JP2000160012A - Polyorganosiloxane composition and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyorganosiloxane composition having a high moisture resistance and mechanical properties without deteriorating its surface properties. SOLUTION: This polyorganosiloxane composition contains a polyorganosiloxane and an interlaminar compound, wherein the interlaminar compound is prepared by mixing a swellable silicate and an amino compound in a dispersing medium, where the amino compound is a 1-25C hydrocarbon compound which has at least one amino group selected from the group consisting of primary, secondary and tertiary amino groups and optionally has at least one substituent selected from the group consisting of hydroxyl group, mercapto group, ether group, carboxyl group, nitro group and chlorine atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyorganosiloxane composition containing a polyorganosiloxane and an intercalation compound, and a method for producing the resin composition.

[0002]

2. Description of the Related Art Polyorganosiloxanes are used in various fields as so-called silicone oils, silicone elastomers, silicone resins, etc., taking advantage of their heat resistance, cold resistance, oxidation resistance, weather resistance and excellent electrical properties. ing.

[0003] As the range of use of polyorganosiloxane has been further expanded, it has been required to improve various physical properties of polyorganosiloxane. For example, among silicone elastomers, a so-called RTV (room temperature condensation curing type) liquid silicone rubber is a silicone rubber composition which is cured by a condensation reaction at room temperature to become a rubber-like elastic body, and is widely used in building sealants and the like. It is used. However, there is a need for improvements in various properties such as improvement in surface peelability and adhesiveness, particularly suppression of deterioration in strength, elastic modulus, and sealability due to hydrolysis of siloxane bonds in a high-temperature and high-humidity environment. To solve the above problem, a technique of filling particulate inorganic substances such as silica, calcium carbonate, titanium oxide, alumina, and quartz powder (Japanese Patent Laid-Open No. 52-2 / 1982)
No. 439, JP-B-55-18454, JP-B-61-2
No. 3940, Japanese Patent Application Laid-Open No. 7-82488, etc.), but it is difficult to improve various properties required in a well-balanced manner by conventional techniques.

[0004] The disadvantages of the compounding of the particulate inorganic material are mainly that, when the amount of the inorganic material is small, the resin is hydrolyzed due to poor dispersion and too large a size of the dispersed particles to suppress moisture absorption. In addition, when the amount of addition is large, it is considered that the strength is reduced due to poor adhesion between the matrix resin and the particulate inorganic material.

On the other hand, in Japanese Patent Application Laid-Open No. 9-175816 and European Patent No. 0780340, a low molecular weight compound (intercalant monomer) such as hexamethylenediamine is used for the purpose of facilitating cleavage of a layered silicate layer. A technique has been disclosed in which an interlayer compound is formed by intercalating between layers.

[0006]

As described above, the intercalation compound is disclosed, but the technique of cleaving the intercalation compound and finely dispersing it in the polyorganosiloxane is not disclosed. It was difficult to finely disperse the layered particles.

Accordingly, a polyorganosiloxane composition having a good balance of adhesiveness, strength, elastic modulus, moisture resistance and surface properties is obtained by cleaving the layered silicate layer and dispersing it in the form of a small thin plate in the polyorganosiloxane. At present, a technique for obtaining a product has not yet been provided, and an object of the present invention is to solve such a conventional problem.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have reached the present invention. That is, a polyorganosiloxane composition obtained by mixing an amino compound having an amino group as an essential functional group and a swellable silicate to form an intercalation compound and dispersing the intercalation compound in the form of a fine plate in polyorganosiloxane. And a method of manufacturing the same.

According to the present invention, a polyorganosiloxane composition according to claim 1 is a polyorganosiloxane composition containing a polyorganosiloxane and an intercalation compound, wherein the intercalation compound is a swellable silicate and an amino compound. Prepared by mixing a compound in a dispersion medium, wherein the amino compound has at least one amino group selected from the group consisting of primary, secondary, and tertiary amino groups; Group, an ether group, a carbonyl group, a nitro group and a chlorine atom, which may have one or more substituents selected from the group consisting of 1 to 25 carbon atoms.
Is a hydrocarbon compound.

[0010] The polyorganosiloxane composition according to the second aspect is the polyorganosiloxane composition according to the first aspect, wherein the average thickness of the interlayer compound is 500 ° or less.

The polyorganosiloxane composition according to the third aspect is the polyorganosiloxane composition according to the first or second aspect, wherein the maximum thickness of the interlayer compound is 2000 ° or less.

The polyorganosiloxane composition according to a fourth aspect is the polyorganosiloxane composition according to the first, second or third aspect, wherein the [N] value of the intercalation compound is 30 or more, and the [N] value here. Is, the area of the resin composition 100μ
It is defined as the number of particles present in m ² per unit ratio of the intercalation compound.

According to a fifth aspect of the present invention, there is provided the polyorganosiloxane composition according to the first, second, third, or fourth aspect, wherein the average aspect ratio (the ratio of layer length / layer thickness) of the intercalation compound is equal to that of the polyorganosiloxane composition. 10 to 300.

The method for producing a polyorganosiloxane composition according to claim 6 is the method for producing a polyorganosiloxane composition according to claim 1, 2, 3, 4 or 5.
(A) a step of preparing a clay dispersion containing an intercalation compound and a siloxane intermediate; and (B) a step of polymerizing and / or curing the siloxane intermediate.

