Organoalkoxysilane-containing composition, method for producing the same, and water-repellent agent

Abstract

To provide a composition to become a water absorption-preventive agent capable of giving excellent water absorption-preventive property onto the surface of a structural material.SOLUTION: An organoalkoxysilane-containing composition includes: (A) an organohydrogenpolysiloxane having a structural unit selected from the group consisting of SiO2, HSiO1.5, R1SiO1.5, R1HSiO, R12SiO, R12HSiO0.5, and R13SiO0.5; (B) an organopolysiloxane having a structural unit selected from the group consisting of SiO2, R2SiO1.5, R1SiO1.5, R1R2SiO, R12SiO, R13SiO0.5, and R12R2SiO0.5 (R2 is an alkenyl group); and (C) an organoalkoxysilane expressed by R3aSi(OR4)4-a and / or a partial hydrolysis condensation product thereof, where the content of (C) is 100-10,000 pts.mass to 100 pts.mass of a total of (A) and (B).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition containing an organoalkoxysilane and / or a partially hydrolyzed condensate of said organoalkoxysilane. The present invention also relates to a water-repellent agent obtained from said composition, a method for producing said composition, and an article treated with said water-repellent agent. [Background technology]

[0002] Inorganic porous materials, wood, and synthetic wood used as building materials and civil engineering structural materials deteriorate when used in outdoor structures due to exposure to rain and water absorption, cracking due to frost damage at low temperatures or salt damage near coastlines, and deterioration of appearance due to the attachment of mold and algae. Therefore, measures are needed to extend the lifespan of these structures.

[0003] Inorganic porous materials include concrete, lightweight concrete, autoclaved lightweight concrete (ALC), mortar, various cement boards, gypsum boards, calcium silicate boards, bricks, roof tiles, tiles, and stone. To suppress the deterioration of these porous materials, as well as wood and synthetic wood, a water-repellent agent is applied to and / or impregnated into the surface of the substrate to make the surface layer hydrophobic and suppress the penetration of moisture and salt into the substrate surface. Silicone-based and silane-based compositions are known as such water-repellent agents.

[0004] Conventionally, silicone-based and silane-based water-repellent agents have included solvent-type water-repellent agents, which are alkylalkoxysilane compounds diluted in organic solvents. However, these water-repellent agents have low alkylalkoxysilane concentrations and low viscosity, making it impossible to impregnate the substrate surface with a sufficient amount of alkylalkoxysilane in a single application, and also failing to form a sufficiently thick hydrophobic layer on the substrate surface. Furthermore, solvent-type water-repellent agents pose risks such as fire, explosion, and poisoning, and generate VOCs (volatile organic compounds) from the organic solvent during application, leading to a deterioration of the working environment and environmental problems. Therefore, in recent years, there has been a demand for non-solvent-based water-repellent agents.

[0005] For example, Patent Documents 1 to 4 describe the use of an aqueous emulsion composition consisting of alkylalkoxysilane, a surfactant (emulsifier), and water as a water-repellent agent. However, because the surfactant remains on the substrate surface after application, this aqueous emulsion composition cannot sufficiently hydrophobize the substrate surface. As a result, there are problems such as the substrate surface becoming partially wet and its appearance deteriorating during rainfall, and insufficient water repellency being achieved.

[0006] Furthermore, when an aqueous emulsion is applied thickly to a substrate surface or to a vertical surface, there is a problem that the aqueous emulsion will run off. Therefore, Patent Document 5 describes using an aqueous cream (paste-like aqueous composition) consisting of alkylalkoxysilane, an emulsifier, and water as a water-repellent agent. However, because this water-repellent agent is in cream form, it has excellent coating properties and can be applied thickly to the substrate surface, but soon after application the emulsion breaks down and the low-viscosity alkylalkoxysilane separates. As a result, when applied to an inclined surface, a vertical surface, or a downward-facing surface, dripping occurs and the active ingredient (alkylalkoxysilane) is washed away, making it impossible to sufficiently impregnate the substrate surface.

[0007] Furthermore, Patent Document 6 describes a water-repellent agent comprising alkylalkoxysilane and cyclodextrin dispersed in water. However, this water-repellent agent has problems such as impairing the appearance of the substrate and failing to provide sufficient water repellency because cyclodextrin, a water-soluble polymer, remains on the substrate surface after application.

[0008] Patent Document 7 describes a water-repellent agent comprising alkylalkoxysilane and silica. However, this water-repellent agent leaves a white silica residue on the surface after application, impairing its appearance. Therefore, it is necessary to remove it with a brush or the like, and when applied to a large area, the burden of this removal work is considerable.

[0009] Patent document 8 describes a water-repellent agent comprising an alkylalkoxysilane and a thixotrope. Typically, commercially available thixotropes are dissolved in organic solvents such as xylene, mineral spirits (mineral turpentine), benzyl alcohol, ethanol, and isopropanol, so water-repellent agents using these will contain organic solvents. Since thixotropes that do not contain organic solvents are in powder form, it has been difficult to disperse them in alkylalkoxysilane.

[0010] Patent documents 9 to 11 describe compositions in which organoalkoxysilane is gelled by using aluminum dicarboxylate, a fatty acid having 6 to 24 carbon atoms, and aluminum oligomers and / or aluminum alkoxides selected from aluminum oxide organoxides and aluminum oxide sylates, and water-repellent agents containing said compositions. However, the gel-like compositions described in the above patent documents are effective for application methods using trowels and spatulas because they are easily torn gels, but they are unsuitable for application using brushes and rollers because the viscosity of the gel is too high and it does not adhere to brushes and rollers.

[0011] On the other hand, silicone is also used in cosmetics. For example, in cosmetic applications, silicone oil is used as a base oil in various compositions, and in particular, in skincare and makeup applications, it is used with a kinematic viscosity of 100 mmHg. 2 Low viscosity silicone oils with a viscosity of less than / s are widely used due to their excellent spreadability, refreshing feel, and high safety.

[0012] However, when preparing a paste-like composition with low fluidity using low-viscosity silicone oil as a base oil, it is necessary to use organic materials such as dextrin fatty acid esters (Patent Documents 12-15), sucrose fatty acid esters (Patent Document 16), trimethylsilylated polyvinyl alcohol or trimethylsilylated polysaccharides (Patent Document 17), fatty acid ester group-containing cellulose ether (Patent Document 18), or organically modified clay minerals (Patent Documents 19-21) as thickeners. Furthermore, separation and discharge of the low-viscosity silicone oil occur over time, making it difficult to maintain a smooth and uniform composition.

[0013] To solve this problem, a method has been proposed to obtain a uniform paste-like composition by using a specific organopolysiloxane as a thickener and treating it with a low-viscosity silicone oil under shear force (Patent Document 22).

