JPH09241338A - Organosilicon polymer composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organosilicon polymer composition having excellent storage stability and showing good workability in mixing with e.g. an inorganic filler without dissolving it in an organic solvent by mixing a specified silicon- containing polymer with a specified low-molecular liquid compound. SOLUTION: This composition contains 15-90 pts.wt. silicon-containing polymer (a) containing at least one R<1> O group [wherein R<1> is hydrogen or a l-5C (un)substituted alkyl, provided that R<1> s may be the same or different from each other when a plurality of R<1> s are present in the molecule] and at least one polysiloxane group at least one of the Si atoms of which is bonded to R<1> O to form an Si-O-C bond in the molecule and being soluble in the following compound (b) and 10-85 pts.wt. (the total is 100 pts.wt.) normally liquid compound (b) having a solubility parameter(SP) of 8 or above and a molecular weight of 190 or above.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organosilicon polymer composition and a method for producing the same.

[0002]

2. Description of the Related Art The surface of an inorganic material is modified by bringing it into contact with an inorganic material to improve the wettability and dispersibility of the inorganic material with respect to the organic medium and the interfacial adhesion between the organic medium and the inorganic material. As a material that can be made,
A silicon-containing polymer disclosed in JP-A-6-228457 is known. It is known that the resin composition for a molding material containing this silicon-containing polymer is excellent in various characteristics such as electric characteristics, heat resistance, flame retardancy, moldability, workability, mechanical strength (see the above publication). ).

[0003]

However, the use of a treatment agent for an inorganic filler used in a molding material or the like containing nearly 100% of the above-mentioned silicon-containing polymer causes the following problems. (1) Since the silicon-containing polymer has a Si—OR group, it hydrolyzes and condenses over time during storage, and thus crosslinks.
Even if it is used as a molding material, the above properties will not be exhibited.

(2) Since the silicon-containing polymer is often a starch syrup-like liquid or a solid that does not fluidize unless heated to a high temperature, it is weighed or mixed with an inorganic filler or the like. The workability at the time is poor, and it takes a long time to mix, or it may be necessary to heat at the time of mixing. In order to solve the problems of (1) and (2) above, it is possible to use it in the form of a commonly used organic solvent solution, but even if such a solution is used, the problem of (1) above can be solved. It cannot be resolved enough. Further, even if the problem (2) above can be solved, a new problem (3) below arises, and it cannot be used as a treating agent or the like.

(3) Since the organic solvent causes foaming during mixing of the molding material and poor appearance of the resulting molded article, a solution prepared by dissolving the silicon-containing polymer in an organic solvent is mixed with an inorganic filler or the like. After that, it is necessary to remove the organic solvent, and large-scale processing equipment is required for that. Then, the subject of this invention is excellent in the storage stability of the said silicon-containing polymer, and is excellent in workability at the time of weighing, mixing with an inorganic filler, etc., even if the said silicon-containing polymer is not dissolved in an organic solvent. An object is to provide an organosilicon polymer composition and a method for producing the same.

[0006]

The organosilicon polymer composition according to the present invention comprises (a) at least one R ¹ O group [R ¹ is a hydrogen atom or a C 1-5 substituted group per molecule. In the case where there are plural R ^{1 s} in one molecule, which are optionally substituted, plural R ^{1 s} may be the same or different from each other. ] And at least one polysiloxane group, and at least one Si atom in the polysiloxane group is bonded to the R ¹ O group to form a Si—O—C bond. The polysiloxane group is Si
A silicon-containing polymer having a structure in which a main chain is directly or indirectly bound by a -C bond and soluble in the following compound (b); and (b) a solubility parameter (S) of 8 or more.
P) and a compound having a molecular weight of 190 or more and being liquid at room temperature, in a total of 100 parts by weight of both, the silicon-containing polymer (a) 15 to 90 parts by weight, the compound (b) 10
It is contained in an amount of about 85 parts by weight.

The composition for treating an inorganic filler according to the present invention comprises the organosilicon polymer composition according to the present invention.
The method for producing the organosilicon-based polymer composition according to the present invention includes the following general formulas:

[0008]

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[0009]

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[0010]

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[Wherein R ¹ is a hydrogen atom or an optionally substituted alkyl group having 1 to 5 C atoms; R ² is a hydrogen atom or a methyl group; R ³ is a divalent organic group; R ⁴ Is a hydrogen atom or an optionally substituted group selected from an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an acyl group, and s, t and u are independently 0.
Or 1, and a plurality of R ^{1 s in} one molecule may be the same or different. ] At least one selected from the reactive silane compounds (A) represented by the following formula and the following general formula: R ⁴ _p Si (OR ¹ ) _4-p ... [In the general formula, R ¹ and R ⁴ are the same as the above; p is 0
It is an integer of 2. A plurality of R ¹ in one molecule may be the same or different. When a plurality of R ⁴ are present in one molecule, the plurality of R ⁴ may be the same or different. And at least one selected from the silane compounds (B) shown below in the presence of a solid catalyst (C) insoluble in the system,
Monofunctional monomer having 0.1 to 50 wt% of a polymerizable polysiloxane (D) obtained by co-hydrolytic condensation and one unsaturated group and copolymerizable with the polymerizable polysiloxane (D). Silicon-containing polymer (a) by copolymerizing (E) 99.9 to 50 wt% in an organic solvent (however, the total amount of (D) and (E) is 100 wt%).
And a step of substituting the organic solvent with a compound (b) having a solubility parameter (SP) of 8 or more and a molecular weight of 190 or more and being liquid at room temperature.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

[Silicon-containing polymer and method for producing the same] Silicon-containing polymer (a) contained in the organosilicon-based polymer composition of the present invention
Improves the wettability and dispersibility of the inorganic filler with respect to the resin for molding materials, and improves the interfacial adhesion between the resin and the inorganic filler, by modifying the surface by contacting with the inorganic filler. It is an ingredient that causes it.

