JP6012546B2 - Gel-like composition and water absorption inhibitor - Google Patents

Description

  The present invention relates to a gel composition containing an organoalkoxysilane. The present invention also relates to a water absorption inhibitor obtained from the gel composition.

  Inorganic porous materials used as building materials and civil engineering structures are cracked due to deterioration due to water absorption due to exposure to rain, frost damage at low temperatures, salt damage near the coast, etc. when used in outdoor structures. Deterioration of the appearance due to adhesion of molds and algae occurs. Therefore, measures for extending the life of the structure are required.

  Examples of inorganic porous materials include concrete, lightweight concrete, lightweight cellular concrete (ALC), mortar, various cement boards, gypsum board, calcium silicate board, bricks, tiles, tiles, and stones. In order to suppress the deterioration of these porous materials, the surface layer of the base material is hydrophobized by applying and impregnating a water absorption inhibitor onto the base material surface to suppress the penetration of moisture and salt into the base material surface. It is. Silicone compositions are known as the water absorption inhibitor.

  Conventionally, as a silicone-based water absorption inhibitor, there is a solvent-type water absorption inhibitor obtained by diluting an alkylalkoxysilane compound in an organic solvent. However, since the water absorption inhibitor has a low alkylalkoxysilane concentration and a low viscosity, a sufficient amount of alkylalkoxysilane cannot be impregnated on the surface of the substrate by a single application. A hydrophobic layer having a sufficient thickness could not be formed on the surface. Further, the solvent-type water absorption inhibitor generates VOC (volatile organic matter) from the organic solvent at the time of application, resulting in a decrease in working environment and environmental problems. Therefore, in recent years, a non-solvent water absorption inhibitor has been desired.

  For example, Patent Documents 1 to 5 describe that an aqueous emulsion composition comprising an alkylalkoxysilane, a surfactant (emulsifier), and water is used as a water absorption inhibitor. However, since the surfactant remains on the surface of the substrate after application, the aqueous emulsion composition cannot sufficiently hydrophobize the surface of the substrate. For this reason, there are problems that the surface of the base material is partially wetted during rain and the appearance is deteriorated, and that sufficient water repellency cannot be obtained.

  Moreover, when apply | coating a water-based emulsion thickly to a base-material surface, or when apply | coating to a perpendicular | vertical surface, there exists a problem that a water-based emulsion will flow out. Therefore, Patent Document 6 describes the use of an aqueous cream (paste-like water-containing composition) comprising an alkylalkoxysilane, an emulsifier, and water as a water absorption inhibitor. However, since the water absorption inhibitor is creamy, it can be applied thickly on the surface of the substrate, but the emulsion is broken shortly after the application, and the low-viscosity alkylalkoxysilane is separated. For this reason, when it is applied to an inclined surface, a vertical surface, or a downward surface, dripping occurs and the active ingredient (alkylalkoxysilane) is washed away, so that the surface of the substrate cannot be sufficiently impregnated.

  Furthermore, Patent Document 7 describes a water absorption inhibitor obtained by dispersing alkylalkoxysilane and cyclodextrin in water. In the water absorption inhibitor, the cyclodextrin, which is a water-soluble polymer, remains on the surface of the base material after coating, so that the appearance of the base material is deteriorated and sufficient water repellency cannot be obtained.

  Patent Document 8 describes a water absorption inhibitor comprising an alkylalkoxysilane and silica. In the composition, white silica remains on the surface after application and the appearance is deteriorated. Therefore, it is necessary to remove it with a brush or the like. When it is applied over a large area, the burden required for the removal work is large. It was.

  Patent Document 9 describes a water absorption inhibitor comprising an alkylalkoxysilane and a thixotropic agent. Usually, thixotropic agents on the market are dissolved in organic solvents such as xylene, mineral spirits (mineral terpenes), benzyl alcohol, ethanol, isopropanol, etc., so the water absorption inhibitor using this contains an organic solvent. become. Since the thixotropic agent containing no organic solvent is a powder, it is difficult to disperse the alkyl alkoxysilane.

Japanese Patent Laid-Open No. 62-197369 Japanese Patent Laid-Open No. 4-111979 JP-A-6-313167 JP-A-9-208938 JP 2004-315631 A Japanese Patent Laid-Open No. 10-81824 JP 2009-155641 A JP 2009-35704 A JP 2012-241100 A

  In view of the above circumstances, an object of the present invention is to provide a water absorption inhibitor capable of imparting excellent water absorption resistance to the surface of a porous material. In particular, it is a water absorption inhibitor containing an organoalkoxysilane, which does not cause dripping during coating, allows the active ingredient (organoalkoxysilane) to penetrate deeply from the surface of the porous material, and does not impair the appearance. It aims at providing the water absorption inhibitor which can provide water absorption prevention property.