[0014] These thickening, gelling, and paste technologies for cosmetic applications have been limited to the use of silicone oil as an oiling agent, and the use of alkoxysilane compounds is not publicly known. Furthermore, their application as water-repellent agents has not been explored until now. [Prior art documents] [Patent Documents]

[0015] [Patent Document 1] Japanese Patent Application Publication No. 197369 / 1983 [Patent Document 2] Japanese Patent Application Publication No. 6-313167 [Patent Document 3] Japanese Patent Application Publication No. 9-208938 [Patent Document 4] Japanese Patent Publication No. 2004-315631 [Patent Document 5] Japanese Patent Application Publication No. 10-81824 [Patent Document 6] Japanese Patent Publication No. 2009-155641 [Patent Document 7] Japanese Patent Publication No. 2009-35704 [Patent Document 8] Japanese Patent Publication No. 2012-241100 [Patent Document 9] Japanese Patent Publication No. 2014-234398 [Patent Document 10] Japanese Patent Publication No. 2015-78305 [Patent Document 11] Japanese Patent Publication No. 2017-200967 [Patent Document 12] Japanese Patent Application Publication No. 62-121764 [Patent Document 13] Japanese Patent Publication No. 143970 / 1983 [Patent Document 14] Japanese Patent Application Publication No. 62-143971 [Patent Document 15] Japanese Patent Application Publication No. 159489 / 1989 [Patent Document 16] Japanese Patent Application Publication No. 63-235366 [Patent Document 17] Japanese Patent Application Publication No. 62-240335 [Patent Document 18] Japanese Patent Application Publication No. 63-260955 [Patent Document 19] Japanese Patent Application Publication No. 62-45656 [Patent Document 20] Japanese Patent Application Publication No. 62-54759 [Patent Document 21] Japanese Patent Application Publication No. 63-72779 [Patent Document 22] Japanese Patent Application Publication No. 2-43263 [Overview of the project] [Problems that the invention aims to solve]

[0016] The present invention has been made in view of the above circumstances, and aims to provide a composition that can serve as a water-repellent agent capable of providing excellent water-repellent properties to the surface of porous materials, structural materials such as wood and synthetic wood. Furthermore, the present invention aims to provide a water-repellent agent comprising the composition, a method for applying the water-repellent agent to the surface of a structural material to impart water-repellent properties, and a structural material surface-treated with the water-repellent agent.

Means for Solving the Problem

[0017] In order to solve the above problems, the present invention provides an organoalkoxysilane-containing composition comprising an addition reaction product of the following (A) organohydrogenpolysiloxane and the following (B) organopolysiloxane, and the following (C) organoalkoxysilane and / or a partial hydrolysis condensate of the organoalkoxysilane, wherein the (C) is 100 to 10,000 parts by mass with respect to 100 parts by mass in total of the (A) and the (B). (A) A structural unit selected from the group consisting of SiO2 units, HSiO 1.5 units, R 1 SiO 1.5 units, R 1 HSiO units, R 1 2SiO units, R 1 2HSiO 0.5 units and R 1 3SiO 0.5 units (where R 1 is a substituted or unsubstituted monovalent hydrocarbon group excluding an aliphatic unsaturated group), and having an average of 1.5 or more hydrogen atoms bonded to silicon atoms in the molecule, an organohydrogenpolysiloxane (B) A structural unit selected from the group consisting of SiO2 units, R 2 SiO 1.5 units, R 1 SiO 1.5 units, R 1 R 2 SiO units, R 1 2SiO units, R 1 3SiO 0.5 units and R 1 2R 2 SiO 0.5 units (where R 1 is the same as above, and R 2 is an alkenyl group), and having an average of 1.5 or more alkenyl groups bonded to silicon atoms in the molecule, an organopolysiloxane (C) Organoalkoxysilane represented by the following formula (1) and / or a partially hydrolyzed condensate of said organoalkoxysilane R 3 a Si(OR 4 ) 4-a (1) (In the formula, R 3 These are monovalent hydrocarbon groups having 1 to 20 carbon atoms, which may independently contain an amino group, an epoxy group, or a halogen atom, and R 4 (Each of the three elements is an independent monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is 1, 2, or 3.)

[0018] The organoalkoxysilane-containing composition of the present invention can serve as a water-repellent agent that provides excellent water-repellent properties to the surface of porous materials, structural materials such as wood and synthetic wood.

[0019] In the present invention, R in formula (1) above 3 However, it is preferable that the alkyl group has 4 to 16 carbon atoms, and more preferably that it has 6 to 12 carbon atoms.

[0020] The organoalkoxysilane-containing composition of the present invention can exhibit superior water-repellent properties by including such component (C).

[0021] Furthermore, in the present invention, it is preferable that the viscosity of the organoalkoxysilane-containing composition, as measured by a rotational viscometer at 25°C, is 100 to 500,000 mPa·s.

[0022] Such a composition prevents dripping when applied to structural materials, resulting in a good appearance and consistent water-repellent properties. Furthermore, it improves workability during application.

[0023] Furthermore, the present invention provides a water-repellent agent characterized by containing the above-mentioned organoalkoxysilane-containing composition.

[0024] Such water-repellent agents can provide excellent water-repellent properties to the surface of structural materials.

[0025] Furthermore, the present invention provides a method for producing the above-mentioned organoalkoxysilane-containing composition, characterized by comprising a first step of obtaining an addition reaction product by addition polymerization of a total of 100 parts by mass of component (A) and component (B) while stirring in the presence of 100 to 1500 parts by mass of component (C).

[0026] The present invention provides a method for producing an organoalkoxysilane-containing composition in which the addition product (polymerization product) of component (A) and component (B) obtained in the first step does not become excessively hard. Furthermore, the reaction rate between component (A) and component (B) is sufficient, and an addition product with sufficient viscosity can be obtained.

[0027] In this case, it is preferable to have a second step in which component (C) is further mixed into the addition reaction product such that the total amount of component (C) is 100 to 10,000 parts by mass relative to 100 parts by mass of the total amount of component (A) and component (B).

[0028] With this method for producing organoalkoxysilane-containing compositions, component (C) is more easily incorporated into the three-dimensional structure of the addition product during dilution in the second step, allowing for the efficient production of a composition with sufficient stability without a decrease in viscosity due to dilution.

[0029] Furthermore, the present invention provides a method for imparting water-repellent properties, characterized by applying the above-mentioned water-repellent agent to the surface of a structural material.

[0030] The present invention's method for imparting water-repellent properties allows for efficient imparting of water-repellent properties to the surface of structural materials.

[0031] In this case, if the viscosity of the water-repellent agent measured by a rotational viscometer at 25°C is 100 to 50,000 mPa·s, it is preferable to apply it using a spray, spray, roller, or brush, and if the viscosity of the water-repellent agent measured by a rotational viscometer at 25°C is 5,000 to 500,000 mPa·s, it is preferable to apply it using a trowel or spatula.

[0032] This method allows for efficient application of the water-repellent agent to the surface of the structural material.

[0033] Furthermore, the present invention provides a method for manufacturing a surface-treated structural material, characterized by surface-treating the structural material with the above-mentioned water-repellent agent.

