JPH06313167A - Emulsion composition based on organosilicon compound - Google Patents

Abstract

PURPOSE:To obtain the subject composition which can improve the water repellency and storage stability of a porous inorganic base material by mixing a specified organoalkoxysilane, a specified organosiloxane, an anionic surfactant and water. CONSTITUTION:100 pts.wt. mixture of 100 pts.wt. organoalkoxysilane (A) of the formula R<1>aSi(OR<2>)4-a (wherein R<1> is a 1-20C monovalent hydrocarbon group; R<2> is a 1-3C monovalent hydrocarbon group; and a is 1 or 2) and 1-20 pts.wt. organosiloxane (B) having at least one organic group of the formula R<3>-Si(R<4>)b(OR<2>)3-6 (wherein R<3> is a divalent hydrocarbon group; R is a monovalent hydrocarbon group; and (b) is 0 to 2) attached to an Si atom in the molecule is mixed with 0.1-50 pts.wt. anionic surfactant (C) and water (D) to form an emulsion so that the total content of components A and B is 5-60wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organosilicon compound emulsion composition. More specifically, the present invention relates to an organosilicon compound emulsion composition which has excellent storage stability and can impart excellent water repellency to a porous inorganic base material (building material) such as concrete, mortar and brick.

[0002]

BACKGROUND OF THE INVENTION Organoalkoxysilanes are widely known to be useful as a water repellent agent for porous inorganic base materials (building materials) such as concrete, mortar and bricks. As such a water repellent, an organic solvent type water repellent obtained by diluting an organoalkoxysilane with various organic solvents has been usually used. However, the organic solvent used as a diluent has toxicity to human body and danger of ignition and causes environmental pollution.Therefore, an emulsion type water repellent obtained by emulsifying organoalkoxysilane with water as a diluent. Agents are under consideration. As such a water repellent, for example, an emulsion composition in which an alkylalkoxysilane is emulsified using a nonionic surfactant having an HLB of 4 to 15 (see Japanese Patent Publication No. 3-13195) and a nonionic surfactant. And an anionic surfactant are used together to emulsify an alkylalkoxysilane (see JP-A-4-114979). However, these compositions have a drawback that they are inferior in storage stability as compared with organic solvent-type water repellents because the alkylalkoxysilane and water are easily separated with time, and this is due to a porous inorganic substrate ( When applied to a building material), the inside of the base material exhibits excellent water repellency, but there is a drawback that the water repellency of the applied surface is insufficient.

[0003]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above-mentioned drawbacks.
That is, the object of the present invention is excellent in storage stability, and
An object of the present invention is to provide an organosilicon compound emulsion composition capable of imparting excellent water repellency to a porous inorganic base material (building material) such as concrete, mortar, brick and the like.

[0004]

Means for Solving the Problems The present invention provides (A) a general formula: R ¹ _a Si (OR ² ) _4-a (wherein R ¹ is the same or different one having 1 to 20 carbon atoms). A hydrocarbon group, R ² is a monovalent hydrocarbon group having 1 to 3 carbon atoms, and a is 1 or 2) 100 parts by weight of organoalkoxysilane, (B) silicon bound to atoms ^{formula: -R 3 -Si (R 4)} b (OR 2) in _3-b (wherein, R ² is a monovalent hydrocarbon group having 1 to 3 carbon atoms, R ³ is two Is a valent hydrocarbon group, R ⁴ is the same or different monovalent hydrocarbon group, and b is 0, 1 or 2.) An organosiloxane having at least one organic group represented by the formula 1 to 200 parts by weight, (C) anionic surfactant, and an amount necessary to emulsify the composition of the present invention and (D) water. And an organosilicon compound-based emulsion composition.

