JP2756359B2 - Organic silicon-based composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention is useful as an aqueous osmosis type water-absorbing inhibitor for concrete, and is an organic silicon-based material having excellent water resistance and mold resistance, such as water. Composition. More specifically, the antifungal property containing (a) an alkylalkoxysilane and / or a condensate thereof and (b) an organosilicon compound containing an alkoxysilyl group and a quaternary ammonium base in the molecule or a condensate thereof. And a water-based emulsifier comprising water and an emulsifier.

(Prior Art) Conventionally, it has been widely known that alkylalkoxysilanes are useful as water repellents for building and civil engineering materials such as concrete. Generally, those obtained by diluting these alkoxysilanes with various solvents have been used. The range of use of such a solvent-type composition is limited by the properties of the solvent used, such as toxicity, volatility and flammability. For example, when isopropyl alcohol, which has relatively low toxicity, is used as a solvent, there is a problem in that the evaporation to the substrate is limited due to rapid evaporation. Conversely, when a solvent that does not easily volatilize is used, the coated surface becomes wet and difficult to dry, and in general, the solvent type cannot be applied to a wet concrete surface.

In order to solve the above problems and use alkylalkoxysilane as a permeation-type water-absorbing agent for concrete, it is ideal to use an aqueous solution or an aqueous dispersion, but alkoxysilane is strongly hydrolyzable and follows. It has been considered that it is extremely difficult to stably exist in water because a condensation reaction easily occurs.

As a means for solving these problems, a method of emulsifying a hydrolyzable organosilicon compound such as an alkyl trialkoxysilane in an aqueous state using a nonionic emulsifier has recently been proposed (Japanese Patent Application Laid-Open No.
62-197369).

However, although the water absorption preventing effect is recognized in each case, the pollution due to the occurrence of mold has recently become a problem. For this purpose, a conventional fungicide is added as needed to cope with the problem. However, since the fungicide is mixed, a long-lasting fungicide has not been obtained.

[Configuration of the invention]

(Means for Solving the Problems) According to the present invention, as a result of intensive studies to solve the above problems, quaternary salts are generally considered to have fungicidal and antibacterial properties. Is a method of post-addition, so that the effect is usually not sustained. Basically, it has excellent fungicidal properties including (a) an alkylalkoxysilane and / or a condensate thereof and (b) an organosilicon compound containing an alkoxysilyl group and a quaternary ammonium base in the molecule or a condensate thereof. The aqueous organosilicon composition obtained by aqueous emulsification using water and an emulsifier, if necessary, further comprises an alkoxysilyl group and a quaternary ammonium base in the molecule. It has been found that, because of this, the alkoxysilyl group reacts with the base material and other alkoxysilanes to form a strong covalent bond, so that remarkably long mold resistance is maintained.

The alkylalkoxysilane and / or condensate thereof used in the present invention is not particularly limited, and examples thereof include alkyltrialkoxysilane, and / or dialkyldialkoxysilane and / or trialkylmonoalkoxysilane. Generally, alkylalkoxysilanes include those in which at least one alkyl group directly bonded to silicon has 1 to 20 carbon atoms, and further, the alkoxy group has 1 to 4 carbon atoms. For example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane Silane,
Undecyltrimethoxysilane, dodecyltrimethoxysilane, tridecyltrimethoxysilane, tetradecyltrimethoxysilane, pentadecyltrimethoxysilane, hexadecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane,
Nonadecyltrimethoxysilane, eicosyltrimethoxysilane, phenyltrimethoxysilane, octylmethyldimethoxysilane, octadecylmethyldimethoxysilane, diphenyldimethoxysilane, dimethyldimethoxysilane, methylvinyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ Methacryloxypropylmethyldimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, nonyltrisilane Ethoxysilane, decyltriethoxysilane, undecyltriethoxysilane, dodecyltriethoxysilane, tri Decyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, octadecyltriethoxysilane, nonadecyltriethoxysilane, eicosyltriethoxysilane, vinyltriethoxysilane Octylmethyldiethoxysilane, octadecylmethyldiethoxysilane, diphenyldiethoxysilane, methylvinyldiethoxysilane or a mixture thereof and / or a condensate thereof, but is not necessarily limited thereto.

