WO2020036073A1

WO2020036073A1 - Silicone resin emulsion composition, method for producing same, coating agent and coated article

Info

Publication number: WO2020036073A1
Application number: PCT/JP2019/030315
Authority: WO
Inventors: 一幸竹脇
Original assignee: 信越化学工業株式会社
Priority date: 2018-08-17
Filing date: 2019-08-01
Publication date: 2020-02-20
Also published as: TW202017977A

Abstract

(A) 100 parts by mass of a silicone resin that has a structure represented by average formula (I) (SiO4/2)a(R1SiO3/2)b(R1 2SiO2/2)c(R1 3SiO1/2)d(R2O1/2)e (B) 2-100 parts by mass of a solvent represented by general formula (II) (C) 1-50 parts by mass of an emulsifying agent (D) 25-2,000 parts by mass of water

Description

Silicone resin emulsion composition, production method thereof, coating agent and coated article

{Circle over (1)} The present invention relates to a silicone resin emulsion composition suitably used as an exterior paint for building materials and the like, a method for producing the same, a coating agent, and a coated article having a cured film made of these. Hereinafter, the “silicone resin emulsion composition” may be referred to as a “composition”.

シリコーン Silicone resins obtained by hydrolyzing and condensing silane compounds are attracting attention in the field of paints and coating agents because they can form films having high hardness and excellent weather resistance, water resistance, heat resistance and water repellency.

In this field, silicone resins are often used after being diluted with various organic solvents, but in recent years, from the viewpoint of measures against environmental pollution and ensuring a safe working environment, organic solvents, especially toluene, xylene, ethylbenzene, etc. It is important to develop a TX-free paint that does not use a specific VOC (volatile organic compound: Volatile Organic Compounds). Further, organic solvents such as toluene and xylene have high volatility, and thus have a problem that defects such as cracks and uneven coating are likely to occur in a coating film in a drying step.

Environmentally friendly glycol ether is a TX-free solvent whose usage has been increasing in recent years because it has a small burden on people and nature and is easy to handle. In addition, it has the advantage that the boiling point is high and the adverse effect on the human body due to exposure to the solvent gas is small. Furthermore, since it is low in volatility, it is excellent in workability and hardly generates defects such as cracks and uneven coating in a coating film, and thus is suitable as a solvent for coating materials.

Patent Document 1: JP-T-2008-53007 discloses an example of a low VOC aqueous latex paint using a low-polymerized ethylene glycol derivative as a solvent. The low-polymerized ethylene glycol derivative functions as both a film-forming solvent and a freeze-thaw stabilizer, and is said to provide a coating film having excellent scratch resistance.

Emulsion compositions using water as the dispersion medium have also been developed. However, all of the currently established formulations of silicone resin emulsions have drawbacks.

For example, an aqueous solution obtained by hydrolyzing an alkoxysilane compound in water can maintain stability only under a low concentration of about several percent or under limited conditions such as a narrow pH range, and a large amount of alcohol is by-produced. However, there is a problem that the system becomes unstable when mixed with other emulsions.

In addition, the method of emulsifying a liquid silicone resin to obtain an emulsion is limited to low molecular weight substances since the silicone resin needs to be in a liquid state, and in order to obtain a cured film after drying, harmful substances such as organic tin are used. There is a problem that a combined use of a metal catalyst and a high-temperature and long-time heating step are required.

On the other hand, since it is difficult to form an emulsion of a normal-temperature solid silicone resin as it is, a solution prepared by dissolving the silicone resin in the above-mentioned environment-friendly glycol ether or the like and then emulsifying the solution has been reported. ing.

Patent Document 2: Japanese Patent Application Laid-Open No. 2008-138059 discloses an organosilicone resin emulsion composition in which a silicone resin is converted into a solution using a water-miscible organic solvent having an SP value of 8.0 to 11.0, and the solution is emulsified. It has been reported.

Patent Document 3: Patent No. 4775543 discloses an organosilicone resin emulsion composition obtained by emulsifying a solution using a water-miscible organic solvent selected from butyl cellosolve, butyl cellosolve acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. Have been.

However, these publications use a silicone resin solution synthesized in toluene or xylene, and perform solvent replacement with a high-boiling water-miscible organic solvent, which is significant for the final silicone resin emulsion composition. There was a problem that an amount of toluene and xylene remained.

Further, butyl cellosolve acetate used as a water-miscible organic solvent, a solvent having an ester bond such as propylene glycol monomethyl ether acetate is hydrolyzed in the emulsion composition, the acid is generated with time, the emulsion composition by the generation. There was a problem of acidification.

