JP6767766B2 - Two-component curable paint composition and coating film - Google Patents

Description

The present invention relates to a two-component curable coating composition and a coating film, specifically, a two-component curable coating composition and a coating film obtained from the composition.

Conventionally, it has been known that a coating film of a silicone resin coating is formed on the surface of various products such as rollers, molds, plates, chutes, hoppers, and cooking utensils to impart non-adhesiveness and water repellency to them. There is.

For example, an anti-adhesion coating composed of a sol-gel material containing a first aqueous composition containing water and silicone oil and a second solution containing methyltrimethoxysilane has been proposed (eg, for example. See Patent Document 1).

Special Table 2010-525095

However, the coating film is required to have higher non-adhesiveness (property having excellent peelability to the adhesive material) and good appearance (smoothness). However, the adhesion prevention coating described in Patent Document 1 has a problem that the above-mentioned requirements cannot be satisfied.

An object of the present invention is to provide a coating film having high non-adhesiveness and good appearance, and a two-component curable coating composition for obtaining the coating film.

In order to achieve the above object, the present invention
[1]
The solution A containing water and the solution B containing trialkoxysilane are contained, the solution A and / or the solution B contains silicone oil, and the solution A and / or the solution B is an oxy. A two-component curable coating composition, which comprises an oxyalkylene group-containing group-modified silicone oil modified by an oxyalkylene group-containing group containing an alkylene group.
[2]
The two-component curable coating composition according to the above [1], wherein the oxyalkylene group is polyoxyethylene.
[3]
The two-component curable coating composition according to the above [1] or [2], wherein both the silicone oil and the oxyalkylene group-containing group-modified silicone oil are contained in the liquid A.
[4]
The two-component curable coating composition according to any one of the above [1] to [3], wherein the silicone oil has a kinematic viscosity of 500 mm ² / s or more at 25 ° C.
[5]
The two-component curable coating composition according to any one of the above [1] to [4], wherein the liquid B further contains an alkoxy group-containing siloxane oligomer.
[6]
A coating composition is prepared by mixing the liquid A and the liquid B in the two-component curable coating composition according to any one of the above [1] to [5], and the coating composition is applied to an object. It is a coating film obtained by curing the coating film.

The coating film obtained from the two-component curable coating composition of the present invention has high non-adhesiveness and good appearance. Therefore, it is possible to impart high non-adhesiveness and good appearance to the object.

One embodiment of the two-component curable coating composition and the coating film of the present invention will be described.

1. 1. Two-component curable coating composition The two-component curable coating composition is a two-component curable coating composition for forming a coating film, and liquid A and liquid B are prepared, respectively, to prepare liquid A and liquid B, respectively. It is prepared as a two-component curable coating composition in which liquid B is blended at the time of use. The two-component curable coating composition contains a water-containing solution A and a trialkoxysilane-containing solution B.

For example, the liquid A contains water, silicone oil, and an oxyalkylene group-containing group-modified silicone oil.

2. Component of solution A 2-1. Water Water is added to the solution A in order to help hydrolyze the trialkoxysilane.

The mixing ratio of water is, for example, 15 parts by mass or more, preferably 30 parts by mass or more, and more preferably 40 parts by mass or more with respect to 100 parts by mass of trialkoxysilane. The mixing ratio of water is, for example, 1,000 parts by mass or less, preferably 300 parts by mass or less, more preferably 170 parts by mass or less, and further preferably 160 parts by mass with respect to 100 parts by mass of trialkoxysilane. It is preferably parts or less, 150 parts by mass or less, more preferably 140 parts by mass or less, 130 parts by mass or less, 120 parts by mass or less, 100 parts by mass or less, and 90 parts by mass or less.

When the mixing ratio of water is equal to or higher than the above lower limit, the hydrolysis of the alkoxy group in the trialkoxysilane is sufficiently advanced to sufficiently generate a silanol group (Si-OH), whereby the curing reaction (dealcohol removal) is carried out. Condensation reaction, dehydration condensation reaction) can be promoted to maintain the shape retention of the coating film. On the other hand, when the mixing ratio of water is not more than the above upper limit, the liquid A can contain a sufficient amount of silicone oil, and a good coating film can be formed.