In the method for producing a polyorganosiloxane composition according to the present invention, the distance between the bottom surfaces of the interlayer compounds in the clay dispersion obtained in the step (A) may be swellable. It is at least three times the bottom spacing of the silicate.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyorganosiloxane used in the present invention has a main chain formed of a siloxane structure having a monovalent substituted or unsubstituted hydrocarbon group. Examples of the hydrocarbon group in the polyorganosiloxane include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a dodecyl group, an aryl group such as a phenyl group, a β-phenylethyl group, and a β-phenylpropyl group. And unsubstituted hydrocarbon groups such as aralkyl groups and vinyl groups such as chloro group, and substituted hydrocarbon groups such as chloromethyl group and 3,3,3-trifluoropropyl group.
In general, a methyl group and a phenyl group are frequently used because of ease of synthesis and the like. Furthermore, when the organic group bonded to the silicon atom is a methyl group, the viscosity is the lowest compared to the ease of synthesis of the raw material intermediate, the degree of polymerization of the obtained polymer, and the composition obtained. It is most preferable from the viewpoint of the physical property balance of the product. When used for applications requiring heat resistance, it is preferable that a part of the organic group bonded to the silicon atom is a phenyl group.

The polyorganosiloxane has a degree of polymerization of
It is used as a silicone oil, silicone elastomer or silicone resin depending on the presence or degree of the crosslinked structure.

Examples of the silicone oil include straight silicone oils substituted with hydrocarbon groups as described above (polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, etc.), non-reacted modified silicone oils, Reaction-type modified silicone oil modified with a group, an epoxy group, an alcohol, a mercapto group, a carboxyl group, or the like. Further, other organic compounds, for example, copolymerized modified silicone oils such as polyoxyalkylenes, higher alcohols, fatty acids and the like can also be mentioned.

The silicone elastomer is a cross-linking reaction product of a base polymer such as a polysiloxane having a monovalent substituted or unsubstituted hydrocarbon group and a cross-linking agent as described above. Depending on the type of cross-linking reaction, Room temperature condensation-curable (RTV type) liquid silicone rubber, heat-curable silicone rubber, and liquid heat-curable (LPS) silicone rubber. The RTV liquid silicone rubber has a low degree of polymerization, and the crosslinking agent is a generally used silane compound. RTV-type liquid silicone rubbers include, depending on the type of components that undergo condensation and elimination during the crosslinking reaction, deacetic acid-type,
Examples include dealcohol-type, deoxime-type, deamidation-type, deacetone-type, deaminoxy-type, and dehydrogenation-type. The heat-curable silicone rubber is linear and has a degree of polymerization of 6,000 to 10
The base resin (raw rubber) as large as 000 is the main raw material,
Besides sulfur, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, -p-chlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dibutyl-
It is obtained by heat crosslinking using a peroxide such as 2,5-di-t-butylperoxyhexane as a vulcanizing agent. Also,
The LPS type silicone rubber has a low degree of polymerization, and is obtained by an addition reaction using a transition metal compound such as γ-ray or a platinum compound as a vulcanizing agent in addition to the above sulfur and peroxide.

The silicone resin is a highly crosslinked resin obtained by copolymerizing a polyfunctional siloxane component in the structure. Generally, a straight silicone resin substituted with a hydrocarbon group is used, but an epoxy-modified or alkyd-modified resin is also used to improve weather resistance and electric insulation.

The intercalation compound used in the present invention refers to a swellable silicate and at least one amino group in a dispersion medium.
It is prepared by mixing with an amino compound having one.

The above-mentioned swellable silicate is mainly composed of a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide, and examples thereof include smectite group clay and swellable mica. Can be When a smectite group clay and swellable mica are used as the swellable silicate, the dispersibility of the swellable silicate in the polyorganosiloxane composition of the present invention, the availability of the swellable silicate, and the improvement of the physical properties of the resin composition It is preferable from the viewpoint of.

The above smectite group clay is represented by the following general formula (1): X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (1) (where X is K, Na, 1 / 2Ca , And 1 / 2Mg
At least one member selected from the group consisting of
e, Mn, Ni, Zn, Li, Al, and at least one member selected from the group consisting of Cr, and Z is at least one member selected from the group consisting of Si and Al. Note that H ₂ O represents a water molecule bonded to an interlayer ion, and n varies remarkably depending on the interlayer ion and the relative humidity. Specific examples of the smectite group clay include, for example, montmorillonite,
Examples include beidellite, nontronite, saponite, iron saponite, hectorite, sauconite, stevensite, bentonite, and the like, and substituted substances, derivatives, and mixtures thereof. The distance between the bottom surfaces of the smectite group clay in the initial aggregation state is about 10 to 1
7 °, and the average particle size of the smectite group clay in the agglomerated state is approximately 1000-1,000,000 °.

The swellable mica is represented by the following general formula (2): X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ (2) (where X is Li, Na, K , Rb, Ca, Ba, and Sr, at least one selected from the group consisting of
g, one or more selected from the group consisting of Fe, Ni, Mn, Al, and Li, and Z is Si, Ge, Al, F
at least one selected from the group consisting of e and B. )
And natural or synthetic. These are substances having the property of swelling in water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. For example, lithium-type teniolite, sodium-type teniolite, lithium-type Examples thereof include silicon mica, sodium tetrasilicic mica, and the like, and substituted substances, derivatives, and mixtures thereof. The distance between the bottom surfaces of the swellable mica in the initial aggregation state is approximately 10 to 17
Å, and the average particle size of the swellable mica in the aggregated state is about 10
It is 00 to 1,000,000 °.

Some of the above-mentioned swellable mica have a structure similar to that of vermiculite, and such an equivalent of vermiculite can also be used. The said vermiculite such equivalent has three octahedral type and dioctahedral the following general formula (3) (Mg, Fe, Al) 2 ~ 3 (Si 4-x Al x) O 10 (OH) 2 · (M ⁺ , M ²⁺ _1/2 ) _x · nH ₂ O (3) (where M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6 to 0.9) , N =
3.5 to 5). In the initial state of aggregation of the vermiculite-equivalent product, the distance between the bottom surfaces is approximately 10 to 17 °, and the average particle size in the aggregated state is approximately 1000 to 5,000,000 °.

