JPH09202876A - Water-based organosilicon composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-based organosilicon composition which contains a specific emulsifier, an alkylalkoxysilane and water, has excellent storage stability for a long period of time and is applied to concrete or the like to penetrate into and bond to its inside, form an excellent waterproof layer after drying and impact durability to the concrete. SOLUTION: This organosilicon composition contains (A) a cationic emulsifier of a compound of the formula: R-NH2 CH3 COOH (R is an 8-18C alkyl), a compound of the formula: [R-N(CH3 )3 ]<+> Cl<-> , a compound of the formula: [(R)2 N (CH3 )2 ]<+> Cl<-> , a compound of formula I or a compound of formula II ((m) and (n) are each 2-20), (B) an alkylalkoxy-silane (for example, one or more alkyl groups directly linking to the silicon atom are each a 6-20C alkyl and it alkoxy group has 1 to 4 carbon atoms) and (C) water, preferably the amount of the component A is 0.1-50wt.% based on the component B, while the component B is 1-70wt.% based on the whole composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous organic silicon-based composition useful as an aqueous osmosis-type water-absorbing agent for architectural and civil engineering materials such as concrete and other stones. More specifically, the present invention relates to an aqueous organosilicon composition characterized in that an alkylalkoxysilane is emulsified in an aqueous solution using a cationic emulsifier.

[0002]

2. Description of the Related Art It has been widely known that alkylalkoxysilanes and their condensates are useful as permeable water-absorption preventing materials for construction and civil engineering materials such as concrete. Compared to the water repellent that gives waterproofing only to the surface, the permeable water-absorbing agent provides a thick hydrophobic layer on the surface layer of concrete, etc., so that the water-absorbing performance lasts for a long time, and various deterioration due to salt and moisture penetration The phenomenon can be suppressed.

[0003] In general, those obtained by diluting these alkoxysilanes with various solvents have been used. However, such a solvent-type composition is not used due to the toxicity, volatility and flammability of the solvent used. The range was limited. For example,
When isopropyl alcohol, which has relatively low toxicity, is used as a solvent, there is a problem 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 the solvent type generally cannot be applied to a wet concrete surface.

In order to solve the above problems and use alkylalkoxysilane as a permeable water-absorbing agent for concrete, it is ideal to use an aqueous solution or an aqueous dispersion. However, alkoxysilane is strongly hydrolyzable. However, it has been considered that it is extremely difficult to stably exist in water because the subsequent condensation reaction is likely to occur.

As a means for solving these problems, recently, a method of aqueous emulsification of a hydrolyzable organosilicon compound such as alkyltrialkoxysilane using a nonionic emulsifier (JP-A-62-197369), etc. Was reported.

As the nonionic emulsifier, a polyhydric alcohol type having a strong lipophilicity is more suitable for emulsifying alkylalkoxysilane than a polyethylene glycol type having a strong hydrophilicity. Are good emulsifiers. However, the polyhydric alcohol fatty acid ester-based emulsifiers tend to separate into two layers over time, lack the sustainability of emulsification, cause thickening and gelation, and reduce water absorption prevention performance, resulting in stable long-term stability. It was difficult to obtain an aqueous emulsion.

[0007]

DISCLOSURE OF THE INVENTION The object of the present invention is that it does not separate for a long period of time, does not limit the inconvenience of use in the field and the application is not restricted, and is excellent as a penetrating water absorption inhibitor. It is an object of the present invention to provide a water-permeation-type water-absorption inhibitor for construction and civil engineering materials such as concrete and other stone materials that also have excellent performance.

[0008]

Means for Solving the Problems That is, the first invention is:
An aqueous organosilicon composition for coating, comprising (a) a cationic emulsifier, (b1) an alkylalkoxysilane, and (c) water.

The second invention is (a) a cationic emulsifier,
(b2) low-condensation product of alkylalkoxysilane, (c) water,
A water-based organosilicon composition for coating containing

The third invention is (a) a cationic emulsifier,
An aqueous organosilicon composition for coating comprising (b1) alkylalkoxysilane, (b2) low-condensation product of alkylalkoxysilane, and (c) water.

A fourth invention is that (a) the cationic emulsifier is
The aqueous organosilicon coating composition according to any one of the first to third inventions, which is one or more selected from the group consisting of alkylamine salts, quaternary ammonium salts, and alkylamine ethylene oxide adducts. It is a system composition.