The polysiloxane group contained in the silicon-containing polymer (a) is a group in which two or more Si atoms are linearly or branched linked by a polysiloxane bond (Si-O-Si bond). is there. S which this polysiloxane group has
The number of i atoms is not particularly limited, but the effect of modifying the surface of the inorganic filler is further improved, whereby the viscosity, fluidity, moldability and workability of the resin composition for a molding material containing the same are improved. In order to further improve the properties and the mechanical strength of the obtained molded body, on average per polysiloxane group,
It is preferably 4 or more, more preferably 11 or more. 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 hydrolyzability of the R ¹ O group bonded to the Si atom and the inorganic filler Reactivity is reduced. The number of polysiloxane groups is at least 1, and particularly preferably 1 to 3 per molecule of the silicon-containing polymer (a). If it is present in excess of 3, the silicon-containing polymer (a) may act as an aggregating agent, and the dispersibility of the inorganic filler may decrease. When there are a plurality of polysiloxane groups in one molecule of the silicon-containing polymer (a), these plurality of polysiloxane groups may be the same or different from each other.

As described above, the silicon-containing polymer (a) has a structure in which the polysiloxane group is directly or indirectly bonded to the 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). .

In the indirect bond between the polysiloxane group and the polymer main chain, examples of the branch branched from the polymer main chain include the following divalent groups. 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, 3 -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.

The main chain of the silicon-containing polymer (a) is mainly composed of carbon, and the number of carbon atoms participating in the main chain bond is 7
Elements such as N, O, S, Si and P account for 0 to 100 mol% and the balance. The presence of this main chain on the surface of the inorganic filler improves the wettability and dispersibility of the inorganic filler used in rubber molding materials, plastic molding materials, etc. to the resin, and the viscosity of the resin composition for molding materials. Can be reduced to improve the moldability and workability of the molded article, and to improve the mechanical strength of the obtained molded article.

Specific examples of the polymer having the above-mentioned main chain include, for example, (meth) acrylic resin; polystyrene; polyvinyl acetate; polyolefins such as polyethylene and polypropylene; polyvinyl chloride; polyvinylidene chloride; polyethylene terephthalate. And a copolymer thereof, a partially modified resin, and the like. The silicon-containing polymer (a) is a Si atom in a polysiloxane group directly or through one or more carbon atoms constituting the main chain of these resins, or through the above divalent group. Has a structure in which

When the silicon-containing polymer (a) is a polymer having at least a (meth) acrylic monomer unit as a repeating unit, it is effective for treating the inorganic filler used in the molding material, It is preferable because the wettability and dispersibility with respect to the resin are improved. The (meth) acrylic monomer unit is not particularly limited,
For example, acrylic acid; methyl acrylate, ethyl acrylate, butyl acrylate, n-octyl acrylate,
Acrylic acid esters such as 2-ethylhexyl acrylate and lauryl acrylate; Methacrylic acid; Methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate Examples thereof include monomer units such as esters, and among these, the ethyl acrylate monomer unit is most preferable because it is particularly effective as a treating agent for an inorganic filler for a molding material.

The silicon-containing polymer (a) is a rubber molding material,
In order to improve the wettability, dispersibility and adhesiveness of the inorganic filler used in the plastic molding material and the like to the resin, those which are compatible with the resin are preferable. Therefore, it is preferable to use the silicon-containing polymer (a) having a value close to the solubility parameter (SP) of the resin used, and more preferably one having a chemical structure similar to that of the resin.

The Si-OR ¹ group in the silicon-containing polymer (a) is a group which serves as a bonding part between the silicon-containing polymer (a) and the inorganic filler, and the silicon-containing polymer (a) is used as the inorganic filler in Si.
By bonding with the —OR ¹ group, the wettability, dispersibility, adhesiveness and the like of the inorganic filler to the resin can be improved in rubber molding materials, plastic molding materials and the like. R
^{The number of 1} O groups is at least 1 per molecule of the silicon-containing polymer (a), preferably 5 to 400 on average, and more preferably 20 to 300. R ¹ O
If there is no group, the bonding point between the silicon-containing polymer (a) and the inorganic filler is lost, and the wettability, dispersibility and adhesiveness of the inorganic filler to the resin are not expressed. (A) may act as an aggregating agent to lower the dispersibility and adhesiveness.

Here, R ¹ is a hydrogen atom or a C number of 1 to
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 atom in the polysiloxane group is bonded only to the R ¹ O group in addition to the direct or indirect bond with the polymer main chain and the polysiloxane bond (Si-O-Si bond). Is preferred. In such a case, the ionicity of the Si atom is further increased, and as a result, the hydrolysis and condensation rate of the R ¹ O group is further increased, and the number of reaction points with the inorganic filler is increased.

The number average molecular weight of the silicon-containing polymer (a) is
Although not particularly limited, for example, 1,000 to 1,0
Preferably within the range of 0,000, 2,000
More preferably, it is in the range of 0 to 200,000. When the molecular weight is smaller than these ranges, the surface modifying effect is small like the silane coupling agent. On the contrary, when the molecular weight is larger than the above range, it is not preferable because it is used by melting when contacted with the inorganic filler.

