JPH09169848A - Polysiloxane compound, its production, and curable composition prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polysiloxane compd. which exhibits improved resistances to scratch and staining when used alone or when compounded with org. components and used as a hard coat, an exterior wall coating, a foundry sand mold, etc., by forming a polysiloxane compd. represented by a specific rational formula. SOLUTION: One (1)mol of a tetraalkoxysilane represented by the formula: Si(OR)4 is subjected to partial hydrolysis and condensation in the presence of 0.80-1.30mol of water. The reaction is conducted such that a water-sol. solvent (e.g. an alcohol, an ether, or a keton) is mixed with 1mol of the tetraalkoxysilane and 1×10<-6> -1×10<-1> mol of a catalyst (e.g. an org. or inorg. acid) and then with a specified amt. of water under stirring; the resultant mixture is allowed to react for 0.5-10hr under reflux at about the b.p. of the solvent or of an alcohol produced as a by-product; the solvent and the by-product alcohol are removed by distillation or by introducing an inert gas; and the distillation is further continued at 100-250 deg.C. Thus is obtd. a polysiloxane compd. represented by the formula: SiOa (OR)b (OH)c (wherein (a) is 0.86-1.30; (b) is 2.18-1.30; (c) is 0.10 or higher; and R is an alkyl.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel siloxane compound, a method for producing the same, and uses thereof. In recent years, a siloxane compound having (SiO) _n units is used alone or in combination with an organic component such as an organic polymer for hard coat, outer wall coating, sand molding material for castings, adhesives, etc. In addition, the stain resistance is improved.
Among them, particularly, an alkoxysilane oligomer, which is a partial hydrolysis-condensation product of an alkoxysilane having an alkoxy group bonded to silicon, has been attracting attention. For example, the inventors have proposed a polysiloxane oligomer represented by the following chemical formula and a polysiloxane oligomer having a storage stability of 1% or less, thereby improving the storage stability (Japanese Patent Laid-Open No. 7-48454). Bulletin).

[0002]

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[0003]

Among these conventionally existing siloxane compounds, a polyalkoxypolysiloxane, which is a compound in which all organic groups are bonded to silicon atoms through oxygen atoms, is known as a polyalkoxypolysiloxane. Then, on the other hand, a cured product having a high hardness and glassy property is produced, but on the other hand, it is difficult to achieve a high degree of polymerization because it gels when the degree of polymerization is increased.

[0004]

Therefore, the inventors of the present invention have made diligent studies and found that a compound in which all organic groups are bonded to a silicon atom through an oxygen atom has a siloxane bond with a high degree of polymerization. In addition, they succeeded in obtaining a polysiloxane compound which stably exists in a liquid state, and reached the present invention. That is, the present invention provides a polysiloxane compound represented by the following rational formula: SiO _a (OR) _b (OH) _c (where a = 0.86 to 1.30, b = 2.18 to 1.
30, c ≦ 0.10, R is an alkyl group) and tetraalkoxysilane, and 0.80 to 1.30 mol of water is hydrolyzed and condensed under reflux, and then hydrolyzed and condensed. Distill off the alcohol produced by
It lies in a method for producing the above compound, which comprises distilling off components flowing out at 30 to 200 ° C., and utilization of the above compound.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the polysiloxane compound of the present invention is represented by the following rational formula. _{SiO a (OR) b (OH} ) c ( although a = 0.86~1.30, b = 2.18~1.
30, c ≦ 0.10, R is an alkyl group) a is 0.86 to 1.30, preferably 0.90 to 1.30.
Twenty. When a <0.86, the degree of polymerization is not sufficient, and the effects such as scratch resistance and stain resistance when the polysiloxane compound is mixed with an organic component such as an organic polymer are poorly expressed. When a> 1.30, the obtained polysiloxane compound tends to gel. When c> 0.10, the composition of the obtained polysiloxane compound is likely to change during storage. Particularly preferably, c ≦ 0.05. Within this range, the composition change during storage is extremely small. On the other hand, b is b = 4-2a-
If a and c are determined from the relational expression of c, they are inevitably determined. R is an alkyl group, and preferably a C1-4 alkyl group is desirable because the resulting polysiloxane compound is highly reactive and a high hardness coating film can be obtained when it is formed into a coating film.