Furthermore, ethylene glycol monoalkyl ethers such as butyl cellosolve have been widely used as solvents for paints, but recently there has been a problem that their use has been avoided due to concerns about toxicity.

JP 2008-53007 A JP 2008-138059 A Japanese Patent No. 4775543

The present invention has been made in view of the above circumstances, compared to the conventional silicone resin emulsion, silicone resin emulsion composition with reduced environmental problems, its production method, and coating properties, crack resistance, It is an object of the present invention to provide a coated article having a cured film having excellent hardness.

As a result of intensive studies to achieve the above object, the present inventors have found that (A) a specific silicone resin, (B) a solvent represented by the general formula (II) (a so-called glycol ether solvent), (C) an emulsifier, and D) It has been found that the above problems can be solved by forming a silicone resin emulsion composition containing water in a specific amount, and the present invention has been accomplished.

Accordingly, the present invention provides:
1. A silicone resin emulsion composition containing the following components (A) to (D) and substantially no organic solvent other than the component (B).
(A) Silicone resin having a structure represented by the following average formula (I): 100 parts by mass

(Wherein, R ¹ independently represents a hydrogen atom, or an alkyl group, an aralkyl group or an aryl group having 1 to 8 carbon atoms which may be substituted by a halogen atom, and R ² represents a hydrogen atom, a methyl group, Represents an ethyl group, an n-propyl group or an i-propyl group, wherein a, b, c, and d are respectively 0 ≦ a <1, 0 <b ≦ 1, 0 ≦ c <1, 0 ≦ d <1, a + b + c + d = 1 and e is a number that satisfies 0 <e ≦ 4.)
(B) a solvent represented by the following general formula (II): 2 to 100 parts by mass

(In the formula, R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. When R ³ is a hydrogen atom, n is 2 or more. In the case where R ³ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, n represents an integer of 1 or more, provided that R ⁴ and R ⁵ are not hydrogen atoms at the same time.)
(C) emulsifier: 1 to 50 parts by mass (D) water: 25 to 2,000 parts by mass 2. The silicone resin emulsion composition according to 1, wherein the component (B) is diethylene glycol diethyl ether or dipropylene glycol dimethyl ether.
3. A coating agent comprising the silicone resin emulsion composition according to 1 or 2.
4. A coated article having a substrate and a cured coating of the coating agent according to 3, which is formed on at least one surface of the substrate directly or via one or more other layers.
5. 3. A method for producing the silicone resin emulsion composition according to 1 or 2, comprising the following steps.
(I) A silane compound having a hydrolyzable group is hydrolyzed and condensed in a solvent represented by the above general formula (II) to form (A) a structure represented by the above average formula (I) Obtaining a mixed solution containing a silicone resin and (B) a solvent represented by the general formula (II);
(II) A step of mixing the mixture obtained in (I), (C) an emulsifier, and (D) water and stirring to emulsify.

According to the present invention, it is possible to obtain a silicone resin emulsion which forms a cured film having a small environmental load and excellent coating properties, crack resistance and hardness, a method for producing the same, and a coated article.

Hereinafter, the present invention will be described in detail.
[(A) component]
The component (A) of the present invention is a silicone resin having a structure represented by the following average formula (I).

In the formula (I), R ¹ independently represents a hydrogen atom or an alkyl group, an aralkyl group or an aryl group having 1 to 8 carbon atoms which may be substituted by a halogen atom, and R ² represents a hydrogen atom, methyl Group, ethyl group, n-propyl group or i-propyl group. a, b, c, and d satisfy 0 ≦ a <1, 0 <b ≦ 1, 0 ≦ c <1, 0 ≦ d <1, a + b + c + d = 1, and e satisfies 0 <e ≦ 4. It is.

The above a is a number that satisfies 0 ≦ a <1, but preferably 0 ≦ a <0.3 from the viewpoint of the crack suppression effect of the obtained cured product (cured film).
The above b is a number satisfying 0 <b ≦ 1, but from the viewpoint of the scratch resistance of the obtained cured product (cured coating), 0.2 ≦ b <1 is preferable.
The above c is a number satisfying 0 ≦ c <1, but from the viewpoint of the curability of the composition and the hardness of the obtained cured product (cured film), 0 ≦ c <0.5 is preferable.
The above d is a number that satisfies 0 ≦ d <1, but from the viewpoint of the curability of the composition and the hardness of the obtained cured product (cured coating), 0 ≦ d <0.4 is preferable.
The above e is a number that satisfies 0 <e ≦ 4, but from the viewpoint that it is effective for suppressing the condensation reaction by the condensable functional group and the crack resistance, water resistance, and weather resistance of the obtained cured product. , E are preferably numbers satisfying 0 <e ≦ 3.

