JP2009001743A - Water-based coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-liquid type water-based coating material, capable of coloring a material while making use of the texture and hand of the material, and suppressing development of wet color or gloss by uneven suction at a repair trace or joint part. <P>SOLUTION: The water-based coating material comprises an organic silicon compound emulsion, a fluorine resin emulsion, an water-based inorganic coating material, and a film forming assistant, in which the solid component of the water-based inorganic coating material includes 350-700 parts by mass of an inorganic pigment component based on 100 parts by mass of a resin solid component. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an aqueous coating material. More specifically, the present invention relates to an aqueous coating material suitably used for coating a substrate such as a porous material.

  Buildings using porous building materials such as mortar and concrete such as ordinary households, buildings, highways, and railways are required to have improved durability and aesthetics, and are therefore usually surface treated with various coating materials. ing.

  Conventionally, as a method for imparting water absorption prevention to porous civil engineering building materials, silane-based, silicone-based, acrylic-based, acrylic-silicone-based, urethane-based, ester-based, oil-based resins or monomers dissolved or dispersed are used. Method of applying, infiltrating and drying (polymerization); Method of applying a fluorine paint such as room temperature drying type one-component fluorine paint, reaction curing type two-component fluorine paint, and forming a coating film on the material surface; A method of applying a material and applying a fluorine paint thereon is known.

  Since the surface of the porous civil construction material is generally large in unevenness, in the method of applying the fluorine paint, pinholes are likely to be generated in the coating film, and the coating film may be peeled off by water entering from the pinhole. In addition, since a glossy coating film is formed, not only is the base material and texture of the material impaired, but it also has the disadvantage of covering up the deterioration state of the substrate.

  On the other hand, permeable and water-absorbing materials such as silanes and silicones have the function of preventing the entry of water and dissipating moisture without forming a coating film on the surface of porous civil engineering and building materials. Often used favorably. However, the ability to prevent water intrusion is maintained for a long time, but under conditions where the porous material is under pressure, such as when exposed to severe wind and rain, or when the outer wall is always in contact with snow in snowy areas, The shortcoming is that the period for preventing water absorption and maintaining the water repellency of the surface and preventing the deterioration of the surface are short.

  The method of applying a permeable water absorption prevention material and applying a highly durable fluorine paint on it is an excellent method of preventing water penetration from pinholes, which is a drawback of fluorine paint, with a water absorption prevention material. is there. However, there is a drawback that the coating process is twice that of the conventional one and the cost is very high. In addition, a one-component semi-clear type in which an organosilicon compound emulsion such as a silane system and a fluororesin emulsion are mixed to complement both disadvantages has been proposed (see Patent Document 1 and Patent Document 2). However, repair marks and joints often found in exposed concrete may cause wet color and gloss due to uneven suction, which may impair the finish.

For this reason, while maintaining good water absorption prevention performance for a long time even under conditions where pressure is applied to the porous material, such as when exposed to severe wind and rain, or when the outer wall is always in contact with snow in snowy areas, A one-component water-based coating that can color the material while leaving the substrate and texture of the material, and can suppress the generation of wet color and gloss due to uneven suction on repair marks and joints. Development of materials is desired.
JP 2002-121543 A JP 2003-26461 A

  The problem of the present invention is that the material can be colored while leaving the texture and texture of the material, and it is possible to suppress the generation of wet color and gloss due to suction unevenness at repair marks and joints. The object is to provide a liquid type aqueous coating material.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a so-called “color clear” with no gloss by using an aqueous coating material containing an organosilicon compound emulsion, a fluororesin emulsion, a specific aqueous inorganic paint and a film-forming aid. We found that construction method can be enforced.

