead of polymerizable polysiloxane (D-1), and 85 g of butyl acrylate was used.
85 g of styrene and 10 g of glycidyl methacrylate
Was replaced with 98 g of cyclohexyl methacrylate and 100 g of lauryl methacrylate.
0 ° C., and 2,2′-
In the same manner as in Example P-1 except that the amount of azobisisobutyronitrile was changed to 1 g, the silicon-containing polymer (P-
5) (98% solids). Table 1 shows the analysis results of the obtained polymer (P-5).

Comparative Example P-6 In Example P-1, 2.3 g of concentrated hydrochloric acid (36% HCl concentration) was used instead of Amberlyst 15, and the amount of water was 11.7 g (0.65 mol). Was obtained in the same manner as in Example P-1 except that the reactive polysiloxane (D-6) having a number average molecular weight of 1100 was changed.

S of the reactive polysiloxane (D-6)
According to the result of elemental analysis of i, the number of Si atoms in (D-6) was 10 on average. The conversion of γ-methacryloxypropyltrimethoxysilane and tetramethoxysilane was 9
0 wt% and 85 wt%, and methanol, γ-methacryloxypropyltrimethoxysilane and tetramethoxysilane remaining in the reactive polysiloxane (D-6) were 5.9 wt%, 4.0 wt%, and 6.2 wt%, respectively. %Met. The obtained reactive polysiloxane (D-
6) gelled after standing for 2 months in a sealed state at room temperature.

Then, in the same manner as in Example P-1, 20 g of the reactive polysiloxane (D-6) was copolymerized with 85 g of butyl acrylate, 85 g of styrene and 10 g of glycidyl methacrylate, to obtain a silicon-containing polymer (P-6) ( (96% solids). Obtained polymer (P-6)
Table 1 shows the analysis results. The obtained silicon-containing polymer (P-6) thickened with time and gelled after being left at room temperature for one month.

Comparative Example P-7 In Example P-1, 120 g of polymerizable polysiloxane (D-4) was used as the polymerizable polysiloxane (D), 38 g of butyl acrylate and 38 g of styrene were used as the monofunctional monomer (E). When 4 g of glycidyl methacrylate was used and they were copolymerized, gelation occurred during the polymerization.

Comparative Production Examples P-8 and P-9} In Example P-1, the polymerizable polysiloxane (D-
In the same manner except that 10 g of 2-methacryloxyethoxytrimethoxysilane (Comparative Production Example P-8) or 10 g of γ-methacryloxypropyltrimethoxysilane (Comparative Production Example P-9) was used instead of 1). Polymerization was carried out to obtain polymer (P-8) (solid content 98%) and polymer (P-9) (solid content 98%).

Examples P-1 , 3, 5 and Reference Example P-
The number-average molecular weight, the polysiloxane group and the R ¹ O group of the silicon-containing polymers obtained in 2 , 4 , Comparative Example P-6, Comparative Production Examples P-8 and P-9 were confirmed, and their solubility in organic solvents was as follows. It was analyzed and evaluated by the following methods. -Number average molecular weight The number average molecular weight in terms of polystyrene was measured by the GPC method.・ Confirmation of polysiloxane group ^{29 By} Si-NMR analysis, polysiloxane bond (Si
95-120 ppm which is a chemical shift of —O—Si)
It was confirmed by the presence or absence of a nearby peak. (If there is no polysiloxane bond, there is a peak around 85 ppm.) ・ Confirmation of R ¹ O group After dissolving the silicon-containing polymer (P) in a hydrophilic organic solvent such as tetrahydrofuran, 1N-NaOH aqueous solution is added. hand,
The Si—O—R ¹ group is hydrolyzed, and the R ¹ O
The presence or absence of H was confirmed. [Solubility in Organic Solvent] 1 g of the silicon-containing polymer was dissolved in 100 g of each of the following organic solvents by stirring at room temperature for 1 hour.
The residue was taken out by filtration using a filter paper of No.
It was vacuum-dried at 0 ° C. for 2 hours and precisely weighed. The symbols in the table are as follows.

