JPH10212354A - Polyalkoxypolysiloxane, its production and curable composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyalkoxypolysiloxane which can hardly be evaporated even when heated, has good storage stability and is useful as a silicone component added to a film-forming composition by selecting the one which gives a molecular weight distribution in which the ratio of the area of a peak having a specified molecular weight or below has a specified value or below when analyzed by GPC. SOLUTION: This polyalkoxypolysiloxane has a molecular weight distribution in which the rate of the area of a peak having a molecular weight of 435 or below is 30% or below when analyzed by GPC and has a tetraalkoxysilane monomer content of 0.5wt.% or below. This is obtained by reacting a tetraalkoxysilane in the presence of 0.8-1.5mol, per mol of the silane, water and optionally a catalyst (desirably hydrochloric acid) in a solvent (e.g. alcohol). In order to obtain a polyalkoxypolysiloxane having properties, especially the property of forming a high-hardness coating film, it is desirable to use methanol and tetramethoxysilane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyalkoxypolysiloxane which is extremely useful as a silicon component to be incorporated in a coating film forming composition, a method for producing the same, and use thereof.

[0002]

2. Description of the Related Art In recent years, an alkoxy group, which is used alone or in combination with an organic component such as an organic polymer to improve the scratch resistance and stain resistance when used in applications such as hard coating, exterior wall coating and adhesives, has been developed. Attention has been drawn to silicon-bonded alkoxysilanes and / or oligomers that are partially hydrolyzed condensates thereof. For example, the present inventors have proposed a polysiloxane oligomer represented by the following chemical formula, and a product in which the storage stability is improved by reducing the content of the monomer to 1% or less (Japanese Patent Application Laid-Open No. 7-1995). 48454
Publication).

[0003]

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[0004]

However, when a liquid composition obtained by blending these conventional hydrolyzable and condensable silicon compounds with an organic component is applied to a substrate and cured, the resulting coating composition is obtained. In some cases, the hardness of the film was not sufficient. Therefore, the present inventors have conducted intensive studies, and in order to obtain a coating film having high hardness from such a liquid composition, it is necessary to bake at a high temperature in a furnace, and the amount of the silicon compound volatilized at this time cannot be ignored. It has been found. Particularly, tetraalkoxysilane, which is a general hydrolyzable and condensable silicon compound, has a low molecular weight, and volatilizes faster by heating than hydrolytic condensation proceeds. In addition, although oligomers obtained by hydrolyzing and condensing tetraalkoxysilane are generally known, it has been found that the amount of volatilization cannot be ignored by using these oligomers. For this reason, it is considered that the silicon content in the obtained coating film does not increase to a desired level, and that the coating characteristics such as hardness are not sufficient. Further, there is a problem that the volatile silicon compound adheres to an exhaust gas treatment facility such as a baking furnace or the like and a furnace wall portion, thereby causing damage to the facility or a coating film defect due to falling off of furnace wall deposits. However, in order to increase the molecular weight of the silicon compound, it is necessary to increase the amount of water at the time of hydrolysis to increase the molecular weight of the oligomer. It was extremely difficult to obtain a condensate of tetraalkoxysilane having a desired molecular weight and good storage stability, for example, the change with time would be remarkable.

[0005]

Means for Solving the Problems Accordingly, the present inventors have conducted intensive studies, and have found that a condensate of a tetraalkoxysilane, which has a molecular weight distribution in which a low molecular weight substance is below a certain specific range, However, the present invention succeeded in obtaining a polyalkoxypolysiloxane which was hardly volatilized and had good storage stability, and reached the present invention. That is, the present invention
A polyalkoxypolysiloxane characterized in that the ratio of the peak area of a portion having a molecular weight of 435 or less to the entire peak area in the molecular weight distribution by C analysis is 30% or less, and the production and use thereof. Hereinafter, the present invention will be described in detail.

First, the polyalkoxypolysiloxane of the present invention has a siloxane skeleton (Si—O) _n as a main chain,
The side chain refers to a silicon compound in which an alkoxy group is bonded to Si. The side chain alkoxy groups may be different from each other. Typically, it is a condensate (oligomer) of tetraalkoxysilane (represented by the chemical formula Si (OR) _4. R is an alkyl group and preferably C1 to C4). Here, the tetraalkoxysilane is not particularly limited as long as it is represented by the above chemical formula, and examples thereof include those obtained by a reaction between silicon and an alcohol or a reaction between a silicon halide and an alcohol.
The former method is preferable because it is easy to prevent the halogen element from remaining. Although a plurality of types of R may be used, in order to obtain a polyalkoxypolysiloxane having characteristics such as formation of a coating film having high hardness, methanol is used as alcohol and tetramethoxysilane is used as tetraalkoxysilane. It is desirable to use