The swellable silicate may be used alone.
It may be used in combination of more than one kind. Of these,
Montmorillonite, bentonite, hectorite, and swellable mica having sodium ions between layers are preferred from the viewpoint of dispersibility in the polyorganosiloxane composition of the present invention, availability, and the effect of improving the physical properties of the resin composition.

The crystal structure of the swellable silicate is desirably high in purity, which is regularly stacked in the c-axis direction, but a so-called mixed layer mineral in which the crystal cycle is disordered and a plurality of types of crystal structures are mixed is also used. Can be done.

The amino compound used in the present invention is 1
Having at least one amino group selected from the group consisting of primary, secondary and tertiary amino groups, and selected from the group consisting of hydroxyl, ether, mercapto, carbonyl, nitro and chlorine. It is a hydrocarbon compound having 1 to 25 carbon atoms which may have one or more selected substituents.

As used herein, the term "hydrocarbon group" refers to a linear or branched (ie, having a side chain) saturated or unsaturated, monovalent or polyvalent aliphatic hydrocarbon group, aromatic hydrocarbon group, or aliphatic hydrocarbon group. It means a cyclic hydrocarbon group, for example, an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a naphthyl group, a cycloalkyl group and the like. In the present specification, the term “alkyl group” is intended to include a polyvalent hydrocarbon group such as an “alkylene group” unless otherwise specified. Similarly, an alkenyl group, an alkynyl group,
The phenyl group, naphthyl group, and cycloalkyl group each include an alkenylene group, an alkynylene group, a phenylene group, a naphthylene group, a cycloalkylene group, and the like.

As specific examples of the above-mentioned amino compounds, examples in which an amino group and a hydrocarbon group having 1 to 25 carbon atoms are constituents include butylamine, N, N-dimethylbutylamine, and 1,2-dimethylpropyl. Amines, dodecylamine, hexylamine, N-methylhexylamine,
3-pentylamine, dimethylaminoethylamine, 2
Octylamine, ethylaminoethylamine, diethylaminoethylamine, tetramethylethylenediamine, 1,2-diaminopropane, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, tetramethyl-1,3-diaminopropane , 1,2-diaminobutane, 1,4-diaminobutane, N- (3-aminopropyl) -1,3-propanediamine, pentamethyldiethylenetriamine, N, N'-bis (aminopropyl) -1,3- Propylenediamine, N, N'-bis (aminopropyl) -1,4-butylenediamine, diallylamine, isoamylamine, N-ethylisoamylamine, 2-hexenylamine, N, N-diisopropylaminoethylamine N, N- diisopropylethylamine, 2-ethylhexylamine, N- ethyl-1,
2-dimethylpropylamine, diisobutylamine, 2
-Ethylhexylamine, aniline, β-naphthylamine, o-phenylenediamine, p-phenylenediamine, toluene-2,4-diamine, N, N′-dimethyl-p-phenylenediamine, divinylpropylamine and the like. Examples of the amino compound having a hydroxyl group include 2- (hydroxymethylamino) ethanol, N-
Isomethyldiethanolamine, 2-aminopropanol, 3-aminopropanol, 3-dimethylaminopropanol, 4-aminobutanol, 4-methylaminobutanol, 2-hydroxyethylaminopropylamine, diethanolaminopropylamine, 1-amino-
3-phenoxy-2-propanol and the like. Examples of amino compounds having an ether group include bis (3
-Aminopropyl) ether, dimethylaminoethoxypropylamine, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy)-
2,2-dimethylpropane, α, ω-bis (3-aminopropyl) polyethylene glycol ether, α, ω-
Bis (3-aminopropyl) diethylene glycol ether, 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2- Ethylhexyloxypropylamine, 3-decyloxypropylamine and the like. Examples of amino compounds having a mercapto group include 2-mercaptoethylamine, N- (2
-Mercaptoethyl) acetamide, 2-mercaptopyridine and the like. Examples of amino compounds having a carbonyl group include formanilide, acetanilide,
Examples include acetoacetanilide, dodecylamide, tetradecylamide, hexadecylamide and the like. Examples of the amino compound having a nitro group include 2-nitroaniline, 3-nitroaniline, 2,4-dinitroaniline,
2,4,6-trinitroaniline. Examples of the amino compound having a chlorine atom include 2-chloroaniline, 3-chloroaniline, and 2,5-dichloroaniline.

Among the above amino compounds, dimethylaminoethylamine, ethylaminoethylamine, diethylaminoethylamine, tetramethylethylenediamine, 1,2-diaminopropane, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropyl Amines, tetramethyl-1,3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, N- (3-aminopropyl) -1,3-propanediamine, pentamethyldiethylenetriamine and N, N ' -Bis (aminopropyl) -1,3-propylenediamine, etc.
An amino compound having two or more amino groups in one molecule,
2- (hydroxymethylamino) ethanol, N-isomethyldiethanolamine, 2-aminopropanol,
Amino having a hydroxyl group such as 3-aminopropanol, 3-dimethylaminopropanol, 4-aminobutanol, 4-methylaminobutanol, 2-hydroxyethylaminopropylamine and 1-amino-3-phenoxy-2-propanol; Compound, bis (3-aminopropyl) ether, dimethylaminoethoxypropylamine, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy) -2,2-
Amino compounds having an ether group such as dimethylpropane, α, ω-bis (3-aminopropyl) polyethylene glycol ether and α, ω-bis (3-aminopropyl) diethylene glycol ether can be preferably used.

Substitutes or derivatives of the above amino compounds may also be used. These amino compounds are used alone,
Alternatively, two or more kinds may be used in combination.

The intercalation compound can be obtained by increasing the distance between the bottom surfaces of the swellable silicate in a dispersion medium, and then adding and mixing the amino compound.