A: Residue is less than 0.2 g O: Residue is 0.2 g or more and less than 0.4 g Δ: Residue is 0.4 g or more and less than 0.6 g X: Residue is 0.6 g or more (organic solvent) Ketone Classes: Acetone Ethers: Tetrahydrofuran (THF) Aromatic hydrocarbons: Toluene Esters: Ethyl acetate

[0108]

[Table 1]

Next, using the polymer obtained above, surface modification of an inorganic material and preparation and molding of a resin composition for a molding material were performed. -Example 1- As a resin (S), 175 parts of a cresol novolak type epoxy resin, a brominated bisphenol A type epoxy resin 12
5 parts, crushed fused silica 65 as inorganic filler (T)
2 parts, antimony trioxide 45 parts, carbon black 3
Part, as the silicon-containing polymer (P), a polymer (P-1) 7
Part, phenol novolak curing agent 140 as curing agent
Parts, 6 parts of 2-methylimidazole as a curing accelerator and 6 parts of carnauba wax as a release agent at 80 ° C. with a heating roll.
The mixture was kneaded for 10 minutes, cooled and pulverized to obtain a resin composition for molding material (1).

Next, the obtained composition (1) was molded by a transfer molding machine (molding conditions: 175 ° C., 2 minutes), and the moldability and the characteristics of the molded body were evaluated. Table 2 shows the results. -Example 2 Resin (S): Cresol novolak type epoxy resin 87 parts Brominated bisphenol A type epoxy resin 63 parts Inorganic filler (T): crushed fused silica 790 parts Antimony trioxide 55 parts Carbon black 5 parts Silicon containing Polymer (P): 40 parts of P-1 Curing agent: 75 parts of phenol novolak-based curing agent Curing accelerator: 4 parts of 2-methylimidazole Release agent: 8 parts of carnauba wax The same procedure as in Example 1 was carried out. Thus, a resin composition (2) for a molding material was obtained. Table 2 shows the results of evaluating the moldability and the properties of the molded body of this composition (2) in the same manner as in Example 1.

Example 3 Resin (S): Cresol novolak type epoxy resin 280 parts Brominated bisphenol A type epoxy resin 170 parts Inorganic filler (T): crushed fused silica 503 parts Antimony trioxide 45 parts Carbon black 2 Part Silicon-containing polymer (P): P-1 11 parts Curing agent: phenol novolak-based curing agent 220 parts Curing accelerator: 2-methylimidazole 5 parts Release agent: carnauba wax 4 parts Similarly, a resin composition for molding material (3) was obtained. Table 2 shows the results of evaluating the moldability and the properties of the molded body of this composition (3) in the same manner as in Example 1.

Comparative Examples 1-4 In Example 2, a silane coupling agent (γ-glycidoxypropyltrimethoxysilane) (Comparative Example 1) and a polymer (P) were used in place of the silicon-containing polymer (P-1). -6)
(Comparative Example 2), Polymer (P-8) (Comparative Example 3), Commercially Available Viscosity Reducing Agent (Polyether-Modified Silicone Compound) (Comparative Example 4), Except Using 40 Parts Each, Same as Example 2 , Resin composition for comparative molding material (4) (Comparative Example 1),
A resin composition for a comparative molding material (5) (Comparative Example 2), a resin composition for a comparative molding material (6) (Comparative Example 3), and a resin composition for a comparative molding material (7) (Comparative Example 4) were obtained. . Table 2 shows the results of the moldability and the properties of the molded articles.

Comparative Example 5 Example 3 was repeated except that 2000 parts of a cresol novolak type epoxy resin and 350 parts of a brominated bisphenol A type epoxy resin were used as the resin (S).
In the same manner as in the above, a resin composition (8) for a comparative molding material was obtained. Table 2 shows the results of the moldability and the properties of the molded body.