The silicone resin (A) of the present invention may be a single composition or a mixture of a plurality of silicone resins having different compositions.

（The weight average molecular weight of the silicone resin (A) of the present invention is preferably from 1,000 to 500,000, more preferably from 2,000 to 300,000 in terms of weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). If the weight average molecular weight is less than 1,000, condensation does not proceed sufficiently, the storage stability of the silicone resin may be low, and there is a possibility that the final emulsion composition may change with time. Further, when the condensation reaction proceeds with time, crack resistance of the cured film (coating film) may be reduced. If the molecular weight is more than 500,000, the silicone resin compound becomes insoluble in the solvent, and there is a possibility that solid foreign matter or uneven coating may occur on the cured film.

(A) The silicone resin (A) of the present invention can be produced according to a general method for producing a silicone resin. For example, the organopolysiloxane of the present invention can be obtained by hydrolytic condensation of a silane compound having a hydrolyzable group.

As a raw material for producing the silicone resin of the component (A), the type of the hydrolyzable group is chloro or alkoxy, and one, two, three or four hydrolyzable groups are contained, and Any hydrolyzable silane having an organic substituent satisfying the above can be used. Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane , Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane , Propyltrimethoxysilane, propyltriethoxysilane, butyltrichlorosilane, butyltrimethoxysilane, butyl Liethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, cyclohexyltrichlorosilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, propylmethyldichloro Silane, propylmethyldimethoxysilane, propylmethyldiethoxysilane, hexylmethyldichlorosilane, hexylmethyldimethoxysilane, hexylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, diphenyldichloro Silane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethylphenylc Rushiran, dimethylphenyl silane, dimethyl phenyl ethoxy silane, and the like of these partial hydrolysis products thereof as the silane compound usable organosilicon compounds which can be used are not limited thereto.

メトキシ It is more preferable to use methoxysilane or ethoxysilane from the viewpoint of operability, easy removal of by-products, and availability of raw materials. One or a mixture of two or more of these silane compounds may be used.

When performing the hydrolysis, a hydrolysis catalyst may be used. As the hydrolysis catalyst, a conventionally known catalyst can be used, and it is preferable to use a catalyst whose aqueous solution shows an acidity of pH 2 to 7. Particularly preferred are acidic hydrogen halides, sulfonic acids, carboxylic acids, acidic or weakly acidic inorganic salts, and solid acids such as ion exchange resins. Examples include hydrogen fluoride, hydrochloric acid, nitric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, formic acid, acetic acid, maleic acid, benzoic acid, lactic acid, phosphoric acid and cation exchange resins having sulfonic or carboxylic acid groups on the surface And the like.

The amount of the hydrolysis catalyst to be used is not particularly limited. However, considering that the reaction proceeds promptly and that the catalyst can be easily removed after the reaction, 0.0002 to 1 mol of the hydrolyzable silane is used. A range of 0.5 mole is preferred.

The ratio of the amount of the hydrolyzable silane to the amount of water required for the hydrolysis and condensation reaction is not particularly limited, but the reaction is sufficiently advanced by preventing the deactivation of the catalyst, and the amount of water after the reaction is reduced. In consideration of easiness, a ratio of 0.1 to 10 mol of water to 1 mol of the hydrolyzable silane is preferable.

The hydrolysis / condensation reaction temperature is not particularly limited, but is preferably −10 to 150 ° C. in consideration of improving the reaction rate and preventing decomposition of the organic functional group of the hydrolyzable silane.

In the hydrolysis-condensation reaction, a solvent represented by the following (B) general formula (II) may be used, or an organic solvent other than the (B) solvent may be used. Specific examples include methanol, ethanol, propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene and the like. When an organic solvent other than the solvent (B) is used, the solvent other than the component (B) is substantially replaced by, for example, replacing the solvent represented by the general formula (II) with a solvent such as a stripping step. Not included.

After the hydrolysis-condensation reaction, a sufficient amount of synthetic hydrotalcite or the like sufficient for neutralization may be added for neutralization, followed by filtration.

[Component (B)]
The component (B) of the present invention is a solvent represented by the following general formula (II), and the glycol ether solvent can be used alone or in an appropriate combination of two or more.

In the formula (II), R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and a monovalent saturated hydrocarbon having 1 to 6 carbon atoms. Groups are preferred. When R ³ is a hydrogen atom, n represents an integer of 2 or more, and when R ³ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, n represents an integer of 1 or more. However, R ⁴ and R ⁵ are not hydrogen atoms at the same time. The upper limit of n is not particularly limited, but may be 10 or less.