The above-mentioned dispersion medium is intended to include water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. Examples of the polar solvent include alcohols such as methanol, ethanol and isopropanol; glycols such as ethylene glycol, propylene glycol and 1,4-butanediol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran. , Amide compounds such as dimethylformamide, and other solvents such as dimethyl sulfoxide and
-Pyrrolidone and the like. These polar solvents may be used alone or in combination of two or more.

The spacing between the bottoms of the swellable silicate can be increased in the dispersion medium by sufficiently stirring and dispersing the swellable silicate in the dispersion medium. The distance between the bottom surfaces after the enlargement is preferably 3 times or more, more preferably 4 times or more, and still more preferably 5 times or more, compared to the initial distance between the bottom surfaces of the swellable silicate. There is no particular upper limit. However, when the distance between the bottom surfaces is increased by about 10 times or more, the measurement of the distance between the bottom surfaces becomes difficult. In this case, the swellable silicate is substantially present in a unit layer. In the present specification, the initial bottom surface interval of the swellable silicate is a bottom surface interval of the particulate swellable silicate in which unit layers are stacked and aggregated before being added to the dispersion medium. Intended. The distance between the bottom surfaces can be confirmed by small angle X-ray diffraction (SAXS) or the like. That is, the X-ray diffraction peak angle value of the mixture comprising the dispersion medium and the swellable silicate is measured by SAXS, and the peak angle value is substituted into Bragg's formula to calculate the bottom surface interval.

In order to efficiently increase the distance between the bottom surfaces of the swellable silicate, stirring may be performed at a speed of several thousand rpm or more, or a method of applying a physical external force as described below. Physical external forces can be applied by using commonly performed wet milling of fillers. As a general wet-milling method of a filler, for example, a method using hard particles can be mentioned. In this method, the hard particles, the swellable silicate, and an optional solvent are mixed and stirred, and the swellable silicate is separated by physical collision between the hard particles and the swellable silicate. Hard particles generally used are filler grinding beads, for example, glass beads or zirconia beads. These grinding beads are selected in consideration of the hardness of the swellable silicate or the material of the stirrer, and are not limited to the above-mentioned glass or zirconia. The particle size is also not specifically limited by a numerical value because it is determined in consideration of the size of the swellable silicate and the like, but a particle having a diameter of 0.1 to 6.0 mm is preferable. . Although the solvent used here is not particularly limited, for example, the above-described dispersion medium is preferable.

As described above, the interval between the bottom surfaces of the swellable silicate is increased in the dispersion medium. In other words, the unit layers that have been aggregated are cleaved and separated to be present independently.
Thereafter, the amino compound is added, and the mixture is sufficiently stirred and mixed to obtain an interlayer compound.

The treatment of the swellable silicate with the amino compound is carried out by adding the amino compound to a mixture containing the swellable silicate having an enlarged bottom surface spacing and a dispersion medium and stirring the mixture. If it is desired to perform the processing more efficiently, the rotation speed of the stirring should be 1000 rpm or more,
Preferably 1500 rpm or more, more preferably 200 rpm
0 rpm or more, or 500 (1 / s) or more, preferably 1000 (1 / s) using a wet mill or the like.
As described above, more preferably, a shear rate of 1500 (1 / s) or more is applied. The upper limit of the number of revolutions is about 25,000 rpm, and the upper limit of the shear rate is about 500,000 (1 / s). It is not necessary to stir at a value larger than the upper limit since stirring does not tend to change the effect even if the stirring is performed at a value larger than the upper limit or shearing is applied. Although the treatment of the swellable silicate with the amino compound can be sufficiently performed at room temperature, the system may be heated if necessary. The maximum temperature during heating is lower than the decomposition temperature of the amino compound used, and
If it is lower than the boiling point of the dispersion medium, it can be set arbitrarily.

The amount of the amino compound used is such that the intercalation compound obtained and the dispersibility in the polyorganosiloxane or clay dispersion (used in the method for producing the polyorganosiloxane composition of the present invention described later) are sufficiently enhanced. Can be prepared. If necessary, a plurality of amino compounds having different structures can be used in combination. Therefore, the amount of the amino compound to be added is not necessarily limited by numerical values, but is 0.1 to 200 parts by weight based on 100 parts by weight of the swellable silicate.
Parts by weight, preferably 0.2 to 180 parts by weight, more preferably 0.3 to 160 parts by weight, still more preferably 0.4 to 140 parts by weight, particularly preferably 0.5 to 180 parts by weight. 120 parts by weight. When the amount of the amino compound is less than 0.1 part by weight, the effect of finely dispersing the obtained interlayer compound tends to be insufficient. Also, 200
When the amount is more than 200 parts by weight, the effect does not change. Therefore, it is not necessary to add more than 200 parts by weight.

The spacing between the bottom surfaces of the interlayer compound obtained as described above can be enlarged as compared with the initial spacing between the bottom surfaces of the swellable silicate due to the presence of the introduced amino compound. For example, the swellable silicate dispersed in the dispersion medium and the bottom surface interval is enlarged, when the amino compound is not introduced, when the dispersion medium is removed, the layers return to a state where the layers are aggregated again. After the dispersion medium is removed by introducing the amino compound after increasing the bottom surface interval, the obtained interlayer compound can exist in a state where the bottom surface interval is increased without agglomeration of the layers. The distance between the bottom surfaces of the interlayer compounds is 1.1 times or more, preferably 1.2 times or more, more preferably 1.3 times or more, and particularly preferably 1.5 times, as compared with the initial distance between the bottom surfaces of the swellable silicate. It is expanding. The distance between the bottom surfaces can be confirmed by small angle X-ray diffraction (SAXS) or the like. In this method, the X-ray diffraction peak angle derived from the (001) plane of the dried and powdered intercalation compound is measured by SAXS,
By substituting into the formula of ragg and calculating, the bottom surface interval can be obtained. Similarly, the base spacing of the initial swellable silicate is measured, and by comparing the two, the expansion of the base spacing can be confirmed. By confirming that the distance between the bottom surfaces is thus increased, it can be confirmed that an interlayer compound has been generated.