That is, the present invention provides an aqueous coating material as shown below.
Item 1. An aqueous coating material comprising an organic silicon compound emulsion, a fluororesin emulsion, a water-based inorganic paint, and a film-forming aid, wherein the composition of the solid component of the water-based inorganic paint is inorganic with respect to 100 parts by mass of the resin solid component. An aqueous coating material having a ratio of 350 to 700 parts by mass of a pigment component.
Item 2. The organosilicon compound emulsion has the general formula (1);
R ¹ _n Si (OR ² ) _4-n (1)
(Wherein R ¹ represents an alkyl group having 4 to 18 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2), and Item 2. The aqueous coating material according to Item 1, containing an alkylalkoxysiloxane.
Item 3. A fluororesin emulsion comprising a homopolymer of an olefin containing a fluorine atom, a copolymer comprising two or more olefins containing a fluorine atom, a copolymer of an olefin containing a fluorine atom and a hydrocarbon monomer, and fluorine Item 3. The aqueous coating material according to Item 1 or 2, comprising at least one fluororesin selected from the group consisting of a mixture of a copolymer of two or more olefins containing atoms and a thermoplastic acrylic resin.
Item 4. Item 4. The aqueous coating material according to any one of Items 1 to 3, wherein the ratio between the organosilicon compound and the fluororesin is 1: 0.01 to 20 in terms of mass ratio.
Item 5. Item 5. The aqueous coating material according to any one of Items 1 to 4, wherein the ratio of the sum of the organosilicon compound and the fluororesin to the solid component of the aqueous inorganic paint is 100: 0.1 to 25 in terms of mass ratio.
Item 6. Item 6. The aqueous coating material according to any one of Items 1 to 5, wherein the film forming aid is at least one selected from the group consisting of butyl carbitol acetate, texanol and diethyl adipate.
Item 7. Item 7. The aqueous coating material according to any one of Items 1 to 6, wherein the ratio between the fluororesin and the film forming aid is 100: 1 to 30 in terms of mass ratio.

  Hereinafter, the present invention will be described in detail.

  The aqueous coating material of the present invention comprises an organosilicon compound emulsion, a fluororesin emulsion, a specific aqueous inorganic paint, and a film forming aid.

  The organosilicon compound emulsion used in the present invention is obtained by blending and dispersing an organosilicon compound in an aqueous medium. The aqueous medium is water such as clean water, industrial water, ion exchange water, and distilled water.

As an organosilicon compound, general formula (1);
R ¹ _n Si (OR ² ) _4-n (1)
(Wherein R ¹ represents an alkyl group having 4 to 18 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2), and It is preferable to use an alkylalkoxysiloxane in combination.

  Examples of the alkyl group having 4 to 18 carbon atoms include butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like.

  Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

  Specific examples of the alkylalkoxysilane include butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, decyltrimethoxysilane, dodecyl Examples include triethoxysilane, octadecyltrimethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dibutyldimethoxysilane and the like. These alkyl alkoxysilanes may be used alone or in combination of two or more. Among these, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, and octyltriethoxysilane are preferably used.

  Examples of the alkylalkoxysiloxane include those obtained by hydrolysis and polycondensation reaction of the above alkylalkoxysilane in water. These may be used individually by 1 type and may use 2 or more types together.

  Commercially available alkylalkoxysiloxanes can be used. Specific examples include the product name “TSR165” of Momentive Performance Materials Japan GK and the product name “SILRES MSE100” of Asahi Kasei Wacker Silicone Co., Ltd. Can be mentioned.

  The ratio of the alkylalkoxysilane and the alkylalkoxysiloxane in the organosilicon compound emulsion is preferably 1: 0.05 to 20 and more preferably 1: 0.1 to 10 in terms of mass ratio.

  In addition to the aqueous medium and the organosilicon compound, the organosilicon compound emulsion may contain a surfactant as necessary.

  As the surfactant, any of a nonionic surfactant, a cationic surfactant, and an anionic surfactant can be used. From the viewpoint of emulsion stability, a nonionic surfactant is preferably used.

  As the nonionic surfactant, a commercially available product can be used, for example, an ether type such as polyoxyethylene lauryl ether (trade names “Nonion K-204” and “Nonion K-240” of Nippon Oil & Fats Co., Ltd.); Polyoxyethylene nonylphenyl ether (Nippon Yushi Co., Ltd. trade name “Nonion NS-215”), Polyoxyethylene octylphenol ether (Nippon Yushi Co., Ltd. trade names “Nonion HS-204”, “Nonion HS-206”, “ Nonionic HS-215 "), etc .; Polyoxyethylene monooleate (Nippon Yushi Co., Ltd. trade name" Nonion O-6 ") ester type; Sorbitan monolaurate (Nippon Yushi Co., Ltd. trade name" Nonion ") LP-20R ") and other sorbitan ester types; polyoxyethylene Sorbitan ester ether type such as rubitan monolaurate (trade name “Nonion LT-221” of Nippon Oil & Fat Co., Ltd.), polyoxyethylene sorbitan monostearate (trade name “Nonion ST-221” of Japan Oil & Fat Co., Ltd.), etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

  1-10 mass parts is preferable with respect to 100 mass parts of organosilicon compounds, and, as for the usage-amount of surfactant, 3-8 mass parts is more preferable. If the amount of the surfactant used is less than 1 part by mass, not only the stability of the emulsion tends to be low, but also the penetration into the inside of the substrate to be coated is poor and a wet color is generated on the surface of the substrate. There is a fear. Moreover, when it exceeds 10 mass parts, there exists a possibility that water absorption prevention property may worsen on the conditions where a pressure is applied to a coating surface.