In order to obtain such a polysiloxane compound of the present invention, for example, the method described below can be mentioned.
That is, tetraalkoxysilane represented by Si (OR) ₄ is partially hydrolyzed and condensed by the specific method described below. First, the molar ratio to tetraalkoxysilane is 0.
80 to 1.30 times equivalent, preferably 0.86 to 1.20
Double equivalent water is added to react. If it is less than 0.8 mol times, it is difficult to set a in the above-mentioned rational formula of the polysiloxane compound to be 0.86. On the other hand, when it exceeds 1.3 mole times, the rational formula a tends to exceed 1.30, and the obtained polysiloxane compound is very likely to gel, and the storage stability is poor and it is difficult to use.

During the reaction, a catalyst can be added as required. For example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like, organic acids such as carboxylic acid, sulfonic acid and the like can be used, but hydrochloric acid is preferable because it can be easily removed by distillation operation after the reaction. The amount of hydrochloric acid used is usually 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol times that of tetraalkoxysilane, preferably 1 × 10 ⁻⁵ , as HCl.
It is about 1 × 10 ^-2 molar amount. When tetramethoxysilane is used as the tetraalkoxysilane, it is 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol times the tetramethoxysilane,
The molar amount is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻³ . Moreover, the reaction can be carried out in the presence of a solvent. For example,
Water-soluble organic solvents such as alcohols, ethers, and ketones can be used, but it is most preferable to use alcohol generated by hydrolysis as the solvent. The amount of the solvent used is 0.1 to 50 times, preferably 0.5 to 3 times the molar amount of the tetraalkoxysilane.

The partial hydrolysis condensation reaction of tetraalkoxysilane to obtain the polysiloxane compound of the present invention is
Generally, the tetraalkoxysilane and the solvent are mixed, and a predetermined amount of water is generally added with appropriate stirring as necessary. Then, the hydrolysis-condensation reaction proceeds by heating, and at this time, the reaction is first carried out in a reflux state at a temperature close to the boiling point of the solvent or the by-product alcohol. The reaction time under reflux depends on the kind of catalyst, but is usually 0.5 to 10 hours, preferably 2 to 5 hours.

Next, the alcohol added as a solvent and the alcohol by-produced by the partial hydrolysis condensation reaction are distilled off. Various distillation and evaporation operations can be applied as this method. That is, a method of heating to a temperature above the boiling point of alcohol for distillation under normal pressure or reduced pressure, or a method of introducing an inert gas such as nitrogen, carbon dioxide, argon, or helium even if the boiling point is lower than the boiling point, etc. There is. Industrially, a method of heating the liquid to 80 to 200 ° C., preferably 120 to 180 ° C. under normal pressure and distilling it off is suitable. When tetramethoxysilane is used as the tetraalkoxysilane to obtain the polysiloxane compound of the present invention, the temperature at this time is 80 to 130 ° C, preferably 100 to 120 ° C.
The time for this distillation is not particularly limited, but is usually 1 to 5 hours. In the case of industrial implementation, the temperature is raised to this range, and then the temperature is kept as it is for 0.5 to 10 hours, preferably 1 to 5 hours to complete the reaction, and a large amount of uniform production is performed. It is efficient to get things.

After almost all the alcohol has been distilled off in this manner, it is further heated at 100 to 250 ° C., preferably 120 to 20.
Continue to evaporate at a temperature of 0 ° C. When tetramethoxysilane is used as the tetraalkoxysilane, the temperature at this time is 130 to 200 ° C, preferably 140 to 170 ° C. If the temperature is too high, the obtained condensate undergoes depolymerization to form a tetraalkoxysilane monomer, which is not desirable. When distilling at this time, various distillation and evaporation operations can be applied as in the case of distilling alcohol. That is, a method of heating and distilling a solution at 100 ° C. or higher under normal pressure or reduced pressure, or nitrogen even if heated below the boiling point,
SV1 with inert gas such as carbon dioxide, argon, helium
The most convenient method is to blow at 100 (1 / Hr).

As described above, the polysiloxane compound of the present invention can be obtained by a relatively simple and easy method and useful for various purposes. Needless to say, the above-mentioned production method is a typical method for obtaining the polysiloxane compound of the present invention, and the polysiloxane compound of the present invention may be obtained by another method. The thus-obtained polysiloxane compound of the present invention has a high degree of polymerization, storage stability of 1 year or more, and can maintain a liquid state that is transparent and does not change in composition. Thus, the polysiloxane compound of the present invention, which has characteristics different from those of the polysiloxane compounds that have hitherto existed, is used, for example, in a hard coat as a hydrolysis solution, or is blended with various resins to impart hydrophilicity and stain resistance. It can be applied to various applications such as improvement of acid resistance and weather resistance, or application of sand mold for casting.