When used as an aqueous emulsion, the alkylalkoxysilane preferably has at least one alkyl group directly bonded to silicon having 6 to 20 carbon atoms, and the alkoxy group is preferably an ethoxy group, and hexyltriethoxysilane and heptyltrisilane. Ethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, undecyltriethoxysilane,
Dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, octadecyltriethoxysilane, nonadecyltriethoxysilane, eicosyltriethoxy Examples include silane, octylmethyldiethoxysilane, octadecylmethyldiethoxysilane, or a mixture thereof.

Here, when used as an aqueous emulsion, when at least one alkyl group directly bonded to silicon has a carbon number of less than 6, hydrolyzability and volatility are extremely high.
Immediately after coating, a part of the silane component reacts with the surface of the base material, delaying further penetration of the aqueous composition, and during that time, unreacted silane components tend to evaporate. Just give Conversely, when the carbon number of at least one alkyl group directly bonded to silicon is larger than 20, the molecular weight is too large and it is difficult to penetrate. When the alkoxy group is a methoxy group, bonding or cross-linking is likely to occur on the surface before penetrating into the base material because of poor stability under alkaline conditions. Conversely, when the alkoxy group is a carbon chain of a propoxy group or more, Even if it penetrates into the inside as much as the stability is good, the bonding with the base material is delayed.

These alkyl trialkoxy silanes and dialkyl dialkoxy silanes can be used without purification by purifying the corresponding α-olefin hydrosilylated with trialkoxy silane and / or alkyl dialkoxy silane as a method of reducing costs. May be. For this catalyst, a transition metal catalyst or a radical initiator used for a usual olefin hydrosilylation reaction can be used. Transition metal catalysts include transition metal complexes or halides such as platinum, cobalt, rhodium, palladium, and nickel. Radical initiators include azobisisobutyronitrile, benzoyl peroxide, and di-peroxide.
t-butyl, t-butyl perbenzoate and the like.
Considering safety, reaction efficiency, economy, reaction conditions, and the like, a method using chloroplatinic acid, which is widely used industrially, is preferable. For example, when chloroplatinic acid is used, the reaction can be carried out in an arbitrary amount. However, it is preferable to reduce the amount of the catalyst as much as possible in consideration of both economic and hygienic aspects. If a chloroplatinic acid catalyst of 0.1 to 5 mmol% based on silane is used, 90
Hydrosilylation with a conversion rate of 98% or more can be performed by heating at 5 ° C. for 5 hours. Usually, these catalysts use a solution dissolved in a solvent or the like. Since this reaction proceeds quantitatively and requires only a very small amount of catalyst, there is no need to purify it unless there is any problem such as residual hydrosilane or catalyst toxicity.

Examples of the organosilicon compound containing an alkoxysilyl group and a quaternary ammonium base in the molecule or a condensate thereof include the following.

A) a reaction product of an organosilicon compound containing an alkoxysilyl group and an epoxy group and an organic amine, which is quaternized with an acid; and b) a reaction product of an organosilicon compound containing an alkoxysilyl group and an amino group with an organic epoxy compound. The reaction product may be quaternized with an acid, or c) aminoalkoxysilane may be quaternized with an acid.

(A) An example of an organosilicon compound containing an alkoxysilyl group and an epoxy group in a reaction product of an organosilicon compound containing an alkoxysilyl group and an epoxy group and an organic amine, which is quaternized with an acid, is γ-glycidic Xypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-gly Hydrolyzable silanes such as sidoxypropyldimethylethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are exemplified.

