JP2011132486A - Coating composition and coated product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition for forming a coating layer having excellent waterdrop slip-down properties. <P>SOLUTION: This coating composition includes the following components (A) to (C): (A) a silicone composition containing a tetrafunctional alkoxysilane represented by Si(OR<SP>1</SP>)<SB>4</SB>(R<SP>1</SP>is a 1-8C hydrocarbon group) and a trifunctional alkoxysilane represented by Si(OR<SP>2</SP>)<SB>3</SB>R<SP>3</SP>(R<SP>2</SP>is a 1-8C hydrocarbon group, R<SP>3</SP>is a 1-8C hydrocarbon group or a phenyl group), where the molar ratio of the former to the latter is in the range of 1:1 to 1:5, or partial hydrolysis polycondensation products thereof; (B) a single-terminus type reactive silicone expressed by formula (1) or (2), having a weight-average molecular weight of 1,000-9,000, and the content to the solid content of the component (A) is in the range of 0.1-10 mass%; and (C) an acidic or basic catalyst; and water. In formula (1), R<SP>1</SP>represents a methyl group, an ethyl group or a propyl group; R<SP>2</SP>represents a methylene group or an ethylene group; and n denotes an integer of 1-100. In formula (2), R<SP>1</SP>s each independently represents a methyl group, an ethyl group or a propyl group; R<SP>2</SP>s each independently represents a methylene group or an ethylene group; and n denotes an integer of 1-100. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a coating composition for forming a coating layer having a large slidability of liquid droplets such as water, and a coated article having the coating layer.

  Conventionally, in order to impart water repellency to the surface of various base materials, a technique of coating with a fluororesin or a silicone resin is well known (Patent Document 1).

  However, even though the surface with water repellency has the property of repelling water, if it is used in an environment exposed to rainwater such as exterior materials, the surface will have traces of water flowing (rain streaks), making it resistant. It cannot be said that it is excellent in pollution. In order to make the best use of the low adhesion due to water repellency and to develop a wide range, it is necessary to improve the surface design, that is, the surface design that drops easily fall off the surface and does not remain on the surface.

  In recent years, not only a simple improvement in water repellency and the formation of a low surface energy surface to achieve the above-mentioned object, but also a technology that focuses on the slidability (water slidability) of water droplets adhering to the surface of the substrate is also known. It is coming.

  For example, in Patent Document 2, the surface of the coating layer is improved by mixing a hydrophilic organosilicon compound having a hydrophilic group (methanesulfonyl group) and a hydrophobic organosilicon compound in the coating composition. It is disclosed.

  Patent Document 3 discloses that the amount of water droplets on the surface of the coating layer is improved by increasing the amount of silicone compound introduced to the substrate surface by coating.

  Further, in Patent Document 4, an attempt is made to improve the slidability of water droplets on the surface of the coating layer by including a hydrocarbon polymer in the coating composition.

JP-A-11-152446 JP 2000-8026 A JP 2000-144056 A JP 2007-291314 A

  However, although the technique described in Patent Document 1 shows a high water repellency in the coating layer, it is not a technique that pays attention to the sliding property, and it is difficult to say that the sliding property is remarkably high.

  Further, the technique described in Patent Document 2 imparts a hydrophilic group and a hydrophobic group to the coating layer, and due to the strong interaction between the hydrophilic group and water, the sliding property is not sufficiently improved. .

  Further, with the technique described in Patent Document 3, simply increasing the silicone component has not been enough to improve the sliding property.

  In the technique described in Patent Document 4, hydrocarbon chains are used as hydrophobic groups. In this case, in order for the coating layer to exhibit high sliding properties, the hydrocarbon chains are highly advanced on the surface layer of the coating layer. It is necessary to make it a smooth film by orienting it, and practical application is difficult.

  This invention is made | formed in view of said point, and it aims at providing the coating composition provided with the coating composition for forming the coating layer which has the outstanding sliding property, and a coating layer.

The coating composition according to the first invention is characterized by containing the following components (A) to (C);
(A) A tetrafunctional alkoxysilane represented by the general formula Si (OR ¹ ) ₄ (R ¹ independently represents a hydrocarbon group having 1 to 8 carbon atoms), and a general formula Si (OR ² ) ₃ R ³ (R ² independently represents a hydrocarbon group having 1 to 8 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 8 carbon atoms or a phenyl group), and a trifunctional alkoxysilane represented by And a silicone composition having a molar ratio of the former to the latter in the range of 1: 1 to 1: 5, or a partially hydrolyzed polycondensate thereof,
(B) It has a structure represented by the following formula (1) or (2), a weight average molecular weight is 1000 to 9000, and the content of the component (A) with respect to the solid content is 0.1 to 10% by mass. One-end type reactive silicones in the range, and (C) acid or base catalyst and water.

(In Formula (1), R ¹ represents a methyl group, an ethyl group or a propyl group, R ² represents a methylene group or an ethylene group, and n represents an integer of 1 to 100. In Formula (2), R ¹ represents each Independently represents a methyl group, an ethyl group or a propyl group, R ² independently represents a methylene group or an ethylene group, and n represents an integer of 1 to 100.)
In 1st invention, the range of 2000-4000 may be sufficient as the weight average molecular weight of the said (B) component.

The coating composition according to the first invention may further contain the following component (D);
(D) A particle component having a dispersed particle size of 20 nm to 5 μm and a content of 10 to 400% by mass with respect to the total amount of solids of the component (A) and the component (B).

  In 1st invention, content of the said (D) component may be the range of 25-150 mass% with respect to the total amount of solid content of the said (A) component and the said (B) component. .

  The coated article according to the second invention is provided with a coating layer formed of the coating composition according to the first invention, and a falling angle of 20 mg of water droplets on the surface of the coating layer is 20 ° or less. And

  A coated article according to a third invention includes a coating layer formed of the coating composition according to the first invention, and a falling angle of 10 mg of water droplets on the surface of the coating layer is 10 ° or less. And

  A coated product according to a fourth invention includes a coating layer formed of the coating composition according to the first invention, and a maximum height Rz of the surface of the coating layer is 200 μm or less.

  According to the present invention, a coating layer having excellent sliding properties and good hardness and crack resistance can be formed from a coating composition. By providing this coating layer on a substrate, excellent A coated product having sliding properties can be obtained.

The excellent slipping property of the coating layer means that liquid droplets such as water easily fall from the surface of the coating layer, and at least the following two points are necessary to improve the slipping property.
(1) The contact angle between the surface of the coating layer and water is increased to reduce the contact area between the droplet and the coating layer.
(2) Lower the surface frictional resistance of the contact surface between the droplet and the coating layer.