The silicon-containing polymer (a) needs to be soluble in the compound (b) described below. The fact that the silicon-containing polymer (a) is soluble in the compound (b) means that the silicon-containing polymer (a) does not have a highly crosslinked structure and exhibits thermoplasticity. It can be examined by the sex test method. The silicon-containing polymer (a) may be soluble in at least one kind or two or more kinds of the compound (b) described below.

The silicon-containing polymer (a) 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-mentioned group, the reaction with the resin or the like is promoted, and the mechanical strength of the obtained molded product is improved. The silicon-containing polymer (a) is, for example, at least one selected from the reactive silane compounds (A) represented by the general formulas to and at least one selected from the silane compound (B) represented by the general formulas. 0.1 to 50 wt% of a polymerizable polysiloxane (D) obtained by co-hydrolysis condensation in the presence of a solid catalyst (C) insoluble in the system, and an unsaturated group of 1
Copolymerizing the polymerizable polysiloxane (D) and the copolymerizable monofunctional monomer (E) 99.9 to 50 wt% (however, the total amount of the above (D) and the above (E)) Is 100 wt%) (hereinafter referred to as method M). However, the present invention is not limited to this, and the silicon-containing polymer (a) may be, for example,
It can also be produced by the methods (i) to (iv) shown below.

(I) After copolymerizing the reactive silane compound (A) with the monofunctional monomer (E), the copolymer obtained and the silane compound (B) and / or the hydrolysis thereof are hydrolyzed. A method of co-hydrolyzing and condensing the condensate in the presence of a catalyst that dissolves in a system such as an inorganic acid or organic acid such as hydrochloric 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 chain transfer ability such as γ-mercaptopropyltrimethoxysilane, the resulting polymer and the silane compound (B) and And / or a method of co-hydrolytically condensing the hydrolyzed condensate thereof in the presence of the above catalyst.

(Iii) A silane compound having chain transfer ability and the silane compound (B) are cohydrolyzed and condensed in the presence of the above catalyst to obtain a polysiloxane compound, and then in the presence of the polysiloxane compound. Said monofunctional monomer (E)
A method of polymerizing. (Iv) After co-hydrolyzing and condensing the reactive silane compound (A) and the silane compound (B) in the presence of the catalyst to obtain a reactive polysiloxane compound, the reactive polysiloxane compound and the above 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 among the methods shown in (i) to (iv) above,
When the unreacted material remains, a foul odor is emitted from the final product such as the molding material. Further, when a catalyst that dissolves in a system such as an inorganic acid or an organic acid or ammonia or an amine is used during the cohydrolytic condensation, gelation occurs during the cohydrolytic condensation or during the polymerization, and the desired silicon-containing polymer ( a) may not be obtained, the obtained silicon-containing polymer (a) may increase in viscosity over time to increase the molecular weight, and in some cases may have poor stability over time such as gelation. is there.
In addition, a method of co-hydrolyzing and condensing after polymerization ((i), (i
In i)), a polysiloxane compound that does not bond to the polymer is generated, and the aggregation of the inorganic filler is promoted to increase the viscosity of the resin composition for molding materials, resulting in a decrease in moldability and workability. is there. Further, in any case, the remaining catalyst may impair the physical properties of the final product (for example, electrical characteristics such as electrical insulation, mechanical strength and durability of the molded product).

On the other hand, the method M has few problems as described above. Therefore, the silicon-containing polymer (a) is most preferably manufactured by this method. Further, in the method M, the polymerizable polysiloxane (D) and the monofunctional monomer (E) are copolymerized in an organic solvent to obtain an organic solvent solution containing the silicon-containing polymer (a). The method of substituting the solvent with the compound (b) described below is particularly preferable because it reduces the mixing of an organic solvent that adversely affects the molding material. [Compound (b)] The compound (b) used in the present invention
Improves the storage stability of the silicon-containing polymer (a) and improves workability during weighing and mixing with an inorganic filler without dissolving the silicon-containing polymer (a) in an organic solvent. It is a component that causes.

The solubility parameter (SP) of the compound (b) is 8 or more. If the SP is lower than this range, the effect of improving the storage stability of the silicon-containing polymer (a) and the workability at the time of weighing and mixing with an inorganic filler becomes insufficient. Further, in order to sufficiently obtain this effect and improve various physical properties (flame retardancy, moldability) of the molding material,
SP is preferably in the range of 8 to 11, and 8.5 to 10.
The range of 5 is more preferable.

Here, the solubility parameter (SP) is a physical property value that can be calculated by the following formula (I) proposed by PS Small, and is applicable to solvents, polymers and the like ("J. Appl. Chem."). Vol. 3, p. 71 (1948)). SP = (d / M) Σ (Δδ) (I) (In the formula, d is the density, M is the molecular weight, and Δδ is a value corresponding to each constituent atomic group shown in Table 1.)

[0032]

[Table 1]

The molecular weight of the compound (b) is 190 or more (preferably 220 or more, more preferably 300 or more).
It is. When the molecular weight is lower than this range, there are problems such as storage stability of the silicon-containing polymer (a), workability during weighing and mixing with an inorganic filler, and poor appearance of the molding material. The compound (b) used is a liquid at room temperature. If a material that is not liquid at room temperature is used, there are problems in the storage stability of the silicon-containing polymer (a), workability during weighing, mixing with an inorganic filler, etc.