In addition, examples of the organic amine include primary, secondary, and tertiary amines. For example, n-propylamine, isopropylamine, n-butylamine, n-amylamine, cyclohexylamine, monoethanolamine,
Aniline, benzylamine, octylamine, oleylamine, stearylamine, γ-aminopropyltriethoxysilane, aminomethyltrimethoxysilane, organosiloxane-modified primary amine, 4-fluoroaniline, 2,2-bis [(4-amino Phenyl) hexafluoropropane], any primary amine such as 4-aminobenzotrifluoride, any secondary amine such as diethylamine, di- (n-propyl) amine, diamylamine, diethanolamine, triethylamine, tributylamine, etc. Of tertiary amines and / or mixtures thereof can be used. The amount of the organic amine to be used is not particularly limited, but preferably 0.1 to 2 mol of the organic amine per 1 mol of the epoxy group in the organosilicon compound containing the alkoxysilyl group and the epoxy group. After mixing these, they are sealed and heated with stirring at 60 to 100 ° C. for 2 to 8 hours to synthesize a silicon-containing amine, to which an equimolar amount of an acid is added and neutralized to obtain a relatively low-molecular-weight quaternary amine. A graded organosilicon compound is obtained.

Any acid can be added as long as it forms an ammonium salt with the generated amine. For example, inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as acetic acid, propionic acid, and benzoic acid; chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, and silicon tetrachloride; titanium tetrachloride; and zirconium tetrachloride. Can be

B) The organosilicon compound containing an alkoxysilyl group and an amino group in a product obtained by quaternizing an organic silicon compound containing an alkoxysilyl group and an amino group and an organic epoxy compound with an acid includes, for example, γ -Aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-
(Β-aminoethyl) -γ-aminopropylmethyldimethoxysilane and the like.

Examples of the organic epoxy compound include, but are not necessarily limited to, allyl glycidyl ether, glycidyl methacrylate, bisphenol type epoxy resin, novolak type epoxy resin, and epoxidized soybean oil. The acids used here may be the same as those described above.

(C) As the aminoalkoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-
(Β-aminoethyl) -γ-aminopropylmethyldimethoxysilane neutralized with an acid. Further examples include Dow Corning's 3- (trimethoxysilyl) -propyloctadecyldimethylammonium chloride.

In the case where an aqueous emulsion is formed as required, these silane compounds can be emulsified using water and an emulsifier. The emulsifier used here is an anionic emulsifier,
Nonionic emulsifiers and cationic emulsifiers can be used. For example, as anionic emulsifiers, fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates,
Alkyl phosphates, polyoxyethylene alkyl or alkyl allyl sulfates, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl phosphates and the like can be mentioned. As nonionic emulsifiers, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, oxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
Examples include glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines. Examples of the cationic emulsifier include an alkylamine salt, a quaternary ammonium salt, an alkyl betaine, an amine oxide, and lecithin. When used, these can be used by optionally mixing them. However, in order not to lower the water resistance, it is preferable to use 0.1% by weight to 20% by weight based on the silane component.

The silane component of the alkylalkoxysilane is 1 to
Preferred is an amount that results in 60% by weight. If it is less than 1% by weight, sufficient performance cannot be obtained unless the number of coatings is increased.
If the content is more than 60% by weight, the storage stability is deteriorated, the viscosity of the solution is increased, and uniform coating becomes difficult. Desirably 5% to 40
If it is% by weight, both characteristics of storage stability and water resistance can be sufficiently obtained.

A commonly used emulsification method is used. For example, an aqueous organosilicon-based composition is obtained by dropping the silane component together with the above-mentioned emulsifier little by little while stirring at a high speed with a homomixer or the like.

Here, the amount of the organosilicon compound or its condensate containing an alkoxysilane group and a quaternary ammonium base in the molecule is not particularly limited, but can be used to such an extent that the water resistance is not reduced. For example, 50% by weight or less is desirable. If the amount is more than 50% by weight, the permeating component is too small, and sufficient waterproof performance may not be obtained.