A fifth invention is that (a) the cationic emulsifier is
It is 1 or more types chosen from the following general formula (1)-(5), It is the water-based organic silicon composition for coating in any one of the 1st invention thru | or 4th invention characterized by the above-mentioned.

General formula (1)

[Chemical 6]

General formula (2)

[0015]

Embedded image General formula (3)

[0016]

Embedded image General formula (4)

[0017]

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General formula (5)

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In the general formulas (1) to (5), R is an alkyl group having 8 to 18 carbon atoms, and m and n are independently 2 to 20.

The sixth invention is that (a) the cationic emulsifier is
Stearyl amine acetate, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyl picolinium chloride,
The aqueous organosilicon composition for coating according to any one of the first to fifth inventions, characterized in that it is one or more selected from polyoxyethylene stearylamine.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The (a) cationic emulsifier used in the present invention is not particularly limited and may be, for example, a general cationic emulsifier. For example, long-chain primary amine salts, quaternary ammonium salts, heterocyclic amines, amine derivatives and the like can be mentioned.

As the long-chain primary amine salt, RNH ₂ .H
Cl, RNH ₂ .CH ₃ COOH and the like can be mentioned.

As the quaternary ammonium salt, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl ethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl pyridinium salt, alkyl quinolinium salt, alkyl isoquinolinium salt, Alkylpyridinium salt, stearamidomethylpyridinium salt, acylaminoethyldiethylamine salt, acylaminoethylmethyldiethylammonium salt, alkylamidopropyldimethylbenzylammonium salt, fatty acid polyethylene polyamide, acylaminoethylpyridinium salt, acylcoraminoformylmethylpyridinium salt , Stearooxymethylpyridinium salt, fatty acid triethanolamine, fatty acid triethanolamine formate, Lioxyethylene fatty acid triethanolamine, fatty acid dibutylaminoethanol, cetyloxymethylpyridinium salt, P-isooctylphenoxyethoxyethyl dimethylbenzylammonium salt and the like can be mentioned. Alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt Is preferred.

As the heterocyclic amine, alkyl imidazoline, 1-hydroxyethyl-2-alkyl imidazoline, 1-acetylaminoethyl-2-alkyl imidazoline, 2-alkyl-4-methyl-4-hydroxymethyl oxazoline are amine derivatives. Examples thereof include polyoxyethylene alkyl amine, N-alkyl propylene diamine, N-alkyl polyethylene polyamine, N-alkyl polyethylene polyamine dimethyl sulfate, alkyl biguanide, long chain amine oxide and the like.

In the present invention, the following general formulas (1) to
The cationic emulsifier (a) represented by (5) is preferable.

General formula (1): long-chain primary amine salts

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General formula (2): alkyl trimethyl ammonium salts

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General formula (3): dialkyldimethylammonium salts

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General formula (4): alkyldimethylbenzyl ammonium salts

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General formula (5): Alkylamine ethylene oxide adduct

Embedded image In the general formulas (1) to (5), R has 8 to 1 carbon atoms.
8 alkyl groups, m and n are each independently 2 to 20, and R is preferably an alkyl group having 18 carbon atoms,
2 is preferable as m and n.

Furthermore, in the general formulas (1) to (5), one or more stearyl groups are attached to the alkyl group portion bonded to nitrogen, for example, stearylamine acetate,
Triethanolamine monostearyl acetate, distearylamine acetate, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, stearylpicolium chloride, stearyldimethylbenzylammonium chloride, polyoxyethylenestearylamine and the like are preferable, among which stearylamine acetate and stearyltrimethyl. Ammonium chloride, distearyl dimethyl ammonium chloride, stearyl picolinium chloride,
Polyoxyethylene stearylamine is especially preferred.

The cationic emulsifier (a) will be described later (b1).
0.1 to 50% by weight, preferably 0.1 to 50% by weight, based on the low condensate of alkylalkoxysilane or (b2) alkylalkoxysilane.
It is sufficient to use 0.1 to 5% by weight. If it is less than 0.1% by weight, it is difficult to obtain a stable emulsion and the functional stability tends to deteriorate. On the other hand, if it is more than 50% by weight, it is difficult to obtain sufficient water absorption prevention performance.

The (b1) alkylalkoxysilane is not particularly limited, and examples thereof include alkyltrialkoxysilane, dialkyldialkoxysilane and trialkylmonoalkoxysilane. Generally, at least one alkyl group directly bonded to silicon of the alkylalkoxysilane has 1 to 20, preferably 6 to 20, carbon atoms, and further, the alkoxy group has 1 to 4 carbon atoms.