  The present inventors have found that the combined use of aluminum dicarboxylate and a fatty acid can gel the organoalkoxysilane well. In addition, the gel composition containing aluminum dicarboxylate, fatty acid, and organoalkoxysilane does not release organoalkoxysilane from the gel composition on the surface of the substrate after being applied to the substrate, and the gel composition The viscosity is not lowered. Therefore, when the gel composition is applied to the surface of the porous material, the organoalkoxysilane is gradually absorbed into the pores of the porous material while maintaining the viscosity in the gel state. Furthermore, in the case of applying to an inclined surface or a vertical surface, the gel-like composition does not drip and the organoalkoxysilane does not flow out, so that the organoalkoxysilane can be impregnated deeply from the surface of the porous material. .

That is, the present invention
(A) Organoalkoxysilane represented by the following formula (1) and / or partially hydrolyzed condensate of the organoalkoxysilane 100 parts by mass R ¹ _a Si (OR ² ) _4-a (1)
(Wherein, R ¹ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is 1, 2, or 3)
(B) a dicarboxylic acid aluminum 0.3 to 20 parts by weight of the following formula _{^{(2) (R 3 COO)}} 2 Al (OH) (2)
(In the formula, R ³ are each independently a monovalent hydrocarbon group having 1 to 25 carbon atoms) and (C) 0.3 to 20 parts by mass of a fatty acid having 6 to 24 carbon atoms, and titanium. Provided are a composition containing no alkoxide and organic titanate , and a water absorption inhibitor comprising the composition. Furthermore, the present invention provides a method for imparting water absorption prevention by applying the water absorption inhibitor to the surface of the porous material, and a porous material surface-treated with the water absorption inhibitor.

  When the gel-like composition of the present invention is applied to the surface of the porous material, the active ingredient (organoalkoxysilane) can penetrate deeply from the surface of the base material, preventing water absorption on the surface of the porous material without impairing the appearance ( Water repellency). Therefore, the gel composition of the present invention can be used favorably as a water absorption inhibitor. Furthermore, the gel composition of the present invention can be in the form of a solventless type that does not contain water and an organic solvent. The solventless gel composition does not generate VOC (volatile organic matter) due to the organic solvent during coating. Therefore, the gel composition of the present invention is particularly useful as a water absorption inhibitor for an inorganic porous material for construction or civil engineering.

Hereinafter, the present invention will be described in more detail.

The component (A) is an organoalkoxysilane represented by the following formula (1) and / or a partial hydrolysis condensate thereof.
R ¹ _a Si (OR ² ) _4-a (1)

R ¹ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a cyclohexyl group, and an octyl group. Group, an isooctyl group (an alkyl group having 8 carbon atoms including a 2,4,4-trimethylpentyl group), an alkyl group such as a decyl group, a dodecyl group or a norbornyl group, an alkenyl such as a vinyl group, an allyl group or a hexenyl group Group. The group represented by R ¹ may be linear, branched, or cyclic. Furthermore, aryl groups such as phenyl groups, aralkyl groups such as styryl groups, amino group-containing alkyl groups such as 3-aminopropyl groups, N- (2-aminoethyl) -3-aminopropyl groups, 3-glycidoxypropyl Examples thereof include an epoxy group-containing alkyl group such as a group, a fluorine-containing group such as a trifluoromethyl group, and a 3,3,3-trifluoropropyl group. Among these, an alkyl group having 3 or more carbon atoms is preferable, and an alkyl group having 6 to 10 carbon atoms is more preferable.

R ² is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, and hexyl group. Of these, a methyl group and an ethyl group are particularly preferable.

  a is 1, 2, or 3, and 1 is particularly preferable.

  Examples of the organoalkoxysilane include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyl Triethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, 2-ethylhexyltri Methoxysilane, 2-ethylhexyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyl Limethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Ethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, trifluoromethyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc. Can be illustrated. Of these, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, methyltriethoxysilane, butyltriethoxysilane, and propyltriethoxy Silane is preferred. The organoalkoxysilane may be a single type or a mixture of two or more types.

