JPH06256072A - Color-protecting material for porous inorganic material for building and civil work - Google Patents

Abstract

PURPOSE:To produce a color-protecting material capable of protecting a porous inorganic material for building and civil work over a long period and imparting the material with beautiful appearance by compounding a (condensed) alkylalkoxysilane, a water-based resin, a pigment, an emulsifier and water. CONSTITUTION:A color-protecting material for porous inorganic material for building and civil work is produced by mixing and emulsifying (A) an alkylalkoxysilane (e.g. methyltrimethoxysilane) and/or its condensate, (B) a water-based resin (e.g. water-soluble anionic acrylic resin), (C) a pigment (e.g. phthalocyanine pigment), (D) an emulsifier (e.g. alkylnaphthalenesulfonic acid salt) and (E) water and emulsifying the mixture. As necessary, the material may be incorporated with an antiseptic or a mildew-proofing agent (e.g. 5- chloro-2-methyl-4-isothiazolin-3-one) for preventing the degradation during storage and the growth of mold on the surface of the coating film or with an alkaline compound (e.g. sodium hydroxide) for adjusting the pH of the material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored protective material for a porous inorganic material for building civil engineering.

[0002]

2. Description of the Related Art Conventionally, houses, public buildings, roads, railways,
The concrete structure used for electric power is recognized as a permanent structure which has excellent durability and is easy to maintain. However, recently, early deterioration phenomena such as salt damage in coastal areas, cracking due to alkali-aggregate reaction, freezing damage in cold regions, neutralization by carbon dioxide in the air, deterioration by acid rain, etc. have become apparent. ， It has become a big social problem. It is said that moisture that invades from the outside is mainly involved in these deterioration phenomena. A coating material is used as a means for preventing moisture from entering, and the coating material includes a film-forming type and a non-film-forming type. Since the film-forming type easily forms pinholes, it has a drawback that salt and water permeate into the concrete and the reinforcing bars in the concrete rust and expand, which deteriorates the concrete. Further, in the film-forming type, at present, peeling of the coating film (called a blister) is likely to occur due to moisture contained in the concrete.

On the other hand, as a non-film-forming type, it is widely known that alkylalkoxysilane is useful as a permeable water-absorption preventing material for building civil engineering materials such as concrete. Generally, these alkoxysilanes diluted with various solvents are used. The non-film-forming type does not change the surface condition of the concrete and penetrates deeply inside to form a thick hydrophobic layer to prevent water from entering, so there is no concern about pinholes or blisters, and long-term water absorption prevention Although it has excellent performance and excellent deterioration control performance for concrete, it cannot prevent neutralization because it does not have perfect water permeation prevention performance in places where water pressure is applied and it allows gas such as carbon dioxide to pass through. It also has the drawback. In addition, the silane-based penetrating water-absorption material is
Since it can be processed without changing the texture of the groundwork, it is ideal for protecting exposed concrete, which is often found in civil engineering structures, but for general building structures that require a beautiful surface, additional topcoating should be performed for coloring purposes. However, there are still some problems such as increase of process, extension of construction period, limitation of material selection.

Further, the coating material is classified into an organic solvent type and an aqueous type. In recent years, however, the organic solvent type composition is limited in its use range due to the toxicity, volatility and flammability of the solvent used. Due to work environment problems, the aqueous type has come to be used. Water-based penetrating water-absorption materials initially had problems with storage stability and water-absorption prevention performance compared with organic solvent-based materials, but recently, materials with good physical properties have been developed. However, under the present circumstances, there is a demand for a material having more excellent physical properties in terms of water repellency and neutralization suppressing property on the surface, and a material capable of being colored at the same time for imparting an aesthetic appearance to the surface.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present invention has revealed that alkylalkoxysilane and / or its condensates, aqueous resins, pigments,
A composition containing an emulsifier and water and, if necessary, an antiseptic or antifungal agent and an alkaline compound, not only has the performance of a permeable water-absorption preventive material for concrete, but also prevents water penetration under high water pressure, prevents neutralization, and imparts an aesthetic appearance to the surface. The inventors have found that the above can be achieved at one time, and are useful as a coloring protective material for porous inorganic materials for building civil engineering, and have completed the present invention.