The viscosity of the compound (b) is not particularly limited, but at 25 ° C., preferably 10 cps or more,
More preferably 15 cps or more, further preferably 25 cps
s or more. When the viscosity is lower than these ranges, there is a problem in that the appearance of the molding material is poor. Specific examples of the compound (b) are not particularly limited, but aromatic carboxylic acid esters such as phthalic acid esters and benzoic acid esters; succinic acid esters, adipic acid esters, sebacic acid esters, etc. Dibasic acid esters of fatty acids; fatty acid esters such as oleic acid esters and stearic acid esters; phosphoric acid esters such as trialkyl phosphates; epoxy compounds such as epoxycarboxylic acid alkyl esters . From the viewpoints of storage stability of the silicon-containing polymer (a), workability at the time of weighing and mixing with an inorganic filler, etc., phthalic acid esters are preferable, and dialkyl phthalates are more preferable. As the alkyl group contained in the acid dialkyl ester, those having a carbon number of C _{1 to} C ₂₀ are preferable, those having C _{4 to} C ₁₂ are more preferable, C ₈ is further preferable, and 2-ethylhexyl group is most preferable.

In the organosilicon polymer composition of the present invention, the amount of the silicon-containing polymer (a) to be blended is 15 to 90 parts by weight (preferably 20 to 80 parts by weight, more preferably 25 to 30 parts by weight).
70 parts by weight), and the compounding amount of the compound (b) is in the range of 85 to 10 parts by weight (preferably 80 to 20 parts by weight, more preferably 75 to 30 parts by weight). The total amount of (a) and (b) is 100 parts by weight). Even if it contains the silicon-containing polymer (a), the compounding amount of the compound (b) is larger than the above range, or the inorganic filler is treated with a composition using another additive instead of the compound (b). Then, the inorganic filler becomes wet and becomes clay-like, so that the inorganic filler cannot be well dispersed in the resin for molding material or the like. Further, when the compounding amount of the compound (b) is less than the above range, the addition effect of the compound (b) (storage stability of the silicon-containing polymer (a), workability at the time of weighing and mixing with an inorganic filler, etc.) 2) is insufficient, and the treatment of the inorganic filler with the silicon-containing polymer (a) is insufficient. [Method for Producing Organosilicon-Based Polymer Composition] The organosilicon-based polymer composition according to the present invention is preferably produced by, for example, the method for producing an organosilicon-based polymer composition according to the present invention, but is not limited thereto. .

The preferred method M for obtaining the above-mentioned silicon-containing polymer (a) is adopted in the method for producing an organosilicon polymer composition according to the present invention. The reactive silane used in this method M is used. The compound (A) is one represented by any one of the above general formulas. R ¹ , R ² and R ³ are the same as described above. R ⁴ is, as described above, a hydrogen atom,
Or, an alkyl group, a cycloalkyl group, an aryl group,
It is an optionally substituted group selected from an aralkyl group and an acyl group. The C number of R ⁴ is preferably 20 or less. R ⁴
When it is a group, specific examples thereof include methyl,
A linear or branched alkyl group such as ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, pentyl, amyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, octadecyl; cyclopentyl And an alicyclic alkyl group such as cyclohexyl; an aryl group such as phenyl, tolyl, and xylyl; an aralkyl group such as benzyl and phenethyl; an acyl group such as acetyl, propiniol, butyryl, ethoxycarbonyl, and propoxycarbonyl. The substituted alkyl group, cycloalkyl group, aryl group, aralkyl group, and acyl group include, for example, one of the hydrogen atoms contained in each of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and acyl group. Or two or more 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; chlorine,
Examples thereof include groups substituted with halogen such as bromine.

Specific examples of the reactive silane compound (A) represented by the above general formula are γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ- Methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, methacryloxyethoxypropyltrimethoxysilane, γ-methacryloxypropylphenyldimethoxysilane and the like.

Specific examples of the reactive silane compound (A) represented by the above general formula are vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane and the like. Specific examples of the reactive silane compound (A) represented by the general formula include 1-hexenyltrimethoxysilane, 1-octenyltrimethoxysilane, vinyloxypropyltrimethoxysilane, 3-vinylphenyltrimethoxysilane, and 3-vinylphenyltrimethoxysilane. (Vinylbenzylaminopropyl)
And trimethoxysilane.

The reactive silane compounds (A) represented by the general formulas (1) to (3) may be used alone or in combination of two or more kinds. Among the reactive silane compounds (A) represented by the general formulas (1) and (2), the reactive silane compound (A) in which s, t, and u are 0 is preferable because it has a high hydrolysis condensation rate and can be easily obtained. 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. .

Silane compound (B) used in the present invention
Is represented by the general formula, and specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane,
i-propyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, alkoxysilane compounds such as dimethoxydiethoxysilane, phenyltrihydroxysilane, diphenyldihydroxysilane, etc. Silanol compounds and the like, each of which is used alone or in combination of two or more. Among the silane compounds (B) represented by the general formula, silane compounds (B) having p = 0
Is preferred because it has a high hydrolysis-condensation rate and can be easily obtained. In particular, the rate of hydrolysis and condensation is high, and the R ¹ O
From the viewpoint that H can be easily removed from the system, those in which R ¹ is an alkyl group having 1 to 3 C atoms are preferable, and those in which R ¹ is a methyl group are particularly preferable.