  The method for producing the organosilicon compound emulsion is not particularly limited. Usually, the mixture of an aqueous medium and a surfactant is stirred at high speed with a homomixer, ultradisperser, high-pressure homogenizer, etc. at room temperature, and then stirred at high speed. And can be produced by gradually adding the organosilicon compound.

  The fluororesin emulsion used in the present invention is obtained by blending and dispersing a fluororesin in an aqueous medium. The aqueous medium is water such as clean water, industrial water, ion exchange water, and distilled water.

  The fluororesin is not particularly limited. For example, a homopolymer of an olefin containing a fluorine atom, a copolymer comprising two or more olefins containing a fluorine atom, an olefin containing a fluorine atom and a hydrocarbon monomer, And a mixture of a copolymer of two or more olefins containing fluorine atoms and a thermoplastic acrylic resin.

  Examples of the olefin containing a fluorine atom include fluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, and vinylidene fluoride. Among these, chlorotrifluoroethylene and vinylidene fluoride are preferably used.

  Examples of the hydrocarbon monomer include vinyl ethers such as cycloalkyl vinyl ether, alkyl vinyl ether, and hydroxyalkyl vinyl ether; vinyl esters such as aliphatic carboxylic acid vinyl ester; methyl (meth) acrylate ["(meth) acryl" “Acrylic” and “methacrylic” are meant. same as below. ], (Meth) acrylic acid esters such as ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Among these, methyl (meth) acrylate and ethyl (meth) acrylate are preferably used.

  Examples of the thermoplastic acrylic resin include homopolymers such as methyl (meth) acrylate, ethyl (meth) acrylate, and isobutyl (meth) acrylate, and copolymers thereof. Two or more thermoplastic acrylic resins may be used in combination.

  In addition to the aqueous medium and the fluororesin, the fluororesin emulsion may contain a surfactant as necessary.

  As the surfactant, any of nonionic type, cationic type and anionic type can be used.

  Commercially available fluororesin emulsions can be used. For example, vinylidene fluoride fluororesin emulsion (trade name “Zeffle SE-310” from Daikin Industries, Ltd.), fluoroolefin vinyl ether fluororesin emulsion (Asahi Glass Co., Ltd.) Trade names “Lumiflon FE-3000”, “Lumiflon FE-4300”) and the like.

  The blending ratio of the fluororesin emulsion is preferably so that the fluororesin in the fluororesin emulsion is 0.01 to 20 parts by mass with respect to 1 part by mass of the organosilicon compound in the organosilicon compound emulsion. It is more preferable to mix | blend so that it may become 1-10 mass parts. (That is, the ratio of the organosilicon compound and the fluororesin is preferably 1: 0.01 to 20 and more preferably 1: 0.1 to 10 in terms of mass ratio.) If it is less than 0.01 parts by mass, the surface of the substrate to be coated tends to deteriorate more easily, and the surface of the substrate after coating tends to deteriorate. In addition, if the blending ratio of the fluororesin exceeds 20 parts by mass, not only the surface of the base material after coating becomes glossy, but the base material and texture of the base material are impaired, and the coating film inhibits moisture permeability. There is a risk of swelling and floating.

  The water-based inorganic coating used in the present invention is obtained by blending and dispersing a solid component composed of a resin solid component and an inorganic pigment component in an aqueous medium. In the solid component, the mass ratio of the inorganic pigment component is larger than that of the resin solid component. The aqueous medium is water such as clean water, industrial water, ion exchange water, and distilled water.

  The resin solid component is not particularly limited, and examples thereof include acrylic resins, vinyl acetate-acrylic copolymer resins, vinyl acetate resins, styrene-acrylic resins, urethane resins, and alkyl silicon resins.