[0034] With the manufacturing method of the present invention, surface-treated structural materials can be manufactured efficiently. [Effects of the Invention]

[0035] The composition of the present invention is easy to apply, less prone to dripping during application, allows the active ingredient (organoalkoxysilane) to penetrate deeply into the surface of porous materials, wood, synthetic wood, and other structural materials, provides water-repellent properties without impairing the appearance, has good workability during application, and exhibits excellent storage stability, maintaining its properties even when stored at high temperatures for extended periods. [Modes for carrying out the invention]

[0036] As described above, there has been a need for the development of organoalkoxysilane-containing compositions that can act as water-repellent agents that provide excellent water-repellent properties to the surface of porous materials, wood, synthetic wood, and other structural materials. In this specification, porous materials, wood, synthetic wood, and other materials used as building materials and civil engineering structural materials are also referred to as structural materials.

[0037] In this regard, if the thickening, gelling, and paste-forming technologies for silicone oils used in conventional cosmetic applications can be applied to water-repellent agents made of alkylalkoxysilane compounds used in building materials and civil engineering structural materials, it may be possible to obtain new compositions that are easy to apply and do not drip during application. Furthermore, since common thickeners and gelling agents often have polar groups, using them to thicken the material often reduces the water-repellent properties of the water-repellent agent. However, the above method is expected to allow thickening, gelling, and paste formation without reducing water repellency.

[0038] However, since the application targets of water-repellent agents, which are mainly applied to structural materials for buildings and civil engineering, and cosmetics, which are mainly applied to the skin of living organisms, are completely different, the above-mentioned applications have never been considered until now.

[0039] As a result of diligent research to achieve the above objectives, the present inventors have found that a composition having the specific formulation shown below is easy to apply, does not drip during application, allows the active ingredient (organoalkoxysilane) to penetrate deeply into the surface of porous materials, structural materials such as wood and synthetic wood, provides water-repellent properties without impairing the appearance, has good workability during application, and has excellent storage stability, maintaining its properties even when stored at high temperatures for a long period of time. This led to the present invention.

[0040] That is, the present invention relates to an organoalkoxysilane-containing composition comprising the following (A) organohydrogenpolysiloxane, the following (B) an addition reaction product of the organopolysiloxane, and the following (C) organoalkoxysilane and / or a partially hydrolyzed condensate of said organoalkoxysilane, characterized in that the amount of (C) is 100 to 10,000 parts by mass relative to 100 parts by mass of the total of (A) and (B). (A) SiO2 units, HSiO 1.5 Unit, R 1 SiO1.5 Unit, R 1 HSiO units, R 1 2 SiO units, R 1 2HSiO 0.5 Units and R 1 3SiO 0.5 Unit (here, R 1 Organohydrogenpolysiloxanes having structural units selected from the group consisting of (substituted or unsubstituted monovalent hydrocarbon groups excluding aliphatic unsaturated groups), and containing an average of 1.5 or more hydrogen atoms bonded to silicon atoms in the molecule. (B) SiO2 units, R 2 SiO 1.5 Unit, R 1 SiO 1.5 Unit, R 1 R 2 SiO units, R 1 2 SiO units, R 1 3SiO 0.5 Units and R 1 2R 2 SiO 0.5 Unit (R here) 1 This is the same as above, and R 2 Organopolysiloxanes having a structural unit selected from the group consisting of alkenyl groups, and containing an average of 1.5 or more alkenyl groups bonded to silicon atoms in the molecule, (C) Organoalkoxysilane represented by the following formula (1) and / or a partially hydrolyzed condensate of said organoalkoxysilane R 3 a Si(OR 4 ) 4-a (1) (In the formula, R 3 These are monovalent hydrocarbon groups having 1 to 20 carbon atoms, which may independently contain an amino group, an epoxy group, or a halogen atom, and R 4 (Each of the three elements is an independent monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is 1, 2, or 3.)

[0041] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0042] [Organoalkoxysilane-containing composition] The organoalkoxysilane-containing composition of the present invention comprises an addition product of a specific (A) organohydrogenpolysiloxane and a specific (B) organopolysiloxane, and a specific (C) organoalkoxysilane and / or a partial hydrolysis condensate of said organoalkoxysilane. Components other than (A) to (C) may be included as needed. Each component will be described in detail below.

[0043] [(A) Organohydrogenpolysiloxane] Component (A) is a component that provides an addition reaction product that forms the base polymer of the organoalkoxysilane-containing composition, and consists of SiO2 units and HSiO2 units. 1.5 Unit, R 1 SiO 1.5 Unit, R 1 HSiO units, R 1 2 SiO units, R 1 2HSiO 0.5 Units and R 1 3SiO 0.5 Unit (here, R 1 This organohydrogenpolysiloxane has a structural unit selected from the group consisting of (a substituted or unsubstituted monovalent hydrocarbon group excluding aliphatic unsaturated groups) and contains an average of 1.5 or more hydrogen atoms bonded to silicon atoms in the molecule.

[0044] The organohydrogenpolysiloxane of component (A) used in the present invention is HSiO 1.5 Unit, R 1 SiO 1.5 Unit, R 1 HSiO units, R 1 2 SiO units, R 1 2HSiO 0.5 Units and R 1 3SiO 0.5 Unit [here, R 1is a substituted or unsubstituted monovalent hydrocarbon group excluding aliphatic unsaturated groups, for example, alkyl groups such as methyl, ethyl, propyl, butyl; aryl groups such as phenyl, tolyl; cycloalkyl groups such as cyclohexyl, etc., and one or more hydrogen atoms of these monovalent hydrocarbon groups are substituted by halogen atoms such as chlorine, bromine, fluorine, cyano groups, etc., such as γ-trifluoropropyl group, chloromethyl group, etc.〕 and those having a structural unit selected from the group consisting of. This organohydrogenpolysiloxane of component (A) may be linear, branched or cyclic, but in order to smoothly proceed with addition polymerization, it is more preferably linear. Further, this organohydrogenpolysiloxane contains on average 1.5 or more, preferably 2 to 25 hydrogen atoms (Si-H bonds) bonded to silicon atoms in one molecule.

[0045] In addition, the proportion of the hydrogen atoms bonded to the silicon atoms in the molecule is usually 0.1 to 50 mol%, preferably 0.2 to 30 mol%, more preferably 0.4 to 10 mol% based on the total of the hydrogen atoms and organic groups bonded to the silicon atoms.

[0046] The organic groups contained in this component (A) (those expressed as R 1 above) can be various, but preferably a methyl group, and particularly preferably 50 mol% or more of R 1 is a methyl group. Typical examples of the above organohydrogenpolysiloxane of (A) include Formula: [(CH3)3SiO 0.5 〕 b 〔(CH3)2HSiO 0.5 〕 c 〔(CH3)2SiO〕 d 〔(CH3 ) HSiO〕 e [Here, b and c are integers satisfying b + c = 2. d is an integer from 0 to 500, preferably an integer from 5 to 300, more preferably an integer from 10 to 200. e is an integer from 0 to 50, preferably an integer from 0 to 30, and even more preferably an integer from 1 to 20.] Although those represented by the above are exemplified, the invention is not limited thereto. Sufficient thickening properties can be obtained by combining with the alkenyl group-containing organopolysiloxane of (B) described later. Further, these may be mixtures and can be suitably used in the invention.