In addition to the above-mentioned polysiloxane compound,
A reactive organic compound having a functional group capable of undergoing a condensation reaction with this and / or a group capable of generating a group capable of undergoing a condensation reaction by hydrolysis can be blended to obtain a silicon-containing composition. That is, an organic compound having a group capable of condensing with an alkoxy group of the polysiloxane compound of the present invention, and / or an organic compound capable of forming a group capable of condensing with an alkoxy group of a polysiloxane compound of the present invention by hydrolysis. Is. Examples of such a reactive organic compound include those having two or more carboxyl groups, hydroxyl groups, alkoxy groups, and the like. Those having a molecular weight of 2000 or less are preferred.

Specific examples include (i) a silane coupler (generally RSiX ₃ : X is a hydrolyzable group, R is an organic group), and (ii) an active hydrogen-containing compound. More specifically, for example, as the silane coupler of (i),

Embedded image Such as methyl acrylate,

Embedded image

Epoxy-based materials such as H ₂ NC ₃ H ₆ Si (OC _{2
H 5) 3, H 2 NC} 2 H 4 NHC 3 H 6 Si (OCH 3) 3, H 2
NCONHC ₃ H ₆ Si (OC ₂ H ₅ ) ₃ , etc., amino-based,
_{CH 2 = CHSi (OC 2 H} 5) 3, CH 2 = CHSi (O
_{CH 3) 3, CH 2 =} CHSi (OC 2 H 4 OCH 3) 3, vinyl _{etc., HS-C 3 H 6 Si} (OCH 3) 3, HS-C
_{3 H 6 Si (OC 2 H} 5) 3, HS-C 3 H 6 Si (OC 2 H 4
OCH ₃ ) ₃ , and the like.

Any of these can be preferably used and may be appropriately selected according to the purpose. For example, when blended with an organic resin described later, compatibility with the resin may be considered. When a hard coat liquid is prepared by mixing with a solvent, it can be appropriately selected according to the type of the substrate to be coated. For example, if an acrylic resin substrate is selected, a methyl acrylate-based resin, a general resin substrate of a vinyl-based resin, and a metal substrate of an epoxy-based silane coupler will obtain a coating having particularly excellent adhesion. Can be. If the substrate is a glass substrate, excellent adhesion can be obtained using any silane coupler. Examples of (ii) include I to I shown below.
Examples include V.

I. Monohydric alcohol Monohydric alcohol having 1 to 12 carbon atoms, for example, ethanol,
There are aliphatic compounds such as butanol, heptanol, octanol and decanol, and compounds containing an aromatic ring such as phenol, benzyl alcohol, 2-phenoxyethanol and 2,4-dimethylphenol. II. Polyether-based alcohol having a molecular weight of 80 to 500 A product obtained by adding an alkylene oxide to a monohydric alcohol or a monocarboxylic acid. Examples of the monohydric alcohol include methanol, ethanol, propanol, butanol, phenol, benzyl alcohol and the like. Examples of the monovalent carboxylic acid include formic acid, acetic acid, butyric acid, and benzoic acid. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.

III. Polyether-based alcohol having a molecular weight of 500 or more (1) Functional group 1 At least 6 mol or more, preferably 10 mol or more of alkylene oxide is added to a monohydric alcohol or a monocarboxylic acid to give a molecular weight of 500 or more, Preferably 500
~ 1500. As the monohydric alcohol, monocarboxylic acid and alkylene oxide, those shown in II can be used. (2) Functional group 2 Alkylene oxide is added to dihydric alcohol or dihydric carboxylic acid at least 8 mol or more, preferably 10 mol or more, and the molecular weight is 500 or more, preferably 800 to 2
As 000. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, butanediol, bisphenol A, hydroquinone, and catechol. Examples of the divalent carboxylic acid include maleic acid, succinic acid, adipic acid, phthalic acid and dimer. As the alkylene oxide, the same alkylene oxide can be used.

IV. Polyester alcohol Diester carboxylic acid and dihydric alcohol are esterified to give a molecular weight of 500 or more, preferably 1000 to 2000.
And what. As the divalent carboxylic acid, the same one as in III can be used. As the dihydric alcohol, alcohols shown in III and those obtained by adding an alkylene oxide to the dihydric alcohol of III can also be used. When the compound (ii) is used, the polysiloxane compound of the present invention can be solubilized in polyisocyanate, so that a useful isocyanate composition can be obtained. In this case, the mixing ratio is such that the polyisocyanate / (polysiloxane compound + active hydrogen compound) ratio is 90/10 to 10/9.
0 (wt / wt), preferably 80 / 20-40 / 60 (wt
/ Wt) is good. Further, another isocyanate, a silicone surfactant and an organic solvent which are soluble in the composition may be further used.