In order to obtain a condensate of tetramethoxysilane, generally, the monomer of tetramethoxysilane is partially hydrolyzed and condensed. In the partial hydrolysis condensation reaction, first, the molar ratio is 0.8 to 1.6 with respect to tetramethoxysilane.
Double equivalent water is added to react. At less than 0.8 mole times,
In the molecular weight distribution of the obtained oligomer by GPC analysis, the ratio of the peak area of a portion having a molecular weight of 435 or less to the entire peak area exceeds 30%, resulting in a large amount of volatile components. On the other hand, if it exceeds 1.6 equivalents,
The resulting polymethoxypolysiloxane is very easy to gel, has poor storage stability, and is difficult to use. During the reaction, a catalyst can be appropriately added as needed.
For example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. formic acid,
Organic acids such as carboxylic acids such as acetic acid and oxalic acid and sulfonic acids such as benzenesulfonic acid, toluenesulfonic acid and ethylbenzenesulfonic acid. Alternatively, a basic substance such as ammonia, caustic soda, and amine can be used.
Of these, hydrochloric acid is preferred because it can be easily removed by distillation after the reaction is completed. Usually, the amount of the catalyst to be used is 1 × 10 ⁻⁶ to 1 × 10 with respect to tetramethoxysilane.
^-2 mole times, preferably 1 × 10 ^-5 to 1 × 10 ^-3 mole times.

[0008] The method of adding the catalyst is not particularly limited,
It may be mixed or dissolved with water to be added, or may be mixed or dissolved with a solvent described below. In addition, the reaction can be performed in the presence of a solvent. For example, a water-soluble organic solvent such as alcohol, ether and ketone can be used, but methanol is most preferably used as a solvent because methanol is produced as a by-product from the hydrolysis-condensation reaction of tetramethoxysilane. The amount of the solvent to be used is 0.1 to 50 mol times, preferably 0.1 mol, per mol of tetramethoxysilane.
It is 5-3.0 mole times. In the partial hydrolysis-condensation reaction of tetramethoxysilane, it is general that tetramethoxysilane and a solvent are mixed, and a predetermined amount of water is added while appropriately stirring as necessary. Thereafter, the mixture is heated to cause the hydrolysis and condensation reaction to proceed in a reflux state. The reflux is carried out at a temperature close to the boiling point of the solvent or the by-produced methanol.

The reaction time under reflux varies depending on the type of catalyst, but is usually 0.5 to 10 hours, preferably 2 to 5 hours. Next, methanol by-produced by the partial hydrolysis condensation reaction is distilled off. Various distillation and evaporation operations can be applied as this method. That is, a method of distilling by heating at or above the boiling point of methanol under normal pressure or reduced pressure, or a method of distilling by introducing an inert gas such as nitrogen, carbon dioxide, argon, and helium even if the boiling point is lower than the boiling point. There is. Industrially, at normal pressure, 80 to 130 ° C, preferably 100 to 130 ° C.
A method of heating to 120 ° C. and distilling off is suitable. In the case of industrial implementation, the temperature is raised to this temperature, and then maintained at that temperature for 0.5 to 10 hours, preferably 1 to 5 hours to complete the condensation reaction and to reduce the by-produced methanol. It is desirable to completely evaporate.

Thus, the polyalkoxypolysiloxane of the present invention, which is a condensate of tetraalkoxysilane, can be obtained. Usually, about 0.6 to 5% of the monomer remains in the polyalkoxypolysiloxane. In particular, when tetramethoxysilane is used, it is desirable to distill off this monomer. This is because the monomer of tetramethoxysilane has toxicity such as irritation to the cornea and the like, which is not preferable in the working environment, and the remaining monomer may affect the storage stability of the oligomer. Generally, if the monomer is removed to 0.5% by weight or less, preferably 0.2% by weight or less, the influence of the monomer vaporized to the surroundings can be extremely reduced.

As a method for removing the monomer, since the monomer is usually the lowest-boiling substance in the reaction solution, various distillation and evaporation operations can be applied as in the case of distilling off the solvent. That is, a method in which a solution is heated and distilled at a pressure not lower than the boiling point of a monomer under normal pressure or reduced pressure. In addition, even if the heating is performed at a temperature lower than the boiling point, an inert gas such as nitrogen, carbon dioxide, argon, and helium is subjected to SV. (Space Velocity) 1-100
The method of blowing with (1 / Hr) is the simplest. If the temperature at this time is set to 200 ° C. or higher, the polymethoxypolysiloxane undergoes depolymerization and a monomer is generated.
The temperature is 30 to 200 ° C, preferably 130 to 170 ° C.
Thus, the polyalkoxypolysiloxane of the present invention useful in various applications can be obtained by a relatively simple and easy method.