[0047] More specific examples of the component (A) include, but are not limited to, those represented by the following formula. [Chemical formula]

[0048] [(B) Organopolysiloxane] The organopolysiloxane of (B) used in the present invention is composed of structural units selected from the group consisting of SiO2 units, R 2 SiO 1.5 units, R 1 SiO 1.5 units, R 1 R 2 SiO units, R 1 2SiO units, R 1 3SiO 0.5 units and R 1 2R 2 SiO 0.5 units (where R 1 is the same as above and R 2 is an alkenyl group), and is an alkenyl group-containing organopolysiloxane containing an average of 1.5 or more, preferably 2 to 25 alkenyl groups bonded to silicon atoms in the molecule. The molecular structure of this organopolysiloxane of (B) may be linear, branched or cyclic.

[0049] Furthermore, the content of this alkenyl group is preferably, for example, 0.1 to 50 mol%, more preferably 0.2 to 30 mol%, and more preferably 0.4 to 10 mol%, of the organic group bonded to silicon. Examples of alkenyl groups include vinyl, allyl, butenyl, pentenyl, and hexenyl groups, with vinyl groups being particularly preferred.

[0050] Other preferred organic groups besides alkenyl groups include, for example, methyl groups, and it is particularly desirable that methyl groups constitute 50 mol% or more of the other organic groups.

[0051] Typical examples of organopolysiloxanes in (B) above include: Formula: [(CH2=CH)(CH3)2SiO 0.5 ] f (CH3)3SiO 0.5 ] g [(CH3)2SiO] h [(CH2=CH)CH3SiO] i [Here, f and g are integers satisfying f+g=2, h is a non-negative integer, i is a non-negative integer, and 3≦f+g+h+i≦1000, preferably 10≦f+g+h+i≦800] Formula: [(CH2=CH)(CH3)2SiO 0.5 ] j (CH3)3SiO 0.5 ] k [(CH3)2SiO] l [(CH2=CH)CH3SiO] m (CH3)SiO 1.5 ] n (CH2=CH)SiO 1.5 ] o [SiO2] p [Here, j is a non-negative integer, k is a non-negative integer, and j+k is...] 2 The integers are as follows: l is a non-negative integer, m is a non-negative integer, n is a non-negative integer, o is a non-negative integer, and p is a non-negative integer, such that 3 ≤ j + k + l + m + n + o + p ≤ 1000, preferably 10 ≤ j + k + l + m + n + o + p ≤ 800. Examples include, but are not limited to, methyl alkenyl polysiloxanes represented by (A). Sufficient thickening properties can be obtained by combining them with the organohydrogen polysiloxane of (A). Furthermore, these may also be mixtures and can be suitably used in the invention.

[0052] More specific examples of component (B) include, but are not limited to, those represented by the following formula. Note that in the following structure, Vi is a vinyl group, and R 5 This represents a hexenyl group. [ka]

[0053] [ka]

[0054] As described above, the number of hydrogen atoms bonded to silicon, which is the reactive group of organohydrogenpolysiloxane (A), and the number of alkenyl groups bonded to silicon, which is the reactive group of organopolysiloxane (B), in each molecule must be at least 1.5 on average. If either of these is less than 1.5, it becomes difficult to form a three-dimensional structure in the polymer obtained by addition polymerization, resulting in poor thickening effect of the target organoalkoxysilane and / or the partially hydrolyzed condensate of the organoalkoxysilane. Furthermore, the content of these reactive groups is preferably, for example, 0.1 to 50 mol%, more preferably 0.2 to 30 mol%, and more preferably 0.4 to 10 mol% in each polysiloxane.

[0055] If the content is 50 mol% or less, the crosslinking density of the three-dimensional structure formed by addition polymerization becomes appropriate, and the organoalkoxysilane of (C) and / or the partially hydrolyzed condensate of said organoalkoxysilane is more easily encapsulated in the three-dimensional structure, improving stability and making it less likely to bleed to the surface. Furthermore, if the content is 0.5 mol% or more, the three-dimensional structure is sufficiently formed, and the organoalkoxysilane of (C) and / or the partially hydrolyzed condensate of said organoalkoxysilane is also encapsulated in the three-dimensional structure. When a relatively large amount of component (C) is used, or when the resulting addition reaction product (polymerization product) is treated under shear force and used together with component (C) as described later, the addition reaction product swells without dissolving in the organoalkoxysilane of (C) and / or the partially hydrolyzed condensate of said organoalkoxysilane, thus the resulting silicone composition can acquire sufficient viscosity.

[0056] Furthermore, in the hydrosilylation reaction of organohydrogenpolysiloxane (A) and alkenyl group-containing organopolysiloxane (B), the molar ratio of total aliphatic unsaturated groups / SiH is not particularly limited, but is preferably 1 / 10 to 10 / 1, and more preferably 8 / 10 to 3 / 1. Within this range, the amount of unreacted organohydrogenpolysiloxane (A) or alkenyl group-containing organopolysiloxane (B) is reduced, and when coated onto porous materials or structural materials such as wood or synthetic wood, appearance defects due to these unreacted components can be avoided.

[0057] [(C) Organoalkoxysilanes and their partially hydrolyzed condensates] Next, the organoalkoxysilane of (C) used in the present invention and / or the partially hydrolyzed condensate of said organoalkoxysilane is represented by the following formula (1). (C):R 3 a Si(OR 4 ) 4-a (1)

[0058] In the above equation (1), R 3These are monovalent hydrocarbon groups, each independently having 1 to 20 carbon atoms, preferably 4 to 16, and more preferably 6 to 12 carbon atoms, which may contain an amino group, an epoxy group, or a halogen atom. Examples of such monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, cyclohexyl, octyl, isooctyl (an alkyl group with 8 carbon atoms including a 2,4,4-trimethylpentyl group), decyl, dodecyl, norbornyl, alkenyl groups such as vinyl, allyl, and hexenyl, aryl groups such as phenyl, and aralkyl groups such as styryl. 3 The group represented by can be linear, branched, or cyclic. Examples include amino group-containing alkyl groups such as 3-aminopropyl group and N-(2-aminoethyl)-3-aminopropyl group, epoxy group-containing alkyl groups such as 3-glycidoxypropyl group, and fluorine-containing groups such as trifluoromethyl group and 3,3,3-trifluoropropyl group. Among these, alkyl groups having 4 to 16 carbon atoms are preferred, and alkyl groups having 6 to 12 carbon atoms are even more preferred.

[0059] R 4 These are, independently of each other, monovalent hydrocarbon groups having 1 to 8 carbon atoms, preferably 1 to 6, and more preferably 1 to 4 carbon atoms. Examples of such monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl groups. Among these, methyl and ethyl groups are particularly preferred. a is 1, 2, or 3, and is particularly preferably 1.