  The content of the resin solid component is preferably 5 to 30% by mass and more preferably 7 to 20% by mass with respect to the total mass of the aqueous inorganic coating material. If the content of the resin solid component is less than 5% by mass, the dispersibility of the inorganic pigment component in the water-based inorganic paint may be reduced, a uniform coating film may be difficult to be formed, or the adhesion of the coating film may be reduced. is there. Moreover, when content of a resin solid component exceeds 30 mass%, there exists a possibility that a glossiness may arise in the base-material surface after coating.

  The inorganic pigment component is not particularly limited, and examples thereof include extender pigments and colored pigments. An extender pigment and a color pigment may be used in combination.

  Examples of extender pigments include montmorillonite clay minerals such as bentonite, aluminum silicates such as silica, clay and kaolin, magnesium silicates such as talc, calcium carbonate, and barium sulfate.

  Examples of the color pigment include white pigments such as titanium white and zinc white; colored pigments such as chrome lead, red pepper and carbon black.

  In the solid component of the aqueous inorganic paint, the blending amount of the inorganic pigment component is 350 to 700 parts by mass, preferably 400 to 600 parts by mass with respect to 100 parts by mass of the resin solid component. (That is, the composition of the solid component of the water-based inorganic paint is a ratio of 350 to 700 parts by mass of the inorganic pigment component with respect to 100 parts by mass of the resin solid component, preferably the inorganic pigment component 400 with respect to 100 parts by mass of the resin solid component. When the blending amount of the inorganic pigment component is less than 350 parts by weight, the surface of the substrate after coating may be glossy or the coating film may not be given the required color. Moreover, when the compounding quantity of an inorganic pigment component exceeds 700 mass parts, the intensity | strength of a coating film will fall, a choking (what is called powder spraying) will be emitted, or a base material of a base material will be concealed and texture may be impaired.

  The production method of the water-based inorganic paint is not particularly limited. Usually, the mixture of the aqueous medium and the resin solid component is stirred at a high speed with a homomixer, an ultradisperser, a high-pressure homogenizer, or the like at room temperature, and then at a high speed. It can manufacture by adding an inorganic pigment component gradually.

  A commercially available thing can also be used for a water-based inorganic coating material, for example, the brand name "Aqua top SEP white", "Aqua top SEP gray", etc. by Sumitomo Seika Co., Ltd. are mentioned.

  The mixing ratio of the water-based inorganic paint is such that the solid component in the water-based inorganic paint is 0.1 to 25 parts by mass with respect to 100 parts by mass of the total mass of the organosilicon compound in the organosilicon compound emulsion and the fluororesin in the fluororesin emulsion. It is preferable to mix | blend so that it may become 1 part, and it is more preferable to mix | blend so that it may become 1-20 mass parts. (That is, the ratio of the sum of the organosilicon compound and the fluororesin to the solid component of the aqueous inorganic coating is preferably 100: 0.1 to 25, more preferably 100: 1 to 20 by mass ratio. .) If the blending ratio of the solid component is less than 0.1 parts by mass, the coating film may be insufficiently colored. Moreover, when the compounding ratio of the solid component exceeds 25 parts by mass, the texture of the base material may be concealed and the texture may be impaired. If the mixing ratio of the solid component is 0.1 to 25 parts by mass, when the substrate is coated, volatilization of the silane component in the organosilicon compound into the air is suppressed, and the penetration depth into the substrate is low. Since there exists a tendency to improve, the effect which durability improves from a viewpoint of base-material protection can be anticipated.

  The film-forming aid used in the present invention is not particularly limited as long as it is generally used in emulsion paints. For example, carbitol, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether acetate, texanol And diethyl adipate. These film forming assistants may be used alone or in combination of two or more. Among these, butyl carbitol acetate, texanol, and diethyl adipate are preferably used.

  The blending ratio of the film forming assistant is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the fluororesin in the fluororesin emulsion. (That is, the ratio of the fluororesin and the film-forming aid is preferably 100: 1 to 30 and more preferably 100: 5 to 25 in terms of mass ratio.) If the amount is less than 1 part by mass, the film formation state of the fluororesin becomes worse, and the appearance after coating may be impaired. If the blending ratio of the film forming auxiliary exceeds 30 parts by mass, an effect corresponding to the blending amount cannot be obtained, which may be disadvantageous economically.