The above-described production method is a typical method for obtaining the polyalkoxypolysiloxane of the present invention, and it goes without saying that the polyalkoxypolysiloxane of the present invention may be obtained by another method. In the thus obtained polyalkoxypolysiloxane of the present invention, the ratio of the peak area of the portion having a molecular weight of 435 or less to the total peak area in the molecular weight distribution by GPC analysis is 30.
% Or less. Further, the ratio of the peak area of the portion having a molecular weight of 435 or less can be set to 20% or less, and further, it can be set to 10% or less. Such a polyalkoxypolysiloxane has never existed before. Such a polyalkoxypolysiloxane of the present invention has a storage stability of one year or more and can maintain a liquid state that is transparent and has no composition change.

In particular, when polymethoxypolysiloxane having a methoxy group as an alkoxy group is used, for the purpose of improving the safety of workers in industrial handling,
Since the content of the highly toxic tetramethoxysilane monomer can be suppressed to 0.5% by weight or less and the content of the solvent or the by-produced alcohol can be controlled to 0.5% by weight or less, the extremely It can be said to be a useful silicon-containing liquid material. As described above, the polyalkoxypolysiloxane of the present invention, which has characteristics different from those of the conventionally existing polyalkoxypolysiloxane, is used for a hard coat as a hydrolysis solution, or is added to various resins to impart hydrophilicity, It can be applied to various uses such as improvement of stain resistance, acid resistance, weather resistance, etc., or use such as sand mold for casting.

The above-mentioned polyalkoxypolysiloxane is blended with a reactive organic compound having a functional group capable of undergoing a condensation reaction with the polyalkoxypolysiloxane and / or a group capable of forming a group capable of undergoing a condensation reaction by hydrolysis. Things. That is, an organic compound having a group condensable with the alkoxy group of the polyalkoxypolysiloxane of the present invention, and / or a group condensable with the alkoxy group of the polyalkoxypolysiloxane of the present invention can be generated by hydrolysis. Organic compounds. 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.

[0015] Specifically, for example, (i) silane couplers (generally RSiX _3: X is a hydrolyzable group, R represents an organic group) (ii) an active hydrogen-containing compounds, and the like.
More specifically, for example, as the silane coupler of (i),

Embedded image Such as methyl acrylate,

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Epoxy compounds 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,} amino-based _{etc., CH 2 = CHSi (OC 2} H 5) 3, CH 2 = CHSi (OCH 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 (O
_{C 2 H 5) 3, HS} -C 3 H 6 Si (OC 2 H 4 OCH 3) 3, mercapto and the like, and the like.

Any of these can be suitably 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.

As (ii), for example, the following I to IV
One. 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 alcohol having a molecular weight of 500 or more (1) Functional group 1 A monohydric alcohol or monohydric carboxylic acid is added with at least 6 mol, preferably 10 mol or more of alkylene oxide 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-Based Alcohol A dihydric carboxylic acid is esterified with a dihydric alcohol to give a molecular weight of 500 or more, preferably 1,000 to 2,000.
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. If the compound (ii) is used, the polyalkoxypolysiloxane of the present invention can be particularly solubilized in a polyisocyanate, so that a useful isocyanate composition can be obtained.
In this case, the mixing ratio is such that the ratio of polyisocyanate / (polyalkoxypolysiloxane + active hydrogen compound) is 90 /
10-10 / 90 (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 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 polyalkoxypolysiloxane of the present invention, and / or condensation with the polyalkoxypolysiloxane of the present invention by hydrolysis. Any of those having a group capable of generating a reactive group can be used. Further, two or more of the above reactive organic compounds may be used in combination depending on the purpose. The amount of the reactive organic compound to be added is not more than equimolar to the alkoxy group of the polyalkoxypolysiloxane, and is usually 0.1 mol.
It is suitably from 1 to 1 mol times. Particularly preferably 0.05
The amount is up to 0.5 mol times, but may be appropriately selected according to the purpose. When a silane coupler is used as the reactive organic compound, silanol groups capable of undergoing a condensation reaction with the polyalkoxypolysiloxane are generated by adding water to hydrolyze the silane coupler.

In blending the polyalkoxypolysiloxane of the present invention with these reactive organic compounds, a solvent, a dispersion medium, a curing catalyst and the like may be added as necessary. 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
Species can be used, or two or more can be used in combination.

Specific examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, and octanol. Examples of glycol derivatives include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol. Glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, and the like. 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.

[0024] 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 polyalkoxypolysiloxane of the present invention. When dispersing (emulsifying), an appropriate amount of water is used and a homomixer is used.
A known method such as a colloid mill and ultrasonic waves can be used.