In the polyorganosiloxane composition of the present invention, the compounding amount of the interlayer compound is typically 0.1 to 50 parts by weight, preferably 0.2 to 45 parts by weight, based on 100 parts by weight of the polyorganosiloxane. Preferably 0.
3 to 40 parts by weight, more preferably 0.4 to 35 parts by weight,
It is particularly preferably adjusted to be 0.5 to 30 parts by weight. If the amount of the interlayer compound is less than 0.1 part by weight, the effect of improving moisture resistance and mechanical properties may be insufficient, and if it exceeds 50 parts by weight, the surface properties tend to be impaired.

The ash content of the polyorganosiloxane composition derived from the intercalation compound is typically 0.1 to 30.
% By weight, preferably 0.2 to 28% by weight, more preferably 0.3 to 25% by weight, still more preferably 0.4 to 23% by weight, particularly preferably 0.5 to 20% by weight. Is done. If the ash content is less than 0.1% by weight, the effect of improving moisture resistance and mechanical properties may be insufficient,
If it exceeds 30% by weight, the surface properties tend to be impaired.

The structure of the intercalation compound dispersed in the polyorganosiloxane composition of the present invention has an agglomerated structure of μm size in which a number of layers are laminated, such as the swellable silicate before compounding. Is completely different. That is, by using an interlayer compound in which an amino compound having an affinity for the matrix resin is introduced and the interval between the bottom surfaces is enlarged as compared with the initial swellable silicate, the layers are cleaved and subdivided independently of each other. Become As a result, the intercalation compound is dispersed in the polyorganosiloxane in a very fine and independent lamellar form, and the number thereof is significantly increased as compared with the swellable silicate as the raw material. Such a dispersion state of the thin plate-like interlayer compound can be expressed by an aspect ratio (ratio of layer length / layer thickness), number of dispersed particles, maximum layer thickness and average layer thickness described below.

First, when the average aspect ratio is defined as the number average value of the ratio of the layer length / layer thickness of the interlayer compound dispersed in the resin, the average of the interlayer compound in the polyorganosiloxane composition of the present invention is defined. The aspect ratio is 10 to 300, preferably 15 to 300. More preferably, 2
0 to 300. Interlayer compound average aspect ratio is 10
If it is less than 3, the effect of improving the elastic modulus and moisture resistance of the polyorganosiloxane composition of the present invention may not be sufficiently obtained. Further, even if it is larger than 300, the effect does not change any more, so that it is not necessary to make the average aspect ratio larger than 300.

When the [N] value is defined as the number of dispersed particles per unit weight ratio of the swellable silicate in an area of 100 μm ² of the polyorganosiloxane composition, the polyorganosiloxane composition of the present invention is defined as follows. The [N] value of the intercalation compound is 30 or more, preferably 4
It is 5 or more, more preferably 60 or more. There is no particular upper limit, but when the [N] value exceeds about 1000, the effect does not change any more. The [N] value can be obtained, for example, as follows. That is, the polyorganosiloxane composition is cut into ultra-thin sections having a thickness of about 50 μm to 100 μm,
On an image of the section taken with a TEM or the like, the area is 100 μm.
^The number can be determined by dividing the number of particles of the intercalation compound present in any of the ^two regions by the weight ratio of the swellable silicate used. Alternatively, on a TEM image, an arbitrary region (area is measured) in which 100 or more particles are present is selected, and the number of particles present in the region is divided by the weight ratio of the swellable silicate used. And the value converted to an area of 100 μm ² is [N]
It may be a value. Therefore, the [N] value can be quantified by using a TEM photograph or the like of the polyorganosiloxane composition.

When the average layer thickness is defined as the number average value of the layer thickness of the interlayer compound dispersed in the form of a thin plate, the upper limit of the average layer thickness of the interlayer compound in the polyorganosiloxane composition of the present invention is as follows. 500 ° or less, preferably 450 °
Å or less, more preferably 400 ° or less. If the average layer thickness is more than 500 °, the effect of improving the moisture resistance and mechanical properties of the polyorganosiloxane composition of the present invention may not be sufficiently obtained. The lower limit of the average layer thickness is not particularly limited, but is about 10 °. Also, the maximum layer thickness is
When it is defined as the maximum value of the layer thickness of the interlayer compound dispersed in the form of a thin plate in the polyorganosiloxane composition of the present invention, the upper limit of the maximum layer thickness of the interlayer compound is 2000 ° or less, preferably 1800 ° or less. And more preferably 1500 ° or less. If the maximum layer thickness is more than 2000 °, the balance of moisture resistance, adhesion, mechanical properties, and surface properties of the polyorganosiloxane composition of the present invention may be impaired. The lower limit of the maximum thickness of the interlayer compound is not particularly limited, but is about 50 °.

The layer thickness and the layer length can be determined from an image obtained by photographing a flake obtained from the polyorganosiloxane composition of the present invention using a microscope or the like.

That is, it is now assumed that the film prepared by the above method is placed on the XY plane. The above film is placed on a plane parallel to the XZ plane or the YZ plane for about 50 minutes.
It can be obtained by cutting out an ultrathin section having a thickness of 100 μm to 100 μm and observing the section with a transmission electron microscope or the like at a high magnification of about 4 to 100,000 or more. The measurement is performed by placing an arbitrary region containing 100 or more intercalation compounds on an elephant of a transmission electron microscope obtained by the above method, forming an image with an image processing device or the like, and performing computer processing. Can be quantified. Alternatively, it can also be obtained by measuring using a ruler or the like.

The method for producing the polyorganosiloxane composition of the present invention is not particularly limited. For example, (A) a step of preparing a clay dispersion containing an interlayer compound and a siloxane intermediate, (B) a siloxane intermediate Is preferred.