  Since the organic silicon compound emulsion is blended in the aqueous coating material of the present invention, a pH adjuster is added for the purpose of stabilizing the alkylalkoxysilane as a component thereof, and the pH of the aqueous coating material is adjusted to 6 to 6. It is preferable to adjust to 9. Although it does not specifically limit as a pH adjuster, For example, alkali metal salt, alkaline-earth metal salt, ammonium salt, etc. of acids, such as carboxylic acid, phosphoric acid, carbonic acid, and a sulfuric acid, are mentioned. These pH adjusters may be used alone or in combination of two or more. Among these, sodium carbonate and sodium hydrogen carbonate are preferably used. The blending amount of the pH adjuster is preferably 20 parts by mass or less with respect to 100 parts by mass of the organosilicon compound in the organosilicon compound emulsion.

  Various thickeners are preferably added to the aqueous coating material of the present invention for the purpose of improving workability during coating. Although it does not specifically limit as a thickener, For example, acrylic thickeners, such as the brand name "Movinyl LDM7010" of Nichigomo vinyl, polyether type thickener, a cellulose type thickener, etc. are mentioned. These thickeners may be used alone or in combination of two or more. Among these, acrylic thickeners are preferably used.

  Additives such as preservatives, antifungal agents, antialgae agents, antifungal agents, ultraviolet absorbers, antioxidants, antifoaming agents, and plasticizers are further added to the aqueous coating material of the present invention, depending on the purpose. May be.

  The production method of the aqueous coating material of the present invention is not particularly limited, but usually, at room temperature, an organosilicon compound emulsion, a fluororesin emulsion, an aqueous inorganic coating material and a film-forming auxiliary are mixed with a homomixer, ultradisperser, high-pressure homogenizer, etc. It can manufacture by stirring at high speed with a stirrer and mixing.

  The aqueous coating material of the present invention is preferably adjusted so that the solid content is 2 to 60% by mass, more preferably 5 to 50% by mass with respect to the total mass of the aqueous coating material. . If the solid content is less than 2% by mass, not only the performance of the aqueous coating material will not be exhibited, but also the time required to apply a large amount of aqueous coating material to achieve the effect, and time to dry the coating film May be required. Moreover, when solid content exceeds 60 mass%, the viscosity of an aqueous coating material will become high, and there exists a possibility that solid content dispersion | distribution and stability may worsen. In addition, in order to adjust the ratio of solid content to the said range, a solvent soluble in water and / or water can be used. Here, the solid content of the aqueous coating material refers to a non-volatile residue obtained by drying according to JIS K6828-1 (2003).

  Although it does not specifically limit as a method of coating the base material with the aqueous coating material of this invention, For example, the method of apply | coating using a roller, a brush, a spray etc., the immersion method, etc. are mentioned. The drying method after coating is not particularly limited, and examples thereof include a method of drying at room temperature, a method of drying in the sun, and a method of drying by heating.

  Although it does not specifically limit as a base material for which the aqueous coating material of this invention is used suitably, For example, porous materials, such as a porous civil engineering building material, are mentioned. Specific examples of porous civil engineering building materials include exposed concrete, lightweight concrete, precast concrete, lightweight foamed concrete (ALC), mortar, joint mortar, asbestos cement board, pulp cement board, wood wool cement board, cemented extruded board , Cement board with glass fiber (GRC), Cement board with carbon fiber, Calcium silicate board, Gypsum board, Hard board, Plaster, Gypsum plaster, Dolomite plaster, Block, Brick, Tile, Tile, Natural stone, Artificial stone, Glass wool, Examples thereof include materials mainly composed of inorganic materials such as rock wool and ceramic fibers; materials mainly composed of organic materials such as wood, plywood and particle board.

  The coating film by the water-based coating material of the present invention includes rainwater leakage due to severe wind and rain, deterioration of materials due to acid rain, infiltration of dirt, salt damage by seawater, frost damage in cold regions, white flower due to elution of salt in materials, etc. It is possible to solve various problems caused by water, and to suppress the occurrence of wet color and gloss due to suction unevenness at repair marks and joints.

  According to the aqueous coating material of the present invention, the material can be colored while leaving the material base and texture. In addition, it is possible to suppress the occurrence of wet color and gloss due to suction unevenness at repair marks and joints.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited only to this Example.

Example 1
A mixed solution of 47 parts by mass of water and 3 parts by mass of sorbitan monolaurate (trade name “LP-20R” from Nippon Oil & Fat Co., Ltd.) was stirred at high speed with a homomixer. Next, 45 parts by mass of hexyltriethoxysilane and 5 parts by mass of alkylalkoxysiloxane (trade name “TSR165” of Momentive Performance Materials Japan) are gradually added while stirring at high speed with a homomixer, and the organosilicon compound An emulsion was obtained.