[0060] The organoalkoxysilanes mentioned above include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, Examples include phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, trifluoromethyltrimethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Of these, methyltriethoxysilane, butyltriethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, and isooctyltriethoxysilane are preferred, and hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, and isooctyltriethoxysilane are even more preferred. The organoalkoxysilanes may be one or a mixture of two or more.

[0061] As component (C) of the present invention, a hydrolysis condensate obtained by hydrolyzing a portion of the alkoxy groups of the organoalkoxysilane and performing an intermolecular condensation reaction may be used. Alternatively, the organoalkoxysilane and the hydrolysis condensate of the organoalkoxysilane may be used in mixture form. A conventionally known method can be used for this hydrolysis condensation.

[0062] As catalysts for hydrolysis condensation, acids such as hydrochloric acid, nitric acid, acetic acid, and maleic acid; alkali metal hydroxides such as NaOH and KOH; ammonia and its salts; amine compounds such as triethylamine, dibutylamine, hexylamine, and octylamine, and salts of amine compounds; bases such as benzyltriethylammonium chloride, tetramethylammonium hydroxide, and tetrabutylammonium hydroxide (quaternary ammonium salts); fluoride salts such as potassium fluoride and sodium fluoride; solid acidic catalysts or solid basic catalysts (ion exchange resin catalysts, etc.); and materials such as iron-2-ethylhexoate, titanium naphthate, zinc stearate, and dibutyltin diacetate. Examples include metal salts of organic carboxylic acids, organotitanium esters such as tetrabutoxytitanium and dibutoxy-(bis-2,4-pentanedionate)titanium, organozirconium esters such as tetrabutoxyzirconium and dibutoxy-(bis-2,4-pentanedionate)zirconium, organometallic compounds such as alkoxyaluminum compounds such as aluminum triisopropoxide, aluminum chelate compounds such as aluminum acetylacetonate complexes, and aminoalkyl-substituted alkoxysilanes such as 3-aminopropyltrimethoxysilane and N-(β-aminoethyl)-3-aminopropyltrimethoxysilane, which may be used alone or in combination.

[0063] [Method for producing organoalkoxysilane-containing compositions] The method for producing the organoalkoxysilane-containing composition of the present invention is not particularly limited, but one example of a method for producing the composition is a first step in which 100 parts by mass of components (A) and (B) combined are added and polymerized while stirring in the presence of 100 to 1500 parts by mass of component (C) to obtain an addition reaction product. Furthermore, the above production method may also include a second step in which component (C) is further mixed into the addition reaction product such that the total amount of component (C) is 100 to 10000 parts by mass relative to 100 parts by mass of components (A) and (B) combined. In this way, an organoalkoxysilane-containing composition containing the addition reaction product of (A) and (B) and (C) can be obtained in one or two steps. Additives described later can be added at any point in the production process as needed. The method for producing the composition will be described below.

[0064] The composition of the present invention can be produced in the first step of addition polymerization of organohydrogenpolysiloxane (A) and organopolysiloxane (B) under stirring in the presence of organoalkoxysilane (C) and / or hydrolysis condensate of said organoalkoxysilane to obtain an addition reaction product of (A) and (B), and then in the second step of dilution with organoalkoxysilane (C) and / or a partial hydrolysis condensate of said organoalkoxysilane until the desired concentration is obtained. At this time, the proportion of organoalkoxysilane (C) and / or hydrolysis condensate of said organoalkoxysilane during the addition polymerization in the first step is in the range of 100 to 1,500 parts by mass, preferably in the range of 150 to 1,300 parts by mass, and more preferably in the range of 200 to 1,000 parts by mass, per 100 parts by mass of the total amount of organohydrogenpolysiloxane (A) and organopolysiloxane (B).

[0065] This is because, if the proportion of organoalkoxysilane and / or the hydrolysis condensate of said organoalkoxysilane is 100 parts by mass or more, the polymerization product obtained in the first step (the addition product of component (A) and component (B)) does not become too hard, and during dilution in the second step, the organoalkoxysilane of (C) and / or the hydrolysis condensate of said organoalkoxysilane are more easily incorporated into the three-dimensional structure of the addition product. As a result, viscosity does not decrease due to dilution, and the product has sufficient stability without immediate separation. Furthermore, if the proportion of organoalkoxysilane (C) and / or the partially hydrolyzed condensate of said organoalkoxysilane is 1,500 parts by mass or less, the reaction rate between organohydrodienepolysiloxane (A) and organopolysiloxane (B) is sufficient, and an addition product with sufficient viscosity can be obtained.

[0066] The aforementioned addition polymerization involves a platinum compound soluble in organic solvents, such as aliphatic alcohols like methanol, ethanol, 2-propanol, and butanol; aromatic hydrocarbons like benzene, toluene, and xylene; aliphatic or alicyclic hydrocarbons like n-pentane, n-hexane, and cyclohexane; and halogenated hydrocarbons like dichloromethane, chloroform, carbon tetrachloride, trichloroethane, trichloroethylene, and fluorinated hydrocarbons (e.g., chloroplatinic acid, alcohol-modified platinum chloride). acid The reaction can be carried out in the presence of a chlorplatinate-vinylsiloxane complex or a rhodium compound.

[0067] Particularly preferred catalysts include chloroplatinic acid, platinum compounds used in hydrosilylation reactions as described in U.S. Patents No. 3,159,601, 3,159,662, and 3,775,452, such as [Pt(PPh3)3], which are complex compounds of vinylsiloxane and platinum compounds, and even better are those modified with alcohol. Among these, chloroplatinic acid as described in Japanese Patent Publication No. 33-9969, or complex compounds of vinylsiloxane and chloroplatinic acid, or complex compounds of vinylsiloxane and platinum are more preferred.

[0068] The specific operation of addition polymerization involves, for example, using a reactor such as a planetary mixer equipped with a suitable stirring device, blending the required amounts of organopolysiloxanes (A), (B), and (C), then adding the catalyst, and stirring for 10 minutes to 24 hours, preferably 30 minutes to 12 hours, and more preferably 1 to 8 hours at a temperature of 50 to 150°C, preferably 55 to 140°C, more preferably 60 to 120°C. This easily yields a polymer (addition product) that is insoluble in the organoalkoxysilane (C) and / or the partially hydrolyzed condensate of the organoalkoxysilane, but swells sufficiently as a result, with the organoalkoxysilane (C) and / or the partially hydrolyzed condensate of the organoalkoxysilane coexisting within it. Note that the reaction temperature and reaction time are not limited to those above, and should be optimized depending on the scale and type of reactor used for addition polymerization, and the types and amounts of (A), (B), and (C).

[0069] In preparing the composition of the present invention, the mixing of the organopolysiloxane polymer (addition reaction product) obtained by the addition reaction of the organohydrogenpolysiloxane of (A) and the organopolysiloxane of (B) below, and the organoalkoxysilane of (C) and / or the partially hydrolyzed condensate of said organoalkoxysilane may be carried out with a normal stirrer, but it is preferable to further knead under shear force. This is because the organopolysiloxane polymer obtained by the addition reaction of the organohydrogenpolysiloxane of (A) and the organopolysiloxane of (B) below has a three-dimensional crosslinked structure that does not dissolve in the organoalkoxysilane of (C) and / or the partially hydrolyzed condensate of said organoalkoxysilane, and by providing sufficient dispersibility under shear force, a paste composition with a smooth appearance can be obtained. The mixing process can be carried out using, for example, a three-roll mill, a two-roll mill, a kneader, a muscoloider, a sand grinder, a colloid mill, a Gaurin homogenizer, a disper, a high-shear mixer, etc., but a method using a three-roll mill or a disper is preferred.