  As a method for evaluating the sliding property, when a droplet with a predetermined mass is placed on the target surface and the target surface is inclined at a constant speed, both the front and rear ends of the contact surface between the droplet and the target surface start to move. A method of measuring the angle at the time is generally used. The angle at the moment when the movement starts is called a sliding angle. The inventors of the present invention have made investigations with the aim of droplets sliding down at a smaller falling angle and droplets of smaller mass sliding down.

  The coating composition according to this embodiment contains the following components (A) to (C).

(A) A tetrafunctional alkoxysilane represented by the general formula Si (OR ¹ ) ₄ (R ¹ independently represents a hydrocarbon group having 1 to 8 carbon atoms), and a general formula Si (OR ² ) ₃ R ³ (R ² independently represents a hydrocarbon group having 1 to 8 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 8 carbon atoms or a phenyl group), and a trifunctional alkoxysilane represented by And a silicone composition having a molar ratio of the former to the latter in the range of 1: 1 to 1: 5, or a partially hydrolyzed polycondensate thereof,
(B) It has a structure represented by the above formula (1) or (2), has a weight average molecular weight of 1000 to 9000, and a content of the component (A) with respect to the solid content is 0.1 to 10% by mass. One-end type reactive silicones in the range, and (C) acid or base catalyst and water.

  The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using standard polystyrene manufactured by Tosoh Corporation.

  As described above, the trifunctional alkoxysilane and the tetrafunctional alkoxysilane are used in a predetermined ratio, and the one-terminal type reactive silicone having a specific structure is used in a predetermined ratio, so that the film forming property and hardness of the coating layer are obtained. Can be improved in a well-balanced manner, and the coating layer can be improved in crack resistance, leveling property, and water repellency, thereby imparting high sliding properties to the coating layer.

  It is preferable that the weight average molecular weight of the said (B) component is the range of 2000-4000. In this case, the crack resistance, leveling property, and water repellency of the coating layer are particularly improved, and the sliding property of the coating layer is further improved.

  The coating composition preferably further contains the following component (D).

  (D) A particle component having a dispersed particle size of 20 nm to 5 μm and a content of 10 to 400% by mass with respect to the total amount of solids of the component (A) and the component (B).

  In this case, the hardness of the coating layer can be improved and the crack resistance can be improved.

  The content of the component (D) is preferably in the range of 25 to 150% by mass with respect to the total amount of the solid content of the component (A) and the component (B).

  A coated product according to an embodiment includes a coating layer formed of the coating composition, and a falling angle of 20 mg of water droplets on the surface of the coating layer is 20 ° or less. Alternatively, the falling angle of a 10 mg water droplet on the surface of the coating layer is 10 ° or less. This drop angle is the slope at the moment when both the front edge and the rear edge of the contact surface between the water drop and the coating layer start moving when a 20 mg water drop is placed horizontally on the surface of the coating layer and the surface of the coating layer is inclined. Is an angle. Thereby, the coated article provided with the coating layer which has the outstanding sliding property can be obtained.

  The coated article which concerns on another embodiment is provided with the coating layer formed with the said coating composition, and the maximum height Rz (JIS B0601: 2001) of the surface of the said coating layer is 200 micrometers or less. Thereby, the coated article provided with the coating layer which has the outstanding sliding property can be obtained.

  Hereinafter, this embodiment will be described in more detail.

  The coating composition contains the following components (A) to (C).

  The component (A) is a component that forms a resin matrix of the coating layer, and contains a tetrafunctional alkoxysilane and a trifunctional alkoxysilane, and a molar ratio of the former to the latter is in the range of 1: 1 to 1: 5. A silicone composition, or a partially hydrolyzed polycondensation product thereof.

  Here, the alkoxysilane is referred to as one functional when having one alkoxy group according to the number of alkoxy groups of Si as the central atom, and four functional if having four. In this embodiment, the balance between the film forming property and the hardness of the coating layer is ensured by blending trifunctional and tetrafunctional alkoxysilanes at a predetermined ratio.

  The ratio of the tetrafunctional alkoxysilane and the trifunctional alkoxysilane is not particularly limited as long as the molar ratio of the former to the latter is in the range of 1: 1 to 1: 5 as described above. If the ratio of the tetrafunctional alkoxysilane is too large, the hardness of the coating layer becomes too high and cracks are likely to occur in the coating layer. Moreover, when there are too many ratios of trifunctional alkoxysilane, the film forming property of a coating layer will worsen and there exists a tendency for a surface state to deteriorate easily.

The tetrafunctional alkoxysilane is represented by the general formula Si (OR ¹ ) ₄ and is also called tetraalkoxysilane. R ¹ in the general formula independently represents a hydrocarbon group having 1 to 8 carbon atoms, and includes a fluorinated alkyl group in which a part of hydrogen atoms of the hydrocarbon group is substituted with a fluorine atom. Specific examples of the hydrocarbon group represented by R ¹ in the general formula include a linear, branched or cyclic alkyl group, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group. Group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neopentyl group, hexyl group, octyl group and the like. Moreover, the fluorinated alkyl group which substituted some hydrogen atoms which these alkyl groups have with the fluorine atom may be sufficient. Among such tetrafunctional alkoxysilanes, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane or tetra-t- Butoxysilane is preferably used.

Trifunctional alkoxysilane is represented by the general formula Si (OR ² ) ₃ R ³ and is also called trialkoxysilane. R ² in the general formula independently represents a hydrocarbon group having 1 to 8 carbon atoms, and includes a fluorinated alkyl group in which a part of hydrogen atoms of the hydrocarbon group is substituted with a fluorine atom. R ³ represents a hydrocarbon group having 1 to 8 carbon atoms or a phenyl group.

  Specific examples of the trifunctional alkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltrimethoxysilane. Isopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, phenyl Triethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane And trialkoxysilane compounds such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane.

All of R ¹ , R ² and R ³ in the general formulas of these tetrafunctional alkoxysilanes and trifunctional alkoxysilanes are particularly preferably alkyl groups having 1 to 4 carbon atoms. In particular, R ¹ , R ² , and R ³ are preferably either a methyl group or an ethyl group from the viewpoint of low surface free energy expression, crosslinkability, chemical resistance, etc. of the coating layer, and in particular, R ¹ , R ² and R ³ are preferably all methyl groups.

When R ¹ , R ² , and R ³ are alkyl groups having more than 4 carbon atoms, the amount of organic solvent required to prepare a uniform coating composition may increase, and hydrolyzability may occur. Decreases, the generation of SiOH groups (silanol groups) in the coating layer becomes slow, and the crosslinkability tends to deteriorate.

  The trifunctional alkoxysilane and the tetrafunctional alkoxysilane constituting the component (A) may all be monomers, or part or all of them may be partially hydrolyzed condensates. . (A) When a component contains the partial hydrolysis-condensation product of alkoxysilane, it is preferable that the weight average molecular weight of this partial hydrolysis-condensation product is the range of 500-10000.