2-2. Silicone oil Silicone oil is a component that imparts non-adhesiveness and water repellency to the coating film. Silicone oil has a linear main chain and has, for example, a polysiloxane repeating structure (− (SiO) _n −). Examples of the silicone oil include straight silicone oils (unmodified silicone oils) such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. In addition to straight silicone oil, silicone oil is modified by modifying the terminal and / or side chain of the main chain with an alkyl group, an alkenyl group (including a vinyl group), an alkynyl group, a phenyl group, an ionic group, or the like. Silicone oil can also be mentioned. Examples of the ionic group include an anionic group such as a mercapto group, and a cationic group such as an amino group.

These silicone oils can be used alone or in combination of two or more.

Examples of the silicone oil include straight silicone oil, and more preferably polydimethylsiloxane.

As the silicone oil, a commercially available product may be used. As the silicone oil, for example, KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.), silicone oil SH200 series (manufactured by Toray Dow Corning Co., Ltd.), TSF451 series (manufactured by Momentive Performance Materials Japan) and the like are used.

The kinematic viscosity of the silicone oil at 25 ° C. is, for example, 1 mm ² / s or more, preferably 500 mm ² / s or more, more preferably 1,000 mm ² / s or more, and for example, 1 million mm ² / s or more. It is s or less, preferably 100,000 mm ² / s or less, and more preferably 10,000 mm ² / s or less. When the kinematic viscosity of the silicone oil is at least the above lower limit, the coating film can have non-adhesiveness. When the kinematic viscosity of the silicone oil is not more than the above upper limit, the appearance of the coating film can be maintained.

The blending ratio of the silicone oil is, for example, 0.1 part by mass or more, preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass with respect to 100 parts by mass of the trialkoxysilane. Further, for example, it is 100 parts by mass or less, preferably 45 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less. The blending ratio of the silicone oil is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, based on the two-component curable coating composition. Yes, for example, 20.0% by mass or less, preferably 10.0% by mass or less, more preferably 8.0% by mass or less, still more preferably 5.0% by mass or less. Further, the blending ratio of the silicone oil is, for example, 0.2% by mass or more, preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and further, with respect to the coating film (solid content). Preferably, it is 3.0% by mass or more, particularly preferably 5.0% by mass or more, most preferably 6.0% by mass or more, and further 6.5% by mass or more, and for example, 35% by mass or less. , Preferably 20% by mass or less, more preferably 15% by mass or less.

When the blending ratio of the silicone oil is equal to or higher than the above lower limit, excellent non-adhesiveness and water repellency can be imparted to the coating film. On the other hand, when the blending ratio of the silicone oil is not more than the above upper limit, the appearance of the coating film can be maintained and the fastness (strength) of the coating film can be maintained.

2-3. Oxyalkylene Group-Containing Group-Modified Silicone Oil Oxyalkylene group-containing group-modified silicone oil is a surfactant (dispersant) for uniformly dispersing silicone oil in a two-component curable coating composition and a coating film. ..

In the oxyalkylene group-containing group-modified silicone oil, for example, the terminal and / or side chain of the main chain of the straight silicone oil described above is modified with an oxyalkylene group-containing group. Further, in the oxyalkylene group-containing group-modified silicone oil, for example, the branched chain in the branched silicone oil having a linear main chain and a branched chain branched from the main chain is modified with an oxyalkylene group-containing group. You may. Further, in the above-mentioned oxyalkylene group-containing group-modified silicone oil, the terminal of the main chain or the branched chain may be modified with a long-chain alkyl group having 6 or more carbon atoms (for example, lauryl). Further, as the oxyalkylene group-containing group-modified silicone oil, for example, a polysiloxane (A) modified with an oxyalkylene group-containing group and a polysiloxane (B) not modified with an oxyalkylene group-containing group are repeatedly bonded. May be.

As an oxyalkylene group-containing group-modified silicone oil, for example, a terminal-modified type in which only the end of the main chain of straight silicone oil is modified with an oxyalkylene group-containing group, for example, both the end and side chains of the main chain of straight silicone oil. Examples include a side chain terminal modified type in which is modified with an oxyalkylene group-containing group, for example, a side chain modified type in which only the side chain of the main chain of straight silicone oil is modified with an oxyalkylene group-containing group. Further, as the oxyalkylene group-containing group-modified silicone oil, for example, a branched chain-modified type in which the branched chain in the branched silicone oil is modified with an oxyalkylene-containing group, for example, the terminal of the main chain or the branched chain is carbon. A long-chain alkyl group co-modified type modified with a long-chain alkyl group of several 6 or more, for example, a polysiloxane (A) modified with an oxyalkylene group-containing group and a polysiloxane not modified with an oxyalkylene group-containing group. An ABn type in which (B) is repeatedly bound is also exemplified.