  20 parts by mass of the obtained organosilicon compound emulsion, 25 parts by mass of fluoroolefin vinyl ether-based fluororesin emulsion (trade name “Lumiflon FE-4300”, resin solid content 50% by mass of Asahi Glass Co., Ltd.), 2 parts by mass of diethyl adipate, 1 part by weight of sodium hydrogen carbonate, 2 parts by weight of acrylic thickener (Nichigo Movinyl Co., Ltd. trade name “Movinyl LDM7010”), water-based inorganic paint (Sumitomo Seika Co., Ltd. trade name “Aqua Top SEP White”), resin 5 parts by mass of inorganic pigment component (containing 450 parts by mass of solid component, 65 parts by mass of solid component) and 45 parts by mass of water were mixed with a three-one motor at 500 rpm with respect to 100 parts by mass of the solid component to obtain an aqueous coating material.

Example 2
A mixed solution of 47 parts by mass of water and 3 parts by mass of sorbitan monolaurate (trade name “LP-20R” from Nippon Oil & Fat Co., Ltd.) was stirred at high speed with a homomixer. Next, while gradually adding 42 parts by mass of octyltriethoxysilane and 8 parts by mass of alkylalkoxysiloxane (trade name “MSE-100” from Asahi Kasei Wacker Silicone Co., Ltd.), the mixture was stirred at high speed with a homomixer, and an organosilicon compound emulsion Got.

  20 parts by mass of the obtained organosilicon compound emulsion, 25 parts by mass of vinylidene fluoride-based fluororesin emulsion (trade name “Zeffle SE-310”, resin solid content 50% by mass of Daikin Industries, Ltd.), 2 parts by mass of diethyl adipate , 1 part by weight of sodium hydrogen carbonate, 2 parts by weight of acrylic thickener (Nichigomo Vinyl Co., Ltd. trade name “Movinyl LDM7010”), water-based inorganic paint (Sumitomo Seika Co., Ltd. trade name “Aqua Top SEP Gray”, 5 parts by mass of inorganic pigment component (550 parts by mass, solid component 65% by mass) and 45 parts by mass of water were mixed with a three-one motor at 500 rpm with respect to 100 parts by mass of the resin solid component to obtain an aqueous coating material.

Comparative Example 1
A mixed solution of 47 parts by mass of water and 3 parts by mass of sorbitan monolaurate (trade name “LP-20R” from Nippon Oil & Fat Co., Ltd.) was stirred at high speed with a homomixer. Next, while gradually adding 42 parts by mass of octyltriethoxysilane and 8 parts by mass of alkylalkoxysiloxane (trade name “MSE-100” from Asahi Kasei Wacker Silicone Co., Ltd.), the mixture was stirred at high speed with a homomixer, and an organosilicon compound emulsion Got.

  20 parts by mass of the obtained organosilicon compound emulsion, 25 parts by mass of vinylidene fluoride-based fluororesin emulsion (trade name “Zeffle SE-310”, resin solid content 50% by mass of Daikin Industries, Ltd.), 2 parts by mass of diethyl adipate , 1 part by weight of sodium hydrogen carbonate, 2 parts by weight of acrylic thickener (Nichigo Movinyl Co., Ltd. trade name “Movinyl LDM7010”) and 50 parts by weight of water are stirred and mixed at 500 rpm with a three-one motor, and an aqueous coating material Got.

Comparative Example 2
A mixed solution of 47 parts by mass of water and 3 parts by mass of sorbitan monolaurate (trade name “LP-20R” from Nippon Oil & Fat Co., Ltd.) was stirred at high speed with a homomixer. Next, while gradually adding 42 parts by mass of octyltriethoxysilane and 8 parts by mass of alkylalkoxysiloxane (trade name “MSE-100” from Asahi Kasei Wacker Silicone Co., Ltd.), the mixture was stirred at high speed with a homomixer, and an organosilicon compound emulsion Got.

  20 parts by mass of the obtained organosilicon compound emulsion, 25 parts by mass of vinylidene fluoride-based fluororesin emulsion (trade name “Zeffle SE-310”, resin solid content 50% by mass of Daikin Industries, Ltd.), 2 parts by mass of diethyl adipate , 1 part by weight of sodium hydrogen carbonate, 2 parts by weight of acrylic thickener (Nichigo Movinyl Co., Ltd., trade name “Movinyl LDM7010”), water-based inorganic paint (Daido Paint Co., Ltd., trade name “Regicon Top White”), resin solid 5 parts by mass of inorganic pigment component (containing 83 parts by mass of solid component, 52 parts by mass of solid component) and 45 parts by mass of water with respect to 100 parts by mass of the component were stirred and mixed at 500 rpm with a three-one motor to obtain an aqueous coating material.