Comparative Example 6 In Example 3, the amount of the silicon-containing polymer (P-1) was changed to 1
A comparative resin composition (9) was obtained in the same manner as in Example 3 except that the amount was 80 parts. Table 2 shows the results of the moldability and the properties of the molded body. As shown in Table 2, in Examples, as a result of the surface modification of the inorganic filler (T) by the silicon-containing polymer (P) by the surface modification method of the inorganic material, the fluidity ( Spiral flow), filling properties, mold release properties, mold dirt properties are improved, and excellent moldability and workability are obtained, and the mechanical strength is improved as a result of bending strength, and the durability is excellent. It was confirmed that it became something.
Since such a resin composition for molding materials does not decrease in volume resistivity and flame retardancy, insulating materials for electric devices and electronic parts, sealing materials, flame-retardant materials, especially, as a result of spiral flow, The composition has improved fluidity and has excellent properties as an IC sealing material.

Comparative Example 1 is an example using a silane coupling agent, but has poor fluidity and poor moldability, workability, and mechanical strength. Comparative Example 2 is a silicon-containing polymer (P)
Is produced by using hydrochloric acid as a catalyst, the moldability and the workability are slightly deteriorated, and the volume resistivity of the molded body is lowered to deteriorate the electric insulation. Further, the bending strength after the moisture resistance test also decreases.

In Comparative Example 3, the polymer used in place of the silicon-containing polymer (P) had a Si—O—C bond between the main chain of the polymer and the Si atom. Strength decreases. Comparative Example 4 is an example in which a commercially available dispersant was used, but the moldability and workability were slightly lowered, and the bending strength after the moisture resistance test was lowered.

In Comparative Example 5, the amount of the inorganic filler (T) was (S)
In an example in which the amount is less than 20% with respect to the total amount of + (T), moldability and workability are deteriorated, and electric insulation and flame retardancy are poor. In Comparative Example 6, the amount of the silicon-containing polymer (P) was 3
Although it exceeds 0%, the moldability and workability slightly deteriorate.

[0118]

[Table 2]

(Evaluation items) Spiral flow: Transfer molding method (molding temperature: 175 ° C., molding pressure: 70 kg / cm) using an EMMI standard mold
Measured according to ² ). The larger the value, the better the moldability. Filling property, mold release property, mold stainability, appearance of molded product: using a mold for encapsulating and molding transistor elements, transfer molding after frame loading (molding temperature 175 ° C, molding pressure 70kg /
cm ² ).

：: good △: normal ×: poor Volume resistivity, bending strength: the test piece was post-cured (175 ° C., 8
The measurement was performed according to JIS K-6911. Flame retardancy: according to US standard UL94. -Example 4 Resin (S): bisphenol A type epoxy resin 400 parts Inorganic filler (T): crystalline silica 100 parts aluminum hydroxide 500 parts Silicon-containing polymer (P): P-3 5 parts Curing agent: anhydrous After kneading 35 parts of phthalic acid at 80 ° C. for 10 minutes using a kneader, the mixture was cooled and pulverized to obtain a resin composition for molding material (10).

Next, the obtained composition (10) was mixed with 500
The mixture was placed in a ml beaker, heated at 120 ° C., and evaluated for viscosity and sedimentation stability when allowed to stand. The composition (1
0) was formed by casting (160 ° C., 10 hours), and the bending strength of the obtained formed body was measured. Table 3 shows the results. -Example 5-In Example 4, instead of crystalline silica and aluminum hydroxide, 500 parts of milled fiber and 50 parts of a silicon-containing polymer (P-3) were used as the inorganic filler (T). In the same manner as in Example 4, a resin composition for molding material (11) was obtained.

Table 3 shows the results of evaluation of viscosity, sedimentation stability and bending strength. -Comparative Examples 7 and 8-In Example 4, instead of the silicon-containing polymer (P-3), 50 parts of a titanate-based coupling agent (tetraoctylbis (ditridecylphosphite) titanate) (Comparative Example 7) or a polymer ( P-9) In the same manner as in Example 4 except that 50 parts (Comparative Example 8) were used, resin compositions (12) and (13) for comparative molding materials were obtained. Table 3 shows the results of evaluation of the viscosity, sedimentation stability and bending strength.