  As the component (A) of the present invention, an oligomer or polymer (hereinafter referred to as a partially hydrolyzed condensate) obtained by hydrolyzing a part of the alkoxy group of the organoalkoxysilane and performing a condensation reaction between molecules is used. May be. Further, the organoalkoxysilane and a partially hydrolyzed condensate of the organoalkoxysilane may be mixed and used. The partially hydrolyzed condensate of organoalkoxysilane can be synthesized by hydrolyzing and condensing organoalkoxysilane in the presence of an acid catalyst or an alkali catalyst.

The component (B) is an aluminum dicarboxylate represented by the following formula (2).
(R ³ COO) ₂ Al (OH) (2)

In the above formula (2), R ^{3 s} are each independently a monovalent hydrocarbon group having 1 to 25 carbon atoms, preferably 3 to 19 carbon atoms. The monovalent hydrocarbon group is particularly an alkyl group or alkenyl group, and is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Examples thereof include alkyl groups such as undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and nonadecyl group, and alkenyl groups having an unsaturated bond in a part of these groups. . The group represented by R ³ may be linear, branched, or cyclic. Of these, a 1-ethylpentyl group is preferable.

  Examples of the aluminum dicarboxylate represented by the above formula (2) include aluminum soaps such as aluminum dioctylate, aluminum distearate, aluminum dilaurate, and aluminum dicaprate. In the present invention, the aluminum dicarboxylate may be one kind or a mixture of two or more kinds.

In particular, the aluminum dicarboxylate is preferably di (2-ethylhexanoic acid) aluminum (that is, aluminum dioctylate) in which R ³ is a 1-ethylpentyl group in the above formula (2). The di (2-ethylhexanoic acid) aluminum is mainly composed of a disoap represented by the formula (R ⁴ COO) ₂ Al (OH), a trisoap represented by the formula (R ⁴ COO) ₃ Al, and the formula (R ⁴ COO) A monosoap represented by Al (OH) ₂ may be contained (in the above formula, R ⁴ COO represents a 2-ethylhexanoic acid residue). In that case, the content of the trisoap and / or monosoap is preferably up to 20% by mass in the total of 100% by mass of the component (B).

  (B) The quantity of a component is 0.3-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.5-10 mass parts, Most preferably, it is good to set it as 1-8 mass parts. When the amount of component (B) is less than the above lower limit, the resulting composition may not be gelled, or the liquid phase may be separated over time after becoming gelled. On the other hand, if the amount of component (B) exceeds the above upper limit, the resulting gel becomes too hard and difficult to handle, which is not preferable.

  (C) A component is a C6-C24 fatty acid, Preferably it is a C6-C22 fatty acid. When the number of carbon atoms is less than 6, the resulting composition does not become a gel, or remains in a liquid state and lacks viscosity, or the liquid phase is separated and does not become a good gel. Moreover, when carbon number exceeds 24, melting | fusing point of a fatty acid will become high, and there exists a problem that it is necessary to make it melt | dissolve at high temperature at the time of a mixing | blending. The shape of the carbon chain may be linear, branched, or cyclic. The fatty acid may be a saturated carboxylic acid or an unsaturated carboxylic acid.

  Examples of the fatty acid include caproic acid (carbon number 6), caprylic acid (carbon number 8), 2-ethylhexanoic acid (carbon number 8), capric acid (carbon number 10), lauric acid (carbon number 12), Myristic acid (14 carbon atoms), palmitic acid (16 carbon atoms), isopalmitic acid (16 carbon atoms), stearic acid (18 carbon atoms), isostearic acid (18 carbon atoms), oleic acid (18 carbon atoms), linole Examples include acids (18 carbon atoms), α-linolenic acid (18 carbon atoms), arachidic acid (20 carbon atoms), behenic acid (22 carbon atoms), and lignoceric acid (24 carbon atoms). The above fatty acids may be used alone or in combination of two or more.

  Of these, linear ones are particularly preferred, and caproic acid (carbon number 6), caprylic acid (carbon number 8), capric acid (carbon number 10), lauric acid (carbon number 12), myristic acid ( 14 carbon atoms, palmitic acid (16 carbon atoms), stearic acid (18 carbon atoms), oleic acid (18 carbon atoms), linoleic acid (18 carbon atoms), α-linolenic acid (18 carbon atoms), arachidic acid ( Carbon number 20) and behenic acid (carbon number 22) are more preferable.