The above-mentioned siloxane intermediate is a cyclic and / or linear siloxane oligomer obtained from a silane compound such as dimethyldichlorosilane and a hydrolyzate thereof, and has a methyl, vinyl or phenyl group as a side chain. And the like, and may have a reactive functional group such as an amino group, an epoxy group, an alcohol, a mercapto group, and a carboxyl group. The viscosity of the siloxane intermediate is such that the clay dispersion can be sufficiently uniformly dispersed, and is 10 to 100,000 cSt, preferably 50 to 5 cSt.
It is 0000 cSt.

The method of preparing the clay dispersion in the above step (A) is not particularly limited. For example, a method of sufficiently mixing an interlayer compound and a siloxane intermediate prepared in advance, or a method of sufficiently mixing an interlayer compound and an organic solvent. After mixing, a method of further adding and mixing a siloxane intermediate may be used.

In the intercalation compound contained in the clay dispersion obtained in the step (A), the initial lamination / agglomeration structure, such as the swellable silicate had, was almost completely eliminated and the interlaminar compound was finely divided into thin plates. Or the distance between the layers is increased, resulting in a so-called swollen state. The bottom surface interval can be used as an index indicating the swelling state. The distance between the bottom surfaces of the intercalation compounds in the clay dispersion is
In order for the intercalation compound to be finely divided into a thin plate shape, it is preferably at least three times, more preferably at least four times, even more preferably at least five times the initial distance between the bottom surfaces of the swellable silicate.

Next, step (B), that is, a step of polymerizing and / or curing the siloxane intermediate may be performed. The method is not particularly limited, and can be carried out by a generally-used method of polymerizing and curing a polyorganosiloxane. Examples of such a method include a method of ring-opening polymerization of a cyclic oligomer and a method of curing using a crosslinking agent.

The reason why the polyorganosiloxane composition of the present invention is excellent in moisture resistance, adhesiveness, mechanical properties, and surface appearance is that the intercalation compound is dispersed in the resin as a large number of fine thin particles. This is because the average layer thickness, the maximum layer thickness, the number of dispersed particles, and the average aspect ratio of the interlayer compound, which are indicators of the dispersion state, are in the ranges described above.

The dispersion state of the intercalation compound can be controlled by one or more steps selected from the step of preparing the intercalation compound and the step (A) in the above-mentioned method for producing a polyorganosiloxane composition.

That is, for example, in the step of preparing the intercalation compound, if the stirring force and the shearing force for dispersing the swellable silicate are constant, the type of the dispersion medium and the case where a plurality of types of dispersion medium are used are used. The swelling / cleaving state of the swellable silicate changes according to the mixing ratio and the order of mixing. For example, when montmorillonite is used as the swellable silicate, if the dispersion medium is water alone, the montmorillonite swells and cleaves to a state close to the unit layer. When an amino compound having a group having a high value is mixed, a dispersion in which an interlayer compound having a unit layer thickness of approximately approximately is dispersed is prepared. on the other hand,
Mixing of a polar solvent such as ethanol, tetrahydrofuran (THF), methyl ethyl ketone (MEK), pyridine, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) with water When a solvent is used as a dispersion medium or when montmorillonite is dispersed in the polar solvent and then water is added, about several to about one hundred and several tens of unit layers are cleaved and subdivided.

If an amino compound is mixed in this state, a dispersion in which an interlayer compound having a thickness of about several to about several hundreds is dispersed is prepared. The dispersion state of the intercalation compound can be controlled by performing steps (A) and (B) in the method for producing a polyorganosiloxane composition so as to maintain those states.

In the step (A), the dispersion state of the interlayer compound changes depending on the type and molecular weight of the siloxane intermediate mixed with the clay dispersion, the type of organic solvent used as required, and the like. The dispersion state of the intercalation compound can be controlled by performing step (B) in the method for producing a polyorganosiloxane composition so as to maintain those states.

The polyorganosiloxane composition of the present invention may contain, if necessary, polybutadiene, butadiene-styrene copolymer, acrylic rubber, ionomer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural Rubber, chlorinated butyl rubber, homopolymer of α-olefin, copolymer of two or more α-olefins (including any copolymer such as random, block, and graft, or a mixture thereof) Alternatively, an impact modifier such as an olefin-based elastomer can be added. If necessary, other thermoplastic resins and thermosetting resins may be used alone or in combination of two or more.

Further, the polyorganosiloxane composition of the present invention may contain a pigment or a dye, a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a plasticizer, a flame retardant, Additives such as antistatic agents can be added. The polyorganosiloxane composition of the present invention can be used as it is, or can be molded by hot press molding, injection molding, or extrusion molding.

The polyorganosiloxane composition of the present invention is excellent in moisture resistance, adhesion, surface properties, mechanical properties and the like.
It is suitably used for various additives, sealants, mechanical / electric parts, automobile parts, and other industrial materials.

In the polyorganosiloxane composition of the present invention, the interlaminar compound is very fine, thin and plate-like, and is uniformly dispersed, so that the surface smoothness is not impaired and the specific gravity is not significantly increased. , Moisture resistance, adhesion,
The mechanical strength can be improved.