[0070] [Additives] The composition of the present invention may further contain other additives. These additives may include known additives used as water-repellent agents, such as antifungal agents, antialgal agents, ultraviolet absorbers, anti-aging agents, pigments, dyes, viscosity modifiers such as thickeners, solvents, waxes, and metal soaps other than aluminum soap. Furthermore, inorganic fillers such as silica, alumina, titania, mica, and talc, and inorganic thickeners such as montmorillonite and bentonite may also be included. However, if the additive is solid, such as silica, alumina, titania, mica, talc, montmorillonite, or bentonite, it may remain on the substrate surface after application and drying, resulting in an undesirable appearance. Therefore, the amount of the additive should preferably be 20 parts by mass or less, more preferably 10 parts by mass or less, and more preferably 4 parts by mass or less, per 100 parts by mass of the final (C) organoalkoxysilane and / or the partially hydrolyzed condensate of the organoalkoxysilane.

[0071] Furthermore, viscosity modifiers such as hydrocarbon compounds, paraffins, and silicones may be added to the composition of the present invention for the purpose of adjusting viscosity. However, while it is possible to add solvents with a boiling point or flash point lower than that of organoalkoxysilane, it is preferable to add compounds with a boiling point or flash point higher than that of organoalkoxysilane. Note that the organoalkoxysilane of (C) and / or the partially hydrolyzed condensate of said organoalkoxysilane penetrate into the interior when coated onto the surface of a substrate such as porous material, wood, or synthetic wood. Therefore, selecting components that easily penetrate these substrates can result in a desirable appearance.

[0072] Regarding the properties of the compositions in this invention, a gel-like composition refers to a solid at 25°C, a paste-like composition refers to a liquid with low fluidity, and a liquid composition refers to a liquid with high fluidity. However, all of these compositions can be applied to a substrate by means of a roller, brush, trowel, spatula, spray, or spray.

[0073] Furthermore, the viscosity of the composition of the present invention is preferably in the range of 100 to 500,000 mPa·s, and more preferably in the range of 500 to 300,000 mPa·s. If the viscosity is 100 mPa·s or higher, when applied to porous materials, wood, synthetic wood, or other structural materials, it will not drip, resulting in a good appearance, and since the impregnation depth of the organoalkoxysilane into the substrate will not vary from place to place, there is no risk of uneven water absorption prevention. If the viscosity is 500,000 mPa·s or lower, the workability during application will be good.

[0074] In this invention, viscosity, unless otherwise specified, is the value measured by a rotational viscometer at a composition temperature of 25°C. The rotor, rotation speed, and rotation time are appropriately selected according to the viscosity based on conventional methods (for example, JIS K 7117-1:1999).

[0075] [Water-repellent agent] The composition of the present invention can be used as a water-repellent agent. By applying this water-repellent agent to the surface of a structural material such as a porous material, wood, or synthetic wood, water-repellent properties can be imparted to the substrate surface. Examples of substrates (structural materials) to which this water-repellent agent can be applied include inorganic porous materials such as concrete, lightweight concrete, autoclaved lightweight concrete (ALC), mortar, various cement boards, gypsum boards, calcium silicate boards, bricks, roof tiles, tiles, and stone. It can also be used on walls made primarily from diatomaceous earth, clay, or plaster, as well as organic porous materials such as paper, wood, and leather.

[0076] The amount of the water-repellent agent of the present invention applied to the substrate is not particularly limited, but for example, 5 to 1,000 g / m² 2 This can be done, preferably 10-300 g / m² 2 It is 5g / m 2 The water-repellent properties can be fully achieved at the above level. 1,000g / m 2 The following conditions ensure sufficient impregnation depth and prevent excessively long drying times.

[0077] [Method for imparting water-repellent properties] As described above, water-repellent properties can be imparted to structural materials by applying the water-repellent agent of the present invention to the surface of the structural material. The method for applying the water-repellent agent of the present invention to a substrate (structural material) is not particularly limited and can be done according to conventionally known methods. For example, rollers, brushes, trowels, spatulas, sprays, and spraying can be used. Usually, a predetermined amount can be applied in one go, but multiple coats may be applied as needed. Drying after application can be left at room temperature, but it may also be heated to about 40-80°C.

[0078] When the viscosity of the water-repellent agent of the present invention, as measured by a rotational viscometer at 25°C, is 100 to 50,000 mPa·s, application using a spray, spray, roller, or brush is recommended. When the viscosity of the water-repellent agent is 5,000 to 500,000 mPa·s, application using a trowel or spatula is recommended for better workability. In the range of 5,000 to 50,000 mPa·s, application can be performed with good workability using any of the above methods.

[0079] [Surface-treated structural materials] A surface-treated structural material can be manufactured by surface-treating the structural material with the water-repellent agent of the present invention. Using a water-repellent agent containing the organoalkoxysilane composition of the present invention allows for easy application, minimizes dripping during application, enables deep penetration of the active ingredient (organoalkoxysilane) into the surface of porous materials, wood, and synthetic wood, imparts water-repellent properties without impairing appearance, offers good workability during application, and boasts excellent storage stability, maintaining its properties even after long-term high-temperature storage. Therefore, such surface-treated structural materials can be manufactured efficiently.

[0080] When the organoalkoxysilane-containing composition of the present invention is applied to a substrate surface, the water-repellent component (C) (active ingredient) penetrates the substrate surface and hydrophobicizes its surface. However, unlike conventional solvent-type water-repellent agents, the composition of the present invention (water-repellent agent) contains the active ingredient stably encapsulated in the three-dimensional structure of the addition reaction product of the non-volatile components (A) and (B). Therefore, the active ingredient can be sufficiently impregnated and penetrated into the surface of the substrate. [Examples]

[0081] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples and comparative examples. The rotational viscosity (absolute viscosity) of the compositions obtained in the examples and comparative examples of this invention was measured using a rotational viscometer at a temperature of 25°C. The rotor, rotational speed, and rotational time should be selected according to the viscosity in accordance with JIS K7117-1:1999. The kinematic viscosity is the value at 25°C when using a Cannon-Fenske viscometer as described in JIS Z8803:2011.

[0082] [Example 1] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the following average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the following average composition formula (3), 100 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller system. Subsequently, another 100 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer to obtain a paste-like composition with a rotational viscosity of 123,200 mPa·s at 25°C.

[0083] [ka]

[0084] [Example 2] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 400 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller mixer. Subsequently, 9,500 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer to obtain a liquid composition with a rotational viscosity of 700 mPa·s at 25°C.