[0123]

[Table 3]

(Evaluation items) Viscosity: Measured with a B-type viscometer Sedimentation stability ：: After 30 minutes of standing, the supernatant is less than 10 ml. Δ: 〃 １０ 10 ml or more and less than 50 ml. ×: 〃 で 50 ml or more. Flexural strength: evaluated according to JIS K-6911.

As shown in Table 3, in Examples, the surface of the inorganic filler (T) was modified by the method of modifying the surface of the inorganic material, and the resulting resin composition for molding material was
It is excellent in moldability and workability due to a decrease in viscosity, and has improved sedimentation stability of the inorganic filler (T) in the composition, has good mechanical strength, and is durable in its strength. It was confirmed that the property was good. Accordingly, the inorganic filler (T) is uniformly dispersed in the obtained molded body, and is useful as an insulating material or a flame-retardant material.

Reference Example 1 Resin (S): 500 parts of ethylene-ethyl acrylate copolymer Inorganic filler (T): 500 parts of aluminum hydroxide Silicon-containing polymer (P): 10 parts of P-4 at 150 ° C. The mixture was kneaded using a Brabender plastmill for 30 minutes, and after cooling, a resin composition for molding material (14) was obtained.

Next, the fluidity of the obtained resin composition for molding material (14) was evaluated by a flow tester.
Further, the stain resistance of the mold at the injection port of the flow tester was also evaluated. Further, the tensile strength was measured according to JIS K-7113. Table 4 shows the results. - Example 6 - Resin (S): PVC 700 parts inorganic filler (T): antimony trioxide 200 parts of calcium 100 parts silicon-containing polymer carbonate (P): P-5 30 parts of plasticizer dioctyl phthalate 250 parts Stabilizer: 20 parts of lead stearate was kneaded using a heating roll at 160 ° C. for 10 minutes, and after cooling, a resin composition for molding material (15) was obtained.

Next, the fluidity, mold stainability and tensile strength of the obtained resin composition for molding material (15) were measured. Table 4 shows the results. -Comparative Examples 9 and 10 -In Comparative Example 1 and Example 6 , except that the silicon-containing polymer (P) was not used, the resin composition for comparative molding material (16) (Comparative Example 9) and Comparative Molding Material Resin composition (1
7) (Comparative Example 10) was obtained, and the fluidity, mold stainability, and tensile strength were measured.

[0129] - In Comparative Example 11 Reference Example 1, except that the inorganic filler aluminum hydroxide (T) had a 4600 parts in the same manner, thereby obtaining a comparative material for molding the resin composition (18), fluidity, The mold stainability and the tensile strength were measured.

[0130]

[Table 4]

As shown in Table 4, in the examples, the moldability and workability are excellent due to the improvement of the fluidity and mold stainability, and the mechanical strength and durability are good. Clearly, it is useful as a flame retardant material . - Example 7 - silicon-containing polymer (P-1) in toluene 40 g 0.1 g
Was dissolved, and 10 g of aluminum hydroxide (powder having an average particle diameter of 0.6 μm) was added thereto. After stirring and mixing well, toluene was distilled off by an evaporator. The resulting powder is then reduced to 110
After drying under reduced pressure at ℃, the surface of aluminum hydroxide was modified with a silicon-containing polymer (P-1). 2.5 g of this powder was mixed with 47.5 g of xylene, and further mixed with glass beads 10.
g was added and shaken for 30 minutes with a paint machine. About
, Aliquot 50ml into test tubes, shake again
, And the sedimentation stability was evaluated . There was no supernatant after 5 minutes.

[0132] - Comparative Example 1 2 - full E sulfonyl trimethoxysilane in xylene 47.5g
0.1 g of calcium carbonate (average particle size 3.1).
2.5 g of powder (μm) and further added glass beads 1
0 g was added, and the mixture was shaken for 30 minutes with a paint machine to evaluate the sedimentation stability. Calcium carbonate sedimented immediately and the supernatant liquid became 35 ml in less than one minute.