Examples of the solvent represented by the general formula (II) include polyethylene glycol monomethyl ether such as diethylene glycol monomethyl ether and triethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and diethylene glycol monoisobutyl. Ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene Recohol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monophenyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl Ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and the like. Among them, diethylene glycol diethyl ether and dipropylene glycol dimethyl ether are preferred.

(4) Ethylene glycol monoalkyl ethers such as butyl cellosolve, which are widely used in paints and coating agents, are not preferred because of the recent problem that their use is evaded due to concerns about toxicity. Solvents having an ester bond such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate react with water in the system when they are formed into an emulsion composition, hydrolyze, and acidify the emulsion composition by generating an acid. It is not preferable because it will be done. Further, TX solvents such as toluene and xylene are not preferred in the above-mentioned points.

In the present invention, organic solvents other than the component (B) are not substantially contained. This is true not only when no organic solvent other than the component (B) is contained, but also when substantially no organic solvent other than the component (B) is contained. A small amount of an organic solvent other than the component (B) may be contained in the composition in an amount of 3% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less. Specifically, the amount of alcohols generated from the alkoxy residue of the component (A), the residue of the solvent used in the synthesis of the component (A), and the like are small enough to have no effect on stability and have no environmental problem. If so, it may be included.

配合 The amount of the component (B) is 2 to 100 parts by mass, preferably 3 to 80 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of the component (A). When the amount of the component (B) is less than 2 parts by mass, the viscosity of the silicone resin solution is high, and it is difficult to form an emulsion. Is undesirable from the point of volatilization.

The viscosity of the silicone resin solution (A) diluted with the component (B) is preferably from 10 to 100,000 mPa · s at 25 ° C., more preferably from 100 to 50,000 mPa · s. The viscosity can be measured by a rotational viscometer, and the concentration of the organosilicone resin (A) in the solution can be 75% by mass.

[(C) component]
The emulsifier, which is the component (C) of the present invention, is not particularly limited as long as it can emulsify and disperse the silicone resin solution in water, and may be used alone or in combination of two or more. Examples of the emulsifier include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene fatty acid ester; alkyl sulfates, alkyl benzene sulfonates, and alkyl sulfosuccinates. Anionic surfactants such as acid salts, alkyl phosphates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkyl phenyl ether sulfates; Cationic surfactants such as quaternary ammonium salts and alkylamine acetates; Examples include amphoteric surfactants such as betaine and alkylimidazoline.

Among them, nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene propylene alkyl ether are preferable from the viewpoint of stability.
Specific examples of these include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene propylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene propylene lauryl ether, polyoxyethylene tridecyl Ether, polyoxyethylene propylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and the like.

The amount of component (C) is 1 to 50 parts by mass, preferably 2 to 30 parts by mass, more preferably 3 to 20 parts by mass, per 100 parts by mass of component (A). If the amount of the component (C) is less than 1 part by mass, it is difficult to form an emulsion, and if it exceeds 50 parts by mass, the hardness, water resistance, heat resistance, water repellency, transparency, and adhesion to the substrate of the coating film are obtained. There is a concern that the properties will be reduced.

[(D) component]
The component (D) of the present invention is water, and is not particularly limited, such as purified water. The silicone resin emulsion composition can be prepared by mixing the above-mentioned components (A) to (C) with water and emulsifying and dispersing according to a conventional method. In this case, the content of water as the component (D) is 25 to 2,000 parts by mass, preferably 50 to 1,000 parts by mass, per 100 parts by mass of the component (A).

[Optional component]
In addition to the components (A) to (D), various additives can be added to the silicone resin emulsion composition of the present invention, if necessary, as long as the object of the present invention is not impaired. Examples of the additive include a pH adjuster, a thickener, a preservative, a rust inhibitor, an antioxidant, an ultraviolet absorber, and the like. Each of the additives may be used alone or in appropriate combination of two or more kinds. Can be used.

[Silicone resin emulsion composition]
The average particle size of the emulsion in the silicone resin emulsion composition of the present invention is preferably from 50 to 1,000 nm, more preferably from 100 to 800 nm. In the present invention, the average particle diameter is a volume average particle diameter (cumulative average diameter D50) by a laser diffraction scattering method, and is, for example, a dynamic light scattering particle diameter distribution measuring device N4 Plus submicron Particle manufactured by Beckman Coulter, Inc. It can be measured by a Size Analyzer.

[Method for producing silicone resin emulsion composition]
In order to obtain the silicone resin emulsion composition of the present invention, predetermined amounts of the above components (A) to (D) are mixed, and the mixture is stirred by a mixer / disperser such as a homomixer, a homodisper, a homogenizer, and a colloid mill. And preferably emulsified, preferably uniformly stirred to emulsify. In particular, after a predetermined amount of the components (A) to (C) is mixed and preferably dispersed uniformly, a part of the predetermined amount of the component (D) is added, and the mixture is stirred and emulsified. A more preferred method is to add the remaining components and mix and stir to prepare a silicone resin emulsion composition.