The organosilicon compound emulsion composition of the present invention will be described in detail. The organoalkoxysilane as the component (A) is the main component of the composition of the present invention. Since this component has a small molecular weight, when the composition of the present invention is applied to a porous inorganic base material (building material), it penetrates into the base material. Then, by reacting with the hydroxyl group existing in the base material and binding with the base material, an excellent water-repellent layer is formed inside the base material. In the above formula, R ¹ is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically, a methyl group,
Ethyl group, propyl group, tert-butyl group, pentyl group,
n-hexyl group, heptyl group, 2-ethylhexyl group,
Alkyl group such as octyl group, dodecyl group, octadecyl group; aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl group such as benzyl group, phenethyl group; fluoromethyl group, 3,3,3-trifluoro group Substituted alkyl groups such as propyl group, 3,3,4,4,5,5-heptafluoropentyl group and difluoromonochloropropyl group are exemplified. Among these, an alkyl group having 4 to 10 carbon atoms is preferable. This is because if the number of carbon atoms is less than 4, the alkyl chain, which is a hydrophobic component, becomes short and water repellency tends to be insufficient. On the other hand, if the number of carbon atoms exceeds 10, the molecular weight becomes large and it becomes porous. This is because the permeability to the inside of the inorganic base material (building material) is likely to decrease. R ² is a monovalent hydrocarbon group having 1 to 3 carbon atoms, and specific examples thereof include a methyl group, an ethyl group and a propyl group. a is 1
Or 2. As this component, one kind of organoalkoxysilane may be used alone, or two or more kinds of organoalkoxysilane may be mixed and used if necessary.

The organosiloxane of component (B) is (A)
It is a component for improving the emulsion stability of the component. In addition, since this component has a larger molecular weight than the component (A),
When the composition of the present invention is applied to a porous inorganic base material (building material), it tends to remain on the applied surface, so that an excellent water-repellent layer is formed on the applied surface. Such a component has at least one organic group represented by the formula: —R ³ —Si (R ⁴ ) _b (OR ² ) _3-b bonded to a silicon atom in one molecule. Here, in the formula, R ² is the same as described above. R ³ is a divalent hydrocarbon group, specifically, ethylene group, n-propylene group,
Examples of the alkylene group include an isopropylene group and an isobutylene group, and of these, an ethylene group is typical.
R ⁴ is the same or different monovalent hydrocarbon group, specifically, an alkyl group such as methyl group, ethyl group, propyl group, octyl group, decyl group, dodecyl group; phenyl group, naphthyl group, tolyl group, etc. And an aralkyl group such as a 2-phenylethyl group and a 2-phenylpropyl group; and a halogenated alkyl group such as a 3,3,3-trifluoropropyl group. b is 0, 1 or 2, but is preferably 0 or 1. The bonding position of the organic group represented by the above formula includes only the molecular chain end, the side chain only, or both the molecular chain end and the side chain. Further, as the group other than the organic group represented by the above formula in this component, the same or different monovalent hydrocarbon groups are preferable, and more preferably a combination of a methyl group and an alkyl group having 4 or more carbon atoms. Is. This component is preferably linear, but may be branched or cyclic. This component may be a homopolymer, or may be a block copolymer or a random copolymer. As this component, for example, the formula:

[Chemical 1] (In the formula, m and n are numbers in the range of 0 to 50). In the above formula, m + n is preferably in the range of 0-50. This is because when m + n exceeds 50, the permeability into the porous inorganic base material (building material) decreases, and a large amount of this component tends to remain on the coated surface. As a result, the color of the applied surface becomes dark and the appearance may be wet.
The blending amount of this component is 1 to 100 parts by weight of the component (A).
It is in the range of 200 parts by weight, and preferably in the range of 10 to 100 parts by weight. This is because if the amount is less than 1 part by weight, the storage stability of the composition of the present invention is lowered and the water repellency of the coated surface becomes insufficient, and if it exceeds 200 parts by weight, the component (A) relative to this component is used. This is because the ratio of (3) becomes small and the amount of the composition of the present invention penetrating into the porous inorganic base material (building material) decreases, resulting in insufficient water repellency inside the base material.

The component (C) anionic surfactant is a component for emulsifying the component (A) and the component (B). Specific examples of this component include alkylbenzenesulfonic acids such as octylbenzenesulfonic acid, dodecylbenzenesulfonic acid and cetylbenzenesulfonic acid; higher alcohol sulfuric acid ester; polyoxyethylene alkyl ether sulfuric acid ester; polyoxyethylene alkylphenyl ether sulfuric acid ester; Examples thereof include sodium salt, potassium salt, lithium salt or amine salt of alkylnaphthyl sulfonic acid and the like. The blending amount of this component may be any amount as long as it can emulsify the composition of the present invention, and it varies depending on the type, but usually the total amount of the (A) component and the (B) component is 100.
It is in the range of 0.1 to 50 parts by weight, and preferably in the range of 0.1 to 10 parts by weight, based on parts by weight.