The compounds (i) and (ii) described above are examples of the reactive organic compounds that can be used in the present invention.
The reactive organic compound that can be used in the present invention is not limited to these, and a functional group capable of undergoing a condensation reaction with the polysiloxane compound of the present invention and / or a condensation reaction with a polysiloxane compound of the present invention by hydrolysis. Any compound can be used as long as it has a group capable of generating a reactive group. Further, two or more of the above reactive organic compounds may be used in combination depending on the purpose. An appropriate amount of the reactive organic compound added is an equimolar amount or less, usually 0.01 to 1 times the molar amount of the alkoxy group of the polysiloxane compound. The molar ratio is particularly preferably 0.05 to 0.5, but may be appropriately selected according to the purpose. When a silane coupler is used as the reactive organic compound, addition of water to hydrolyze the silane coupler produces a silanol group capable of undergoing a condensation reaction with the polysiloxane compound.

When blending the polysiloxane compound of the present invention with these reactive organic compounds, if necessary,
A solvent, a dispersion medium, a curing catalyst, etc. may be added. For example, in the case of film formation described below, particularly when using a spray method or a dipping method, in order to prepare a coating liquid having a viscosity and a nonvolatile component content according to the coating film conditions and the physical properties of the target film such as a film thickness, these solvents or dispersion media are used. Can be added.
As the solvent, those having compatibility with both the polyalkoxypolysiloxane and the reactive organic compound are preferable. For example, alcohols, glycol derivatives, hydrocarbons, esters, ketones and ethers can be used alone or in combination of two or more.

Specific examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, and octanol, and examples of glycol derivatives include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene. Examples thereof include glycol mono n-propyl ether and ethylene glycol mono n-butyl ether. Benzene, kerosene, toluene, xylene and the like can be used as hydrocarbons, and methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like can be used as esters. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetylacetone, and ethers such as ethyl ether, butyl ether, 2-α-methoxyethanol, 2-α-ethoxyethanol, dioxane, furan, and tetrahydrofuran can be used.

In some cases, a dispersion medium can also be used. As a dispersion medium to be used, for example, a water-surfactant system is suitable, and as the surfactant, an anionic, cationic or nonionic surfactant is generally used. As anionic surfactants, carboxylate, sulfonate,
Cationic compounds such as sulfates and phosphates include salts of organic or inorganic acids of primary to tertiary amines,
Quaternary ammonium salts, polyoxyethylene alkylamine salts, and the like, and nonionic compounds include sorbitan dialkyl ester, ethylene glycol condensate of sorbitan alkyl ester, aliphatic alcohol polyethylene glycol condensate, alkylphenol polyethylene glycol condensate, polypropylene Glycol polyethylene glycol condensate and the like.

These surfactants are preferably used in an amount of about 0.1 to 5% with respect to the polysiloxane compound of the present invention. When dispersing (emulsifying), an appropriate amount of water is used and a homomixer, A known method such as colloid mill or ultrasonic wave can be used. The content of the hydrolyzate is preferably 50 to 30 with respect to 100 parts by weight of the organic compound copolymer resin.
The amount is 0 parts by weight, more preferably 100 to 250 parts by weight. If it is 50 parts by weight or less, the bending rigidity is lowered, which is not preferable, and if it is 300 parts by weight or more, the adhesion to the substrate is lowered, which is not preferable. Of these solvents and dispersion media, it is usually preferable to use a solvent, because the physical properties of the cured product and the stability of the curable composition are excellent. The type of solvent may be selected as appropriate for the properties of the desired cured product, processing conditions, etc., but for applications such as coating, for example, hydrocarbons such as benzene, toluene, xylene, and the like, When using ketones such as methyl ethyl ketone,
Since the desolvation rate at the time of film curing is appropriate, the surface gloss of the obtained film is particularly excellent, and the desired film thickness can be easily obtained. In addition, in general, it may be appropriately selected depending on the type of reactive organic compound used and desired film characteristics.