製造 In the case of using the solvent represented by the general formula (II) (B) during the hydrolysis-condensation during the production of the component (A), for example, a solvent having the following steps is preferable.

(I) a silane compound having a hydrolyzable group is hydrolyzed and condensed in a solvent represented by (B) a general formula (II), and (A) a silicone having a structure represented by an average formula (I) A step of obtaining a mixed solution containing the resin and (B) the solvent represented by the general formula (II),
(II) A step of mixing the mixture obtained in (I), (C) an emulsifier, and (D) water, and stirring and emulsifying the mixture. In the solvent represented by the general formula (II), May contain an organic solvent other than the component (B) in a range that does not substantially contain an organic solvent other than the component (B) in the obtained silicone resin emulsion composition.

In addition, the above (II) can also be the following steps.
(II-1) a step of mixing the mixture obtained in (I), (C) an emulsifier, and part of (D) water, and stirring and emulsifying the mixture.
(II-2) Step of adding remaining water (D) to the emulsion obtained in (II-1) and mixing / stirring In the above production method, the blending amount and the like are the same as above.

[Curable composition]
The silicone resin emulsion composition of the present invention can form a cured film by drying at room temperature and under heating conditions. However, in order to accelerate the curing rate or obtain excellent film properties, the silicone resin emulsion composition When the product is used, a condensation curing catalyst may be added to obtain a condensation reaction curable composition.

As the condensation curing catalyst, conventionally known ones can be used. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, n-hexylamine, tributylamine, diazabicycloun Basic compounds such as decene; tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, cobalt octylate, cobalt acetylacetonate, zinc Octylate, zinc acetylacetonate, iron octylate, iron acetylacetonate, tin acetylacetonate, dibutyltin dioctylate, dibutyltin dilaurate, dibutyltin Metal-containing compounds such as oxides; acidic compounds such as p-toluenesulfonic acid and trichloroacetic acid; and fluorine-containing compounds such as potassium fluoride, sodium fluoride, tetramethylammonium fluoride, and sodium hexafluorosilicate. Can be These condensation curing catalysts are preferably used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the silicone resin (A).

[Coating agent and coated article]
The above-described composition of the present invention can be suitably used as a coating agent, particularly as an outer wall paint, but can also be applied to other uses. For example, at least one surface of a substrate, or one surface, directly or via one or more other layers, the composition of the present invention is applied and cured to form a coating, A coated article can be obtained having a cured coating of a coating formed on at least one side, directly or via one or more other layers.

The substrate is not particularly limited, and examples thereof include transparent or opaque substrates such as metals, ceramic inorganic materials, glass, wood, paper products, and plastics.

When the base material is metal, it should be suitably used for surface protection of iron, stainless steel building structure materials, aluminum sash building materials, etc., base treatment such as anticorrosion coating, or coating for electrodeposition coating for automobiles or electric appliances. Can be.

When the base material is inorganic material, for surface protection coating or surface treatment of mortar, concrete or cement exterior wall material, ceramic panel, ALC board, sizing board, gypsum board, brick, glass, ceramic, artificial marble, etc. Can be applied as a paint.

The method of applying the coating agent to the substrate may be appropriately selected from known methods, and examples thereof include flow coating, spin coating, bar coater, wire bar, brush coating, spraying, dipping, roll coating, curtain coating, and knife. Various coating methods such as coating can be used.

(4) The amount of coating is not particularly limited, but is usually preferably an amount such that the thickness of the cured film after drying is 0.1 to 1,000 μm, and more preferably 1 to 100 μm.

(5) Examples of the method for curing the composition include room temperature curing and heat curing. The heating temperature is not particularly limited, but is preferably in the range of 100 to 300 ° C, more preferably in the range of 150 to 250 ° C.

Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, “parts” represents “parts by mass”, and “%” represents “% by mass”.
In the following, the weight average molecular weight is a value measured using GPC (gel permeation chromatography, HLC-8220 manufactured by Tosoh Corporation) using tetrahydrofuran (THF) as a developing solvent. The values of a to e in the average formula (I) were calculated from the results of ¹ H-NMR and ²⁹ Si-NMR measurements.