  Examples of such a partially hydrolyzed condensate of alkoxysilane include “MKC silicate MS51”, “MKC silicate MS51” manufactured by Mitsubishi Chemical Corporation as a polymethoxypolysiloxane that is a partially hydrolyzed condensate of tetramethoxysilane, which is a tetrafunctional alkoxysilane. MKC silicate MS56 "etc. are mentioned.

  The component (B) is a one-end type reactive silicone having one or two hydroxyl groups and having a structure represented by the following formula (1) or (2).

In the following formula (1), R ¹ represents a methyl group, an ethyl group or a propyl group, R ² represents a methylene group or an ethylene group, and n represents an integer of 1 to 100.

In Formula (2), R ¹ independently represents a methyl group, an ethyl group, or a propyl group, R ² independently represents a methylene group or an ethylene group, and n represents an integer of 1 to 100.

  This component (B) is used to improve the crack resistance, leveling property and water repellency of the coating layer. The improvement of water repellency by using this component (B) greatly contributes to the improvement of the sliding property of the coating layer.

  The weight average molecular weight of this (B) component is the range of 1000-9000, Preferably it is the range of 2000-4000.

  Here, in order to impart high sliding properties to the coating layer, the component (B) is bonded to silanol and fixed at the surface layer, a diol-modified one-end type reactive silicone oil, or a carbinol-modified one-end type reaction. Preferably, it is a sex diol. In the case of both-end type reactive oil and side-chain type reactive silicone oil, the reactive sites are at both ends in the molecule, so that it is taken into the resin matrix during the curing process, and it is considered that no sliding property is expressed. .

  Content of (B) component in a coating composition shall be in the range of 0.1-10 mass% with respect to the solid content of (A) component. If the content is less than 0.1% by mass, the effect of improving the water repellency of the coating layer tends to be small, and the expression of high sliding property tends to be low or cannot be obtained. Moreover, when this content exceeds 10 mass%, there exists a tendency for the hardness of a coating layer to become low or for a cure rate to become slow.

  Component (C) is an acid or base catalyst and water, and promotes hydrolysis of component (A) and a condensation reaction between component (A) and component (B) in the coating composition. Demonstrates the effect of curing.

  Although it does not specifically limit as an example of the acid or base catalyst of (C) component, For example, alkyl titanates; Carboxylic acid metal salts, such as tin octylate, dibutyltin dilaurate, dioctyltin dimaleate; Dibutylamine-2-hexoate, Amine salts such as dimethylamine acetate and ethanolamine acetate; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N Amine-based silane coupling agents such as β-aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate, ants Alkali metal salts such as lithium, sodium formate, potassium phosphate, potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, titanium tetraacetylacetonate; halogens such as methyltrichlorosilane, dimethyldichlorosilane, trimethylmonochlorosilane Silanes and the like. However, other than these, there is no particular limitation as long as it is effective for promoting the condensation reaction between the component (A) and the component (B).

  The content of the acid or base catalyst in the coating composition is not particularly limited, but is preferably 0.0001 to 10 mass with respect to 100 mass parts of the total solid content of the component (A) and the component (B), for example. In the range of 0.0005 to 8 parts by mass, more preferably in the range of 0.0007 to 5 parts by mass. If the content of the acid or base catalyst is too small, the curability of the coating composition is lowered, and the hardness of the coating layer tends to be lowered. Further, if the content of the acid or base catalyst is excessive, the heat resistance of the coating layer may be lowered, or the hardness of the coating layer may be excessively increased and cracks may easily occur.

  Moreover, the content of water is preferably in the range of 5 to 45 parts by weight with respect to 100 parts by weight as a total of the solid contents of the components (A) and (B). If the water content is too small, the reaction of the resin becomes insufficient, and the hardness of the coating layer tends to decrease. On the other hand, if the amount is excessive, the hardness of the coating layer becomes too high and cracks are likely to occur, or the component (B) is not compatible because of its hydrophobicity and may not be taken into the resin.

  The coating composition may contain the following component (D) in addition to the components (A) to (C).

Component (D) is a particle component and is effective in improving the hardness of the coating layer and improving crack resistance. Further, when the component (D) having a predetermined dispersed particle size is blended in the coating composition in a predetermined blending amount, the sliding property of the droplets in the coating layer is further improved.
The material of the component (D) is not particularly limited. For example, bead particles such as crosslinked polymethyl methacrylate beads and synthetic silica beads; metal oxides such as silica, zirconia, and titania; carbon black, quinacridone, naphthol red, cyanine blue, And pigments such as organic pigments such as cyanine green, hansa yellow, fluororesin pigments, and acrylic resin pigments.

  Further, as the component (D), a particle sol such as water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used. Generally, such a dispersed sol contains 20 to 50% by mass of a particle component as a solid content, and the blending amount of the particle component can be determined from this value. When the water dispersible fine particle sol is used, water existing as a component other than the solid content can be used as the water of the component (C), and can be used for hydrolysis of the component (A). It can be used as a curing agent. In the organic solvent-dispersible particle sol, the type of the solvent in which the particle component is dispersed is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, Examples include ethylene glycol derivatives such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. One or two selected from the group consisting of these More than seeds can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, and the like can also be used.

  The component (D) preferably has a dispersed particle size of 20 nm to 5 μm. When the dispersed particle size is larger than 5 μm, the particle size is too large, so that the particles protrude from the coating layer, and the hardness of the coating layer is reduced, or the surface roughness of the coating layer is too large and the sliding property is reduced. Tend to occur. Even if the dispersed particle size is smaller than 20 nm, such a small dispersed particle size does not adversely affect the sliding property. However, when the dispersed particle diameter of the component (D) is in the range of 20 nm to 5 μm, a continuous fractal shape is imparted to the surface layer of the coating layer by the particles constituting the component (D). By imparting a fractal shape, the surface area of the coating layer becomes larger than when the coating layer is smooth, which makes it easier for droplets to wet and repel in the coating layer (Wenzel theory). The effect by the Wenzel theory and the improvement of the slipperiness of the coating layer by the component (B) act in a complex manner so that smaller water droplets slide down at a low angle (10 mg water droplets are 10 ° or less) in the coating layer. become.

  Moreover, it is preferable that content of (D) component in a coating composition is the range of 10-400 mass% with respect to the total amount of solid content of (A) component and (B) component. When this content is 10% by mass or more, the effect of improving the hardness of the coating layer by the component (D) is exhibited. In addition, when the content is 400% by mass or less, the amount of the component that does not contribute to the sliding property in the coating layer is suppressed, the high sliding property is maintained, and the amount of the component that does not contribute to the film formation is suppressed. The physical properties such as hardness are improved.