[0063]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

The main raw materials used in Examples and Comparative Examples are summarized below. Unless otherwise specified, the raw materials were not purified. Montmorillonite: Natural montmorillonite from Yamagata Prefecture (bottom spacing = 13 °) was used. Swellable mica: A mixture obtained by mixing 25.4 g of talc and 4.7 g of finely pulverized sodium silicofluoride and heat-treating the mixture at 800 ° C. (bottom interval = 12 °) was used. -2-hydroxyethylamino-3-propylamine:
An amino compound manufactured by Koei Chemical Co., Ltd. (hereinafter referred to as HEAPA) was used. -1,2-bis- (3-aminopropoxy) ethane: An amino compound manufactured by Koei Chemical Co., Ltd. (hereinafter referred to as BAPE) was used.・ Phenyltrimethoxysilane: Shin-Etsu Silicone Co., Ltd.
LS-2750 (hereinafter, referred to as LS2750).・ Heat-cured silicone rubber: Shin-Etsu Chemical Co., Ltd.
KE931U (hereinafter, referred to as KE931U) was used.・ Silicone oil: KF96, manufactured by Shin-Etsu Chemical Co., Ltd.
(Hereinafter referred to as KF96).・ Liquid silicone rubber: KE4 manufactured by Shin-Etsu Chemical Co., Ltd.
5 (hereinafter referred to as KE45). The evaluation methods in Examples and Comparative Examples are summarized below. (Preparation of Specimen) The composition was applied on glass according to JIS A5758. Then, it was left at 20 ° C. and 55% RH for 7 days and further at 30 ° C. for 7 days to prepare a cured test body. (Measurement of Dispersion State) The interlayer compound was measured as follows using TEM.

An ultra-thin section having a thickness of 50 to 100 μm was used from the cured test specimen. Transmission electron microscope (JEOL JEM-
1200EX) at an acceleration voltage of 80 kV and a magnification of 40,000-
The dispersion state of the interlayer compound was observed and photographed at 1,000,000 times. T
In the EM photograph, an area where 100 or more dispersed particles are present is selected, and the number of particles ([N] value), layer thickness and layer length are measured by hand using a ruler with a scale or, if necessary, interpolated. The measurement was performed by processing using an image analyzer PIASIII manufactured by Quest. The average aspect ratio was a number average value of the ratio between the layer length and the layer thickness of each interlayer compound.
[N] value was measured as follows. First, TE
On the M image, the number of particles of the intercalation compound present in the selected region is determined. Separately from this, the ash content of the resin composition derived from the interlayer compound is measured. Divide the number of particles by the ash content,
The value converted to the area of 100 μm ² was defined as the [N] value.

The average layer thickness was the number average of the layer thicknesses of the individual interlayer compounds, and the maximum layer thickness was the maximum value among the layer thicknesses of the individual interlayer compounds.

If the dispersed particles are large and observation with a TEM is inappropriate, the [N] value can be determined using an optical microscope (optical microscope BH-2 manufactured by Olympus Optical Co., Ltd.) in the same manner as described above. I asked.

The aspect ratio of the dispersed particles that do not disperse in a plate shape was the value of major axis / minor axis. Here, the long diameter is intended to be the long side of the rectangle assuming a rectangle having the smallest area among rectangles circumscribing the target particle in a microscope image or the like. Further, the minor axis means the short side of the minimum rectangle. (Measurement of bottom spacing by small angle X-ray diffraction (SAXS))
Using an X-ray generator (RU-200B, manufactured by Rigaku Corporation), target CuKα ray, Ni filter, voltage 4
0 kV, current 200 mA, scanning angle 2θ = 0.2 to 16.0
°, the step angle = 0.02 ° under the measurement conditions, the bottom spacing was measured.

The distance between the bottom surfaces is represented by a small angle X-ray diffraction peak angle value of B
It was calculated by substituting into the formula of ragg. However, when it is difficult to confirm the small-angle X-ray peak angle value, it is confirmed that the layer has been sufficiently cleaved and the crystallinity has substantially disappeared, or the peak angle value is approximately 0.8 ° or less. Was considered difficult, and the evaluation result of the bottom surface spacing was set to> 100 °. (Tensile strength, elongation, tear strength) JIS K6301-19
75. (Moisture resistance) Tensile tests similar to the above were conducted after immersion in warm water at 80 ° C. for 7 days and 14 days. (Surface properties) The surface properties were evaluated by center line average roughness. The center line surface roughness is a surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd .;
com1500A. (Ash content) The ash content of the polyorganosiloxane composition derived from the intercalation compound was measured according to JIS K7052.

(Example 1) Step (A) 125 g of montmorillonite was added to 3500 g of ion-exchanged water, and the mixture was wet-milled at 5000 rpm by Nippon Seiki Co., Ltd.
m, and mixed by stirring for 5 minutes. Then, 18g of HEAP
A was added, and the mixture was further stirred under the conditions shown in Table 1 to prepare an interlayer compound. (Confirmation of the intercalation compound was carried out by separating, drying and pulverizing the solid content, and measuring the bottom interval by SAXS. The results are shown in Table 1). Then, 1000 g of diethyl carbonate was added and mixed well, and then heated to remove water. Then 1
A clay dispersion was prepared by thoroughly mixing 600 g of KE45. The spacing between the bottom surfaces of the intercalation compounds in the clay dispersion was> 100 °. Step (B) Further, 35 g of LS2750 and 1.6 g of dibutyltin laurate were sufficiently mixed. Then, after removing the solvent and degassing, the composition was subjected to dealcoholization-condensation curing at room temperature in accordance with the preparation of the above-mentioned test specimen, thereby obtaining a polyorganosiloxane composition of the present invention. The ash content and properties are shown in Table 2 together with the following examples.

(Example 2) In step (A), HEA
The same procedure was performed as in Example 1 except that the amount of PA was changed to 12 g (the distance between the bottom surfaces of the interlayer compounds in the clay dispersion was> 100 °).
Met. ), A polyorganosiloxane composition containing an intercalation compound was obtained and evaluated.

(Example 3) In step (A), HEA
The same procedure was performed as in Example 1 except that 26 g of BAPE was used instead of PA (the bottom surface interval of the intercalation compound in the clay dispersion was> 100 °), and the polyorganosiloxane containing the intercalation compound was used. The composition was obtained and evaluated.

(Example 4) The same procedure as in Example 1 was carried out except that swelling mica was used in place of montmorillonite and that the amount of HEAPA was 30 g in step (A). The distance between the bottom surfaces was 65 °), and a polyorganosiloxane composition containing an interlayer compound was obtained and evaluated.