(Effect of the Invention) The composition thus obtained can be relatively easily synthesized and has a wide selection of materials, so that the material can be designed inexpensively, and further, a quaternary ammonium base-containing organosilicon compound can be used. As a result, an excellent coated product having long-lasting fungicidal and antibacterial properties can be obtained. Also, by using an emulsifier, it can be made into an aqueous emulsion even though it is an aqueous coating, and penetrates deep inside the building civil engineering base material such as concrete and reacts with the hydrophilic groups inside the base material to bond and waterproof. By forming a layer, excellent water resistance and mold resistance can be imparted to the object to be coated. Further, the composition of the present invention exhibited excellent storage stability without increasing the viscosity even after storage at 50 ° C. for one month. Thus, it has been found that the present invention is an aqueous organosilicon-based composition which is extremely useful in the field of architectural civil engineering.

Example 1 20 g of n-octyltriethoxysilane, 3.98 g of polyoxyethylene stearyl ether and 0.02 g of sodium lauryl sulfate, γ-aminopropyltriethoxysilane 1
g, 36% hydrochloric acid (0.1 g) were mixed, and the mixture was stirred at a high speed of 1,000 rpm or more, and water (75 g) was gradually added thereto, whereby a white emulsion stable at room temperature for more than six months was obtained.

Example 2 5.04 g of a mixture obtained by mixing 26.8 g (0.1 mol) of oleylamine and 23.6 g (0.1 mol) of γ-glycidoxypropyltrimethoxysilane and heating and reacting at 75 ° C. for 6 hours in a sealed container.
And 25 g of n-hexyltrimethoxysilane,
Add 0.6 g of acetic acid and 70 g of isopropyl alcohol to 60 ° C
For 3 hours.

Example 3 A mixture obtained by mixing 14.2 g (0.1 mol) of glycidyl methacrylate and 22.1 g (0.1 mol) of γ-aminopropyltriethoxysilane and reacting by heating at 75 ° C. for 6 hours in a sealed container was used to prepare 3.63.
g, n-butyltriethoxysilane 26.37 g,
0.101 g of 36% hydrochloric acid and 70 g of ethanol were added and reacted at 60 ° C. for 3 hours.

Example 4 50 g of octadecyltriethoxysilane, 10 g of hexyltrimethoxysilane, 0.2 g of polyoxyethylene stearyl ether, 0.04 g of sodium lauryl sulfate, and 1 g of 3- (trimethoxysilyl) -propyloctadecyldimethylammonium chloride were mixed at 1000 rpm or more. The mixture was stirred at a high speed and gradually added with 40 g of water to obtain a white emulsion which was stable at room temperature for 6 months or more.

Example 5 100 g of isopropyl alcohol, 95 g of methyltrimethoxysilane, 5 g of a 0.1N aqueous hydrochloric acid solution, and hydrolyzed polycondensation for 5 hours at 60 ° C., 20 g, n-octyltriethoxysilane 30 g, N- (β-amino Ethyl) -γ-aminopropyltrimethoxysilane (1 g) was mixed, and 50 g of isopropyl alcohol was further added to obtain an alcohol solution having a silane concentration of about 50%.

Example 6 100 g of isopropyl alcohol, 95 g of methyltrimethoxysilane, 5 g of 0.1N hydrochloric acid aqueous solution, and hydrolyzed polycondensation at 60 ° C. for 5 hours, 20 g, n-hexyltriethoxysilane 30 g, 3- (trimethoxysilyl) ) -Propyloctadecyldimethylammonium chloride (1 g) is added, polyoxyethylene stearyl ether (0.2 g) and sodium lauryl sulfate (0.04 g) are mixed and stirred at 1,000 rpm or more, and water (50 g) is gradually added thereto at room temperature for 6 months or more. A stable white emulsion was obtained.