[1] Synthesis of Silicone Resin Compound Containing (B) Solvent (Preparation of Silicone Resin Solution)
[Synthesis Example 1-1]
Methyltrimethoxysilane: KBM-13 (Shin-Etsu Chemical Co., Ltd.) 953.4 g (7.0 mol), Phenyltrimethoxysilane: KBM-103 (Shin-Etsu Chemical Co., Ltd.) 594.9 g (3.0 mol) ), 8.6 g of methanesulfonic acid and 367.4 g of diethylene glycol diethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) in a reactor. When the mixture became homogeneous, 324.0 g of ion-exchanged water was added. Stirred for hours. Magnesium / aluminum / hydroxide / carbonate / hydrate: 42.9 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

[Synthesis Example 1-2]
Methyltrimethoxysilane: KBM-13 (Shin-Etsu Chemical Co., Ltd.) 272.4 g (2.0 mol), Dimethyldimethoxysilane: KBM-22 (Shin-Etsu Chemical Co., Ltd.) 480.8 g (4.0 mol) Phenyltrimethoxysilane: 793.2 g (4.0 mol) of KBM-103 (Shin-Etsu Chemical Co., Ltd.), 9.5 g of methanesulfonic acid, and 406.1 g of diethylene glycol diethyl ether (Nippon Emulsifier Co., Ltd.) The mixture was blended in a vessel, and when it became uniform, 280.8 g of ion-exchanged water was added, followed by stirring at 70 ° C. for 2 hours. Magnesium aluminum hydroxide carbonate hydrate: 47.4 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

[Synthesis Example 1-3]
Methyltrimethoxysilane: 408.6 g (3.0 mol) of KBM-13 (Shin-Etsu Chemical Co., Ltd.), 793.2 g (4.0 mol) of phenyltrimethoxysilane: KBM-103 (Shin-Etsu Chemical Co., Ltd.) ), Diphenyldimethoxysilane: 733.2 g (3.0 mol) of KBM-202 (manufactured by Shin-Etsu Chemical Co., Ltd.), 13.1 g of methanesulfonic acid, and 562.8 g of diethylene glycol diethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) The mixture was blended in a vessel, and when it became uniform, 291.6 g of ion-exchanged water was added, followed by stirring at 70 ° C. for 2 hours. Magnesium aluminum hydroxide carbonate hydrate: 65.7 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

[Synthesis Example 1-4]
Methyltrimethoxysilane: KBM-13 (Shin-Etsu Chemical Co., Ltd.) 408.6 g (3.0 mol), Dimethyldimethoxysilane: KBM-22 (Shin-Etsu Chemical Co., Ltd.) 360.6 g (3.0 mol) Phenyltrimethoxysilane: KBM-103 (Shin-Etsu Chemical Co., Ltd.) 594.9 g (3.0 mol), diphenyldimethoxysilane: KBM-202 (Shin-Etsu Chemical Co., Ltd.) 244.4 g (1.0 mol) ), 10.1 g of methanesulfonic acid and 432.7 g of diethylene glycol diethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) in a reactor. When the mixture became homogeneous, 280.8 g of ion-exchanged water was added. Stirred for hours. Magnesium / aluminum / hydroxide / carbonate / hydrate: 50.5 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

[Synthesis Example 1-5]
Methyltrimethoxysilane: KBM-13 (Shin-Etsu Chemical Co., Ltd.) 953.4 g (7.0 mol), Phenyltrimethoxysilane: KBM-103 (Shin-Etsu Chemical Co., Ltd.) 594.9 g (3.0 mol) ), 8.6 g of methanesulfonic acid and 367.4 g of dipropylene glycol dimethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) in a reactor. When the mixture became homogeneous, 324.0 g of ion-exchanged water was added. Stir for 2 hours. Magnesium / aluminum / hydroxide / carbonate / hydrate: 50.5 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

[Synthesis Example 1-6]
76.1 g (0.5 mol) of tetramethoxysilane, 953.4 g (7.0 mol) of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 405.9 g (2.5 mol) of hexamethyldisiloxane , 9.1 g of methanesulfonic acid and 388.2 g of dipropylene glycol dimethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) in a reactor. When the mixture became homogeneous, 248.4 g of ion-exchanged water was added. Stirred for hours. Magnesium aluminum hydroxide carbonate hydrate: 45.3 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

[Synthesis Example 1-7]
Methyltrimethoxysilane: KBM-13 (Shin-Etsu Chemical Co., Ltd.) 953.4 g (7.0 mol), Phenyltrimethoxysilane: KBM-103 (Shin-Etsu Chemical Co., Ltd.) 594.9 g (3.0 mol) ), 8.6 g of methanesulfonic acid and 367.4 g of toluene were blended in a reactor. When the mixture became homogeneous, 324.0 g of ion-exchanged water was added, followed by stirring at 70 ° C. for 2 hours. Magnesium / aluminum / hydroxide / carbonate / hydrate: 42.9 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and stirred for 2 hours to neutralize. After filtration, volatile components such as methanol and toluene were removed by distillation under reduced pressure, and 367.4 g of diethylene glycol diethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) was added, followed by purification by pressure filtration.