The component (D) water is composed of the components (A) and (B).
It is a dispersion medium for the components. The blending amount of this component is not particularly limited as long as the composition of the present invention is an O / W type emulsion, but the total concentration of the (A) component and the (B) component is 5 to 60.
The amount is preferably such that the amount is 10% by weight, more preferably 10 to 50% by weight.

The composition of the present invention comprises the above-mentioned component (A)
Although it is composed of the component (D), addition of other components known as an additive of the organosilicon compound emulsion composition may be added thereto, as long as the object of the present invention is not impaired. Examples of such additives include nonionic surfactants and pH adjusters.
Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, sorbitan alkyl esters, polyethylene glycol, and polypropylene glycol. Is exemplified.
When such a nonionic surfactant is added to the composition of the present invention, the storage stability of the composition of the present invention may be further improved. Further, in the composition of the present invention, a pH adjusting agent can be used to adjust the pH. The pH of the composition of the present invention is usually in the range of 6 to 8, preferably 6 to 7. This is because when the pH is out of this range, the hydrolysis reaction and the condensation reaction of the component (A) and the component (B) are likely to occur. As a result, the molecular weights of the component (A) and the component (B) increase, and the permeability to the inside of the porous inorganic base material (building material) may decrease. Specific examples of the pH adjusting agent include sodium hydroxide, potassium hydroxide, ammonia, various amines, sodium hydrogen carbonate, and sodium oleate. Other additives include iron, zinc, titanium, tin,
Organometallic compounds such as cobalt; synthetic resins such as polyester resins and acrylic resins; rubber latex such as styrene / butadiene copolymer rubber and natural rubber; rust preventives; antiseptic;
Colorants can be mentioned.

The composition of the present invention can be easily produced by using the production means used in the conventional production method of emulsion. For example, (A) component, (B) component,
The components (C) and (D) are mixed by a stirring spring,
This can be produced by emulsifying with an emulsifying machine such as a homomixer, a line mill, a homogenizer. Further, it can be produced by emulsifying the component (A) and the component (B) with the component (C) and the component (D), respectively, and then mixing these emulsions.

The composition of the present invention can be applied to a porous inorganic base material (building material) such as concrete, mortar and bricks by a method such as spray coating, roll coating and brush coating.

Since the composition of the present invention as described above uses the organoalkoxysilane of the component (A) and the organosiloxane of the component (B) in combination, it is more emulsified than the composition using the organoalkoxysilane alone. Easy and has excellent storage stability. In addition, the composition of the present invention may be used for porous inorganic base materials (building materials) such as concrete, mortar and bricks.
When applied to, the (A) component organoalkoxysilane penetrates into the inside of the base material and binds to the base material to form an excellent water repellent layer inside, and the (B) component organosiloxane is applied to the coated surface. An excellent water repellent layer is formed. Therefore, the porous inorganic base material (building material) coated with the composition of the present invention has excellent water repellency, and particularly excellent surface water repellency. further,
The composition of the present invention can retain excellent water repellency even after long-term storage. Such a composition of the present invention is a porous inorganic base material (building material) such as concrete, mortar and brick.
Is extremely useful as a water repellent.

[0013]