Of these solvents and dispersion media, the solvent is usually used, but when used as a curable composition described below,
This is desirable because the stability and physical properties of the cured product are excellent. In addition, the type of the solvent may be selected from those suitable for the properties of the target cured product, processing conditions, and the like,
For example, for the application of coating film, for example, benzene, toluene,
When a hydrocarbon such as xylene or a ketone such as methyl ethyl ketone is used, since the desolvation rate during film curing is appropriate, the surface gloss of the obtained film is particularly excellent, and the desired film thickness is obtained. Can be easily obtained. Others
In general, it may be appropriately selected according to the type of the reactive organic compound used and the desired film properties. Note that, depending on the type of the reactive organic compound, there are many functional groups, and it may be desirable to further add a catalyst to improve the curing speed after the treatment.

Examples of the catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, organic acids such as acetic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, formic acid and oxalic acid, and potassium hydroxide. Catalysts such as sodium hydroxide, sodium hydroxide, calcium hydroxide, ammonia, etc., organic metals, metal alkoxides, for example, organic tin compounds such as dibutyltin dilaurate, dibutyltin dioctate, 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 ( Metal chelate compounds such as cetyl acetonate) and zirconium bis (isopropoxy) bis (acetylacetonate), boron butoxide,
Although there is a boron compound such as boric acid, the storage stability of the silicon-containing composition, the hardness and flexibility of the coating film obtained when used as a coating solution, and the properties such as flexibility are excellent. From the viewpoint of preventing corrosion of the base material, one or more of acetic acid, maleic acid, oxalic acid, fumaric acid, and metal alkoxides are preferably used.

The respective components in the silicon-containing composition, in particular, the polyalkoxypolysiloxane and the above-mentioned reactive organic compound may be present in the liquid in a condensed state, or may be in a state of being simply mixed. May be present. 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, when various powders are treated using the polyalkoxypolysiloxane of the present invention or the silicon-containing composition of the present invention, a general wet method or dry method can be used. 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 polyalkoxypolysiloxane or a silicon-containing composition are charged and stirred at room temperature until the surface of the raw material powder is sufficiently wet, and then heated to 100 to 150 ° C. while stirring is continued. By promoting the crosslinking reaction of the polyalkoxypolysiloxane or the silicon-containing composition, and evaporating volatile components such as water, a surface-treated powder can be obtained. When the raw material powder is difficult to wet uniformly with a predetermined amount of the polyalkoxypolysiloxane or the silicon-containing composition, the predetermined amount of the polyalkoxypolysiloxane or the silicon-containing composition may be diluted with water or the like before use. Good. In particular, when enhancing the affinity with the matrix, the raw material powder is subjected to a surface treatment in advance with a polyalkoxypolysiloxane, particularly the polyalkoxypolysiloxane of the present invention or a liquid obtained by diluting these with water or the like. After drying or the like, the composition can be further treated with the curable composition of the present invention.

Since the polyalkoxypolysiloxane and the silicon-containing composition of the present invention have excellent compatibility with various substrates, the raw material powder to be treated is not particularly limited. For example, glass, cement, concrete, iron Metals such as copper, nickel, gold, silver, aluminum, rare earth and cobalt, carbon materials such as carbon black, graphite, carbon fiber, activated carbon, carbon hollow spheres, silica, alumina, titanium oxide, beryllium oxide, iron oxide, and oxide Oxides such as zinc, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, hydroxides such as aluminum hydroxide and magnesium hydroxide, carbonates such as calcium carbonate and magnesium carbonate, and sulfates such as calcium sulfate , Talc, clay, mica, calcium silicate, glass, glass hollow , Silicates such as glass fiber,
Other general-purpose fillers such as various inorganic powders such as calcium titanate, lead zirconate titanate, aluminum nitride, silicon carbide, and cadmium sulfide, wood powder, starch, various organic pigments, and organic fillers such as polystyrene and nylon. And conductive, electromagnetic wave shielding, magnetism, sound insulation, thermal conductivity, slow burning, flame retardant. Regardless of whether it is a functional filler for imparting abrasion resistance or the like, it can be treated with the polyalkoxypolysiloxane or the silicon-containing composition of the present invention. Then, the surface-treated powder obtained by treating these raw material powders with the polyalkoxypolysiloxane of the present invention or the silicon-containing composition is, for example, an oil-based paint, a synthetic resin paint, a water-soluble resin paint, an emulsion. Paints, emulsion paints with aggregates, traffic paints, paints such as putty and caulking, shoe soles, electric wires, tires, industrial supplies, belts, hoses, rubberized cloth, rubber glue, adhesive tape, latex, rubber products such as backsizing , Coating, filling, paper use such as synthetic paper, synthetic resin products such as PVC, polyolefin, epoxy phenol, unsaturated polyester, electric welding rod, glass, acid neutralization, medicine, food, sugar, toothpaste , Used for various fillers such as cleanser, bunker sand, pesticide, compound feed, building materials, etc. The type, FRP (Fiber
Reinforced Plastic).