  The amount of the component (C) is 0.3 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the component (A). Good. If the amount of component (C) is less than the above lower limit value, the resulting composition may not be gelled, and it may not be preferable because it may require a high temperature of 60 ° C. or longer and a long time to form a gel. . On the other hand, if the amount of component (C) exceeds the above upper limit, the resulting gel may become soft, or the resulting composition may remain in a liquid state and may not be gelled.

  In addition to the components (A) to (C), the gel composition of the present invention further comprises (D) a polyorganosiloxane in which the number of dimethylsiloxane units relative to the total number of siloxane units is 20% or more, preferably 40% or more. Can be contained. The component (D) functions to improve the water repellency of the gel composition.

Examples of the polyorganosiloxane include a compound represented by the following formula (3).
(R ⁵ ₃ SiO _0.5 ) _p (R ⁵ ₂ SiO) _q (R ⁵ SiO _1.5 ) _r (SiO ₂ ) _s (3)
In the above formula, p, r, and s are integers of 0 or more, q is an integer of 1 or more, and the value of p + q + r + s is such that the weight-average molecular weight of the polyorganosiloxane is 5,000 or less, preferably 3, Any number that is 000 or less is acceptable. If the weight average molecular weight exceeds the above upper limit, the impregnation property of the water absorption inhibitor into the substrate may be lowered, or the substrate surface may be colored in a wet color. In the present invention, the weight average molecular weight is a weight average molecular weight in terms of polystyrene as determined by gel permeation chromatography (GPC) analysis. The polyorganosiloxane may be used alone or in combination of two or more.

In the above formula (3), R ⁵ is independently a hydrogen atom, or a substituted or unsubstituted monovalent optionally having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, which may have an oxygen atom. It is a hydrocarbon group. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, an octyl group, and a decyl group; Alkenyl groups such as allyl group and isopropenyl group; aryl groups such as phenyl group, xylyl group and tolyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; and hydrogen atoms of these hydrocarbon groups A halogen-substituted monovalent hydrocarbon group such as a chloromethyl group, a bromoethyl group, a trifluoropropyl group or the like partially or entirely substituted with a halogen atom such as chlorine, fluorine, or bromine can be exemplified. Moreover, the group by which some hydrogen atoms of the alkyl group were substituted by the polyether group, the amino group, the epoxy group, the carboxyl group, or the organic group containing these groups may be sufficient.

In the compound represented by the above formula (3), a part of the group represented by R ⁵ may be an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, or a hydrogen atom. In particular, the polyorganosiloxane preferably contains an alkoxy group or a hydroxyl group bonded to a silicon atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an isopropoxy group. However, in the above formula (3), it is preferable that 40% or more of the total number of groups represented by R ⁵ is a methyl group. However, in the present invention, the polyorganosiloxane represented by the above formula (3) is dimethylsiloxane based on the total number of siloxane units represented by R ⁵ _n SiO _{(4-n) / 2} (n is an integer of 0 to 3). The number of units ((CH ₃ ) ₂ SiO) is 20% or more, preferably 40% or more.

As described above, in the present invention, the polyorganosiloxane represented by the above formula (3) may have a siloxane unit having a hydroxyl group or an alkoxy group bonded to a silicon atom in the molecule. Examples of the siloxane unit include (R ⁶ O) R ⁵ ₂ SiO _0.5 unit, (R ⁶ O) R ⁵ SiO unit, and (R ⁶ O) SiO _1.5 unit. Examples of R ⁶ include a methyl group, an ethyl group, an isopropyl group, and a hydrogen atom. When the polyorganosiloxane has a hydroxyl group or an alkoxy group, the content thereof is preferably 5% by mass or less, more preferably 3% by mass or less, based on the mass of the polyorganosiloxane. The minimum of content of a hydroxyl group or an alkoxy group is not specifically limited. If the content of the hydroxyl group or alkoxy group in the polyorganosiloxane exceeds the above upper limit, the gel formation rate decreases, which is not preferable.

  (D) The compounding quantity of a component is the range of 0.1-50 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.5-30 mass parts. When the amount of the component (D) exceeds the above upper limit value, the impregnation property of the obtained water absorption inhibitor into the substrate may be lowered, or the substrate surface may be colored in a wet color.