[0133] Example 7, as shown in Comparative Example 1 2, by using a silicon-containing polymer (P), sedimentation stability of the inorganic filler (T) is improved. -Example 8 -A solution in which a silicon-containing polymer (P-1) is dissolved in an acrylic-urethane paint ("Arotan 2060" manufactured by Nippon Shokubai Co., Ltd., resin solid content 60%) in toluene (polymer concentration:
50%) is added to the resin solids by 4%, and titanium oxide (powder having an average particle diameter of 0.3 μm) as a white pigment is added to the resin solids by 41%, and the paint shaker is used for 30 minutes together with the glass beads. A white paint was prepared by mixing.

On the other hand, a colored paint was prepared in the same manner except that iron oxide was used as a pigment instead of titanium oxide at 20% based on the resin solid content. The white paint and the colored paint were mixed at a weight ratio of 8: 2, and were flow-coated on a tin plate, and the color difference between the flow-coated surface and the portion rubbed with a finger when semi-dried was measured (the coated film was coated). Immediately after (in this case, there is no color separation because the pigment is well mixed) and in semi-dry (in this case, if the dispersion of the pigment is poor, the sedimentation of one of the pigments is fast and the color separation occurs). Measurement) and color separation, ΔL (degree of whiteness) was 0.12.
ΔE (degree of yellowness) was 0.10, and there was almost no color separation.

On the other hand, a trimer of hexamethylene diisocyanate (NC
37% based on the resin solid content was added to the untreated steel sheet and coated with a film applicator. The film thickness before drying was 76 μm. Then, after drying at room temperature for 10 hours, it was further heated at 80 ° C. for 1 hour to form a coating film. The obtained coating film had no roughness, the adhesion of the coating film was 100/100, and the pencil hardness was 3H.

[0136] - Comparative Example 1 3 to 1 5 - In Example 8, the type of silicon-containing polymer was performed in the same manner as in Example 8 except that as shown in Table 5. Table 5 shows the results.

[0137]

[Table 5]

As shown in Table 5, the silicon-containing polymer (P)
Is used, the dispersibility of the inorganic filler (T) is improved. As a result, color separation was prevented, the roughness of the obtained coating film was eliminated, and the adhesion between the coating film and the substrate, the surface hardness of the coating film, and its durability were improved.

[0139]

According to the present invention, a surface modifier for an inorganic material is provided.
Is composed of the specific silicon-containing polymer (P), and the method for modifying the surface of an inorganic material according to the present invention uses the silicon-containing polymer (P). Adhesion and durability can be improved. For example, when the inorganic material is an inorganic filler (T), the dispersibility of the inorganic filler (T) in various organic media and the adhesion between the organic medium and the inorganic filler (T) in plastics and rubbers are improved. At the same time, the strength of the finally obtained product and its durability can be increased. In the paint, the sedimentation stability is increased by improving the dispersibility of the inorganic filler (T), and the finally obtained coating film is free from color separation and roughness, and improves the strength and durability of the coating film. be able to. Also,
When the inorganic material is an inorganic substrate, the wettability, adhesion (adhesion), and durability of the inorganic substrate with the paint, adhesive, adhesive, and sealing agent are improved.

The above-mentioned improvement effect is maintained for a long period of time even when the surface-modified inorganic material of the present invention is placed in a heated and humid atmosphere or in hot and cold water for a long time. The resin composition for a molding material according to the present invention has a low viscosity, is excellent in workability and moldability, and can be highly filled with an inorganic filler (T). The sedimentation stability is improved. The molded article has an increased mechanical strength, and the strength is maintained for a long period of time, and the durability is improved. Therefore, the resin composition for molding materials is useful in various fields, for example, insulating materials (high-voltage insulating materials, high-frequency insulating materials, wiring boards, switchboards, etc.) for electric equipment and electronic parts, sealing materials ( It is suitably used as an IC sealing material, a flame-retardant material (electric wires, cables, electric products, etc.), a flame-retardant building material (ceiling material, artificial marble, etc.), and the like.