When the polyalkoxypolysiloxane or the silicon-containing composition of the present invention is impregnated into a porous material such as paper, the material is tipped on the polyalkoxypolysiloxane or the silicon-containing composition and then dried. I just need. If the crosslinking reaction proceeds at room temperature or under heating, characteristics such as flame retardancy and smoothness can be imparted. When the polyalkoxypolysiloxane or silicon-containing composition of the present invention is used for bonding, apply the polyalkoxypolysiloxane or silicon-containing composition to the surface to be bonded and press the surfaces to be bonded together before completely curing. I do. Alternatively, if the surface to be bonded is pre-coated in advance with the polyalkoxypolysiloxane of the present invention or a hydrolyzed solution thereof, the bonding strength is further increased.

Further, a curable composition obtained by adding a pigment to the silicon-containing composition of the present invention or the polyalkoxypolysiloxane of the present invention, or blending various inorganic or organic fillers. And cured to form 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 polyalkoxypolysiloxane of the present invention,
Alternatively, a composition obtained by further blending an organic resin such as a polyester, a polyurethane, an acrylic resin, or a silicone resin with the silicon-containing composition can be used as the curable composition.
In addition, the above-mentioned various pigments or various fillers are dispersed in the curable composition, or those in which these are dispersed in an organic resin in advance and the polyalkoxypolysiloxane of the present invention, or a silicon-containing composition are blended to form a paint or composite. Use as a material is particularly useful. As the pigment, a lead compound such as lead white as an inorganic pigment, zinc white, a zinc compound such as lithopone, a titanium compound such as titanium oxide, aureoline, cobalt green, cerulean blue 2, cobalt blue, a cobalt compound such as cobalt violet, Iron compounds such as iron oxide; chromium compounds such as chromium oxide, lead chromate and barium chromate; cadmium compounds such as cadmium sulfate and cadmium sulfate selenide; and carbon black. As organic pigments, water-insoluble phthalocyanine, dioxazine, anthraquinone,
Examples include colored compounds such as quinophthalones, and metal-containing compounds thereof. It goes without saying that any compounds other than the listed compounds can be used as long as they can be used for coloring the liquid composition of the present invention. These can be used alone or in combination of two or more.

Examples of the filler include carbon materials such as carbon black, graphite and carbon fiber, oxides such as silica, alumina and magnesium oxide, hydroxides such as aluminum hydroxide and magnesium hydroxide, calcium carbonate and magnesium carbonate. Inorganic fillers such as carbonates, lead sulfates such as calcium sulfate, silicate compounds such as talc, clay, mica, calcium silicate, and glass fiber. And polystyrene,
Organic polymer compounds such as polyethylene, polypropylene, and nylon; and organic fillers such as wood flour and starch. These can be used alone or in combination of two or more.

The compounding ratio of the organic resin to the polyalkoxypolysiloxane or the silicon-containing composition is usually from 1 to 500 parts by weight of the organic resin as a nonvolatile component based on 100 parts by weight of the polyalkoxysiloxane and / or the silicon-containing composition.
Effective when used in a wide range of 0 parts by weight. For example, when importance is placed on the development of the properties, such as hardness and high heat resistance, of the polyalkoxypolysiloxane of the present invention, the range of the organic resin is preferably 1 to 400 parts by weight. At this time, the concentration in terms of SiO 2 in the nonvolatile component of the blended liquid is 10 to 95%.
Is preferable. On the other hand, by using a polyalkoxypolysiloxane or a silicon-containing composition as an additive, while maintaining the properties of the organic resin such as flexibility and thickening, the coating film or the like containing an organic resin as a main component has low contamination. When importance is placed on imparting properties, weather resistance, etc., the organic resin should be 50
It is preferable to mix in the range of 0 to 5000 parts by weight.
At this time, the concentration in terms of SiO2 in the nonvolatile component of the mixture is preferably 1 to 10%. Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 Tetramethoxysilane 608 was added to a glass 1-liter, 5-necked corbene equipped with a stirrer, a Dimroth condenser, a thermometer and a nitrogen blowing tube.
g and 192 g of methanol and stirred for 5 minutes.
A mixture of 1.6 g and 0.15 g of 20% hydrochloric acid was added.
At this time, the amount of water relative to tetramethoxysilane was 1.
It corresponds to 0 mole times. Thereafter, the mixture was heated until a reflux state (65 ° C.) was reached, and reacted under reflux for 4 hours.