[0006]

[Means for Solving the Problems] That is, the present invention is
(a) alkylalkoxysilane and / or its condensate,
A colored protective material for a porous inorganic material for building civil engineering, which comprises (b) an aqueous resin, (c) a pigment, (d) an emulsifier, and (e) water. The alkylalkoxysilane and its condensate are not particularly limited, and examples thereof include alkyltrialkoxysilane, dialkyldialkoxysilane, trialkylmonoalkoxysilane and condensates thereof. Generally, an alkylalkoxysilane is a compound in which at least one alkyl group having 1 to 20 carbon atoms and at least one alkoxy group having 1 to 4 carbon atoms are directly bonded to silicon.

Examples of alkylalkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, and butyltriethoxysilane. , Pentyltrimethoxysilane, Pentyltriethoxysilane, Hexyltrimethoxysilane,
Hexyltriethoxysilane, Heptyltrimethoxysilane, Heptyltriethoxysilane, Octyltrimethoxysilane, Octyltriethoxysilane, Nonyltrimethoxysilane, Nonyltriethoxysilane, Decyltrimethoxysilane, Decyltriethoxysilane, Undecyltrimethoxysilane , Undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltri Ethoxysilane,
Hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, eicosyltrimethoxysilane Alkyltrialkoxysilanes such as silane and eicosyltriethoxysilane, dimethyldimethoxysilane, octylmethyldimethoxysilane, dialkyldialkoxysilanes such as octadecylmethyldimethoxysilane, Toshiba Silicone XC95-
Examples thereof include fluoroalkylsilanes such as 418, XC95-468, XC95-470 and XC95-472, and partial condensates thereof.

In the case of aqueous emulsification, when at least one alkyl group directly bonded to silicon has a carbon number of less than 6, the hydrolyzability and volatility are very high, and a part of it reacts with the surface of the substrate after coating. Not only is the permeation of the aqueous composition further delayed, but unreacted silane components are likely to evaporate during that time, resulting in only imparting water repellency only to the substrate surface. Therefore, it is preferable to use a partially hydrolyzed and condensed product. Further, if the number of carbon atoms of the alkyl group directly bonded to silicon is larger than 20, the molecular weight becomes large and it becomes difficult to permeate into the base material. Therefore, it is preferable to use the one having 20 or less carbon atoms. When the alkoxy group is a methoxy group, the stability under strong alkaline conditions is poor and bonding or cross-linking easily occurs on the surface before it penetrates into the base material. Also, the stability in water is poor and the high molecular weight when stored for a long time. It is preferable to use an ethoxy group, because it may be converted into a base material and may not penetrate into the substrate. On the other hand, in the case of an alkoxy group having a carbon chain of propoxy or more, since the stability is good, the bond with the base material tends to be delayed even if it penetrates into the base material.

As the water-based resin, there are anion type, nonion type, cation type water-soluble resin and emulsion resin, and acrylic, epoxy, urethane, silicon, polyester, acrylic silicon, fluorine resin and the like are used. Examples thereof include those solubilized in water, those dispersed in water, those emulsion-polymerized, and the like, but are not necessarily limited thereto. For example, anionic water-soluble resins include anionic acrylic water-soluble resins, α-olefin-maleic anhydride resins, and liquid maleated polybutadiene, and nonionic water-soluble resins include polyvinyl alcohol, cellulose derivatives, and cationic water-soluble resins. Examples of water-soluble resins include cationic acrylic water-soluble resins, chitosan, polyethyleneimine, and polyacrylic acid hydrazide. Emulsion resins include styrene-butadiene emulsion copolymer, ethylene-vinyl acetate emulsion copolymer, vinylidene chloride-chloride. Examples thereof include vinyl emulsion copolymers, and those obtained by using colloidal silica or alumina sol in combination therewith.

Examples of the pigment include phthalocyanine pigments,
Organic pigments such as thioindico type, anthraquinone type, perylene type, dioxazine type, quinacridone type, coupling azo type, condensed azo type, chelate type azo type, chrome yellow, zinc yellow, cadmium yellow, Naples yellow (antimony yellow), Nickel Titanium Yellow, Ultramarine Yellow, Cinderine Yellow, Chrome Red, Cadmium Red, Mercury Cadmium Sulfide,
Molybdenum red, molybdenum orange (chrome vermillion), red iron oxide, yellow iron oxide, Prussian blue (dark blue), ultramarine (ultra-blue), chrome green,
Examples thereof include inorganic pigments such as zinc green, manganese purple, titanium oxide, chromium oxide, zinc oxide (zinc white), and carbon, but are not necessarily limited thereto.