Comparative Example 3
A mixed solution of 47 parts by mass of water and 3 parts by mass of sorbitan monolaurate (trade name “LP-20R” from Nippon Oil & Fat Co., Ltd.) was stirred at high speed with a homomixer. Next, while gradually adding 42 parts by mass of octyltriethoxysilane and 8 parts by mass of alkylalkoxysiloxane (trade name “MSE-100” from Asahi Kasei Wacker Silicone Co., Ltd.), the mixture was stirred at high speed with a homomixer, and an organosilicon compound emulsion Got.

  20 parts by mass of the obtained organosilicon compound emulsion, 25 parts by mass of vinylidene fluoride-based fluororesin emulsion (trade name “Zeffle SE-310”, resin solid content 50% by mass of Daikin Industries, Ltd.), 2 parts by mass of diethyl adipate , 1 part by weight of sodium bicarbonate, 2 parts by weight of acrylic thickener (Nichigomo Vinyl Co., Ltd., trade name “Movinyl LDM7010”), water-based inorganic paint (Daido Paint Co., Ltd., trade name “matte white for hexodyne external”) In addition, 300 parts by mass of an inorganic pigment component and 59 parts by mass of a solid component) and 45 parts by mass of water were stirred and mixed at 500 rpm with a three-one motor to obtain an aqueous coating material. .

Comparative Example 4
A mixed solution of 47 parts by mass of water and 3 parts by mass of sorbitan monolaurate (trade name “LP-20R” from Nippon Oil & Fat Co., Ltd.) was stirred at high speed with a homomixer. Next, while gradually adding 42 parts by mass of octyltriethoxysilane and 8 parts by mass of alkylalkoxysiloxane (trade name “MSE-100” from Asahi Kasei Wacker Silicone Co., Ltd.), the mixture was stirred at high speed with a homomixer, and an organosilicon compound emulsion Got.

  20 parts by mass of the obtained organosilicon compound emulsion, 25 parts by mass of vinylidene fluoride-based fluororesin emulsion (trade name “Zeffle SE-310”, resin solid content 50% by mass of Daikin Industries, Ltd.), 2 parts by mass of diethyl adipate , 1 part by weight of sodium bicarbonate, 2 parts by weight of acrylic thickener (Nichigo Movinyl Co., Ltd., trade name “Movinyl LDM7010”), water-based inorganic paint (Sumitomo Seika Co., Ltd., trade name “Aqua Top SEP White”) Add an inorganic pigment component and add 800 parts by mass of inorganic pigment component to 100 parts by mass of resin solid component, adjust to 70% by mass of solid component) and stir 5 parts by mass and 45 parts by mass of water at 500 rpm with a three-one motor. By mixing, an aqueous coating material was obtained.

[Evaluation test]
About the coating film formed using the aqueous coating material obtained in Examples 1-2 and Comparative Examples 1-3, (1) Appearance, (2) Penetration depth, (3) Water absorption ratio, (4) Water repellency (5) The contact angle was evaluated by the following procedure. Moreover, the accelerated weather resistance test was implemented with respect to the coating film, and (3) water absorption ratio, (4) water repellency, and (5) contact angle were evaluated. The results are shown in Table 1.

  In addition, the aqueous coating material obtained in Comparative Example 4 was similarly coated by the following sample preparation method. However, since the coating surface emitted choking (so-called powder blowing), the above (1) to (1)- Evaluation of (5) was not performed.

(Sample preparation)
JIS mortar (70 x 70 x 20 mm thick) conforming to JIS R5201 (1992) was used as a specimen, and an aqueous coating material was applied to the coating surface (one side of 70 x 70 mm) with a brush at 200 g / m ^2. A sample was prepared by curing for 7 days in a constant temperature and humidity chamber at a temperature of 20 ° C. and a relative humidity of 65%. In the following (1) Appearance test and (3) Water absorption ratio evaluation test, an uncoated sample is used as a control, but this is the same without applying an aqueous coating material in the preparation of the above sample. Obtained by processing and preparing.