  The gel composition of the present invention can further contain other additives. As the additive, a known additive used for a water absorption inhibitor can be used, for example, a fungicide, an algae, an ultraviolet absorber, a pigment, a thickener, a solvent, a wax, and the above-mentioned additives. Metal soap other than aluminum soap. Furthermore, inorganic fillers such as silica, alumina and titania, and inorganic thickeners such as montmorillonite and bentonite can be blended. What is necessary is just to adjust the compounding quantity of this additive suitably in the range which does not impair the effect of this invention according to the conventional method.

  Moreover, you may add a hydrocarbon compound, paraffins, etc. to the gel-like composition of this invention in order to adjust the intensity | strength of a gel. However, it is preferable to add a compound having a boiling point or flash point higher than that of the organoalkoxysilane, but it is not preferable to add a solvent having a boiling point or flash point lower than that of the organoalkoxysilane.

  The gel composition of the present invention can be prepared by mixing the above components. The mixing method and the apparatus to be used may be a conventionally known method, and are not particularly limited. For example, mixers with paddle type or propeller type stirring blades, anchor mixers, disper mixers, planetary mixers, kneaders, batch mixers, static mixers, line mixers, colloid mills, etc. A mixer used in a continuous mixing apparatus can be used.

  Although mixing temperature is not specifically limited, It is good that it is -10 degreeC or more and below the boiling point of the organoalkoxysilane to be used. Usually, what is necessary is just to set it as 0-80 degreeC and 10-70 degreeC. If necessary, it can be heated to 30 to 70 ° C. to promote gelation.

  The gel composition of the present invention can be used as a water absorption inhibitor. By applying the water absorption inhibitor to the surface of the porous material, water absorption resistance can be imparted to the surface of the substrate. Examples of the base material to which the water absorption inhibitor is applied include concrete, lightweight concrete, lightweight cellular concrete (ALC), mortar, various cement boards, gypsum board, calcium silicate board, bricks, tiles, tiles, stones, And inorganic porous materials. It can also be used for walls made mainly of diatomaceous earth, clay, plaster, and organic porous materials such as paper, wood and leather.

The amount of the water absorption inhibitor of the present invention applied to the substrate is not particularly limited, but can be, for example, 5 to 1000 g / m ² . If it is 5 g / m ² or less, the water absorption preventing property cannot be sufficiently exhibited. Even if it is 1000 g / m ² or more, the impregnation depth is not deeper than a certain level, and it takes more time than necessary for drying.

  The method for applying the water absorption inhibitor of the present invention to the substrate is not particularly limited, and may be a conventionally known method. For example, brush, roller, spatula, trowel, spray, spray, etc. can be used. Usually, a predetermined amount can be applied at one time, but may be overcoated as necessary. Drying after application may be allowed to stand at room temperature, but may be heated to about 40 to 80 ° C.

  The present inventors consider the mechanism of gelation of the composition in the present invention as follows. For example, when di (2-ethylhexanoic acid) aluminum is added to various low-polar organic solvents, di (2-ethylhexanoic acid) aluminum forms a high-molecular-weight linear aggregate in the organic solvent. The aggregates are entangled with each other, and an organic solvent can be taken into the gap to form a gel. Similarly, in the composition of the present invention, it is considered that the aluminum dicarboxylate forms an aggregate in the organoalkoxysilane, and the organoalkoxysilane is taken into the gap. In addition, it is considered that the fatty acid serves to promote the dissolution of the long chain aggregate formed from aluminum dicarboxylate in the organoalkoxysilane. In the composition of the present invention, the composition can be gelled by combining aluminum dicarboxylate and fatty acid in organoalkoxysilane. If the composition of the present invention does not contain any one of aluminum dicarboxylate and fatty acid, the organoalkoxysilane cannot be gelled.

  When the gel composition of the present invention is applied to a porous material, the organoalkoxysilane can be absorbed into the pores while maintaining the gel state and deeply impregnated from the substrate surface. Therefore, excellent water absorption prevention (water repellency) can be imparted to the porous surface without causing dripping during application. Here, since aluminum dicarboxylate has low polarity and does not have an affinity for water, it does not dissolve in water and is not further dispersed. Moreover, since fatty acid is similarly low in polarity, it does not dissolve or hardly dissolves in water. For this reason, even after the organoalkoxysilane is impregnated in the base material, water-resistant components (water repellency) can be obtained because no component having affinity for water remains on the base material surface.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In the following, the viscosity is a value measured with a BM type rotational viscometer at 25 ° C.