Comparative Example 1 After sufficiently mixing 125 g of montmorillonite and 1000 g of diethyl carbonate, 1600 g of KE45 was sufficiently mixed. The bottom spacing of the montmorillonite in the mixture was 14 °. Further, 35 g of LS2750 and 1.6 g of dibutyltin laurate were mixed well. Thereafter, a polyorganosiloxane composition was obtained in the same manner as in Example 1. The ash content and properties are shown in Table 3 together with the following comparative examples.

(Comparative Example 2) 18 g of HEAPA was directly sprayed on 125 g of montmorillonite using a spray.
The montmorillonite was amino treated by mixing for 1 hour. Amino-treated montmorillonite bottom spacing is 13
Was Å.

The polyorganosiloxane composition was prepared in the same manner as in Comparative Example 1 except that the above-mentioned amino-treated montmorillonite was used instead of montmorillonite (the distance between the bottoms of the amino-treated montmorillonite in the mixture was 14 °). Obtained and evaluated.

(Comparative Example 3) 125 g of montmorillonite was added to 3500 g of ion-exchanged water, and the mixture was stirred for 5 minutes at 5000 rpm using a wet mill (manufactured by Nippon Seiki Co., Ltd.). Then, 18 g of n-butyraldehyde manufactured by Wako Pure Chemical Industries, Ltd.
Was added and further stirred at 5000 rpm for 3 hours. Then, 1000 g of diethyl carbonate was added thereto, mixed well, and then heated to remove water (bottom spacing of n-butyraldehyde-treated montmorillonite was 14 °). A siloxane composition was obtained and evaluated.

(Example 5) Step (A) 125 g of montmorillonite was added to 3500 g of ion-exchanged water, and the mixture was mixed with a wet mill manufactured by Nippon Seiki Co., Ltd. for 500 minutes.
The mixture was stirred at 0 rpm for 5 minutes and mixed. Thereafter, 25 g of HEAPA was added, and the mixture was further stirred at 5000 rpm for 2 hours to prepare an interlayer compound. Then 1
A clay dispersion was prepared by adding 600 g of KE931U and sufficiently kneading with a kneader. The distance between the bottom surfaces of the intercalation compounds in the clay dispersion was 62 °. Step (B) 35 g of KF96 was added to the above clay dispersion and kneaded. This was taken out and kneaded with two rolls, and 8 g of benzoyl peroxide as a curing agent was added and mixed. Under heating,
While removing water, a polyorganosiloxane composition containing an interlayer compound was obtained by press molding and evaluated. The ash content and characteristics are shown in Table 4 together with the following comparative examples.

Comparative Example 4 125 g of montmorillonite and 1600 g of KE931U were sufficiently kneaded in a kneader. The bottom spacing of montmorillonite in the kneaded material is 1
It was 3Å. Next, 35 g of KF96 was added and further kneaded, and a polyorganosiloxane composition was obtained and evaluated in the same manner as in Example 5.

[0080]

As described in detail above, in the polyorganosiloxane, the unit layers of the swellable silicate are separated and cleaved to form a large number of aggregated particles of the swellable silicate. Subdivision into very small lamellar layers, that is, an average layer thickness of 500 mm or less, or a maximum layer thickness of 2000 mm or less as required, or an average aspect ratio (layer length / layer) Thickness ratio) is 10 to 300
By making the number of particles per unit ratio of the intercalation compound present in an area of 100 μm ² 30 or more,
Moisture resistance and mechanical properties can be improved without impairing surface properties. In order to subdivide the swellable silicate into a thin plate as described above in the polyorganosiloxane, it is essential to introduce an amino compound into the swellable silicate to form an interlayer compound.

The polyorganosiloxane composition of the present invention can be produced, for example, by the production method of the present invention, that is, (A) a step of preparing a clay dispersion containing an interlayer compound and a siloxane intermediate, and (B) a step of preparing a siloxane intermediate. And a step of polymerizing and / or curing.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

Claims (7)

[Claims] 1. A polyorganosiloxane composition comprising a polyorganosiloxane and an intercalation compound,
The intercalation compound is prepared by mixing a swellable silicate and an amino compound in a dispersion medium, wherein the amino compound is at least one selected from the group consisting of primary, secondary and tertiary amino groups. It has at least one amino group and may have one or more substituents selected from the group consisting of a hydroxyl group, a mercapto group, an ether group, a carbonyl group, a nitro group and a chlorine atom. 25. A polyorganosiloxane composition comprising 25 hydrocarbon compounds. 2. The composition according to claim 1, wherein the average thickness of the interlayer compound in the composition is 50.
The polyorganosiloxane composition according to claim 1, wherein the angle is 0 ° or less. 3. The maximum thickness of the intercalation compound in the composition is 20.
The polyorganosiloxane composition according to claim 1, wherein the composition is not more than 00 °. 4. An interlayer compound having an [N] value of 30.
Here, the [N] value is the area 10 of the resin composition.
The polyorganosiloxane composition according to claim 1, 2 or 3, which is defined as the number of particles per unit ratio of the intercalation compound present in 0 μm ² . 5. The polyorganosiloxane composition according to claim 1, wherein an average aspect ratio (ratio of layer length / layer thickness) of an intercalation compound in the composition is from 10 to 300. 6. The method according to claim 1, further comprising: (A) a step of preparing a clay dispersion containing an intercalation compound and a siloxane intermediate; and (B) a step of polymerizing and / or curing the siloxane intermediate. 6. The method for producing a polyorganosiloxane composition according to 4 or 5. 7. The bottom surface interval of the intercalation compound in the clay dispersion obtained in the step (A) is 3 times the bottom surface interval of the swellable silicate.
The method for producing a polyorganosiloxane composition according to claim 6, wherein the ratio is at least twice.