EXAMPLES The present invention will be described in detail with reference to Examples. In the examples, the viscosity value is a value measured at 25 ° C. Parts represent parts by weight,% represents% by weight and cS is centistokes. Further, the evaluation of the organosilicon compound emulsion composition was carried out by the following test method. ○ Storage stability The emulsion composition was enclosed in a 100 cc glass bottle, left in a sealed state at room temperature for 3 months, and the change in its appearance was observed with the naked eye. Good: No separation of the water layer and the oil layer was observed even after 3 months. Poor: Separation of water layer and oil layer was observed within 3 months. In this case, the number of days when separation of the water layer and the oil layer was observed was shown. ○ Surface water repellency A mortar slurry having a mixing ratio of cement: sand: water of 1: 2: 0.6 was cast into a stainless steel mold of 100 × 100 × 16 mm, and demolded after 2 days. Then add this to temperature 2
A mortar test body was prepared by curing for 20 days at 0 ° C. and a humidity of 85%. The emulsion composition was applied to the surface of this mortar test body (coating amount: 300 g / m ² ), and then cured at a temperature of 20 ° C. and a humidity of 65% for 7 days to make the mortar test body water repellent. Approximately 0.03 g of water droplets were dropped on each of three points on the surface of the water-repellent treated mortar specimen, and the shape change of the water droplets was visually observed. The evaluation results are reported in the following five stages. A: Water droplets were kept spherical even after 10 minutes, and the water repellency was very good. ◯: Water repellency was good although the water droplets collapsed into a hemisphere after 5 minutes. (Triangle | delta): Although the water droplet collapsed after 3 minutes, it was not absorbed by the mortar and the water repellency was rather good. X: Water droplets were absorbed by the mortar after 1 minute and the water repellency was poor. ○ Water absorption rate A mortar test piece that has been subjected to water repellent treatment in the same manner as above is
The whole surface was soaked in distilled water at 20 ° C. for 24 hours. afterwards,
The water absorption rate (%) was determined from the weight increase of this mortar test body. Water absorption rate (%) = (weight after immersion-weight before immersion) /
Weight before immersion × 100

[0014]

Example 1 20 parts of n-hexyltriethoxysilane,
formula:

[Chemical 2] Organosiloxane 10 having a viscosity of 21 cS represented by
Parts, polyoxyethylene (2 mol) sodium lauryl ether sulfate 0.5 parts, sodium oleate 0.05 parts and ion-exchanged water 69.45 parts were mixed. Put this mixture in a homogenizer and add 300kg / cm
^{It was} passed twice at a pressure of 2 to obtain a milky white organosilicon compound emulsion composition having a pH of 6.9. The storage stability, surface water repellency and water absorption of this emulsion composition were measured. The results of these measurements are shown in Table 1.

[0015]

Example 2 In Example 1, 0.5 part of sodium polyoxyethylene (2 mol) lauryl ether sulfate was changed to 0.3 part of sodium lauryl sulfoacetate, and the content of sodium oleate was 0.02 part. A milky white organosilicon compound emulsion composition having a pH of 6.5 was obtained in the same manner as in Example 1 except for the above. The storage stability, surface water repellency and water absorption of this emulsion composition were measured. The results of these measurements are shown in Table 1.

[0016]

Example 3 In Example 1, 0.5 part of sodium polyoxyethylene (2 mol) lauryl ether sulfate was changed to 0.25 part of sodium N-laurylmethyl taurine, and the content of sodium oleate was 0.01 part. A milky white organosilicon compound emulsion composition having a pH of 6.7 was obtained in the same manner as in Example 1 except for the above. The storage stability, surface water repellency and water absorption of this emulsion composition were measured. The results of these measurements are shown in Table 1.

[0017]

Example 4 In Example 1, 0.5 part of sodium polyoxyethylene (2 mol) lauryl ether sulfate was added to 0.2 part of polyoxyethylene (2 mol) sodium lauryl ether sulfate and polyoxyethylene (6 mol).
A milky white organosilicon compound emulsion composition having a pH of 6.8 was obtained in the same manner as in Example 1 except that the content of sodium oleate was changed to 0.02 part instead of 0.3 part of lauryl ether. The storage stability, surface water repellency and water absorption of this emulsion composition were measured. The results of these measurements are shown in Table 1.

[0018]

Example 5 In Example 1, an organosiloxane having a viscosity of 21 cS was prepared by the formula:

[Chemical 3] Dimethylsiloxane 10 having a viscosity of 7.5 cS represented by
A milky white organosilicon compound emulsion composition having a pH of 6.8 was obtained in the same manner as in Example 1 except that the parts were changed. The storage stability, surface water repellency and water absorption of this emulsion composition were measured. The results of these measurements are shown in Table 1.

[0019]

Example 6 25 parts of n-hexyltriethoxysilane,
formula:

[Chemical 4] Dimethylsiloxane 5 with a viscosity of 7.5 cS
Parts, 0.3 parts of sodium lauryl sulfoacetate, 0.02 parts of sodium oleate and 69.68 parts of ion-exchanged water were mixed. The mixture was put in a homogenizer and passed through the homogenizer twice at a pressure of 300 kg / cm ² to adjust the pH.
A milky white organosilicon compound emulsion composition of 6.8 was obtained. The storage stability, surface water repellency and water absorption of this emulsion composition were measured. The results of these measurements are shown in Table 1.