(Accelerated weather resistance test)
About the sample obtained by the above, using a sunshine weather meter (trade name “Ducycle Sunshine Super Long Life Weather Meter WEL-SUN-DCH type” of Suga Test Instruments Co., Ltd.), black panel temperature: 63 ° C., humidity: The accelerated weather resistance test was conducted under the test conditions of about 50%, rainfall conditions: rain for 12 minutes in 60 minutes and 1000 hours. About the sample after a test, the following (3) water absorption ratio, (4) water repellency, and (5) contact angle were evaluated.

(1) Appearance Appearance changes in the wet color, gloss, and finish of the coating surface were visually observed. The criteria for evaluation are as follows. Any change in appearance is evaluated using an uncoated sample as a control.
○: There is no wet color or gloss, and a natural finish feeling is shown.
Δ: There are wet colors and gloss, and the finished feeling is impaired.
X: Remarkable wet color and gloss are present, and the finished feeling is greatly impaired.

(2) Penetration depth The sample was cut perpendicular to the coating surface of the sample, water was poured on the cut surface, and the water-repellent portion was measured with a caliper.

(3) Water absorption ratio The entire circumference of the side surface of the coating surface is sealed with epoxy resin, and the sample [Wa (g)] whose mass has been measured in advance is immersed in water to a half depth with the coating surface facing down. After immersion for 24 hours (immersion depth 10 mm), the sample was taken out of the water, excess water was wiped off with a dry cloth, and the mass after immersion was measured [Wb (g)]. Moreover, it processed similarly about the uncoated sample and measured the mass [Wc (g)] before immersion, and the mass [Wd (g)] after immersion. The water absorption ratio was calculated from the following equation. In addition, when a water absorption ratio is 0.1 or less, it can be judged that the coating film is excellent in water absorption prevention property.
Water absorption ratio = (Wb−Wa) ÷ (Wd−Wc).

(4) Water repellency A 0.5 ml water drop was dropped on the coating surface, and after standing for 1 minute, the surface state was visually observed. The criteria for evaluation are as follows.
○: Good water repellency.
Δ: Slightly poor in water repellency (wet marks remain where water drops were dropped).
X: No water repellency (water droplets are absorbed).

(5) Contact angle A water drop having a diameter of 2 mm was dropped on the coating surface, and after standing for 1 minute, the contact angle meter (trade name “CA-S150 type” manufactured by Kyowa Interface Science Co., Ltd.) was used.

  From the results shown in Table 1, it can be seen that the aqueous coating materials of Examples 1 and 2 have a coating surface that suppresses the generation of wet color and gloss and makes use of the base material and texture of the substrate. Moreover, it turns out that the water absorption prevention performance equivalent to the comparative example 1 (water-based inorganic coating additive-free) is maintained.

Claims (7)

  An aqueous coating material comprising an organic silicon compound emulsion, a fluororesin emulsion, a water-based inorganic paint, and a film-forming aid, wherein the composition of the solid component of the water-based inorganic paint is inorganic with respect to 100 parts by mass of the resin solid component. An aqueous coating material having a ratio of 350 to 700 parts by mass of a pigment component. The organosilicon compound emulsion has the general formula (1);
R ¹ _n Si (OR ² ) _4-n (1)
(Wherein R ¹ represents an alkyl group having 4 to 18 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2), and The aqueous coating material according to claim 1, comprising an alkylalkoxysiloxane.   A fluororesin emulsion comprising a homopolymer of an olefin containing a fluorine atom, a copolymer comprising two or more olefins containing a fluorine atom, a copolymer of an olefin containing a fluorine atom and a hydrocarbon monomer, and fluorine The aqueous coating material according to claim 1 or 2, comprising at least one fluororesin selected from the group consisting of a mixture of a copolymer of two or more olefins containing atoms and a thermoplastic acrylic resin.   The water-based coating material according to any one of claims 1 to 3, wherein a ratio of the organosilicon compound and the fluororesin is 1: 0.01 to 20 by mass ratio.   The aqueous coating material according to any one of claims 1 to 4, wherein a ratio of a total of the organosilicon compound and the fluororesin to a solid component of the aqueous inorganic paint is 100: 0.1 to 25 by mass ratio.   The aqueous coating material according to any one of claims 1 to 5, wherein the film forming aid is at least one selected from the group consisting of butyl carbitol acetate, texanol and diethyl adipate.   The ratio of a fluororesin and the film-forming aid is 100: 1-30 by mass ratio, The aqueous coating material of any one of Claims 1-6.