Comparative Example 1 n-octyltriethoxysilane (20 g), polyoxyethylene stearyl ether (3.98 g) and sodium lauryl sulfate (0.02 g) were mixed, rapidly stirred at 1,000 rpm or more, and then water (75 g) was gradually added thereto. Thus, a stable white emulsion was obtained.

Comparative Example 2 n-hexyltrimethoxysilane 25 g, concentration 36% hydrochloric acid
0.101 g and isopropyl alcohol 75 g were added and reacted at 60 ° C. for 3 hours to obtain an alcohol solution having a silane concentration of about 25%.

Comparative Example 3 100 g of isopropyl alcohol, 95 g of methyltrimethoxysilane, 5 g of a 0.1 N hydrochloric acid aqueous solution, and hydrolyzed polycondensation at 60 ° C. for 5 hours, 20 g of n-octyltriethoxysilane, and 30 g of n-octyltriethoxysilane were further mixed. 50 g of isopropyl alcohol was added to obtain an alcohol solution having a silane concentration of about 50%.

Comparative Example 4 20 g of n-octyltriethoxysilane, 3.98 g of polyoxyethylene stearyl ether, 0.02 g of sodium lauryl sulfate, and 0.1 g of a commercially available fungicide having no alkoxysilyl group in the molecule of 0.1 g were mixed and rapidly stirred at 1000 rpm or more. Then, 75 g of water was gradually added thereto to obtain a white emulsion which was stable at room temperature for 6 months or more.

As described above, the following physical property tests were performed on Examples 1 to 6 and Comparative Examples 1 to 3. The results are shown in the table.

 The test method is described below.

[Storage stability test] --- After preparing the sample, put 20 g in a 30 ml sample bottle, leave it at room temperature, and observe the change in its appearance.

[Water absorption test] --- 4cm x 4cm x 8cm mortar test piece (JIS
R-5201) was coated on the entire surface at 300 g / m2, dried at room temperature for 12 hours and at 100 ° C for 2 hours, and the water absorption ratio was determined for 24 hours according to JISA-1404.

The sample separated immediately after preparation due to poor storage stability was well shaken to make it uniform after temporary coating.

[Permeability test] --- 100 ° C 1
After drying for hours, the section was coated with a 0.5% aqueous solution of methylene blue and the depth of the water-repellent portion that was not stained was measured at five locations on one side, for a total of twenty locations, and the average was determined.

[Mold prevention test method] --- The test method conformed to the JIS-Z-2911 general test method.

[Bacteria used]

Aspergillus niger FERM S-2 Penicillium funiculosum FERM S-6 Cladosporium Cladosporioides FERMS-8 Aureobasidium pullulans FERM S-9 Griocladium virens FERM S-10 [Used medium] glucose / peptone / agar / Purified water = 40/10/25/1000 [Test method] After 100 hours of a test specimen coated on a mortar of 3 cm x 3 cm was subjected to a duty cycle test, which is an accelerated weathering test, the test piece was placed on the above-mentioned plate medium. A fungus mixed suspension is prepared, sprayed onto a sample and a medium, and cultured at a temperature of 28 ± 2 ° C. and a humidity of 95% or more.

〔Evaluation method〕

3: No hyphal growth was observed in the inoculated portion of the sample or test piece.

2: The area of the hyphal growth area observed in the inoculated portion of the sample or test piece does not exceed 1/3 of the total area.

1: The area of the hyphal growth area observed in the inoculated portion of the sample or test piece exceeds 1/3 of the total area.

Claims (2)

(57) [Claims] 1. A method comprising: (a) an alkylalkoxysilane and / or a condensate thereof; and (b) an organosilicon compound containing an alkoxysilyl group and a quaternary ammonium base in the molecule or a condensate thereof. An organosilicon composition having excellent mold resistance. 2. An aqueous organosilicon composition obtained by subjecting the organosilicon composition according to claim 1 to aqueous emulsification with water and an emulsifier.