Next, the Jimroth condenser was replaced with a Liebig condenser equipped with a toe tube and a distilling receiver.
The methanol was distilled off while heating until the internal temperature reached 150 ° C. Then, while keeping the temperature at 150 ° C, high-purity nitrogen gas was blown into the liquid at SV = 10 for about 2 hours to distill the remaining tetramethoxysilane. Then, a colorless and transparent liquid polymethoxypolysiloxane was obtained in the Kolben. Sampling the contents after natural cooling to room temperature and GPC
As a result of analysis, as shown in FIG. 1, the ratio of the peak area of the portion having a molecular weight of 435 or less to the total peak area was 9.
8%, and the weight average molecular weight determined from all peaks was 11
90. Further, according to GC (gas chromatograph) analysis, the content of tetramethoxysilane was 0.2% by weight or less (lower detection limit or less), and the content of methanol was 0.18% by weight.
Met. GPC analysis and GC analysis conditions are shown below.

[GPC analysis conditions] Apparatus: Waters high temperature GPC 150C Column: PLgel 500Å (5μ) 2 +1
00Å (5μ) 1 tube Temperature: Column 40 ° C, Inlet 30 ° C, Pump 30 ° C Solvent: Ethyl acetate 1.0 ml / min Detector: RI detector 32 × 1 RIU / FS sample: Ethyl acetate Diluted to 4 wt% in terms of SiO2 and injected 100 μl. Chart speed: 5 mm / min. Data processing: CP-8000 manufactured by Tosoh. GPC calibration curves were prepared using standard polypropylene glycol and tetramethoxysilane oligomer. .

[GC analysis conditions] Apparatus: GC-14A made by Shimadzu Corporation Column: Capillary column (J & W fused megabore column DB-5) Detector: TCD Carrier gas: Helium 8 ml / min Makeup gas: Helium 60ml / min Column temperature: 40-250 ° C, 10 ° C / min Heated gas chromatography Inlet temperature: 270 ° C Detector temperature: 270 ° C Current current: 75mA Internal standard substance: m-xylene or sec-butylbenzene (xylene-containing sample) Injection amount of sample: 0.5 μl Internal standard / sample: 0.2 / 2 g Further, this polymethoxypolysiloxane was sealed in a sealed container for 50 minutes.
An accelerated storage test was conducted at 45 ° C. for 45 days (equivalent to about one year in terms of room temperature).
It increased only about 1 cp, and was a liquid material having good storage stability.

Example 2 The same operation as in Example 1 was carried out except that the amount of water was changed to 79.2 g (corresponding to 1.1 mol times of tetramethoxysilane). A polysiloxane was obtained. When the obtained polymethoxypolysiloxane was subjected to GPC analysis in the same manner as in Example 1, as shown in FIG. 2, the ratio of the peak area of the portion having a molecular weight of 435 or less to the total peak area was 5.9%. The weight average molecular weight determined from all peaks was 1891. From the same GC (gas chromatograph) analysis as in Example 1, the teramethoxysilane content was 0.2% by weight or less (lower detection limit or less), and the methanol content was 0.06%.
% By weight. Further, the polymethoxypolysiloxane was subjected to an accelerated storage test at 50 ° C. for 45 days (equivalent to about one year in terms of room temperature) in a sealed state.
It increased only from 4.6 cp to about 86.6 cp, and was a liquid having good storage stability.

Example 3 381.0 g of tetramethoxysilane and 120.0 g of methanol were placed in a 1-liter glass four-necked round-bottomed flask equipped with a stirrer, a Dimroth condenser and a thermometer, and stirred for 5 minutes. A mixed solution of 5.0 g of 0.1 N hydrochloric acid solution and 49.0 g of water was added. At this time, the amount of water with respect to tetramethoxysilane is equivalent to 1.2 mol times. Thereafter, the mixture was heated until a reflux state (65 ° C.) was reached, and reacted under reflux for 4 hours. Thereafter, this was cooled to about 56 ° C., and 382.5 g of xylene was added. Further heat gradually with stirring until the internal temperature is about 13
The methanol component was distilled off until the temperature reached 5 ° C.
Nitrogen gas was blown in at 5 ° C. and maintained for 5 hours. Thereafter, the mixture was cooled to room temperature to obtain a colorless and transparent liquid polymethoxypolysiloxane. This was subjected to GPC analysis in the same manner as in Example 1. As shown in FIG. 3, the ratio of the peak area of the portion having a molecular weight of 435 or less to the total peak area was 7.0%.
And the weight average molecular weight determined from all peaks was 2585.
Met. Further, from the same GC (gas chromatograph) analysis as in Example 1, the content of tetramethoxysilane was found to be 0.1%.
2% by weight or less (lower limit of detection or less), methanol content of 0.
It was 10% by weight and xylene 57.0% by weight. Furthermore,
This polymethoxypolysiloxane is sealed at 50 ° C.
An accelerated storage test was performed for 5 days (corresponding to about 1 year at room temperature), but the liquid viscosity was unchanged from the initial value of 2.1 cp, indicating that the liquid material had good storage stability.