The oxyalkylene group-containing group-modified silicone oil is preferably a terminal-modified type (double-ended modified type, one-ended modified type, etc.), a side chain terminal-modified type (side chain double-ended modified type, side chain single-ended modified type, etc.). , ABn type, more preferably both end-modified type, side chain both-ended modified type, and further preferably side chain both-ended modified type.

The oxyalkylene group-containing group is a group containing an oxyalkylene group. The oxyalkylene group is a hydrophilic segment in the oxyalkylene group-containing group-modified silicone oil.

Examples of the oxyalkylene group include oxyethylene, polyoxyethylene (degree of polymerization is, for example, 2 or more and 200 or less), and oxyethylene-oxypropylene block polymer (degree of polymerization of oxyethylene is, for example, 2 or more). , 200 or less. The degree of polymerization of oxypropylene is, for example, 2 or more and 200 or less.) Preferred is polyoxyethylene.

The oxyalkylene group-containing group-modified silicone oil modified at both ends of the side chain is specifically represented by the following formula (1).
: Equation (1)

(In the formula (1), R ^{1 to} R ⁵ are the same or different from each other and represent monovalent hydrocarbon groups. N is an integer of 1 or more and 1,000 or less. M is 1 or more, It is an integer of 100 or less. A indicates an oxyalkylene group-containing group.)
Examples of the monovalent hydrocarbon group in R ^{1 to} R ⁵ include an alkyl group such as methyl and an aryl group such as phenyl, more preferably an alkyl group, and further preferably methyl.

The oxyalkylene group-containing group represented by A is represented by, for example, the following formula (2).
: Equation (2)

(In the formula (2), R ⁶ represents a divalent hydrocarbon group which may have an imino group. B represents an oxyalkylene group. R ⁷ represents a hydrogen atom, an alkyl group and an amino group. , And at least one of the aminoalkyl groups. Y is an integer of 1 or more and 100 or less.)
Represented by R ^6, the divalent hydrocarbon group which may have an imino group, e.g., methylene, ethylene, propylene, butylene, pentylene, such as hexylene, 1 or more carbon atoms, 6 following alkylene groups Examples thereof include linear divalent hydrocarbon groups. Preferred examples of the linear divalent hydrocarbon group include propylene. The imino group that the divalent hydrocarbon group may have is, for example, interposed in the middle of the linear divalent hydrocarbon group. Further, the hydrogen atom in the divalent hydrocarbon group may be substituted with a substituent such as a hydroxyl group (-OH) or an amino group (-NH ₂ ).

Examples of the oxyalkylene group represented by B include oxyethylene (C ₂ H ₄ O), polyoxyethylene (C ₂ H ₄ O) _a (a is, for example, an integer of 2 or more and 200 or less), and oxy. Ethylene-oxypropylene block polymer (the degree of polymerization of oxyethylene is, for example, 2 or more and 200 or less. The degree of polymerization of oxypropylene is, for example, 2 or more and 200 or less) can be mentioned. Examples of the oxyethylene-oxypropylene block polymer represented by B include (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b , [(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b. ] _C , (C ₃ H ₆ O) _b (C ₂ H ₄ O) _a , [(C ₃ H ₆ O) _b (C ₂ H ₄ O) _a ] _c , (C ₂ H ₄ O) _a (C) ₃ H ₆ O) _b (C ₂ H ₄ O) _d , [(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _d ] _e , (C ₃ H ₆ O) _Examples thereof include _a (C ₂ H ₄ O) _b (C ₃ H ₆ O) _c , [(C ₃ H ₆ O) _a (C ₂ H ₄ O) _b (C ₃ H ₆ O) _c ] _d . a to d are the same or different from each other, and are, for example, integers of 2 or more and 200 or less.

Examples of the alkyl group represented by R ⁷ include alkyl groups having 1 or more and 3 or less carbon atoms such as methyl, ethyl, n-propyl and isopropyl, and methyl is preferable.

Examples of the aminoalkyl group represented by R ⁷ include aminomethyl (-CH ₂ NH ₂ ), amino ethyl (-CH ₂ CH ₂ NH ₂ ), aminopropyl (-CH ₂ CH ₂ CH ₂ NH ₂ ), 3- ( 2-Aminoethylamino) propyl (-CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ ), aminophenoxymethyl (-CH ₂ OC ₆ H ₄ NH ₂ ) (eg 2-aminophenoxymethyl, 3-aminophenoxy) Aminoalkyls such as methyl, 4-aminophenoxymethyl, etc.) may be mentioned, and the hydrogen atom of these amino groups may be replaced with an alkyl group (eg, methyl, ethyl, propyl, butyl, etc.) to form a secondary amine or 3 Examples thereof include those made into a secondary amine and those made into a quaternary ammonium salt. Preferred are aminopropyl (-CH ₂ CH ₂ CH ₂ NH ₂ ).