The above-mentioned reactive silane compound (A) and silane compound (B) may be used in arbitrary ratios, but the organosilicon polymer composition is used as a treating agent for inorganic fillers or a resin composition for molding materials. When used, at least one reactive silane compound (A) selected from the general formulas-and at least one silane compound (B) represented by the general formula are used, and their use ratio is (A). And (B), the total amount of (A) is 0.1 to 30 mol%, preferably 1 to 20 mol%, and (B) is 99.9 to 70 mol%, preferably 99 to 80 mol%. It is within the range of%.
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 double bond groups in the polymerizable polysiloxane (D) is preferably 1 to
There are four ranges. The solid catalyst (C) insoluble in the system used in the present invention is used in order to improve the temporal stability of the obtained silicon-containing polymer (a) and not to deteriorate the physical properties of the final product. Is (A), (B), water,
There is no particular limitation as long as it is insoluble in both 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 (from Rohm and Haas); Dowex MWC-1
-H, Dowex 88, Dowex HCR-W2
(The above is a product of Dow Chemical Company); Levatit SPC-1
08, Levatit SPC-118 (manufactured by Bayer AG); Diaion RCP-150H (manufactured by Mitsubishi Kasei); Sumikaion KC-470, Duolite C26
-C, Duolite C-433, Duolite-464
(Above, 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 (or more, ROHM
And Haas). (C-3) A group containing a protonic acid group is bound to the surface
Inorganic solid : Zr (O ₃ PCH ₂ CH ₂ SO ₃ H)
₂ , Th (O ₃ PCH ₂ CH ₂ COOH) _{2 and the} like. (C-4) Polyorganosiloxane containing a protonic acid group
Sun : 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, tantalic 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 etc. (C-13) a group containing an amino group bonded to the surface
Inorganic solids : such as solids obtained by reacting aminopropyltriethoxysilane on silica gel. (C-14) Polyorganosiloxa containing amino group
Down: an amino-modified silicone resin.

At least one of these catalysts is used to carry out the cohydrolysis condensation reaction of the compound (A) and the compound (B). 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)
Since it affects the storage stability of and the gelation suppression when it is further subjected to polymerization, water is preferably 70 to 140 mol%, more preferably 90 to 140 mol% with respect to the total number of moles of (A) and (B). It is preferable to use it in a ratio within 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 it is 70 mol% or more based on the total number of moles of (A) and (B), the average number of Si atoms in the polymerizable polysiloxane (D) is 4 or more, preferably 11 or more,
Therefore, the number of Si atoms in the obtained polysiloxane group of the silicon-containing polymer (a) is determined by the polysiloxane group 1
It is easy to set an average of 4 or more per piece, preferably 11 or more on average.

The hydrolysis reaction of the compounds (A) and (B) is
It can be carried out by the conventional method,
Below or can dissolve (A), (B) and water
The reaction is performed in a solvent inert to these compounds. As a solvent
Means methanol, ethanol, propanol, butanol
Alcohols such as acetone, methyl ethyl ketone, etc.
Ketones; A such as tetrahydrofuran and dioxane
Ters etc. can be used, but preferably the boiling point is 100 ° C or higher.
The one below. This is done by distilling the solvent.
This is because it can be easily removed. Reaction temperature and time are raw materials
The temperature varies from room temperature to 150 ° C.
Preferably at a temperature of 50-100 ° C for 10 minutes to 5 hours
It is preferable to carry out within the range. High temperature or long reaction time
Is preferred because polymerization of the double bond group of (A) occurs.
Not good. The pressure during the reaction is 1 × 10 ^-3~ 7600 Torr
A range is preferred.

A polymerization inhibitor may be added to this reaction system. 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 has, 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 acid esters. , Methacrylic acid esters, crotonic acid esters, itaconic acid esters, maleic acid esters, fumaric acid esters and other unsaturated carboxylic acid esters; acrylamides; methacrylamides; allyl compounds; vinyl ethers; vinyl esters At least one compound selected from styrenes, vinyl nitriles, and the like.
Above all, when the monofunctional monomer (E) is a monomer containing at least a (meth) acrylic monomer such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, the inorganic filler for a molding material is It is preferable because it is effective as a treating agent.

The ratio of (D) and (E) when the polymerizable polysiloxane (D) and the monofunctional monomer (E) are copolymerized 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%. If the content of (D) is less than 0.1 wt%, the content of the silicon-containing polymer having a polysiloxane group in the silicon-containing polymer (a) may be small. May occur, and the stability of the obtained silicon-containing polymer with time may deteriorate.

The method for copolymerizing the polymerizable polysiloxane (D) and the monofunctional monomer (E) is not particularly limited, and a conventionally known method can be adopted. For example, in the presence of a radical initiator, Any method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization may be used. However, in methods other than solution polymerization, the resulting silicon-containing polymer becomes a polymer having a high degree of cross-linking structure and is insoluble in compound (b), so surface modification of the inorganic filler becomes insufficient, and Even as a resin composition for a molding material, the dispersibility of the inorganic filler cannot be improved, and the effect is difficult to be exhibited. 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, but when used in a large amount, the amount of heat generated increases and it becomes difficult to control the reaction. On the other hand, when used in a small amount, a highly crosslinked structure is generated, and the compound Since it is likely to become insoluble in (b), it is preferably used in the range of 0.5 to 7 wt%, more preferably 1 to 4 wt% with respect to the total amount of (D) and (E).

The organic solvent used for the solution polymerization is not particularly limited as long as it can dissolve the polymerizable polysiloxane (D) and the monofunctional monomer (E), and specific examples thereof include ketones, esters and aromatics. 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 compound (b) may be used as an organic solvent. In this case, the replacement step described below is unnecessary.