[Example 1]
100 parts by mass of octyltriethoxysilane, octotop aluminum T ((CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) COO) ₂ Al (OH) di (2-ethylhexanoic acid) aluminum, Hope Pharmaceutical Co., Ltd. When 4 parts by mass) and 4 parts by mass of oleic acid were mixed at room temperature for about 2 hours using a planetary mixer, a colorless and transparent gel-like composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 2]
When 100 parts by weight of octyltriethoxysilane, 0.4 parts by weight of Octopu Aluminum T, and 0.4 parts by weight of oleic acid were mixed at 50 ° C. for about 8 hours using a planetary mixer, a colorless and transparent gel composition was gotten. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 3]
When 100 parts by mass of octyltriethoxysilane, 2.5 parts by mass of Octopu Aluminum T, and 2.5 parts by mass of oleic acid were mixed at room temperature for about 2 hours using a planetary mixer, a colorless and transparent gel-like composition was obtained. Obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 4]
When 100 parts by weight of octyltriethoxysilane, 2.5 parts by weight of Octopu Aluminum T, and 0.7 parts by weight of oleic acid were mixed at 50 ° C. for about 6 hours using a planetary mixer, a colorless and transparent gel composition was gotten. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 5]
90 parts by mass of hexyltriethoxysilane, 10 parts by mass of polydimethylsiloxane represented by the following formula (5)
(CH ₃ ) ₂ (HO) SiO [(CH ₃ ) ₂ SiO] ₁₀ Si (CH ₃ ) ₂ (OH) (5),
When 2.5 parts by mass of Octopu Aluminum T and 2.5 parts by mass of oleic acid were mixed at room temperature for about 2 hours using a planetary mixer, a colorless and transparent gel-like composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 6]
90 parts by mass of octyltriethoxysilane, 10 parts by mass of polydimethylsiloxane represented by the above formula (5), 2.5 parts by mass of Octopu Aluminum T, and 2.5 parts by mass of oleic acid at room temperature using a planetary mixer When mixed for about 2 hours, a colorless and transparent gel-like composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 7]
90 parts by mass of propyltriethoxysilane, 10 parts by mass of polydimethylsiloxane represented by the above formula (5), 2.5 parts by mass of Octopu Aluminum T, and 2.5 parts by mass of oleic acid at room temperature using a planetary mixer When mixed for about 2 hours, a colorless and transparent gel-like composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 8]
90 parts by mass of methyltriethoxysilane, 10 parts by mass of polydimethylsiloxane represented by the above formula (5), 2.5 parts by mass of Octopu Aluminum T, and 2.5 parts by mass of oleic acid at room temperature using a planetary mixer When mixed for about 2 hours, a colorless and transparent gel-like composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 9]
Using a planetary mixer, 98 parts by weight of octyltriethoxysilane, 2 parts by weight of polydimethylsiloxane represented by the above formula (5), 2.5 parts by weight of Octopu Aluminum T, and 0.7 parts by weight of oleic acid were mixed at 50 ° C. And mixing for about 6 hours, a colorless and transparent gel composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 10]
Using a planetary mixer, 90 parts by mass of octyltriethoxysilane, 10 parts by mass of polydimethylsiloxane represented by the above formula (5), 2.5 parts by mass of Octopu Aluminum T, and 0.7 parts by mass of oleic acid were mixed at 50 ° C. And mixing for about 6 hours, a colorless and transparent gel composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 11]
Using a planetary mixer, 90 parts by weight of hexyltriethoxysilane, 10 parts by weight of polydimethylsiloxane represented by the above formula (5), 2.5 parts by weight of Octopu Aluminum T, and 2.5 parts by weight of caproic acid are used at room temperature. When mixed for about 2 hours, a colorless and transparent gel-like composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 12]
Using a planetary mixer, 90 parts by weight of hexyltriethoxysilane, 10 parts by weight of polydimethylsiloxane represented by the above formula (5), 2.5 parts by weight of Octopu Aluminum T, and 2.5 parts by weight of caprylic acid at room temperature. When mixed for about 2 hours, a colorless and transparent gel-like composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 13]
90 parts by mass of hexyltriethoxysilane, 10 parts by mass of polydimethylsiloxane represented by the above formula (5), 2.5 parts by mass of Octopu Aluminum T, and 2.5 parts by mass of stearic acid (melted at 80 ° C.) When mixed for about 2 hours at 50 ° C. using a planetary mixer, a colorless and transparent gel composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Example 14]
90 parts by mass of hexyltriethoxysilane, 10 parts by mass of polydimethylsiloxane represented by the above formula (5), 2.5 parts by mass of Octopu Aluminum T, and 2.5 parts by mass of behenic acid (melted at 80 ° C.) When mixed for about 2 hours at 50 ° C. using a planetary mixer, a colorless and transparent gel composition was obtained. When 50 g of the gel composition was put into a container having a capacity of 100 mL and the container was inverted, the gel composition did not flow out.