  It is also preferable that the content of the component (D) in the coating composition is in the range of 25 to 150 mass% with respect to the total amount of the solid content of the component (A) and the component (B). In this case, a continuous and optimal fractal shape that maximizes the combined action with the component (B) is imparted to the coating layer. As a result, not only small water droplets roll at a low angle in the coating layer, but also when the 10 mg water droplet is dropped onto the coating layer inclined at 10 °, the water droplet rolling speed increases, for example, the average falling speed is It becomes 1.0 mm / sec or more, and a small water droplet comes to roll quickly.

  This coating composition may contain a leveling agent, a dye, an antibacterial agent, an antioxidant, an antistatic agent, an ultraviolet absorber, and the like as required, as long as the effects of the present invention are not adversely affected.

  The coating composition may contain an organic solvent. For example, the handleability of the coating composition can be improved by diluting the coating composition with various organic solvents. Moreover, you may make it add an organic solvent at the time of use of a coating composition.

  The organic solvent is not particularly limited, but examples thereof include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene such as ethylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate. Examples include glycol derivatives; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol, and the like. These organic solvents can be used alone or in combination. The amount of the organic solvent used is not particularly limited, and the dilution ratio may be appropriately determined as necessary.

  A coated product having a coating layer can be obtained by coating the coating composition on various base materials.

  As a base material, an inorganic base material, a ceramic base material, an organic base material, an inorganic organic composite base material, etc. can be used, and a material is not specifically limited.

  Examples of the inorganic base material include a metal base material; a glass base material; enamel; an inorganic building material such as a water glass decorative board and an inorganic hardened body; and ceramics.

  As a metal base material, what was formed from various metals and alloys can be used, for example, the base material formed from non-ferrous metals, such as aluminum alloys, such as aluminum and duralumin, copper, and zinc; Substrates formed from steel materials such as steel, hot-dip galvanized steel, (rolled) stainless steel, and tinplate can be used.

  Examples of the glass substrate include substrates formed from sodium glass, Pyrex (registered trademark) glass, quartz glass, alkali-free glass, and the like.

  The enamel is obtained by baking and coating a glassy enamel glass on a metal surface. Examples of the base metal include, but are not limited to, mild steel plate, steel plate, cast iron, and aluminum. The enameled glass may be a normal one, and is not particularly limited.

  The water glass decorative board refers to, for example, a decorative board obtained by applying sodium silicate to a cement base material such as slate and baking it. The inorganic hardened body is not particularly limited. For example, fiber reinforced cement board, ceramic siding, wood wool cement board, pulp cement board, slate / wood wool cement laminate, gypsum board product, clay roof tile, thick slate It refers to all substrates made of cured and molded inorganic materials such as ceramic tiles, concrete blocks for construction, terrazzo, prestressed concrete double T slabs, ALC panels, hollow prestressed concrete panels, and ordinary bricks.

  Examples of the ceramic substrate include substrates formed from alumina, zirconia, silicon carbide, silicon nitride, and the like.

  Examples of the organic base material include plastic, wood, wood, paper and the like. Examples of the plastic substrate include thermosetting or thermoplastic plastics such as polycarbonate resin, acrylic resin, ABS resin, vinyl chloride resin, epoxy resin, and phenol resin, and these plastics are reinforced with organic fibers such as nylon fibers. Examples thereof include a base material formed from fiber reinforced plastic (FRP) or the like.

  As an inorganic organic composite base material, the base material formed from the fiber reinforced plastic (FRP) etc. which reinforced the said plastic with inorganic fiber, such as glass fiber and carbon fiber, for example is mentioned.

  Alternatively, an organic film may be formed on the substrate with an organic resin composition, and a coating layer may be formed on the organic film of the coated substrate obtained as a result. The organic film constituting the coating substrate is not particularly limited. For example, organic films such as acrylic, alkyd, polyester, epoxy, urethane, acrylic silicone, chlorinated rubber, phenol, and melamine Examples thereof include a cured film of a coating material containing a resin.

  A coating layer can be formed on a base material by applying a coating composition on these base materials to form a coated product.

  As a method for applying the coating composition, a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, a brush coating method, a sponge coating method, or the like can be suitably used. As a curing method, it can be carried out by polymerization by heat treatment, standing at room temperature or the like.

  The maximum height Rz of the surface of the coating layer in this coated product is preferably 200 μm or less. Thus, by lowering the maximum height Rz of the surface of the coating layer, it is possible to suppress the catching of water droplets on the surface of the coating layer, and thus it is possible to particularly improve the sliding property of the surface of the coating layer. Even when the surface of the coating layer is roughened or uneven, if the maximum height of the surface is 200 μm or less, the sliding property of the surface of the coating layer can be maintained at a high level. it can. In general, in order to realize a surface having a high sliding property, the surface is required to have smoothness at the atomic level, and the surface is required to have extremely high uniformity. When the coating composition having a predetermined composition as described above is used, if the maximum surface height Rz is 200 μm or less, excellent sliding properties can be realized.

  The lower limit value of the maximum height Rz of the surface of the coating layer is not particularly limited, and the smaller the value, the higher the sliding property. However, the general inorganic base material, ceramic base material, organic base material, inorganic organic composite Even if the substrate is smooth, it has a maximum height Rz of at least about 0.1 μm, so the lower limit of the maximum height Rz is substantially 0.1 μm.

  In addition, when a continuous fractal shape is imparted to the coating layer in the coated product, the sliding property of water droplets in the coating layer can be further improved. In this case, for example, the falling angle of a 10 mg water droplet in the coating layer can be 10 ° or less. For example, a fractal shape is imparted to the coating layer by blending the particle component such as the component (D) in the coating composition. Or a fractal shape may be provided to a coating layer by giving a fractal shape to the base material used as a foundation | substrate.

  When the surface of the coating layer is roughened or uneven, the method includes blending a filler in the coating composition, blending a foamable component in the coating composition, and after forming the coating layer. And a method of making the surface of the coating layer uneven by an embossing roll or the like. Moreover, after making the surface where the coating of a base material is given uneven | corrugated shape by an embossing roll, press work, etc., a coating layer can also be formed on this surface.

  The coating composition and the coated article as described above are applied to the following uses, for example.

1) Vehicle uses requiring water repellency Specific application examples include automobile bodies (organic coating plates) windshields, side mirrors, sunroofs, trains and other vehicles, masking films, and the like.

2) Domestic use in which pollution prevention is required Specific examples of applications include bathtubs, bathroom inner walls, toilets, and the like.

3) General outdoor structures that require high surface durability Specific examples of applications include outer walls, gutters, tombstones, tents, various vending machines, and other general outdoor structures.