The temperature at the time of copolymerization can be appropriately selected depending on the polymerization method and the radical polymerization initiator used, but from the viewpoint of easy control of the reaction, it is 30 to 200 ° C., preferably 50 to 150 ° C. The range is. 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 carrying out the polymerization is, for example, 1 to 1.
2 hours

The method of replacing the organic solvent with the compound (b) after copolymerizing the polymerizable polysiloxane (D) and the monofunctional monomer (E) in the organic solvent is not particularly limited. , For example, a polymerizable polysiloxane (D) and a monofunctional monomer (E) are copolymerized in an organic solvent having a lower boiling point than the compound (b) to obtain a silicon-containing polymer (a).
The compound (b) is added to the organic solvent solution of, and the organic solvent is distilled off by heating under conditions such as normal pressure, reduced pressure, or increased pressure; from the organic solvent solution of the silicon-containing polymer (a). The organic solvent under normal pressure, under reduced pressure or pressure, etc.,
Examples include a method of adding the compound (b) after heating and distilling. [Use of Organosilicon-Based Polymer Composition] The inorganic filler-treating composition of the present invention comprises the above-mentioned organosilicon-based polymer composition.

The inorganic filler treated with the organosilicon polymer composition of the present invention is not particularly limited, but is preferably one selected from the groups Ia to Va, Ib to VIIb and VIII of the periodic table. Oxides, hydroxides, sulfides, carbides, nitrides, sulfates, carbonates, phosphates and ferrocyanides of the above metals; carbon; and Periodic Table IIIa
It is at least one selected from metal materials composed of at least one metal element selected from Group Ib to Group IIb to Group VIII. Specific shapes of the inorganic filler include, but are not limited to, a granular shape, a spherical shape, a hollow shape, a fibrous shape, a scale shape, a plate shape (or a flake shape), and the like.
The following are more specific examples.

-Inorganic filler- (Oxide): titanium dioxide, zinc oxide, ferric oxide, acid
Chromium oxide, cuprous oxide, cupric oxide, antimony trioxide,
Antimony pentoxide, silicon dioxide, alumina, tin oxide,
Potassium titanate, magnesium oxide, cobalt blue
(CoO nAl_TwoO_Three), Cobalt green (CoO)
・ NZnO), titanium green (TiO) _Two・ CoO ・ N
iO.ZnO), titanium yellow (TiO)_Two・ NiO ・
Sb_TwoO _Three), Iron black (Fe_ThreeO_Four), Talc [Mg_ThreeS
i_FourO_Ten(OH)_Two], Leadtan (Pb_ThreeO_Four), Sub-oxidation
Lead, basic lead chromate (PbCrO_Four・ PbO), lead acid
Calcium, zinc chromate, clay, barium ferrai
G, 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_Three・ Mg (OH)_Two・ 4H_TwoO] and the like. (Phosphate): Zinc phosphate, zinc potassium phosphate, Kova
Ruto purple [Co_Three(PO _Four)_Two〕etc.

(Borate): Zinc borate, etc. (Ferocyanide): Dark blue (Fe ₃ K ₃ [Fe (C
N) ₆ ] ₃ ), cyanide lead, etc. (Carbon): carbon black, graphite and the like. (Metal): Al, Zn, Ni, Cu, Fe, Ag, Au
etc.

The method of modifying the surface of the inorganic filler using the organosilicon polymer composition of the present invention is carried out, for example, in the following manner, but is not limited to these manners. A method of mixing an organosilicon-based polymer composition and an inorganic filler;
A method of spraying on a well-stirred inorganic filler; a method of adding an organosilicon polymer composition when melt-kneading a resin and an inorganic filler and performing extrusion molding or injection molding; polymerization for synthesizing a resin A method in which an organosilicon polymer composition is added to and dissolved in the previous monomer or oligomer, and then an inorganic filler is added to form a slurry, and then cast polymerization or the like is performed; The surface of the inorganic filler is surface-modified with the organosilicon polymer composition by contacting the composition with the inorganic filler.

When the inorganic filler and the organosilicon polymer composition are brought into contact with each other, the ratio of the silicon-containing polymer (a) to the inorganic filler is preferably 0.1 to 30% by weight, more preferably 0.5. 10 to 10 wt%. When the proportion of the silicon-containing polymer (a) is small, the amount of the silicon-containing polymer (a) bound to the inorganic filler is small, and therefore the dispersibility and adhesiveness of the inorganic filler to the organic medium may be low. On the contrary, since the silicon-containing polymer (a) which remains without being bonded to the surface of the filler exists, the adhesiveness may be lowered.

As described above, when the surface-modified inorganic filler is added during the melt-kneading of the resin, or the surface of the inorganic filler is modified during the melt-kneading of the resin, the inorganic filler is added to the resin. While the dispersibility is improved, the fluidity of the compound at the time of extrusion molding or injection molding is increased, and the high filling of the inorganic filler and the workability are improved. Moreover, since the adhesiveness at the interface between the resin and the inorganic filler is improved, the strength of the finally obtained plastic product or rubber product is increased. When melt-kneading is performed, the temperature at which the melt-kneading is performed is preferably a temperature equal to or higher than the melting point of the resin and lower than the decomposition temperature.