The emulsifier is not particularly limited, and anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers and the like can be used. Examples of anionic emulsifiers include fatty acid salts, alkyl sulfate salts, alkylaryl sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl ether sulfates. Examples thereof include salts, polyoxyethylene alkylaryl ether sulfates, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl phosphate ester salts, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters.

As the nonionic emulsifier, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid Examples thereof include esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines and the like. Further, in addition to general nonionic emulsifiers, fluorine-based nonionic emulsifiers and silicone nonionic emulsifiers can also be used.

Examples of the silicone-based nonionic emulsifier include compounds represented by the formula (I)

[Chemical 1]

Or formula (II)

[Chemical 2] And a polyalkylene-modified polydimethylsiloxane compound represented by

As the fluorine-based nonionic emulsifier,
For example, formula (III)

[Chemical 3] And a fluorinated alkyl group-containing polyalkylene oxide compound represented by the following.

Examples of the cationic emulsifier include alkylamine salts, quaternary ammonium salts, alkylpyridinium salts, alkylimidazolium salts and the like. Examples of the amphoteric emulsifier include alkylbetaine, alkylamine oxide, phosphadylcholine (also called lecithin) and the like. Furthermore, these emulsifiers can be used by optionally mixing them.

From the above-mentioned (a) alkylalkoxysilane and / or its condensate, (b) aqueous resin, (c) pigment, (d) emulsifier and (e) water, the desired colored protective material is obtained by the following method. However, the present invention is not limited to these. (1) An aqueous dispersion of an alkylalkoxysilane and / or a condensate thereof, an aqueous resin and a pigment, which has been previously hydrophilized with an emulsifier, is mixed. (2) An alkylalkoxysilane and / or a condensate thereof is mixed and dispersed in an aqueous paint comprising an aqueous resin, a pigment, an emulsifier and water. (3) The alkylalkoxysilane and / or its condensate, the aqueous resin and the pigment are aqueous emulsified at once using an emulsifier.

The mixing ratio of each component in the color protective material is not particularly limited as long as it can be mixed or dispersed uniformly.
It can be set arbitrarily according to the application, but generally, in order to form a hydrophobic layer with a sufficient thickness to protect concrete, alkylalkoxysilane and its condensate are 10% by weight or more, and the concrete surface is coated and colored. The water-based resin needs to be 10% by weight or more, and it is preferable to control the emulsifier to 5% by weight or less in order to sufficiently exhibit the water absorption preventing property and the water resistance property.

Further, if necessary, an antiseptic or antifungal agent may be added for the purpose of antiseptic during storage and antifungal of the coated surface. The antiseptic or antifungal agent is not particularly limited as long as it is a compound that acts as an antiseptic agent until the use of a general emulsion coating and an antifungal agent on the coated surface. Haloallyl sulfone-based, iodopropargyl-based, N- Haloalkylthio type, benzimidazole type, nitrile type,
Pyridine, 8-oxyquinoline, benzothiazole, isothiazoline, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, inorganic salt and Examples include brominated indanone compounds. Among these antiseptics or antifungal agents, those which are easily soluble in water are used as antiseptics, and those which are poorly soluble in water are used as antifungal agents, either alone or as a mixture of two or more kinds.

Further, particularly by combining an antiseptic and a fungicide, both antiseptic properties up to use and antifungal properties on the coated surface can be provided. It should be noted that any antiseptic / antifungal agent having both properties can be used alone. Furthermore, by combining a water-soluble mildew-proofing fungicide and an oil-soluble mildewproofing fungicide, it is possible to suppress the generation of mildew at each stage. However, these antiseptic or antifungal agents must be selected while paying attention to toxicity, emulsion stability and dispersibility.

A particularly effective antiseptic or antifungal agent is 5-chloro-2-methyl-4-isothiazoline-which has a strong antiseptic effect.
3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, and strong antifungal effect 2-
A mixture of isothiazoline compounds such as n-octyl-4-isothiazolin-3-one may be mentioned. The antiseptic or antifungal agent is not particularly limited as long as its effect is exhibited, and any amount can be added within a range that does not impair the stability of the emulsion. Generally, the concentration at which the performance is effectively expressed is about 0.05 to 1% by weight based on the total amount.

Further, an alkaline compound can be added to adjust the pH. The alkaline compound is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, amines and the like. It is desirable to add the amount of the alkaline compound so that the pH of the emulsion after production is 7-10. If the pH is out of this range, condensation is likely to occur. Especially pH
If less than 7, hydrolysis is promoted and condensation proceeds rapidly. Further, when the pH exceeds 10, not only becomes unstable, but also a problem in working occurs.