4) Printing press rolls and electrophotographic rolls that are required to prevent adhesion of ink and toner Specific examples of application include a fixing roll, a photosensitive drum, a guide roll, a separation claw, a SURF, and a pressure roll.

  5) Applications that require high durability and water repellency.

  As a specific application example, providing a coating layer on a substrate such as a fiber, glazing, a solar battery cover, or a sports equipment.

  In obtaining the coated product as described above, the coating composition may be directly applied to at least a part of the surface of each of the above-mentioned various materials and articles, and a coating layer may be formed by forming a cured film. Without limitation, for example, a coating film is applied to the surface of a resin film to form a cured film, or a coating composition is applied to a metal plate to form a cured film, and thus a resin film on which a coating layer is formed Alternatively, a coating layer may be provided on these various materials and articles by attaching or winding the metal plate to at least a part of the surfaces of the various materials and articles. Examples of the material of the resin film include resins such as polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, vinyl chloride resin, acrylic resin, fluororesin, polypropylene (PP) resin, and composite resins thereof. However, there is no particular limitation.

  The coated product obtained as described above includes a coating layer having excellent sliding properties. In this coated product, the sliding property of the coating layer can be improved to such an extent that the falling angle of a 20 mg water droplet is 20 ° or less. Alternatively, the sliding property of the coating layer can be improved to such an extent that the falling angle of a 10 mg water droplet is 10 ° or less.

  Hereinafter, the present invention will be described in more detail by presenting examples of the present invention.

[Example 1]
In a reaction vessel, 29 parts by mass of methyl polysilicate (hydrolyzed polycondensate of tetramethoxysilane; manufactured by Colcoat Co., Ltd., trade name: methyl silicate 51; solid content: 100% by mass), methyltrimethoxysilane (momentive performance Carbinol-modified one-end-type reactive silicone oil (manufactured by Shin-Etsu Silicone Co., Ltd.) having a structure shown in Formula (1): 17 parts by mass, manufactured by Materials Japan G.K., product number TSL-8113; solid content: 100% by mass Product number X22-170BX; solid content 100% by mass; weight average molecular weight 2800) 0.5 parts by mass, ion exchanged water 9 parts by mass, 0.1 mol / l HCl aqueous solution 0.5 parts by mass, methanol 45 A coating composition was prepared by charging parts by mass and stirring for 7 hours.

  A test plate made of SUS304 (manufactured by Nippon Test Panel Co., Ltd.) was used as a base material, and the coating composition was applied to the base material by air spray so that the dry film thickness was 0.5-2 μm, and 150 ° C. A coated product was obtained by baking at a temperature of 10 minutes.

[Example 2]
The amount of methylpolysilicate used is 36 parts by weight, the amount of methyltrimethoxysilane used is 10 parts by weight, and the amount of carbinol-modified one-terminal reactive silicone oil having the structure shown in formula (1) is 0.5 parts by weight. Part, the amount of ion-exchanged water used is 9 parts by weight, the amount of HCl aqueous solution with a concentration of 0.1 mol / l is 0.5 parts by weight, and the amount of methanol used is 43 parts by weight. A coated product was obtained under the conditions.

[Example 3]
The amount of methylpolysilicate used is 25 parts by mass, the amount of methyltrimethoxysilane used is 22 parts by mass, and the amount of carbinol-modified single-ended reactive silicone oil having the structure shown in Formula (1) is 0.5 parts by mass. Part, the amount of ion-exchanged water used is 9 parts by weight, the amount of HCl aqueous solution with a concentration of 0.1 mol / l is 0.5 parts by weight, and the amount of methanol used is 43 parts by weight. A coated product was obtained under the conditions.

[Example 4]
The amount of methylpolysilicate used is 18 parts by weight, the amount of methyltrimethoxysilane used is 27 parts by weight, and the amount of carbinol-modified one-end-type reactive silicone oil having the structure shown in formula (1) is 0.5 parts by weight. Part, the amount of ion-exchanged water used is 9 parts by weight, the amount of HCl aqueous solution with a concentration of 0.1 mol / l is 0.5 parts by weight, and the amount of methanol used is 43 parts by weight. A coated product was obtained under the conditions.

[Example 5]
The amount of methylpolysilicate used is 29 parts by mass, the amount of methyltrimethoxysilane used is 17 parts by mass, and the amount of carbinol-modified one-terminal reactive silicone oil having the structure shown in formula (1) is 0.5 parts by mass. Part, the amount of ion-exchanged water used is 9 parts by weight, the amount of 0.1 mol / l HCl aqueous solution used is 0.007 parts by weight, and the amount of methanol used is 45 parts by weight. A coated product was obtained under the conditions.

[Example 6]
The amount of methylpolysilicate used is 28 parts by mass, the amount of methyltrimethoxysilane used is 16 parts by mass, and the amount of carbinol-modified single-ended reactive silicone oil having the structure shown in formula (1) is 0.4 parts by mass. Parts, ion exchange water use amount of 8 parts by mass, 0.1 mol / l HCl aqueous solution use amount of 5 parts by mass, methanol use amount of 42 parts by mass, otherwise the same conditions as in Example 1. A painted product was obtained.

[Example 7]
Instead of carbinol-modified one-end type reactive silicone oil having the structure shown in formula (1) (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-170BX; solid content: 100% by mass; weight average molecular weight 2800), formula (1) A carbinol-modified one-end-type reactive silicone oil having a structure shown in (8) manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-170DX; solid content 100% by mass; weight average molecular weight 5900) was used. A coated product was obtained under the conditions.

[Example 8]
The amount of methylpolysilicate used is 26.3 parts by mass, the amount of methyltrimethoxysilane used is 15.7 parts by mass, and the amount of carbinol-modified one-end type reactive silicone oil having the structure shown in formula (1) is used. Example 5: 5 parts by mass, 8 parts by mass of ion-exchanged water, 0.5 parts by mass of HCl aqueous solution having a concentration of 0.1 mol / l, and 44 parts by mass of methanol. A coated product was obtained under the same conditions.

[Example 9]
The amount of methylpolysilicate used is 29 parts by mass, the amount of methyltrimethoxysilane used is 17 parts by mass, and the amount of carbinol-modified single-ended reactive silicone oil having the structure shown in Formula (1) is 0.05 parts by mass. Part, the amount of ion-exchanged water used is 9 parts by weight, the amount of HCl aqueous solution with a concentration of 0.1 mol / l is 0.5 parts by weight, and the amount of methanol used is 43 parts by weight. A coated product was obtained under the conditions.

[Example 10]
Instead of methylpolysilicate (hydrolyzed polycondensate of tetramethoxysilane; manufactured by Colcoat Co., Ltd., trade name: methylsilicate 51; solid content: 100% by mass), tetraethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product number KBE-04); A solid was obtained under the same conditions as in Example 1 except that the solid content was 100% by mass.