As described above, when the surface-modified inorganic filler is added to the monomer or oligomer before polymerization for synthesizing the resin, or when the slurry is prepared, the inorganic filler is surface-modified. The slurry thinning effect (the viscosity of the monomer-containing liquid decreases as compared with the case of adding the conventional surface-modified filler) and the dispersibility of the inorganic filler are increased, so that the slurry is highly filled and workability is improved. improves. Further, as a result of improving the adhesiveness at the interface between the generated resin and the filler, the strength of the obtained plastic product or rubber product is increased. When the silicon-containing polymer (a) has a reactive group such as an epoxy group, a hydroxyl group, an amino group or an acidic functional group, the resin and the silicon-containing polymer (a) are polymerized in the polymerization process.
And are combined, and the adhesiveness is further improved.

[0062]

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.
Unless otherwise specified, "%" and "part" are "wt".
"%" And "parts by weight" are shown. First, a silicon-containing polymer was produced by the following method.

-Example 1- In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube, 49.6 g (..0%) of γ-methacryloxypropyltrimethoxysilane as a reactive silane compound (A).
2 mol), tetramethoxysilane 121.6 g (0.8 mol) as a silane compound (B), methanol 100 g as a solvent, water 18 g (1 mol), and Amberlyst 15 (Rohm and Haas as a solid catalyst (C)).・ 5 g of a cation exchange resin manufactured by Japan Co., Ltd.) was added, and the mixture was stirred and reacted for 2 hours under reflux of methanol (65 ° C.). After cooling to room temperature, Amberlyst 15 was filtered off to obtain a polymerizable polysiloxane (D-1) having a number average molecular weight of 1000 (solid content: 40.4%).

[0064] Then, a stirrer, a dropping inlet, a thermometer, a methanol 300g entered as 1 liter organic solvent in a glass reactor equipped with a condenser and N ₂ gas inlet, N ₂
While introducing gas, methanol was adjusted to a temperature of 64 ± 2 ° C. Then, with stirring, 49.5 g of the polymerizable polysiloxane (D-1), 170 g of ethyl acrylate and 10 g of butyl methacrylate, and 4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator. The mixed solution was dropped from the dropping port over 4 hours. After stirring for 1 hour at the same temperature after dropping,
0.4 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added twice every 1 hour, and the mixture was heated for 2 hours to carry out copolymerization, whereby the silicon-containing polymer (a) became methanol. A dissolved solution (solid content 39%) was obtained.

Di-2-ethylhexyl phthalate (solubility parameter (SP) as compound (b) was added to this solution.
8.85, molecular weight 390.6, viscosity 54 cps (25 ° C)) 3
After adding 00 g, methanol was distilled off under reduced pressure to obtain 40% of the silicon-containing polymer (a) and di-2-phthalic acid.
An organosilicon polymer composition (1) consisting of 60% ethylhexyl was obtained.

-Example 2- In Example 1, as the compound (b), di-phthalic acid was used.
Diethyl phthalate instead of 2-ethylhexyl (solubility parameter (SP) 10.1, molecular weight 222.2,
A silicon-containing polymer (a) 8 was prepared in the same manner as in Example 1 except that a viscosity of 13 cps (25 ° C.) was used.
An organosilicon polymer composition (2) consisting of 0% and diethyl phthalate 20% was obtained.

Example 3 In Example 1, as the compound (b), phthalic acid di-
Ditridecyl phthalate (solubility parameter (SP) 8.79, molecular weight 53 instead of 2-ethylhexyl)
An organosilicon polymer comprising 20% of the silicon-containing polymer (a) and 80% of ditridecyl phthalate was obtained by performing the same operation as in Example 1 except that 0.8 and the viscosity was 327 cps (25 ° C.)). A composition (3) was obtained.

-Comparative Example 1-Methanol was distilled off under reduced pressure from the solution of the silicon-containing polymer (a) dissolved in methanol obtained in Example 1, and then ethylene glycol monobutyl ether acetate (solubility parameter (SP) 8. 67, molecular weight 160.22) was added to obtain a comparative organosilicon polymer composition (1) consisting of 40% of the silicon-containing polymer (a) and 60% of ethylene glycol monobutyl ether acetate.

Comparative Example 2-Methanol was distilled off under reduced pressure from the solution of the silicon-containing polymer (a) dissolved in methanol obtained in Example 1, and then hexadecane (solubility parameter (SP) 7.83, molecular weight 226). ) Was added to obtain a comparative organosilicon polymer composition (2) composed of 25% of the silicon-containing polymer (a) and 75% of hexadecane.

Comparative Example 3-Di-2-ethylhexyl phthalate was added to the solution obtained in Example 1 in which the silicon-containing polymer (a) was dissolved in methanol, and then methanol was distilled off under reduced pressure. ,
A comparative organosilicon polymer composition (3) consisting of 95% of the silicon-containing polymer (a) and 5% of di-2-ethylhexyl phthalate was obtained.

Comparative Example 4-Di-2-ethylhexyl phthalate was added to the solution of the silicon-containing polymer (a) dissolved in methanol obtained in Example 1, and the methanol was distilled off under reduced pressure. ,
A comparative organosilicon polymer composition (4) consisting of 10% of the silicon-containing polymer (a) and 90% of di-2-ethylhexyl phthalate was obtained.

Each organosilicon polymer composition obtained was evaluated by the following methods. Storage stability : Each composition was examined by allowing it to stand at 50 ° C. Treatment of magnesium hydroxide : Magnesium hydroxide powder 1
Each composition was weighed and added so that the silicon-containing polymer (a) became 5 parts with respect to 00 parts, and the magnesium hydroxide powder was treated by mixing with a Henschel mixer at room temperature. went.