粘度 The viscosity and nonvolatile content (%) of the reaction product obtained in the synthesis example, the weight average molecular weight of the obtained silicone compound, and the values of a to e in the average formula (I) are shown in Tables 1 and 2 below.

[2] Preparation of emulsion composition using Synthesis Examples 1-1 to 1-7 [Examples 2-1 to 2-7]
60 parts of the silicone resin solution obtained in Examples 1-1 to 1-7, and polyoxyalkylene decyl ether ("Neugen XL-40" (trade name, manufactured by Daiichi Kogyo Seiyaku Co., HLB = 10.5)) as an emulsifier 2 3.5 parts of Neugen XL-400D (trade name: polyoxyalkylene decyl ether, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., 65% aqueous solution of HLB = 18.4) and 34.0 parts of deionized water. The mixture was emulsified and dispersed using a homodisper to obtain a silicone resin emulsion composition (Examples 2-1 to 2-7).

[3] (B) Synthesis of Solvent-Free Silicone Resin Compound (Preparation of Silicone Resin Solution)
[Comparative Synthesis Example 1-1]
Methyltrimethoxysilane: KBM-13 (Shin-Etsu Chemical Co., Ltd.) 953.4 g (7.0 mol), Phenyltrimethoxysilane: KBM-103 (Shin-Etsu Chemical Co., Ltd.) 594.9 g (3.0 mol) ), 8.6 g of methanesulfonic acid and 367.4 g of toluene were blended in a reactor. When the mixture became homogeneous, 324.0 g of ion-exchanged water was added, followed by stirring at 70 ° C. for 2 hours. Magnesium / aluminum / hydroxide / carbonate / hydrate: 42.9 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and stirred for 2 hours to neutralize. After filtration, volatile components such as methanol were removed by a water washing step, and purification was performed by pressure filtration.

[Comparative Synthesis Example 1-2]
Methyltrimethoxysilane: KBM-13 (Shin-Etsu Chemical Co., Ltd.) 272.4 g (2.0 mol), Dimethyldimethoxysilane: KBM-22 (Shin-Etsu Chemical Co., Ltd.) 480.8 g (4.0 mol) Phenyltrimethoxysilane: 793.2 g (4.0 mol) of KBM-103 (manufactured by Shin-Etsu Chemical Co., Ltd.), 9.5 g of methanesulfonic acid, and 406.1 g of toluene were mixed in a reactor to obtain a uniform mixture. Meanwhile, 280.8 g of ion-exchanged water was added, and the mixture was stirred at 70 ° C. for 2 hours. Magnesium aluminum hydroxide carbonate hydrate: 47.4 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and neutralized by stirring for 2 hours. After filtration, volatile components such as methanol were removed by a water washing step, and purification was performed by pressure filtration.

[Comparative Synthesis Example 1-3]
Methyltrimethoxysilane: KBM-13 (Shin-Etsu Chemical Co., Ltd.) 953.4 g (7.0 mol), Phenyltrimethoxysilane: KBM-103 (Shin-Etsu Chemical Co., Ltd.) 594.9 g (3.0 mol) ), 8.6 g of methanesulfonic acid and 367.4 g of toluene were blended in a reactor. When the mixture became homogeneous, 324.0 g of ion-exchanged water was added, followed by stirring at 70 ° C. for 2 hours. Magnesium / aluminum / hydroxide / carbonate / hydrate: 42.9 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and stirred for 2 hours to neutralize. After filtration, volatile components such as methanol and toluene were removed by distillation under reduced pressure, and 367.4 g of methyl ethyl ketone (MEK) was added, followed by purification by pressure filtration.

[Comparative Synthesis Example 1-4]
Methyltrimethoxysilane: KBM-13 (Shin-Etsu Chemical Co., Ltd.) 953.4 g (7.0 mol), Phenyltrimethoxysilane: KBM-103 (Shin-Etsu Chemical Co., Ltd.) 594.9 g (3.0 mol) ), 8.6 g of methanesulfonic acid and 367.4 g of toluene were blended in a reactor. When the mixture became homogeneous, 324.0 g of ion-exchanged water was added, followed by stirring at 70 ° C. for 2 hours. Magnesium / aluminum / hydroxide / carbonate / hydrate: 42.9 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged and stirred for 2 hours to neutralize. After filtration, volatile components such as methanol and toluene were removed by distillation under reduced pressure, and 367.4 g of ethyl acetate was added, followed by purification by pressure filtration.