Incidentally, depending on the kind of the reactive organic compound,
In many cases, it is desirable to add more catalyst to improve the cure rate after processing because of the large number of functional groups. Examples of the catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, acetic acid,
Organic acids such as paratoluene sulfonic acid, benzoic acid, phthalic acid, maleic acid, formic acid, oxalic acid, potassium hydroxide,
Alkali catalysts such as sodium hydroxide, calcium hydroxide, ammonia, organic metals, metal alkoxides, such as organotin compounds such as dibutyltin dilaurylate, dibutyltin dioctiate, dibutyltin diacetate, aluminum tris (acetylacetonate), titanium tetrakis (Acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate), zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate) And zirconium bis (isopropoxy)
There are metal chelate compounds such as bis (acetylacetonate) and boron compounds such as boron butoxide and boric acid, but the storage stability of the silicon-containing composition, the hardness of the coating film obtained when used as a coating liquid, the flexibility In terms of excellent properties such as properties, and from the viewpoint of preventing corrosion of the substrate to be treated, acetic acid, maleic acid, oxalic acid, fumaric acid,
It is preferable to use one or more of the metal alkoxides.

The respective components in the silicon-containing composition, particularly the polysiloxane compound and the above-mentioned reactive organic compound, may be present in the liquid in a condensed state, or may be present simply in a mixed state. You may. What is necessary is just to select suitably according to a use and the kind of organic compound. The condensation reaction can be promoted by heating and / or removing the by-produced alcohol out of the system. In addition, the treatment method when various powders are treated with the polysiloxane compound of the present invention or the silicon-containing composition of the present invention can be a general wet method or dry method. For example, in the case of the dry method, it is preferable to use a device equipped with a mixing stirrer such as a Henschel mixer and capable of drying.

A raw material powder and a predetermined amount of a polysiloxane compound or a silicon-containing composition were charged, and the mixture was stirred at room temperature until the surface of the raw material powder was sufficiently wet, and then heated to 100 to 150 ° C. while stirring. A surface-treated powder can be obtained by promoting the crosslinking reaction of the polysiloxane compound or the silicon-containing composition and evaporating volatile components such as water. When the raw material powder is difficult to uniformly wet with a predetermined amount of polysiloxane compound or silicon-containing composition, the predetermined amount of polysiloxane compound or silicon-containing composition may be diluted with water or the like. When the affinity with the matrix is particularly enhanced, the raw material powder is surface-treated in advance with a siloxane compound, particularly the polysiloxane compound of the present invention or a liquid obtained by diluting these with water or the like, and dried if necessary. And the like, and then further treated with the silicon-containing composition of the present invention.

Since the polysiloxane compound or the silicon-containing composition of the present invention has excellent affinity with various substrates, the raw material powder to be treated is not particularly limited, and examples thereof include glass, cement, concrete, iron, Copper, nickel, gold,
Metals such as silver, aluminum, rare earths and cobalt, carbon materials such as carbon black, graphite, carbon fiber, activated carbon and carbon hollow spheres, silica, alumina, titanium oxide, beryllium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide. , Oxides such as antimony oxide, barium ferrite, strontium ferrite, aluminum hydroxide,
Hydroxides such as magnesium hydroxide, calcium carbonate, carbonates such as magnesium carbonate, sulfates such as calcium sulfate, talc, clay, mica, calcium silicate, glass, glass hollow spheres, silicates such as glass fibers, Other general-purpose fillers such as calcium titanate, lead zirconate titanate, aluminum nitride, silicon carbide, cadmium sulfide, and other inorganic powders, wood flour, starch, various organic pigments, polystyrene, nylon, and other organic fillers. And conductivity, electromagnetic wave shielding, magnetism, sound insulation, thermal conductivity, slow flame retardancy, flame retardancy. Regardless of whether it is a functional filler for imparting abrasion resistance or the like, it can be treated with the polysiloxane compound or the silicon-containing composition of the present invention. Then, the surface-treated powders obtained by treating these raw material powders with the polysiloxane compound or the silicon-containing composition of the present invention are, for example, oil paints, synthetic resin paints, water-soluble resin paints, emulsion paints, Emulsion paint with aggregate, traffic paint, paint such as putty and caulk, shoe sole, electric wire, tire, industrial goods, belt, hose, rubberized cloth, rubber glue, adhesive tape, latex, rubber products such as backsizing, coating For industrial use, internal filling, paper use such as synthetic paper, synthetic resin products such as PVC, polyolefin, epoxy phenol, unsaturated polyester, electric welding rod, glass, acid neutralization, pharmaceuticals, food, sugar production, toothpaste, cleanser , Bunker sand, pesticides, mixed feed, various filling materials such as building materials, or as a filling material mixed with fiber and resin components, molded,
FRP (Fiber Reinforced Plas)
tic) can also be used.