[Comparative Example 1]
When 100 parts by weight of hexyltriethoxysilane, 0.2 parts by weight of Octopu Aluminum T and 0.2 parts by weight of oleic acid were mixed at 50 ° C. for about 8 hours using a planetary mixer, It was not obtained.

[Comparative Example 2]
When 100 parts by mass of hexyltriethoxysilane and 2.5 parts by mass of Octopu Aluminum T were mixed at 50 ° C. for about 8 hours using a planetary mixer, a gel-like product was not obtained while remaining liquid.

[Comparative Example 3]
When 100 parts by mass of hexyltriethoxysilane and 2.5 parts by mass of oleic acid were mixed at 50 ° C. for about 8 hours using a planetary mixer, a gel-like product was not obtained while remaining liquid.

[Comparative Example 4]
About 90 parts by mass of hexyltriethoxysilane, 10 parts by mass of polydimethylsiloxane represented by the above formula (5), 2.5 parts by mass of Octopu Aluminum T, and 2.5 parts by mass of butyric acid were measured at room temperature using a planetary mixer. When mixed for 2 hours, the viscosity increased, but after 2 days it returned to a liquid state and a stable gel was not obtained.

[Comparative Example 5]
Nonionic surfactant Emulgen 104P (Kao) containing 8.5 parts by mass of amino group-containing polydimethylsiloxane (viscosity 1600 mPa · s, N (2-aminoethyl) -3-aminopropyl group in the side chain, amine equivalent 10000) 0.14 parts by mass), Emulgen 123P (manufactured by Kao Corporation), 0.79 parts by mass, and 4.6 parts by mass of water were mixed and emulsified using a homomixer. To this, 76.5 parts by mass of hexyltriethoxysilane was added little by little, and further mixed with a homomixer. After the total amount of hexyltriethoxysilane was added, it was further mixed with a disper mixer. Next, 9.5 parts by mass of water was added for dilution to obtain a white cream emulsion (silicone content: 85%) having a viscosity of 100,000 mPa · s or more. When the emulsion composition was applied to a test piece, significant dripping occurred and a part was washed away to the side.

[Comparative Example 6]
Hexyltriethoxysilane 100 parts by mass, amino group-containing polydimethylsiloxane (viscosity 3700 mPa · s. N (2-aminoethyl) -3-aminopropyl group in side chain, amine equivalent 2000) 6 parts by mass, hydrophobic dry type 12 parts by mass of silica (Aerosil R812, manufactured by Nippon Aerosil Co., Ltd.) was mixed for about 10 minutes at room temperature using a disper mixer to obtain a uniform paste. When this paste-like composition was applied to a test piece, the appearance of the surface became white because silica was present on the application surface.

  The dripping, appearance, water repellency, and impregnation depth of each composition obtained in Examples 1 to 14 and Comparative Examples 5 and 6 were evaluated by the methods described below. The results are shown in Tables 1-3. In addition, since the composition obtained in Comparative Examples 1-3 did not become a gel form and the composition obtained in Comparative Example 4 was not stable in gel state, the following test was not performed.

(1) Dripping A mortar test piece (length 70 mm × width 70 mm × height 25 mm) prepared according to JIS R5201 was used as a test specimen. Each composition was mounted in an amount of 200 g / m ² on the surface of the mortar test piece having a length of 70 mm and a width of 70 mm, and coated with a spatula as uniformly as possible. Immediately after application, the test piece was allowed to stand so that the application surface was vertical, and it was visually observed whether or not the applied composition was cast.

(2) Appearance Each composition was applied to a mortar test piece in the same manner as (1) above. The test piece was allowed to stand at 25 ° C. and 50% RH for 7 days and then cured. Thereafter, the ratio of the wet color remaining on the surface coated with the composition was visually observed and evaluated according to the following indicators.
5: Of the total area of the coated surface, the area of the portion where the wet color remains is 5% or less (that is, it has the same appearance as the test piece to which the composition is not coated).
4: Of the total area of the coated surface, the area of the portion where the wet color remains is more than 5% to less than 25%.
3: Of the total area of the coated surface, the area of the portion where the wet color remains is 25% to less than 75%.
2: Of the total area of the coated surface, the area of the portion where the wet color remains is 75% to less than 95%.
1: The area of the portion where the wet color remains out of the total area of the coated surface is 95% or more.