The inorganic filler dispersion and the composite material according to the present invention are conveniently used for the above resin composition for molding materials and the like.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 101/00 C08L 101/00 C09C 1/28 C09C 1/28 (56) References JP-A-62-197423 ( JP, A) JP-A-5-25278 (JP, A) JP-A-4-198278 (JP, A) JP-A-60-163973 (JP, A)

Claims (10)

(57) [Claims] 1. A (meth) acrylic resin, polystyrene,
Polyvinyl acetate, polyolefin, polyvinyl chloride,
Vinylidene chloride, polyester resin, copolymerization of these
In the body and in resins that have been modified from some of these resins
The backbone of the al chosen polymer, directly or indirectly by Si-C bonds, at least one polysiloxane group
And have a number average molecular weight of 1,000 to 1,000.
In the range of 0,000, all a silicon-containing polymer is soluble in an organic solvent, except that all of the Si atoms of the previous SL in the polysiloxane group is whether polysiloxane bond binds to a main chain, R ¹ O group [R ¹ is an alkyl group which may be substituted hydrogen atom or a C number 1 to 5, R ¹
Are present in one molecule, a plurality of R ¹ may be the same or different from each other. And a surface modifier for an inorganic material comprising a silicon-containing polymer. 2. The method according to claim 1, wherein the silicon-containing polymer is a reactive silane described below.
At least one selected from compounds (A) and
At least one selected from the compound (B)
Obtained by co-hydrolytic condensation in the presence of a soluble solid catalyst (C).
0.1 to 50% by weight of the polymerizable polysiloxane (D)
The polymerizable polysiloxane (D) having one unsaturated group,
Monofunctional monomer (E) copolymerizable with 99.9-50
wt% (however, the total amount of (D) and (E)
Is 100% by weight).
The surface modifier for an inorganic material according to claim 1. (A) a reactive silane compound represented by the following general formula
Stuff. [Wherein R ¹ is a hydrogen atom or a C 1-5
An alkyl group which may be substituted; R ² is a hydrogen atom or
Is a methyl group; R ³ is a divalent organic group;
The numbers R ¹ may be the same or different. ] (B) a silane compound represented by the following general formula. Si (OR ¹ ) ₄ ... [In the general formula, R ¹ is the same as described above. Multiple in one molecule
The numbers R ¹ may be the same or different. ] 3. The method according to claim 1, wherein the surface modifier is
A method for modifying the surface of an inorganic material, which is brought into contact with an inorganic material. 4. The method according to claim 3, wherein the inorganic material is inorganic particles.
The method for modifying a surface of an inorganic material as described above. 5. The method according to claim 1, wherein the inorganic material is an inorganic filler.
0.1-30wt% of surface modifier based on filler
The table of the inorganic material according to claim 3, wherein the inorganic material is brought into contact.
Surface modification method. 6. The surface modifier according to claim 1 or 2,
At least one resin and at least one inorganic filler;
As an essential component, the mixing ratio of the inorganic filler is the resin
In the range of 20 to 90% by weight based on the total amount of
And the surface modifier with respect to the inorganic filler.
For molding materials whose compounding ratio is in the range of 0.1 to 30 wt%
Resin composition. 7. The resin in which an epoxy resin is essential.
The inorganic filler is fused silica and / or crystalline silica
The molding material according to claim 6, wherein Rica is essential.
Resin composition. 8. The method according to claim 1 or 2, wherein
The inorganic filler attached to the surface is dispersed in the organic medium.
, An inorganic filler dispersion. 9. A surface modifier according to claim 1 or 2,
An inorganic filler component obtained by mixing an inorganic filler and an organic medium.
Dispersal. 10. The surface modifier according to claim 1 or 2.
Is a composite material formed by adhering to inorganic particles.