When the polysiloxane compound or the silicon-containing composition of the present invention is impregnated into a porous material such as paper, the material may be tipped to the polysiloxane compound or the silicon-containing composition and then dried. If the crosslinking reaction proceeds at room temperature or under heating, characteristics such as flame retardancy and smoothness can be imparted. When the polysiloxane compound or the silicon-containing composition of the present invention is used for bonding, the surfaces to be bonded are pressure-bonded to each other before the surfaces to be bonded are coated with the polysiloxane compound or the silicon-containing composition and completely cured. Alternatively, if the surface to be adhered is pre-coated with the polysiloxane compound of the present invention or a hydrolyzed solution thereof or the like, the adhesive strength is further increased. Further, these silicon-containing composition of the present invention or the polysiloxane compound of the present invention is further added with a pigment to prepare a coating composition, or a curable composition prepared by mixing various inorganic and organic fillers, and cured. It can also be made into a composite material. In the case of the polyalkoxypolysiloxane of the present invention, or a coating obtained by further adding a pigment to the silicon-containing composition, a silicon-containing coating film in which the pigment is uniformly dispersed can be easily obtained if the coating is dispersed in a reactive organic compound in advance. be able to.

The polysiloxane compound of the present invention or the silicon-containing composition further mixed with an organic resin such as polyester, polyurethane, acrylic resin or silicone resin may be used as a curable composition. The compounding ratio of the organic resin and the polysiloxane compound or the silicon-containing composition is usually 100% by weight of the polysiloxane compound and / or the silicon-containing composition as the non-volatile component.
Effective when used in a wide range of 1 to 5000 parts by weight of organic resin. For example, when the expression of properties such as hardness and high heat resistance of the polysiloxane compound of the present invention is emphasized, the organic resin content is preferably in the range of 1 to 400 parts by weight. At this time, the concentration of SiO _{2 in} the non-volatile components of the mixed solution is 1
A range of 0 to 95% is preferred. On the other hand, the use of polysiloxane compounds or silicon-containing compositions as additives while maintaining the properties such as flexibility and thickening of organic resins have low contamination on coatings and the like that are mainly composed of organic resins. When giving importance to imparting weather resistance, the organic resin is 5
It is preferable to mix in the range of 00 to 5000 parts by weight. At this time, the SiO ₂ conversion concentration in the non-volatile components of the blended liquid is preferably 1 to 10%. Hereinafter, the present invention will be described in more detail with reference to examples.

[0030]

Example 1 [Production of Silicate Oligomer] Tetramethoxysilane 1 was added to a glass 3 liter 5-necked Korben equipped with a stirrer, Dimroth condenser, thermometer and nitrogen blowing tube.
After charging 520 g and 480 g of methanol and stirring for 5 minutes, a mixed solution of 179 g of water and 0.36 g of 20% hydrochloric acid was added. At this time, the amount of water relative to tetramethoxysilane is equivalent to 1.0 mole times. Then, the reflux state (65
° C) and reacted under reflux for 4 hours.

Next, the Dimroth condenser was replaced with a Liebig condenser equipped with a branch pipe (T-shaped pipe) and a distillation receiver, and a slight amount of residual methanol was distilled while heating until the internal temperature reached 150 ° C. After letting go, 15
High-purity nitrogen gas at SV = 10 while maintaining 0 ° C
The components that were blown into the liquid and distilled off for about a time were distilled off to obtain a polysiloxane compound as a colorless and transparent liquid substance in Kolben. After naturally cooling to room temperature, the contents are sampled and subjected to GC analysis, ¹ H-NMR analysis, FT-IR analysis and silica analysis to obtain a, b and c of SiO _a (OR) _b (OH) _c. It was

[GC analysis] To the sampling liquid of Example 1 described above, in a dioxane solvent, water and a catalyst in an amount equal to or more than the amount capable of completely hydrolyzing the alkoxy group (methoxy group) of the sample were added, and the mixture was allowed to stand at room temperature for 24 hours. It was left to stand for complete hydrolysis. The concentration of the produced methanol in this hydrolyzed solution was determined by GC
It was 5.05% by weight, which was 0.0185 mol / g (sampling liquid) in terms of methoxy group, as determined from analysis.