[0085] [Example 3] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 400 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller mixer. Subsequently, 1,500 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer to obtain a liquid composition with a rotational viscosity of 2,790 mPa·s at 25°C.

[0086] [Example 4] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 400 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller mixer. Subsequently, 500 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer to obtain a paste-like composition with a rotational viscosity of 34,700 mPa·s at 25°C.

[0087] [Example 5] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 400 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller mixer. Subsequently, 166.6 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer to obtain a paste-like composition with a rotational viscosity of 88,100 mPa·s at 25°C.

[0088] [Example 6] In a reactor, 21.0 parts by mass of (A-2) organohydrogenpolysiloxane represented by the average composition formula (4) below, 79.0 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3) above, 400 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller mixer. Subsequently, 1,500 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer to obtain a liquid composition with a rotational viscosity of 2,680 mPa·s at 25°C.

[0089] [ka]

[0090] [Example 7] In a reactor, 15.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2) above, 84.8 parts by mass of (B-2) organopolysiloxane represented by the average composition formula (5) below, 400 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller mixer. Subsequently, 1,500 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer to obtain a liquid composition with a rotational viscosity of 3,500 mPa·s at 25°C.

[0091] [ka]

[0092] [Example 8] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 100 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller mixer. Subsequently, 50 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer to obtain a paste-like composition with a rotational viscosity of 186,200 mPa·s at 25°C.

[0093] [Example 9] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 1,500 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller mixer. Subsequently, 400 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer to obtain a liquid composition with a rotational viscosity of 1,060 mPa·s at 25°C.

[0094] [Example 10] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 400 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller system. Subsequently, 1,500 parts by mass of octyltriethoxysilane and 76 parts by mass of hydrophobic dry silica were added and mixed under shear force using a disper mixer to obtain a liquid composition with a rotational viscosity of 1,320 mPa·s at 25°C. For the hydrophobic dry silica used, we employed AEROSIL RY300 (manufactured by Nippon Aerosil).

[0095] [Example 11] In the reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 400 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, after which it was kneaded under shear force using a three-roller system. Subsequently, 1,500 parts by mass of octyltriethoxysilane and a kinematic viscosity of 1,000 mmHg at 25°C were added. 2 A liquid composition with a rotational viscosity of 3,600 mPa·s at 25°C was obtained by adding 300 parts by mass of polydimethylsiloxane at 25°C and mixing under shear force using a disper mixer.

[0096] [Comparative Example 1] In Comparative Example 1, octyltriethoxysilane was used alone according to the evaluation method described below. The kinematic viscosity of octylethoxysilane at 25°C is 2.1 mm³. 2 It was / s.

[0097] [Comparative Example 2] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 80 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. After stirring for 2 hours while maintaining the internal temperature at 75-85°C, a gel-like composition was obtained by kneading under shear force using a three-roller system, but it was too hard to measure viscosity.

[0098] [Comparative Example 3] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 60 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller mixer. Subsequently, 20 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer to obtain a gel-like composition, but it was too hard to measure viscosity.

[0099] [Comparative Example 4] In a reactor, 13.2 parts by mass of (A-1) organohydrogenpolysiloxane represented by the average composition formula (2), 86.8 parts by mass of (B-1) organopolysiloxane represented by the average composition formula (3), 12,000 parts by mass of octyltriethoxysilane, and 0.10 parts by mass of a 3% chlorinated platinumic acid ethanol solution were charged. The mixture was stirred for 2 hours while maintaining the internal temperature at 75-85°C to obtain a cross-linked organopolysiloxane polymer swollen with octyltriethoxysilane, which was then kneaded under shear force using a three-roller mixer. Subsequently, 20 parts by mass of octyltriethoxysilane were added and mixed under shear force using a disper mixer until the kinematic viscosity at 25°C was 3.9 mm. 2A composition with a value of / s was obtained.

[0100] [evaluation] The evaluation methods for each composition obtained from the examples and comparative examples are as follows.

[0101] (1) Dripping A mortar test piece (70 mm long x 70 mm wide x 25 mm high) prepared in accordance with JIS R5201 was used as the test specimen. 200 g / m² of each composition obtained in the above examples and comparative examples was applied to the 70 mm x 70 mm surface of the test piece. 2 The required amount was applied and spread as uniformly as possible using a brush or spatula. Immediately after application, the test piece was placed upright with the applied surface perpendicular to the surface, and it was visually observed whether or not the applied organoalkoxysilane-containing composition would flow.

[0102] (2) Exterior The compositions obtained in the above examples and comparative examples were applied to mortar test pieces in the same manner as in (1) above. The test pieces were left to cure at 25°C and 50% RH for 7 days. After that, the percentage of wet color remaining on the surface coated with the organoalkoxysilane-containing composition was visually observed and evaluated according to the following indicators. (index) 5. The area where the wet color remains is 5% or less of the total surface area of ​​the coated surface (i.e., it has an appearance similar to that of a test piece that has not been coated with the organoalkoxysilane-containing composition). 4: The area where the wet color remains is more than 5% but less than 25% of the total surface area of ​​the coated surface. 3: The area where the wet color remains is between 25% and 75% of the total surface area of ​​the coated surface. 2: The area where the wet color remains is between 75% and 95% of the total surface area of ​​the coated surface. 1: The area where the wet color remains is 95% or more of the total surface area of ​​the coated surface.

[0103] (3) Water repellency Each composition was applied to a mortar test piece in the same manner as described in (1) above. The test piece was left to cure at 25°C and 50% RH for 7 days. After running water over the surface coated with each composition for 5 minutes using a shower, the degree of water repellency and the percentage of wet color on the surface coated with each composition were visually observed and evaluated according to the following indicators. <Repel> 5. The area where water is repelled is 95% or more of the total surface area of ​​the coated surface. 4: Of the total surface area of ​​the coated surface, the area where water was repelled was between 75% and 95%. 3: Of the total surface area of ​​the coated surface, the area that repelled water was between 25% and 75%. 2: Of the total surface area of ​​the coated surface, the area where water was repelled was 5% or more but less than 25%. 1: The area of ​​the coated surface that repelled water was less than 5% of the total surface area. <Wet look> 5. The area where the wet color remains is 5% or less of the total surface area of ​​the coated surface. 4: The area where the wet color remains is more than 5% but less than 25% of the total surface area of ​​the coated surface. 3: The area where the wet color remains is between 25% and 75% of the total surface area of ​​the coated surface. 2: The area where the wet color remains is between 75% and 95% of the total surface area of ​​the coated surface. 1: The area where the wet color remains is 95% or more of the total surface area of ​​the coated surface.

[0104] (4) Impregnation depth Each composition was applied to a mortar test piece in the same manner as in (1) above. The test piece was left to cure at 25°C and 50% RH for 7 days. The test piece was split vertically so as to divide the surface to which the composition was applied into two parts, and water was sprayed onto the split surface. The depth of the area that did not absorb water and did not change color was measured and defined as the impregnation depth.