[Example 11]
Instead of methyltrimethoxysilane (Momentive Performance Materials Japan GK, product number TSL-8113; solid content 100% by mass), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd., product number KBM- 503; solid content 100% by mass), and a coated product was obtained under the same conditions as in Example 1 except that.

[Example 12]
The substrate was treated before coating so that the maximum surface height Rz was 200 μm, and a coated product was obtained under the same conditions as in Example 1 except that.

[Example 13]
The amount of methylpolysilicate used is 3.5 parts by weight, the amount of methyltrimethoxysilane used is 2.1 parts by weight, and the amount of carbinol-modified one-end-type reactive silicone oil having the structure shown in Formula (1) is used. 0.3 parts by mass, the amount of ion-exchanged water used was 1 part by mass, the amount of HCl aqueous solution having a concentration of 0.1 mol / l was 0.1 parts by mass, and the amount of methanol used was 70.4 parts by mass. In the reaction vessel, 10 parts by mass of diacetone alcohol and 12.5 parts of silica sol (manufactured by Nissan Chemical Industries, trade name Snowtex 20L; particle size 40-50 nm; solid content 20% by mass) are added together with the above components. Part by mass was added. Otherwise, a coated product was obtained under the same conditions as in Example 1.

[Example 14]
The amount of methylpolysilicate used is 3.5 parts by weight, the amount of methyltrimethoxysilane used is 2.1 parts by weight, and the amount of carbinol-modified one-end-type reactive silicone oil having the structure shown in Formula (1) is used. 0.3 parts by mass, the amount of ion-exchanged water used was 1 part by mass, the amount of HCl aqueous solution having a concentration of 0.1 mol / l was 0.1 parts by mass, and the amount of methanol used was 70.4 parts by mass. In addition to the above components, 12.5 parts by mass of silica sol (manufactured by Nissan Chemical Industries, trade name Snowtex 20L; particle size 40-50 nm; solid content 20% by mass) was charged into the reaction vessel. The substrate was treated before coating so that the maximum surface height Rz was 200 μm. Otherwise, a coated product was obtained under the same conditions as in Example 1.

[Example 15]
The amount of methylpolysilicate used is 3.9 parts by mass, the amount of methyltrimethoxysilane used is 2.3 parts by mass, and the amount of carbinol-modified one-end type reactive silicone oil having the structure shown in formula (1) is used. 0.3 parts by mass, 1 part by mass of ion-exchanged water, 0.1 part by mass of 0.1 mol / l HCl aqueous solution, and 78 parts by mass of methanol were used. In addition to the above components, 10 parts by mass of diacetone alcohol and 2.8 parts by mass of acrylic beads (manufactured by Ganz Chemicals, product number GB-08S; particle size 8 μm; solid content 100% by mass) were charged into the reaction vessel. Otherwise, a coated product was obtained under the same conditions as in Example 1.

[Example 16]
Instead of carbinol-modified one-end type reactive silicone oil having the structure shown in formula (1) (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-170BX; solid content: 100 mass%; weight average molecular weight 2800), formula (2) The same conditions as in Example 1 except that the diol-modified one-end-type reactive silicone oil having the structure shown in (1) is used (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-176DX; solid content: 100% by mass; weight average molecular weight: 3600). I got a painted product.

[Example 17]
The amount of methylpolysilicate used is 6.9 parts by mass, the amount of methyltrimethoxysilane used is 4 parts by mass, and the amount of carbinol-modified one-end-type reactive silicone oil having the structure shown in Formula (1) is 0.00. 6 parts by mass, 2 parts by mass of ion-exchanged water, 0.1 part by mass of 0.1 mol / l HCl aqueous solution, and 75 parts by mass of methanol were used. In the reaction vessel, 10 parts by mass of diacetone alcohol and 2.7 mass of silica sol (manufactured by Nissan Chemical Industries, trade name Snowtex 20L; particle size 40-50 nm; solid content 20%) together with the above components. Part. Otherwise, a coated product was obtained under the same conditions as in Example 1. The molar ratio of tetraethoxysilane and methyltrimethoxysilane was 1: 2.

[Example 18]
The amount of methylpolysilicate used is 6.3 parts by mass, the amount of methyltrimethoxysilane used is 3.8 parts by mass, and the amount of carbinol-modified one-end type reactive silicone oil having the structure shown in Formula (1) is used. 0.5 parts by mass, 2 parts by mass of ion-exchanged water, 0.1 parts by mass of HCl aqueous solution having a concentration of 0.1 mol / l, and 75 parts by mass of methanol were used. In the reaction vessel, together with the above components, 10 parts by mass of diacetone alcohol and 5.6 parts by mass of silica sol (manufactured by Nissan Chemical Industries, trade name Snowtex 20L; particle size 40-50 nm; solid content 20%) Part. Otherwise, a coated product was obtained under the same conditions as in Example 1. The molar ratio of tetraethoxysilane and methyltrimethoxysilane was 1: 2.

[Example 19]
The amount of methylpolysilicate used is 1.5 parts by mass, the amount of methyltrimethoxysilane used is 1 part by mass, and the amount of carbinol-modified single-ended reactive silicone oil having the structure shown in Formula (1) is 0.00. 1 part by mass, 2 parts by mass of ion-exchanged water, 0.1 part by mass of an aqueous HCl solution having a concentration of 0.1 mol / l, and 75 parts by mass of methanol were used. Further, in the reaction vessel, 10 parts by mass of diacetone alcohol and 21.2 mass of silica sol (manufactured by Nissan Chemical Industries, trade name Snowtex 20L; particle size 40-50 nm; solid content 20%) together with the above components. Part. Otherwise, a coated product was obtained under the same conditions as in Example 1. The molar ratio of tetraethoxysilane and methyltrimethoxysilane was 1: 2.

[Example 20]
The amount of methylpolysilicate used is 6.9 parts by mass, the amount of methyltrimethoxysilane used is 4 parts by mass, and the amount of carbinol-modified one-end-type reactive silicone oil having the structure shown in Formula (1) is 0.00. 6 parts by mass, 2 parts by mass of ion-exchanged water, 0.1 part by mass of an aqueous HCl solution having a concentration of 0.1 mol / l, and 77 parts by mass of methanol were used. In the reaction vessel, 10 parts by mass of diacetone alcohol and 1.4 parts by mass of silica sol (manufactured by Nissan Chemical Industries, trade name Snowtex 4540M; particle size 450-500 nm; solid content 40%) are combined with the above components. Part. Otherwise, a coated product was obtained under the same conditions as in Example 1. The molar ratio of tetraethoxysilane and methyltrimethoxysilane was 1: 2.