Example 4 456.6 g of tetramethoxysilane and 144.0 g of methanol were charged into a 1-liter glass four-necked round-bottomed flask equipped with a stirrer, a Dimroth condenser, and a thermometer, and stirred for 5 minutes. A mixture of 6.0 g of 1N hydrochloric acid and 48.0 g of water was added. At this time, the amount of water relative to tetramethoxysilane is equivalent to 1.0 mole times. Thereafter, the mixture was heated until a reflux state (65 ° C.) was reached, and reacted under reflux for 4 hours. Thereafter, the mixture was cooled to about 56 ° C., and 44.4 g of n-butanol was added. The mixture was further heated gradually with stirring, and refluxed (6
7 ° C.) for 1 hour, and then replace the Dimroth condenser with a Liebig condenser equipped with a T-shaped tube and a distilling receiver. While maintaining the above, high-purity nitrogen gas was blown into the liquid at SV = 7 for about 5 hours to distill out the remaining tetramethoxysilane and alcohol components. Thereafter, the mixture was cooled to room temperature to obtain a colorless and transparent liquid polyalkoxypolysiloxane having a methoxy group and a butoxy group. This was subjected to GPC analysis in the same manner as in Example 1. As shown in FIG. 4, the ratio of the peak area of the portion having a molecular weight of 435 or less to the total peak area was 14.
7%, and the weight average molecular weight determined from all peaks was 10%.
62. From the same GC (gas chromatograph) analysis as in Example 1, the content of tetramethoxysilane was 0.2% by weight or less (lower detection limit or less), the content of methanol was 0.05% by weight, and the weight of n-butanol was 0.2% by weight. % (Lower than the lower detection limit). Further, this polyalkoxypolysiloxane was subjected to an accelerated storage test at 50 ° C. for 45 days (equivalent to about one year in terms of room temperature) in a sealed state.
It increased only from 6.4 cp to about 16.8 cp, and was a liquid material having good storage stability.

Example 5 The same operation as in Example 4 was carried out except that the amount of water was 54.5 g (corresponding to 1.05 mol times with respect to tetramethoxysilane) and the amount of n-butanol was 42.2 g. Was carried out to obtain a colorless and transparent liquid polyalkoxypolysiloxane having a methoxy group and a butoxy group. When this was subjected to GPC analysis in the same manner as in Example 1, as shown in FIG. 5, the ratio of the peak area of the portion having a molecular weight of 435 or less to the total peak area was 7.4%, and was determined from all the peaks. Its weight average molecular weight was 1599. Also,
According to the same GC (gas chromatography) analysis as in Example 1, the content of tetramethoxysilane was 0.2% by weight or less (lower detection limit or less), the content of methanol was 0.05% by weight,
n-Butanol was 0.2% by weight (lower than the lower limit of detection). Further, the polyalkoxypolysiloxane was subjected to an accelerated storage test at 50 ° C. for 45 days (equivalent to about one year in terms of room temperature) in a closed state, but the liquid viscosity did not increase from the initial 52 cp, and the storage stability was good. Liquid substance.

Example 6 The same operation as in Example 4 was carried out except that the amount of water was 59.4 g (corresponding to 1.10 mol times of tetramethoxysilane) and the amount of n-butanol was 40.0 g. Was carried out to obtain a colorless and transparent liquid polyalkoxypolysiloxane having a methoxy group and a butoxy group. This was subjected to GPC analysis in the same manner as in Example 1, and as shown in FIG. 6, the ratio of the peak area of the portion having a molecular weight of 435 or less to the total peak area was 4.2%, which was obtained from all the peaks. Its weight average molecular weight was 2,847. Also,
According to the same GC (gas chromatography) analysis as in Example 1, the content of tetramethoxysilane was 0.2% by weight or less (lower limit of detection), the methanol content was 0.06% by weight,
n-Butanol was 0.2% by weight (lower than the lower limit of detection). Further, this polyalkoxypolysiloxane was subjected to an accelerated storage test at 50 ° C. for 45 days (equivalent to about one year in terms of room temperature) in a sealed state.
It increased only about 87 cp, and was a liquid substance having good storage stability.