(3) Water Repellency Each composition was applied to a mortar test piece in the same manner as (1) above. The test piece was allowed to stand at 25 ° C. and 50% RH for 7 days and then cured. The surface coated with the composition was sprayed with running water for 5 minutes using a shower, and then the water repellent degree and the wet color ratio on the surface coated with the composition were visually observed and evaluated according to the following indicators.
Repelling 5: Of the total area of the coated surface, the area where water is repelled is 95% or more.
4: The area of the part which repelled water among the total area of an application surface is 75%-less than 95%.
3: The area of the part which repelled water among the total area of an application surface is 25% or more-less than 75%.
2: The area of the part which repelled water among the total area of an application surface is 5% or more and less than 25%.
1: The area of the part where water was repelled out of the total area of the coated surface was less than 5%.
Wet color 5: Of the total area of the coated surface, the area of the portion where the wet color remains is 5% or less.
4: Of the total area of the coated surface, the area of the portion where the wet color remains is more than 5% to less than 25%.
3: Of the total area of the coated surface, the area of the portion where the wet color remains is 25% to less than 75%.
2: Of the total area of the coated surface, the area of the portion where the wet color remains is 75% to less than 95%.
1: The area of the portion where the wet color remains out of the total area of the coated surface is 95% or more.

(4) Impregnation depth Each composition was applied to a mortar test piece in the same manner as in (1) above. The test piece was allowed to stand at 25 ° C. and 50% RH for 7 days and then cured. The test piece was split vertically so that the surface to which the composition was applied was divided into two, and water was sprayed onto the split surface. The depth of the portion that did not absorb water and was not colored wet was measured and defined as the impregnation depth.

  As shown in Tables 1 and 3 above, the organoalkoxysilane can be favorably gelled by combining aluminum dicarboxylate and a predetermined fatty acid together with the organoalkoxysilane. On the other hand, as shown in Table 2, if any one of aluminum dicarboxylate and fatty acid is not included, the organoalkoxysilane cannot be gelled. Further, as shown in Tables 1 and 3 above, the gel composition of the present invention can be deeply impregnated from the surface of the porous material without causing dripping even when applied to a vertical surface and without impairing the appearance. Excellent water absorption prevention (water repellency) can be imparted to the surface of the porous material.

  The gel composition of the present invention allows the organoalkoxysilane to penetrate deeply from the surface of the porous material without causing dripping even when applied to a vertical surface, and without impairing the appearance. It is possible to impart water absorption preventing property. Furthermore, the gel composition of the present invention can be in the form of a solventless type that does not contain water and an organic solvent. The solventless gel composition does not generate VOC (volatile organic matter) due to the organic solvent during coating. Therefore, the gel composition of the present invention is particularly useful as a water absorption inhibitor for an inorganic porous material for construction or civil engineering.

Claims (7)

(A) Organoalkoxysilane represented by the following formula (1) and / or partially hydrolyzed condensate of the organoalkoxysilane 100 parts by mass R ¹ _a Si (OR ² ) _4-a (1)
(Wherein, R ¹ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is 1, 2, or 3)
(B) a dicarboxylic acid aluminum 0.3 to 20 parts by weight of the following formula _{^{(2) (R 3 COO)}} 2 Al (OH) (2)
(In the formula, R ³ are each independently a monovalent hydrocarbon group having 1 to 25 carbon atoms) and (C) 0.3 to 20 parts by mass of a fatty acid having 6 to 24 carbon atoms, and titanium. A composition containing no alkoxide and organic titanate . (D) The polyorganosiloxane in which the number of dimethylsiloxane units with respect to the total number of siloxane units is 20% or more is further contained in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass of component (A). Item 2. The composition according to Item 1. The composition of Claim 1 or 2 which does not contain water and an organic solvent. The water absorption inhibitor which consists of a composition of any one of Claims 1-3. A method for imparting water absorption prevention properties by applying the water absorption inhibitor according to claim 4 to the surface of a porous material. The method of claim 5, wherein the porous material is inorganic. A porous material surface-treated with the water absorption inhibitor according to claim 4.