[Example 21]
The amount of methylpolysilicate used is 6.3 parts by mass, the amount of methyltrimethoxysilane used is 3.8 parts by mass, and the amount of carbinol-modified one-end type reactive silicone oil having the structure shown in Formula (1) is used. 0.5 parts by mass, 2 parts by mass of ion-exchanged water, 0.1 parts by mass of HCl aqueous solution having a concentration of 0.1 mol / l, and 78 parts by mass of methanol were used. In addition to the above components, 10 parts by mass of diacetone alcohol and 2.8 masses of silica sol (manufactured by Nissan Chemical Industries, trade name Snowtex 4540M; particle size 450-500 nm; solid content 40%) are contained in the reaction vessel. Part. Otherwise, a coated product was obtained under the same conditions as in Example 1. The molar ratio of tetraethoxysilane and methyltrimethoxysilane was 1: 2.

[Example 22]
The amount of methylpolysilicate used is 3.5 parts by weight, the amount of methyltrimethoxysilane used is 2.1 parts by weight, and the amount of carbinol-modified one-end-type reactive silicone oil having the structure shown in Formula (1) is used. 0.3 parts by mass, the amount of ion-exchanged water used was 1 part by mass, the amount of HCl aqueous solution having a concentration of 0.1 mol / l was 0.1 parts by mass, and the amount of methanol used was 77 parts by mass. Further, in the reaction vessel, together with the above components, 10 parts by mass of diacetone alcohol and 6.3 parts by mass of silica sol (manufactured by Nissan Chemical Industries, trade name Snowtex 4540M; particle diameter 450-500 nm; solid content 40%). Part. Otherwise, a coated product was obtained under the same conditions as in Example 1. The molar ratio of tetraethoxysilane and methyltrimethoxysilane was 1: 2.

[Example 23]
The amount of methylpolysilicate used is 1.5 parts by mass, the amount of methyltrimethoxysilane used is 1 part by mass, and the amount of carbinol-modified single-ended reactive silicone oil having the structure shown in Formula (1) is 0.00. 1 part by mass, 2 parts by mass of ion-exchanged water, 0.1 part by mass of an aqueous HCl solution having a concentration of 0.1 mol / l, and 85 parts by mass of methanol were used. In the reaction vessel, 10 parts by mass of diacetone alcohol and 10.6 parts by mass of silica sol (trade name Snowtex 4540M manufactured by Nissan Chemical Industries, Ltd .; particle diameter 450 to 500 nm; solid content 40%) are combined with the above components. I put it in. Otherwise, a coated product was obtained under the same conditions as in Example 1. The molar ratio of tetraethoxysilane and methyltrimethoxysilane was 1: 2.

[Example 24]
The amount of methylpolysilicate used is 3.5 parts by weight, the amount of methyltrimethoxysilane used is 2.1 parts by weight, and the amount of carbinol-modified one-end-type reactive silicone oil having the structure shown in Formula (1) is used. 0.3 parts by mass, the amount of ion-exchanged water used was 1 part by mass, the amount of HCl aqueous solution having a concentration of 0.1 mol / l was 0.1 parts by mass, and the amount of methanol used was 70.4 parts by mass. In the reaction vessel, together with the above components, 10 parts by mass of diacetone alcohol and 12.5 parts by mass of silica sol (manufactured by Nissan Chemical Industries, trade name Snowtex O; particle size 10-20 nm; solid content 20%) Part. Otherwise, a coated product was obtained under the same conditions as in Example 1. The molar ratio of tetraethoxysilane and methyltrimethoxysilane was 1: 2.

[Comparative Example 1]
50 parts by mass of a polyol resin having a dimethylsiloxane group in the skeleton and a hydroxyl group as a crosslinking group (manufactured by Fuji Kasei Kogyo Co., Ltd., product number ZX-022; solid content: 45% by mass), blocked isocyanate of HDI (Asahi Kasei Corporation) Manufactured, trade name Duranate MF-B60X) 15 parts by mass and n-butanol 150 parts were mixed and stirred for 5 minutes to obtain a coating composition.

  A slide glass (manufactured by Matsunami Glass, product number S9111) was used as the base material, and the coating composition was applied to the base material by air spray so that the dry film thickness was 2 to 3 μm. After leaving still for 30 minutes, it heated at 180 degreeC for 30 minutes, and obtained the coated product.

[Comparative Example 2]
The amount of methylpolysilicate used is 45 parts by mass, the amount of methyltrimethoxysilane used is 1.5 parts by mass, and the amount of carbinol-modified one-terminal reactive silicone oil having the structure shown in Formula (1) is 0.00. Example 5: 5 parts by mass, 9 parts by mass of ion-exchanged water, 0.5 part by mass of HCl aqueous solution having a concentration of 0.1 mol / l, and 44 parts by mass of methanol. A coated product was obtained under the same conditions.

[Comparative Example 3]
The amount of methylpolysilicate used is 40 parts by mass, the amount of methyltrimethoxysilane used is 5.8 parts by mass, and the amount of carbinol-modified one-end-type reactive silicone oil having the structure shown in formula (1) is 0.00. Example 5: 5 parts by mass, 9 parts by mass of ion-exchanged water, 0.5 part by mass of HCl aqueous solution having a concentration of 0.1 mol / l, and 44 parts by mass of methanol. A coated product was obtained under the same conditions.

[Comparative Example 4]
The amount of methylpolysilicate used is 13.5 parts by mass, the amount of methyltrimethoxysilane used is 33.1 parts by mass, and the amount of carbinol-modified one-end type reactive silicone oil having the structure shown in formula (1) is used. 0.5 parts by mass, 9 parts by mass of ion-exchanged water, 0.5 parts by mass of 0.1 mol / l HCl aqueous solution, and 44 parts by mass of methanol were used. A coated product was obtained under the same conditions as in Example 1.

[Comparative Example 5]
Instead of carbinol-modified one-end type reactive silicone oil having the structure shown in formula (1) (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-170BX; solid content: 100 mass%; weight average molecular weight 2800), formula (2) A diol-modified one-end-type reactive silicone oil having the structure shown in FIG. 1 (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-176F; solid content: 100% by mass; weight average molecular weight: 18000) was used. A painted product was obtained.

[Comparative Example 6]
20 parts by mass of methylpolysilicate, 12 parts by mass of methyltrimethoxysilane, 14 parts by mass of carbinol-modified one-end type reactive silicone oil having the structure shown in formula (1), The amount of ion-exchanged water used is 6 parts by mass, the amount of 0.1 mol / l HCl aqueous solution used is 0.5 parts by mass, and the amount of methanol used is 47 parts by mass. A painted product was obtained.