[0105] (5) Storage stability (25℃ / 1 month) 50g of each composition was placed in a 100mL container, sealed tightly, and stored in a 25°C incubator. After storage, the properties were checked every month for a total of 6 months, and the time until some or all of the composition separated was evaluated.

[0106] (6) Storage stability (40℃ / 1 (months) 50g of each composition was placed in a 100mL container, sealed tightly, and stored in a 40°C incubator. After storage, the properties were checked every month for a total of 6 months, and the time until some or all of the composition separated was evaluated.

[0107] The evaluation results are shown in Tables 1 and 2. Note that dimethyl silicone in Table 1 refers to polydimethylsiloxane.

[0108] [Table 1]

[0109] [Table 2]

[0110] In Examples 1-11 using the organoalkoxysilane-containing composition of the present invention, dripping does not occur when applied to mortar (concrete), the active ingredient (organoalkoxysilane) can penetrate deeply from the mortar surface, and excellent water repellency (water absorption prevention) can be imparted without impairing the appearance. Furthermore, it has good workability during application and excellent storage stability, maintaining its properties even when stored at high temperatures for a long period of time. On the other hand, Comparative Example 1, which did not contain components (A) and (B), exhibited dripping during application, insufficient penetration depth of the active ingredients (impregnation depth), and poor water repellency. Furthermore, Comparative Examples 2 and 3, which contained insufficient amounts of component (C), produced a gel-like composition that was too hard to apply, while Comparative Example 4, which contained too much of component (C), exhibited dripping during application, insufficient impregnation depth, poor water repellency, and poor storage stability.

[0111] When the organoalkoxysilane-containing composition of the present invention is applied to a substrate surface, the water-repellent (C) component (active ingredient) penetrates the substrate surface and makes its surface hydrophobic. In particular, the organoalkoxysilane-containing composition of the present invention has a three-dimensional crosslinked structure in which the addition product of component (A) and component (B) does not dissolve in component (C), and component (C) is stably encapsulated within the three-dimensional structure of the addition product. Furthermore, since the addition product swells without dissolving in component (C), the composition of the present invention can acquire sufficient viscosity to facilitate application and can contain a large amount of component (C). For this reason, when applying the organoalkoxysilane-containing composition (water-repellent agent) of the present invention to structural materials, the workability is improved, the appearance is also improved, and the impregnation depth of component (C) into the substrate does not vary from place to place, thus reducing unevenness in water-repellent properties.

[0112] Unlike conventional solvent-based water-repellent agents, in the composition of the present invention, component (C) (active ingredient) is stably encapsulated in the three-dimensional structure of the addition reaction product of the non-volatile components (A) and (B), and does not require an organic solvent. Therefore, there is no risk of fire, explosion, or poisoning, the working environment during application is good, and no environmental problems arise. Furthermore, unlike conventional aqueous emulsions, there is no problem of runoff, nor is there a problem with alkylalkoxysilane separation after application in aqueous creams. Even when applied to inclined, vertical, or downward-facing surfaces, the addition reaction product of components (A) and (B) remains swollen and retained on the substrate surface without dissolving in component (C), allowing the active ingredient to be sufficiently impregnated and penetrated into the substrate surface.

[0113] [Industrial applicability] By using the composition containing the organoalkoxysilane and / or the partially hydrolyzed condensate of said organoalkoxysilane as a water-repellent agent, application is easy, no dripping occurs during application, the active ingredient (organoalkoxysilane) can penetrate deeply into the surface of porous materials, wood, synthetic wood, etc., and water-repellent properties can be imparted without impairing the appearance. Furthermore, it has good workability during application and excellent storage stability, maintaining its properties even when stored at high temperatures for a long period of time.

[0114] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. An organoalkoxysilane-containing composition comprising (A) an organohydrogenpolysiloxane, (B) an addition product of an organopolysiloxane, and (C) an organoalkoxysilane, wherein (C) is present in an amount of 100 to 10,000 parts by mass relative to 100 parts by mass of the total of (A) and (B), The organoalkoxysilane-containing composition is characterized in that, when the organoalkoxysilane-containing composition is applied to the surface of a porous material substrate, (C) penetrates from the surface of the substrate. (A) SiO ２ unit, HSiO １．５ unit, R １ SiO １．５ unit, R １ HSiO unit, R １ ２ SiO unit, R １ ２ HSiO ０．５ unit and R １ ３ SiO ０．５ unit (where R １ is a substituted or unsubstituted monovalent hydrocarbon group excluding an aliphatic unsaturated group), and has a structural unit selected from the group consisting of, and contains on average 1.5 or more hydrogen atoms bonded to silicon atoms in the molecule, an organohydrogenpolysiloxane (B) SiO ２ Unit, R ２ SiO １．５ Unit, R １ SiO １．５ Unit, R １ R ２ SiO units, R １ ２ SiO units, R １ ３ SiO ０．５ Units and R １ ２ R ２ SiO ０．５ Unit (R here) １ The same as above, R ２ Organopolysiloxanes having a structural unit selected from the group consisting of alkenyl groups, and containing an average of 1.5 or more alkenyl groups bonded to silicon atoms in the molecule, (C) Organoalkoxysilane represented by the following formula (1) R ３ ａ Si(OR ４ ) ４－ａ (1) (In the formula, R ３ These are alkyl groups having 4 to 16 carbon atoms, R ４ (Each of the three elements is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is 1, 2, or 3.)

2. R in formula (1) ３ The organoalkoxysilane-containing composition according to claim 1, characterized in that it is an alkyl group having 6 to 12 carbon atoms.

3. The organoalkoxysilane-containing composition according to claim 1 or 2, characterized in that the viscosity of the organoalkoxysilane-containing composition measured by a rotational viscometer at 25°C is 100 to 500,000 mPa·s.

4. A water-repellent agent characterized by comprising an organoalkoxysilane-containing composition according to any one of claims 1 to 3.

5. A method for producing an organoalkoxysilane-containing composition according to any one of claims 1 to 3, A method for producing an organoalkoxysilane-containing composition, characterized by comprising a first step of adding 100 parts by mass of a total of 100 parts by mass of Component (A) and Component (B) while stirring in the presence of 100 to 1500 parts by mass of Component (C) to obtain an addition reaction product.

6. A method for producing an organoalkoxysilane-containing composition according to claim 5, characterized by comprising a second step of further mixing component (C) with the addition reaction product such that the total amount of component (C) is 150 to 10,000 parts by mass relative to 100 parts by mass of the total amount of component (A) and component (B).

7. A method for imparting water-repellent properties, characterized by applying the water-repellent agent described in claim 4 to the surface of a structural material.

8. A method for imparting water-repellent properties according to claim 7, characterized in that when the viscosity of the water-repellent agent measured by a rotational viscometer at 25°C is 100 to 50,000 mPa·s, the agent is applied using a spray, spray, roller or brush, and when the viscosity of the water-repellent agent measured by a rotational viscometer at 25°C is 5,000 to 500,000 mPa·s, the agent is applied using a trowel or spatula.

9. A method for producing a surface-treated structural material, characterized by surface-treating the structural material with the water-repellent agent described in claim 4.

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