For example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, Pentyltriethoxysilane, Hexyltrimethoxysilane, Hexyltriethoxysilane, Heptyltrimethoxysilane, Heptyltriethoxysilane, Octyltrimethoxysilane, Octyltriethoxysilane, Nonyltrimethoxysilane, Nonyltriethoxysilane, Decyltrimethoxysilane, Decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxy Silane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, Heptadecyltrimethoxysilane, heptadecyltriethoxysilane,
Alkyltrialkoxysilanes such as octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, eicosyltrimethoxysilane, eicosyltriethoxysilane, dimethyldimethoxysilane, octylmethyldimethoxysilane, etc. Examples thereof include fluoroalkylalkoxysilanes such as dialkyldialkoxysilane, XC95-418, XC95-468, XC95-470, and XC95-472 (manufactured by Toshiba Silicone Co., Ltd.) and mixtures thereof.

When the number of carbon atoms of at least one alkyl group directly bonded to silicon is less than 6, the volatility is very high and unreacted silane components are easily evaporated, resulting in low efficiency of forming the hydrophobic layer and economically. Since it is disadvantageous, it is preferable to use a partially hydrolyzed polycondensed product. If the alkyl group directly bonded to silicon has more than 20 carbon atoms, the molecular weight is so large that it is difficult to penetrate into the base material. Therefore, it is desirable to use those having 20 or less carbon atoms. When the alkoxy group is a methoxy group, stability under strong alkaline conditions is poor, and bonding or cross-linking is likely to occur in a shallow portion before penetrating into the inside of the base material. Since it may become molecular weight and not penetrate into the base material,
It is preferable to use an ethoxy group. On the other hand, in the case of an alkoxy group having a carbon chain of a propoxy group or more, the bond with the base material tends to be slow even if it penetrates into the inside because the stability is good.

The low condensate of (b2) alkylalkoxysilane is a low condensate of the above alkylalkoxysilane (b1). In general, when a composition containing a compound in which the condensation of alkylalkoxysilane has progressed is applied to a concrete or the like, a state in which the surface of the concrete or the like is wet with water even after the dispersion medium such as water is volatilized, It has a so-called “painting color”. In the case of “soaked concrete,” where the appearance and aesthetics of the concrete itself are important,
Such a “painting color” state is not preferable because it impairs the appearance and beauty of concrete. However, even when the alkylalkoxysilane is condensed, if the condensation is at a low level, almost no "painting color" occurs. That is, the low-condensation product of the (b2) alkylalkoxysilane of the present invention is a low-condensation product that does not give a "wet color" when coated and dried on concrete.

The above-mentioned (b1) alkylalkoxysilane or
(b2) The low-condensation products of alkylalkoxysilanes may be used alone or as a mixture. (b
The low condensate of 1) alkylalkoxysilane and (b2) alkylalkoxysilane, or a mixture thereof, is preferably 1 to 70% by weight in the aqueous coating composition. If the content is less than 1% by weight, a sufficiently thick hydrophobic layer cannot be obtained on the surface of concrete or the like.
Water absorption prevention performance is difficult to maintain. On the other hand, if it exceeds 70% by weight, not only may the emulsification become very difficult or the stable state of the emulsification may not be maintained, but also the water content becomes relatively small, which facilitates drying, resulting in alkylalkoxysilane. Before it penetrates deep enough into concrete,
Bonding or cross-linking is likely to occur relatively near the surface of concrete or the like, and it is difficult to obtain high water absorption prevention performance.

While the above-mentioned mixture of (b1) alkylalkoxysilane or (b2) alkylalkoxysilane low condensate and (a) cationic emulsifier is rapidly stirred with a homomixer or the like, (c) water is gradually added dropwise. As a result, the desired aqueous organosilicon composition is obtained. The stirring method is not particularly limited, and may be any type from a general dissolver type or homomixer type stirrer to a homogenizer type that performs emulsification using a shearing force / impact force from a low pressure to a high pressure.

If necessary, the composition of the present invention may be diluted with water, dyes, pigments, emulsifiers, preservatives,
It is also possible to add various functions by adding a fungicide, a pH adjuster and the like.

[0040]

【Example】

Example 1 20 g of n-octyltriethoxysilane and 1 g of stearylamine acetate were mixed to obtain 1000 rp.
The mixture was stirred at m or more, and 79 g of water was gradually added to this to obtain a white aqueous emulsion stable for 6 months or more at room temperature. The water absorption was determined and the results are shown in Table 1.