粘度 The viscosity and non-volatile content (%) of the reaction product obtained in the comparative synthesis example, the weight average molecular weight of the obtained silicone resin compound, and the values of a to e in the average formula (I) are shown in Table 4 below.

[4] Preparation of emulsion composition using Comparative Synthesis Examples 1-1 to 1-4 [Comparative Examples 2-1 to 2-4]
60 parts by mass of the silicone resin solution obtained in Comparative Synthesis Examples 1-1 to 1-4, and "Neugen XL-40" (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, HLB = 10. 5) 2.5 parts by mass, 3.5 parts by mass of “Neugen XL-400D” (trade name: polyoxyalkylene decyl ether, 65% aqueous solution of HLB = 18.4, manufactured by Daiichi Kogyo Seiyaku) and deionized water 34 parts by mass were emulsified and dispersed using a homodisper to obtain silicone resin emulsion compositions (Comparative Examples 2-1 to 2-4).

[5] Performance Evaluation of Coated Article The silicone resin emulsion compositions prepared in Examples 2-1 to 2-6 and the silicone resin emulsion compositions prepared in Comparative Examples 2-1 to 2-4 were cleaned. A polished steel plate was coated using a wire bar so that the film thickness after curing was about 10 μm, and was cured by heating at 150 ° C. for 1 hour.
About the obtained coated article, the evaluation of the appearance of the cured coating film (coating film) and the adhesion were measured visually. The results are shown in Tables 6 and 7 below.

(1) Appearance of Cured Coating Visually, a coating having a uniform coating surface and no cracks was evaluated as OK, and one having a crack during curing was evaluated as NG.
(2) Adhesion test A cross-cut test was performed using 25 squares according to JIS K5600-5-6. (Number of squares remaining without peeling) / 25.
(3) Coating hardness The scratch hardness (pencil method) was measured according to JIS K5600.
(4) Presence or absence of TX solvent Evaluation was made in three stages of ～ to × based on the following criteria.
-No TX solvent used during synthesis and no TX solvent contained in final product: ○
・ TX solvent used during synthesis and no TX solvent contained in final product:
・ TX solvent used during synthesis and TX solvent contained in final product: ×

The silicone resin emulsion compositions of Examples 2-1 to 2-7 were different from the silicone resin emulsion compositions of Comparative Examples 2-1 to 2-4 in terms of cured coating appearance, adhesion, coating hardness, and environmental load. , Which indicates the superiority of the silicone resin emulsion composition of the present invention.

Claims

A silicone resin emulsion composition containing the following components (A) to (D) and substantially no organic solvent other than the component (B).
(A) Silicone resin having a structure represented by the following average formula (I): 100 parts by mass

(Wherein, R 1 independently represents a hydrogen atom, or an alkyl group, an aralkyl group or an aryl group having 1 to 8 carbon atoms which may be substituted by a halogen atom, and R 2 represents a hydrogen atom, a methyl group, Represents an ethyl group, an n-propyl group or an i-propyl group, wherein a, b, c, and d are respectively 0 ≦ a <1, 0 <b ≦ 1, 0 ≦ c <1, 0 ≦ d <1, a + b + c + d = 1 and e is a number that satisfies 0 <e ≦ 4.)
(B) a solvent represented by the following general formula (II): 2 to 100 parts by mass

(In the formula, R 3 , R 4 and R 5 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. When R 3 is a hydrogen atom, n is 2 or more. In the case where R 3 is a monovalent hydrocarbon group having 1 to 8 carbon atoms, n represents an integer of 1 or more, provided that R 4 and R 5 are not hydrogen atoms at the same time.)
(C) emulsifier: 1 to 50 parts by mass (D) water: 25 to 2,000 parts by mass
The silicone resin emulsion composition according to claim 1, wherein the component (B) is diethylene glycol diethyl ether or dipropylene glycol dimethyl ether.
A coating agent comprising the silicone resin emulsion composition according to claim 1 or 2.
(4) A coated article having a base material and a cured coating of the coating agent according to claim 3 formed directly or through one or more other layers on at least one surface of the base material.
3. A method for producing the silicone resin emulsion composition according to claim 1, comprising the following steps.
(I) A silane compound having a hydrolyzable group is hydrolyzed and condensed in a solvent represented by the above general formula (II) to form (A) a structure represented by the above average formula (I) Obtaining a mixed solution containing a silicone resin and (B) a solvent represented by the general formula (II);
(II) A step of mixing the mixture obtained in (I), (C) an emulsifier, and (D) water and stirring to emulsify.