[Comparative Example 7]
The amount of methylpolysilicate used is 29 parts by weight, the amount of methyltrimethoxysilane used is 17 parts by weight, and the amount of carbinol-modified one-terminal reactive silicone oil having the structure shown in Formula (1) is 0.01 parts by weight. Parts, 9 parts by mass of ion-exchanged water, 0.5 parts by mass of HCl aqueous solution having a concentration of 0.1 mol / l, and 45 parts by mass of methanol, and the rest is the same as in Example 1. A coated product was obtained under the conditions.

[Comparative Example 8]
Instead of carbinol-modified one-end type reactive silicone oil having the structure represented by formula (1) (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-170BX; solid content: 100% by mass; weight average molecular weight 2800), both carbinol-modified A terminal-type reactive silicone oil (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-160AS; weight average molecular weight 1000; solid content 100 mass%) was used, and a coated product was obtained under the same conditions as in Example 1.

[Comparative Example 9]
Instead of carbinol-modified one-end type reactive silicone oil having the structure represented by formula (1) (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-170BX; solid content: 100% by mass; weight average molecular weight 2800), the carbinol-modified side A coated product was obtained under the same conditions as in Example 1 except that chain-type reactive silicone oil (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-4039; weight average molecular weight 3917; solid content: 100% by mass) was used.

[Comparative Example 10]
Instead of carbinol-modified one-end type reactive silicone oil having the structure represented by formula (1) (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-170BX; solid content: 100% by mass; weight average molecular weight: 2800), a methacryloxy-modified side chain A coated product was obtained under the same conditions as in Example 1 except that type reactive silicone oil (manufactured by Shin-Etsu Silicone Co., Ltd., product number X22-2426; weight average molecular weight 12926; solid content 100% by mass) was used.

[Evaluation test]
(Sliding evaluation)
The coated product obtained in each Example and Comparative Example was fixed horizontally to a contact angle meter (model number CA-VP, manufactured by Kyowa Interface Science Co., Ltd.) with the painted surface facing upward. 10 mg of distilled water was dropped on the painted surface to form water droplets. In this state, the angle of the coated product was tilted by 5 °, and the tilt angle of the coated product when the water droplet started to roll was measured. Based on this result, the sliding property was evaluated as follows.
A: A 10 mg water droplet starts rolling at an angle of 10 ° or less.

For coated products that were not evaluated as ◎, the coated surface was fixed horizontally on a contact angle meter (model number CA-VP, manufactured by Kyowa Interface Science Co., Ltd.) with the painted surface facing upward. 20 mg of distilled water was dropped on the surface to form water droplets. In this state, the angle of the coated product was tilted by 5 °, and the tilt angle of the coated product when the water droplet started to roll was measured. Based on this result, the sliding property was evaluated as follows.
○: Water droplets begin to roll at an angle of 20 ° or less.
Δ: Water droplets start rolling at an angle of 21-30 °.
X: Water drops do not roll even at an angle of 31 °.

(Limit thickness measurement)
The coating compositions prepared in each Example and Comparative Example were applied with air spray with different dry film thicknesses in the range of 0.5 μm to 2 μm, and baked at a temperature of 150 ° C. for 10 minutes. Different coating layers were formed. The coating layer was visually observed to check for cracks and evaluated as follows.
○: No cracks with a dry film thickness of 2 μm.
(Triangle | delta): There is no crack by dry film thickness 0.6-1.9micrometer.
X: Cracks at a dry film thickness of 0.5 μm.

(Surface condition observation)
The coating composition prepared in each example and comparative example was applied by air spray so that the dry film thickness was 1 μm, and baked at a temperature of 150 ° C. for 10 minutes to form a coating layer. The surface of this coating layer was visually observed and evaluated as follows.
○: No abnormality is observed.
Δ: Bleed material is observed on the surface.
X: Generation | occurence | production of an unevenness | corrugation or a twist is recognized on the surface.

(Coating hardness measurement)
The pencil hardness of the coating layer in the coated product obtained in each Example and Comparative Example was measured according to JISK5600-5-4.

(Falling speed measurement)
Of the coated products obtained in each of the examples and comparative examples, a contact angle meter (Kyowa Interface) inclined about 10 ° so that the coated surface is directed upward with respect to the coated products that have been evaluated as ◎ for sliding properties. It fixed to the scientific company make, model number CA-VP), and 10 mg of distilled water was dripped on the coating surface of this coating product, and the water droplet was formed. The falling speed of the water droplet in this state was measured, and based on this result, the falling speed was evaluated as follows.
○: The average falling speed is 1.0 mm / sec or more.
(Triangle | delta): An average fall speed is 0.1-0.99 mm / sec.
X: Do not fall.

  In Comparative Examples 2 and 4, there are items that cannot be evaluated due to generation of cracks in the coating layer and insufficient curing.

Claims (7)

A coating composition comprising the following components (A) to (C):
(A) A tetrafunctional alkoxysilane represented by the general formula Si (OR ¹ ) ₄ (R ¹ independently represents a hydrocarbon group having 1 to 8 carbon atoms), and a general formula Si (OR ² ) ₃ R ³ (R ² independently represents a hydrocarbon group having 1 to 8 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 8 carbon atoms or a phenyl group), and a trifunctional alkoxysilane represented by And a silicone composition having a molar ratio of the former to the latter in the range of 1: 1 to 1: 5, or a partially hydrolyzed polycondensate thereof,
(B) It has a structure represented by the following formula (1) or (2), a weight average molecular weight is 1000 to 9000, and the content of the component (A) with respect to the solid content is 0.1 to 10% by mass. One-end type reactive silicones in the range, and (C) acid or base catalyst and water.

(In Formula (1), R ¹ represents a methyl group, an ethyl group or a propyl group, R ² represents a methylene group or an ethylene group, and n represents an integer of 1 to 100. In Formula (2), R ¹ represents each Independently represents a methyl group, an ethyl group or a propyl group, R ² independently represents a methylene group or an ethylene group, and n represents an integer of 1 to 100.)   The coating composition according to claim 1, wherein the component (B) has a weight average molecular weight in the range of 2000 to 4000. The coating composition according to claim 1, comprising the following component (D):
(D) A particle component having a dispersed particle size of 20 nm to 5 μm and a content of 10 to 400% by mass with respect to the total amount of solids of the component (A) and the component (B).   The content of the component (D) is in the range of 25 to 150 mass% with respect to the total amount of the solid content of the component (A) and the component (B). Coating composition.   A coating comprising a coating layer formed of the coating composition according to any one of claims 1 to 4, wherein a falling angle of 20 mg of water droplets on the surface of the coating layer is 20 ° or less. Goods.   A coating comprising a coating layer formed of the coating composition according to any one of claims 1 to 4, wherein a falling angle of 10 mg of water droplets on the surface of the coating layer is 10 ° or less. Goods.   A coated article comprising a coating layer formed of the coating composition according to any one of claims 1 to 4, wherein a maximum height Rz of the surface of the coating layer is 200 µm or less.