(Comparative Example 1) A polymethoxypolysiloxane manufactured by Company A was analyzed by the same analysis method as in Example 1, and as shown in FIG.
The ratio of the peak area of the portion of 5 or less is 31.4%,
The weight average molecular weight determined from all peaks was 679.
Also, from the same GC (gas chromatograph) analysis as in Example 1, the teramethoxysilane content was 1.29% by weight,
The methanol content was 1.33% by weight. (Comparative Example 2) Polymethoxypolysiloxane manufactured by Company B was
When analyzed by the same analysis method as in Example 1, as shown in FIG. 8, the ratio of the peak area of the portion having a molecular weight of 435 or less to the total peak area was 31.0%, and the weight determined from all the peaks was obtained. The average molecular weight was 639. Example 1
According to the same GC (gas chromatograph) analysis as in the above, the content of teramethoxysilane was 2.26% by weight, and the content of methanol was 0.30% by weight.

[0045]

According to the present invention, a high-molecular-weight polyalkoxypolysiloxane, which is hardly volatilized by heating and has good storage stability, can be transparently prepared by having a low-molecular weight substance having a molecular weight distribution of a specific range or less. It can be obtained in an appropriate liquid. The polyalkoxypolysiloxane or silicon-containing composition of the present invention has a high degree of polymerization, but has a storage stability of one year or more, and can maintain a liquid state that is transparent and has no composition change. For example, used as a hydrolysis solution for hard coat, or because it has excellent compatibility with organic resins and the like,
The curable composition obtained by blending with an organic resin in which a pigment or a filler is dispersed is used to impart hydrophilicity, stain resistance, acid resistance, chemical resistance, and weather resistance to a coating film obtained by curing the composition. In addition, characteristics such as heat resistance can be improved. Further, it is a novel polyalkoxypolysiloxane that can be applied to various uses such as a binder use such as a sand mold for casting and can provide an extremely useful curable composition.

[Brief description of the drawings]

FIG. 1 is a GPC measurement chart of the polymethoxypolysiloxane obtained in Example 1.

FIG. 2 is a GPC measurement chart of the polymethoxypolysiloxane obtained in Example 2.

FIG. 3 is a GPC measurement chart of the polymethoxypolysiloxane obtained in Example 3.

FIG. 4 is a GPC measurement chart of a polyalkoxypolysiloxane having a methoxy group and a butoxy group obtained in Example 4.

FIG. 5 is a GPC measurement chart of a polyalkoxypolysiloxane having a methoxy group and a butoxy group obtained in Example 5.

FIG. 6 is a GPC measurement chart of the polyalkoxypolysiloxane having a methoxy group and a butoxy group obtained in Example 6.

FIG. 7 is a GPC measurement chart of polymethoxypolysiloxane manufactured by Company A of Comparative Example 1.

FIG. 8 is a GPC measurement chart of polymethoxypolysiloxane manufactured by Company B of Comparative Example 2.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07F 7/18 C07F 7/18 C Q (72) Inventor Hozumi Endo 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu City Mitsubishi Chemical Corporation Kurosaki In business office

Claims (16)

[Claims] 1. In a molecular weight distribution by GPC analysis,
A polyalkoxypolysiloxane wherein the ratio of the peak area of a portion having a molecular weight of 435 or less to the total peak area is 30% or less. 2. The polyalkoxypolysiloxane according to claim 1, wherein the content of the tetraalkoxysilane monomer is 0.5% by weight or less. 3. The polyalkoxypolysiloxane according to claim 1, wherein the alkoxy group is a methoxy group. 4. An alkoxy group having a methoxy group and 2 carbon atoms
The polyalkoxypolysiloxane according to claim 1, which is an alkoxy group of from 15 to 15. 5. The poly according to claim 1, wherein the tetraalkoxysilane is hydrolyzed and condensed with 0.8 to 1.6 times the molar amount of water. A method for producing an alkoxypolysiloxane. 6. The method for producing a polyalkoxypolysiloxane according to claim 5, wherein the alkoxy group is a methoxy group. 7. An organic compound having a group capable of undergoing a condensation reaction with the polyalkoxypolysiloxane according to claim 1 and / or a group capable of forming a group capable of undergoing a condensation reaction by hydrolysis. A silicon-containing composition formulated. 8. The silicon-containing composition according to claim 7, wherein a silane coupler is used as the organic compound. 9. The silicon-containing composition according to claim 8, wherein one or more components having the following structural formula 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 10. The silicon-containing composition according to claim 8, wherein the organic compound is an active hydrogen-containing compound. 11. A curable composition comprising the silicon-containing composition according to claim 7 and an organic resin. 12. A curable composition comprising the polyalkoxypolysiloxane according to claim 1 and an organic resin. 13. A curable composition comprising the silicon-containing composition according to claim 8 and an isocyanate. 14. A curable composition obtained by mixing a powder with the silicon-containing composition according to claim 8. 15. A curable composition obtained by further mixing a powder with the curable composition according to claim 11. 16. A cured product obtained by applying and curing the curable composition according to claim 11 on a substrate.