The composition of the hydrolyzed solution and the conditions for GC analysis are shown below. (Sample hydrolyzate preparation composition) -Sample 2.0668g-Dioxane 20.0432g-1N-HCl water 2.0562g (GC analysis conditions) GC apparatus: Shimadzu GC-7A Detector: 7CD Column: Waters Porapak type Q, 80-100mesh, 3mmφ ×
3m Carrier gas: He 40cc / min Inlet temperature: 250 ° C Column temperature: 180 ° C 4min → 180-250 ° C
(16 ° C / min) → 250 ° C constant Detector temperature: 200 ° C Current current: 100 mA Internal standard: acetonitrile Sample injection volume: 0.5 μl Internal standard / sample: 0.2 / 2 g

[ ¹ H-NMR Analysis] To 0.0139 g of the sampling liquid of Example 1, 0.0122 g of TBE (tetrabromoethane) as an internal standard substance was added, and CDCl 3 was added.
(Deuterated chloroform) diluted with 1.0177g, ¹
When the methoxy group content was determined by H-NMR analysis,
It was 0.0190 mol / g (sampling liquid).

The ¹ H-NMR analysis conditions are shown below, and the measurement chart is shown in FIG. ( ¹ H-NMR analysis conditions) Apparatus: JEOL (JEOL) α-400 type Fourier transform nuclear magnetic resonance apparatus Resonance frequency: 400 MHz Measurement temperature: 23 to 26 ° C. Pulse width: 4.80 μsec Acquisition time: 2.05 seconds Delay time: 4.95 sec Observation frequency width: 8000 Hz Number of data points: 16384 Accumulation number: 32 times Reference substance (0 ppm): Tetramethylsilane Diluting solvent: Deuterated chloroform Internal standard substance for quantitative analysis: Tetrabromoethane

[FT-IR Analysis] The silanol group content in the sampling liquid of Example 1 was measured as a methanol OH-equivalent silanol group content using FT-IR (Fourier transform infrared absorption spectrum measuring apparatus). By the way
It was 0.027% by weight. The FT-IR analysis conditions are shown below. Apparatus: FT-IR (Nicolet Co. Magna750) Measurement method: liquid cell method (CaF ₂ 5 mm width) Reagents: methanol (Ishizu Seiyaku guaranteed reagent) extinction coefficient calculated for carbon tetrachloride (produced by Wako Pure Chemical Industries, Ltd. guaranteed reagent) Sample dilution Sample dilution ratio: Sample / carbon tetrachloride = 1/9 weight ratio Silanol group absorption band: 3400 cm ^-1 Difference spectrum method: Corrected by subtracting the absorption spectrum of methanol contained in a very small amount.

[Silica analysis] 3.013 g of the sampling liquid of Example 1 was precisely weighed in a 25 ml platinum crucible, and 3.0 g of 14% ammonia water was added thereto to hydrolyze and gel. Next, methanol and residual water produced on a hot plate were dried to dryness, and then baked in an electric furnace at 900 ° C. for 2 hours to obtain 1.700 g of white silica solid content. The silica content in the sample liquid is 56.4% by weight.

[Analysis of Analytical Results: Calculation of Rational Formula] Rational Formula: Calculation of a, b, and c of SiO _a (OR) _b (OH) _c (1) Obtained in Example 1 from silica analysis results The number of moles of Si in 100 g of the polysiloxane compound is (100 g × 56.4 / 100) ÷ 60.1 = 0.93.
8 mol (2) b: Amount of methoxy group The amount of methoxy group in 100 g of the polysiloxane compound obtained in Example 1 is 100 g × 0.0185 mol / g≈1.90 mol from the GC analysis result and 1 H-NMR analysis. The result was 100 g × 0.0190 mol / g = 1.90 mol, which were almost the same. Also, if converted per mol of Si, 1.90 ÷ 0.938 = 2.03 mol / Si

(3) c: Amount of silanol groups The amount of silanol groups in 100 g of the polysiloxane compound obtained in Example 1 was calculated by FT-IR analysis to be (100 g × 0.027 / 100) ÷ 17≈1.6 × 1
0 ^-3 mol Also, if converted per mol of Si, it is 1.6 x 10 ^-3 ÷ 0.938 = 1.71 x 10 ^-3 mol /
Si (4) a: Amount of siloxane group a = (4-bc) / 2 From the relational expression of a = (4-2.03-1.71 × 10 ⁻³ ) /2=0.9
It becomes 84 mol / Si. The above results are shown by a rational formula: SiO _0.984 (OC
H ₃ ) _2.03 (OH) _0.00171 .