[0020]

Example 7 Example 6 was repeated except that the amount of n-hexyltriethoxysilane was 15 parts and the amount of diorganosiloxane having a viscosity of 7.5 cS was 15 parts. A milky white organosilicon compound emulsion composition having a pH of 6.8 was obtained. The storage stability, surface water repellency and water absorption of this emulsion composition were measured. The results of these measurements are shown in Table 1.

[0021]

Comparative Example 1 30 parts of n-hexyltriethoxysilane,
Polyoxyethylene (2 mol) sodium lauryl ether sulfate 0.5 part, sodium oleate 0.05 part and ion-exchanged water 69.45 parts were mixed. This mixture was put into a homogenizer and passed through the homogenizer twice at a pressure of 300 kg / cm ² , to obtain a milky white emulsion composition having a pH of 6.8. The storage stability, surface water repellency and water absorption of this emulsion composition were measured. The results of these measurements are shown in Table 1.

[0022]

Comparative Example 2 30 parts of n-hexyltriethoxysilane,
2 parts of polyoxyethylene (6 mol) lauryl ether and 68 parts of ion-exchanged water were mixed. This mixed solution was put into a homogenizer and passed through the homogenizer twice at a pressure of 300 kg / cm ² , to obtain a milky white emulsion composition having a pH of 6.6. Storage stability of this emulsion composition,
Surface water repellency and water absorption were measured. The results of these measurements are shown in Table 1.

[0023]

Comparative Example 3 30 parts of n-hexyltriethoxysilane,
2 parts of polyoxyethylene (2 mol) lauryl ether and 68 parts of ion-exchanged water were mixed. This mixed solution was put in a homogenizer and passed through the homogenizer twice at a pressure of 300 kg / cm ² , to obtain a milky white emulsion composition. The storage stability, surface water repellency and water absorption of this emulsion composition were measured. The results of these measurements are shown in Table 1.

[0024]

Comparative Example 4 30 parts of n-hexyltriethoxysilane,
0.2 parts of sodium polyoxyethylene (2 mol) lauryl ether sulfate, 0.3 parts of polyoxyethylene (6 mol) lauryl ether, 0.02 part of sodium oleate and 69.48 parts of ion-exchanged water were mixed. Put this mixture in a homogenizer and add 300kg / cm
^Two passes at a pressure of 2 gave a milky white emulsion composition with a pH of 6.7. The storage stability, surface water repellency and water absorption of this emulsion composition were measured. The results of these measurements are shown in Table 1.

[0025]

[Table 1]

[0026]

The organosilicon compound emulsion composition of the present invention comprises the components (A) to (D), and particularly contains the organoalkoxysilane (A) and the organosiloxane (B). Therefore, when it is applied to porous inorganic base materials (building materials) such as concrete, mortar, bricks, etc., it has excellent storage stability and excellent repellent properties for these porous inorganic base materials (building materials). It has a feature that it can be rendered water-based.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Isao Ona 2-2 Chikusaigan, Ichihara, Chiba Toray Dow Corning Silicone Co., Ltd.

Claims (3)

[Claims] 1. (A) General formula: R ¹ _a Si (OR ² ).
_4-a (In the formula, R ¹ is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is 1 to 3 carbon atoms.
Is a monovalent hydrocarbon group, and a is 1 or 2. ) Organoalkoxysilane represented by
100 parts by weight, (B) wherein bonded to a silicon ^{atom: -R 3 -Si (R 4)} b (OR 2) 3-b ( wherein, R ² is a monovalent hydrocarbon having 1 to 3 carbon atoms Group, R ³ is a divalent hydrocarbon group, R ⁴ is a monovalent hydrocarbon group of the same type or a different type, and b is 0, 1 or 2. 1 molecule of an organic group represented by 1 to 200 parts by weight of organosiloxane having at least one of them, (C) anionic surfactant, an amount necessary for emulsifying the composition of the present invention, and (D) water, an organosilicon compound Emulsion composition. 2. The organosilicon compound emulsion composition according to claim 1, wherein the component (A) is n-hexyltriethoxysilane. 3. The organosilicon compound emulsion composition according to claim 1, which is a water-repellent agent for porous inorganic substrates.