[0023]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, "%" represents "% by weight". [Production Example 1] n-hexyltriethoxysilane 600 g, polyoxyethylene stearyl ether 3.0 g, sodium lauryl sulfate 0.03 g, 1% aqueous solution of sodium hydroxide 1.0 g,
Mix 0.5 g of 1,2-benzisothiazolin-3-one and 2.0 g of 2-n-octyl-4-isothiazolin-3-one, stir at high speed with a homomixer, and add 400 g of water to it at room temperature. A stable white aqueous emulsion was obtained for 6 months or longer.

Example 1 Aqueous dispersion of n-hexyltriethoxysilane obtained in Production Example 1 70 g, nanocryl B
CX-2799 (Toyo Ink Mfg. Co., Ltd. aqueous acrylic emulsion) 70 g, EM White FX-9048 (Toyo Ink Mfg. Co., Ltd. aqueous pigment dispersion) 40 g, EM Blue 2G (Toyo Ink Mfg. Co., Ltd. aqueous pigment A blue paint was prepared by mixing 2 g of dispersion) and 18 g of water.

Comparative Example 1 70 g of an aqueous dispersion of n-hexyltriethoxysilane obtained in Production Example 1, EM White F
X-9048 (Water pigment dispersion manufactured by Toyo Ink Mfg. Co., Ltd.) 40
A blue paint was prepared by mixing 2 g of EM blue 2G (a water-based pigment dispersion manufactured by Toyo Ink Mfg. Co., Ltd.) and 88 g of water.

Comparative Example 2 Nanocryl BCX-2799 (Aqueous acrylic emulsion manufactured by Toyo Ink Mfg. Co., Ltd.) 70 g, EM
A blue paint was prepared by mixing 40 g of white FX-9048 (water-based pigment dispersion manufactured by Toyo Ink Mfg. Co., Ltd.), 2 g of EM blue 2G (water-based pigment dispersion manufactured by Toyo Ink Mfg. Co., Ltd.) and 88 g of water.

The coating materials obtained in Example 1 and Comparative Examples 1 and 2 were coated on the entire surface of a 10 cm × 10 cm × 10 cm concrete test piece (60% water cement ratio) at 300 g / m ² and exposed indoors for at least 7 days. After the middle curing, the following tests were conducted and the results shown in Table 1 were obtained. (Painted surface) ○: Color cannot be removed even if the surface is wiped with a dry waste cloth. X: The color (pigment) can be removed by wiping the surface with a dry waste cloth. (Permeability test) Water is applied to the fractured surface of the test piece, and the depth of the water-repellent portion of the surface layer is measured at 5 points to obtain the average penetration depth.

(Water Absorption Test) One surface of a test piece is immersed in water having a depth of 1 cm to obtain a water absorption rate for 24 hours. 24-hour water absorption rate (%) = (24-hour water absorption amount (g) / weight of test piece before water absorption test (g)) x 100 (salt permeability test) The test piece was completely immersed in 3% salt water for 6 months. After immersion, the chloride ion concentration was determined by potentiometric titration and the salt content was calculated. (Accelerated Neutralization Test) The test piece was placed in an accelerated neutralization tank at 20 ° C, 60% RH, CO ₂ 5% for 3 months, then cleaved, and the cross-section was sprayed with a phenolphthalene solution and colored red. The area ratio of the part not to be measured was measured. (Area measurement) Image processing was performed by a computer.

[0029]

[Table 1]

[0030]

EFFECTS OF THE INVENTION The colored protective material of the present invention is applied to a porous inorganic material for building civil engineering such as concrete, so that the silane component penetrates deeply into the interior by a single coating and reacts with the hydrophilic groups on the surface layer. At the same time as binding to form a hydrophobic layer, the aqueous resin component forms a coating film of an arbitrary color on the surface and protects the coated object for a long period of time, and can give a beautiful appearance. Thus, the colored protective material of the present invention is extremely useful in the field of building civil engineering.

Claims (3)

[Claims] 1. An (a) alkylalkoxysilane and / or a condensate thereof, (b) an aqueous resin, (c) a pigment, (d) an emulsifier and
(e) A colored protective material of a porous inorganic material for building civil engineering containing water. 2. The colored protective material according to claim 1, which contains an antiseptic or antifungal agent. 3. The method according to claim 1, which contains an alkaline compound.
The colored protective material described.