[0040]

Example 2 The amount of water added was 144 g, and hydrochloric acid was 10%.
A colorless and transparent liquid polysiloxane compound was obtained in the same manner as in Example 1 except that 0.10 g of hydrochloric acid water was used. The amount of water with respect to tetramethoxysilane at this time corresponds to 0.8 mol times. Next, 1 H-NMR analysis, FT-IR analysis and silica analysis were performed by the same analysis operation as in Example 1. ^{The 1} H-NMR chart is shown in FIG.
The results of each analysis are shown below. Silica content: 53.4% by weight (Si content 0.889
Mol / 100 g) Methoxy group amount: 2.03 mol / 100 g (2.28 mol / Si) Silanol group amount: 0.011% by weight (7.7 × 10 ⁻⁴ mol / Si) Siloxane group amount: (4- 2.28-7.7 × 10 ^-4 ) ÷
2 = 0.860 mol / Si When the above result is shown by a rational formula, SiO _0.860 (OCH ₃ ) _2.28
(OH) was _0.00077 .

[0041]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a polysiloxane compound represented by a specific range of a rational formula, which is a transparent liquid material having a siloxane bond having a high degree of polymerization and having excellent storage stability. . The polysiloxane compound obtained by the present invention is used as a hydrolyzed liquid in a hard coat, or is mixed with various resins to be used as a coating agent or paint, or as a binder for sand molds for casting, or various powders. Various applications such as surface treatment can be applied. Among polysiloxane compounds, polyalkoxypolysiloxanes are particularly suitable for imparting hydrophilicity, stain resistance, acid resistance, chemical resistance, weather resistance, electrical insulation, A remarkable effect can be exhibited in heat resistance and the like.

[Brief description of the drawings]

1 shows the polysiloxane compound obtained in Example 1. FIG.
¹ H-NMR chart

FIG. 2 shows the polysiloxane compound obtained in Example 2.
¹ H-NMR chart

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hozumi Endo Hozumi Endo 1-1, Kurosaki Shiroishi, Hachimansai-ku, Kitakyushu Mitsubishi Chemical Corporation Kurosaki Development Laboratory (72) Inventor Haruo Katsumata 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Sanryo Chemical Co., Ltd. New Business Development Room

Claims (13)

[Claims] 1. A polysiloxane compound represented by the following rational formula. _{SiO a (OR) b (OH} ) c ( although a = 0.86~1.30, b = 2.18~1.
30, c ≦ 0.10, R is an alkyl group) 2. The polysiloxane compound according to claim 1, wherein R is a methyl group. 3. Tetraalkoxysilane and 0.80 to 1.30 mol of water are hydrolyzed and condensed under reflux, and then the alcohol produced by the hydrolytic condensation is distilled off. Furthermore, the component which distils at 130-200 degreeC is distilled off, The manufacturing method of the polysiloxane compound of Claim 1 or 2 characterized by the above-mentioned. 4. A polysiloxane compound according to claim 1 or 2 is blended with an organic compound having a group capable of undergoing a condensation reaction therewith and / or a group capable of producing a group capable of undergoing a condensation reaction by hydrolysis. Silicon-containing composition. 5. The silicon-containing composition according to claim 4, wherein a silane coupler is used as the organic compound. 6. The silicon-containing composition according to claim 5, wherein one or more components having the following structural formulas are used as the silane coupler. Embedded image Embedded image _{H 2 NC 3 H 6 Si (} OC 2 H 5) 3 H 2 NC 2 H 4 NHC 3 H 6 Si (OCH 3) 3 H 2 NCONHC 3 H 6 Si (OC 2 H 5) 3 CH 2 = CHSi (OC _{2 H 5) 3 CH 2 =} CHSi (OCH 3) 3 CH 2 = CHSi (OC 2 H 4 OCH 3) 3 HS-C 3 H 6 Si (OCH 3) 3 HS-C 3 H 6 Si (OC 2 H _{5) 3 HS-C 3 H} 6 Si (OC 2 H 4 OCH 3) 3 7. The silicon-containing composition according to claim 4, wherein the organic compound is an active hydrogen-containing compound. 8. A curable composition obtained by blending the silicon-containing composition according to claim 4 with an organic resin. 9. A curable composition obtained by blending the polysiloxane compound according to claim 1 or 2 with an organic resin. 10. A curable composition obtained by blending the silicon-containing composition according to claim 4 with an isocyanate. 11. A curable composition comprising a powder containing the silicon-containing composition according to claim 4. 12. A curable composition obtained by further mixing a powder with the curable composition according to claim 8. 13. A cured product obtained by applying and curing the curable composition according to claim 8 on a substrate.