[0041]

Example 2 A white aqueous emulsion stable for 6 months or more at room temperature was obtained in the same manner as in Example 1 except that 1 g of stearylamine acetate was changed to 1 g of distearyldimethylammonium chloride. The water absorption was determined and the results are shown in Table 1.

[0042]

Example 3 50 g of n-octyltriethoxysilane and 1.5 g of distearyldimethylammonium clide. Were mixed and stirred at 1000 rpm or more, and 48.5 g of water was gradually added thereto to obtain a white aqueous emulsion stable for 6 months or more at room temperature. The water absorption was determined and the results are shown in Table 1.

[0043]

Example 4 20 g of n-hexyltriethoxysilane and 1 g of distearyldimethylammonium clyde were mixed and stirred at 1000 rpm or more, and 79 g of water was gradually added thereto to obtain a white aqueous emulsion stable for 6 months or more at room temperature. Was given. The water absorption was determined and the results are shown in Table 1.

[0044]

Comparative Example 1 20 g of n-octyltriethoxysilane and 2 g of polyoxyethylene stearyl ether (HLB 9.4)
And stirred at 1000 rpm or more.
A white aqueous emulsion was obtained by slowly adding, but separated into two layers one day later. The water absorption was determined and the results are shown in Table 1.

[0045]

Comparative Example 2 Polyoxyethylene stearyl ether (
A white aqueous emulsion was obtained in the same manner as in Comparative Example 1, except that 2 g of HLB9.4) was changed to polyoxyethylene sorbitan monooleate (HLB15), but separated into two layers after 3 days. The water absorption was determined and the results are shown in Table 1.

[0046]

Comparative Example 3 20 g of n-octyltriethoxysilane, polyoxyethylene sorbitan monolaurate (HLB 16.7
) 0.5 g with sorbitan sesquioleate (HLB 3.7)
1.5 g was mixed and stirred at 1000 rpm or more, and 78 g of water was gradually added to this to obtain a white aqueous emulsion, but after 5 days, two layers were separated. The water absorption was determined and the results are shown in Table 1.

[0047]

Comparative Example 4 50 g of n-octyltriethoxysilane, polyoxyethylene sorbitan monooleate (HLB 15)
3 g and stirred at 1000 rpm or more.
A white aqueous emulsion was obtained by the slow addition of 7 g, which separated into two layers after 3 days. The water absorption was determined and the results are shown in Table 1.

[0048]

[Table 1]

[0049]

INDUSTRIAL APPLICABILITY The composition of the present invention, which has an alkoxy group which is easily condensed by hydrolysis, covers the surrounding oil droplets with a cationic emulsifier to stabilize the oil droplets of silane in water. Therefore, it is possible to provide a stable emulsion without separation even during a long period of 6 months at room temperature, and without causing thickening, gelation or deterioration of performance as a water absorption inhibitor. The composition of the present invention is applied to a civil engineering and construction base material such as concrete to penetrate deeply into the inside and bond to form an excellent waterproof layer after drying, prevent deterioration of the base material, Extremely useful, which can provide durability.

Claims (6)

[Claims] 1. An aqueous organosilicon composition for coating comprising (a) a cationic emulsifier, (b1) an alkylalkoxysilane, and (c) water. 2. An aqueous organosilicon composition for coating comprising (a) a cationic emulsifier, (b2) a low condensate of an alkylalkoxysilane, and (c) water. 3. An aqueous organosilicon composition for coating containing (a) a cationic emulsifier, (b1) an alkylalkoxysilane, (b2) a low condensate of an alkylalkoxysilane, and (c) water. 4. The cationic emulsifier (a) is one or more selected from the group consisting of alkylamine salts, quaternary ammonium salts, and alkylamine ethylene oxide adducts. An aqueous organosilicon composition for coating as described above. 5. The aqueous organosilicon coating composition according to claim 1, wherein (a) the cationic emulsifier is one or more selected from the following general formulas (1) to (5). System composition. General formula (1) General formula (2) General formula (3) General formula (4) General formula (5) In the general formulas (1) to (5), R has 8 to 1 carbon atoms.
8 alkyl groups, m and n are 2 to 20 independently. 6. The (a) cationic emulsifier is one or more selected from stearylamine acetate, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, stearylpicolinium chloride, and polyoxyethylenestearylamine. The aqueous organosilicon composition for coating according to claim 1.