(Workability): Workability during weighing and mixing. When it was good, it was marked with ◯, and when it was bad, it was marked with x. (State of treated powder): When there was no large agglomerate and the powder had fluidity, it was marked with ◯, and when it was a clay-like or large agglomerate, it was marked with x. (Uniformity of treatment): O was good and X was bad.

Table 2 shows the results.

[0075]

[Table 2]

As shown in Table 2, it was confirmed that the organosilicon-based polymer composition of the example was superior in all performances to the organosilicon-based polymer composition of the comparative example.

[0077]

Since the organosilicon polymer composition according to the present invention contains the specific compound (b) in the specific amount,
By contacting with an inorganic filler, its surface is modified to improve the wettability and dispersibility of the inorganic filler with respect to the resin for molding materials, and to improve the interfacial adhesion between the resin and the inorganic filler. The storage stability of the silicon-containing polymer (a) that can be obtained is improved, and the work at the time of weighing and mixing with an inorganic filler, etc., even if the silicon-containing polymer (a) is not dissolved in an organic solvent. Excellent in performance.

Since the composition for treating an inorganic filler according to the present invention comprises the above-mentioned organosilicon polymer composition, when the inorganic filler is treated with this composition, the inorganic filler is largely agglomerated or clay-like. In addition, since the inorganic filler is uniformly treated, the inorganic filler can be satisfactorily dispersed in the resin composition for molding material and the like.

According to the method for producing an organosilicon-based polymer composition of the present invention, the above excellent organosilicon-based polymer composition can be obtained with almost no problems as compared with other methods.

Claims (6)

[Claims] (A) At least one R per molecule.
¹ O group [R ¹ is a hydrogen atom or an optionally substituted alkyl group having 1 to 5 C atoms, and when there are plural R ¹ 's in one molecule, the plural R ^1's may be the same or different from each other. May be. ] And at least one polysiloxane group, and at least one Si atom in the polysiloxane group
Each has a structure in which the R ¹ O group is bonded to form a Si—O—C bond, and the polysiloxane group is bonded directly or indirectly to the main chain by a Si—C bond. A silicon-containing polymer that is soluble in the following compound (b), and (b) a compound that has a solubility parameter (SP) of 8 or more and a molecular weight of 190 or more and is liquid at room temperature, The above silicon-containing polymer (a) in 100 parts by weight.
An organosilicon polymer composition containing 15 to 90 parts by weight and 10 to 85 parts by weight of the compound (b). 2. The organosilicon polymer composition according to claim 1, wherein the compound (b) is a phthalic acid ester. 3. The following general formulas: Embedded image Embedded image Wherein R ¹ is a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms; R ² is a hydrogen atom or a methyl group; R ³ is a divalent organic group; R ⁴ is a hydrogen atom Or an optionally substituted group selected from an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an acyl group, wherein s, t, and u are each independently 0 or 1; A plurality of R ¹ may be the same or different. ] At least one selected from the reactive silane compounds (A) represented by the following formula and the following general formula: R ⁴ _p Si (OR ¹ ) _4-p ... [In the general formula, R ¹ and R ⁴ are the same as the above; p is 0
It is an integer of 2. A plurality of R ¹ in one molecule may be the same or different. When a plurality of R ⁴ are present in one molecule, the plurality of R ⁴ may be the same or different. And at least one selected from the silane compounds (B) shown below in the presence of a solid catalyst (C) insoluble in the system,
The polymerizable polysiloxane (D) obtained by co-hydrolysis condensation (0.1 to 50 wt%) and one unsaturated group, and the polymerizable polysiloxane (D)
Monofunctional monomer (E) 99.9-50 copolymerizable with
wt% (provided that the total amount of (D) and (E) is 100 wt%) to obtain a silicon-containing polymer (a), and the organic solvent, Solubility parameter (SP) of 8 or more
And the step of substituting the compound (b) having a molecular weight of 190 or more and being liquid at room temperature, the organosilicon polymer composition according to claim 1 or 2. 4. A composition for treating an inorganic filler, which comprises the organosilicon-based polymer composition according to any one of claims 1 to 3. 5. The following general formulas: Embedded image [Chemical 6] Wherein R ¹ is a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms; R ² is a hydrogen atom or a methyl group; R ³ is a divalent organic group; R ⁴ is a hydrogen atom Or an optionally substituted group selected from an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an acyl group, wherein s, t, and u are each independently 0 or 1; A plurality of R ¹ may be the same or different. ] At least one selected from the reactive silane compounds (A) represented by the following formula and the following general formula: R ⁴ _p Si (OR ¹ ) _4-p ... [In the general formula, R ¹ and R ⁴ are the same as the above; p is 0
It is an integer of 2. A plurality of R ¹ in one molecule may be the same or different. When a plurality of R ⁴ are present in one molecule, the plurality of R ⁴ may be the same or different. And at least one selected from the silane compounds (B) shown below in the presence of a solid catalyst (C) insoluble in the system,
The polymerizable polysiloxane (D) obtained by co-hydrolysis condensation (0.1 to 50 wt%) and one unsaturated group, and the polymerizable polysiloxane (D)
Monofunctional monomer (E) 99.9-50 copolymerizable with
wt% (provided that the total amount of (D) and (E) is 100 wt%) to obtain a silicon-containing polymer (a), and the organic solvent, Solubility parameter (SP) of 8 or more
And a step of substituting the compound (b), which has a molecular weight of 190 or more and is liquid at room temperature, for producing an organosilicon polymer composition. 6. The method according to claim 5, wherein the compound (b) is a phthalic acid ester.