In the formula (1), the oxyalkylene group-containing group represented by A is represented by, for example, the formula (3).
: Equation (3)

(In the formula (3), y is the same as that exemplified in the above formula (2).)
Examples of the oxyalkylene group-containing group-modified silicone oil include JP-A-2001-39819, eg, J. Am. Jpn. Soc. Color Mater. , 85 [5], 201-207 (2012), for example, Shin-Etsu Chemical Co., Ltd. catalog "Reactive / non-reactive modified silicone oil (issued in December 2013)", for example, Toray Dow Corning Co., Ltd. catalog "Resin modification" Silicone for use (issued in October 2008) ”.

Examples of the method for producing an oxyalkylene group-containing group-modified silicone oil include a method of adding a polysiloxane having a Si—H group and a polyether having a carbon-carbon double bond at the molecular end under a platinum catalyst, Si. a method of reacting a polyether with dehydrogenation having a hydroxyl group in the polysiloxane and the molecular ends having a -H group, an amino-modified polysiloxane and the glycidyl group with an Si-C ₃ H ₆ -NH ₂ group at the molecular end There is a method of reacting with polyether.

As the oxyalkylene group-containing group-modified silicone oil, a commercially available product may be used. Specific examples of the oxyalkylene group-containing group-modified silicone oil include KF-889, KF-6012, KF-6016, KF-6017, KF-352A, KF-353, KF-6004, KF-6020, and KF-. 6028, KF-6038, KF-6048 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-201, SF8427, SF8428, FZ-2162, 501W, L-7001, FZ-2110, L-7002, SH8400, FZ-2203 (The above is manufactured by Toray Dow Corning Co., Ltd.). Preferably, KF-889 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.

KF-889 is an oxyethylene group-containing group-modified silicone oil modified at both ends of the side chain. In the above formula (1), R ^{1 to} R ⁵ are all methyl, and A is the above formula (1). It is a divalent hydrocarbon group having an imino group and being substituted with a hydroxyl group, as shown in 3).

The blending ratio of the oxyalkylene group-containing group-modified silicone oil is, for example, 1 part by mass or more, preferably 10 parts by mass or more, and for example, 1,000 parts by mass or less, based on 100 parts by mass of the silicone oil. It is preferably 300 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 80 parts by mass or less, particularly preferably 50 parts by mass or less, and most preferably 30 parts by mass or less. Further, the blending ratio of the oxyalkylene group-containing group-modified silicone oil is, for example, 0.1% by mass or more, preferably 0.2% by mass or more, and for example, with respect to the two-component curable coating composition. It is 10.0% by mass or less, preferably 5.0% by mass or less.

When the blending ratio of the oxyalkylene group-containing group-modified silicone oil is not less than the above lower limit and not more than the upper limit, the silicone oil can be sufficiently dispersed in the two-component curable coating composition and further in the coating film.

2-4. Components preferably contained in the liquid A The liquid A may further contain, for example, a pigment, a wetting agent, and a filler.

The pigment is not particularly limited, and is appropriately selected depending on the intended use and purpose. Examples of the pigment include inorganic pigments and organic pigments, preferably inorganic pigments, and more preferably oxides.

Examples of the oxide include metal oxides such as zinc oxide, aluminum oxide, chromium oxide, titanium oxide (TiO ₂ ), and iron oxide (iron oxyhydroxide (FeOOH), etc.). Further, as metal oxides, for example, CuCr ₂ O ₄ , Cu (Cr, Mn) ₂ O ₄ , Cu (Fe, Mn) ₂ O ₄ , Co (Fe, Cr) ₂ O ₄ , CoAl ₂ O ₄ , Co. ₂ Includes metal composite oxides such as TiO ₄ .

Further, examples of the pigment include pearl mica (a pigment obtained by coating natural mica or synthetic mica with a metal oxide such as titanium oxide or tin oxide), aluminum particles, aluminum pieces, silver particles, silver pieces and the like.

Pigments can be used alone or in combination. As the pigment, for example, a commercially available product may be used.

The average particle size of the pigment is, for example, 0.01 μm or more, preferably 0.1 μm or more, and for example, 500 μm or less, preferably 200 μm or less, more preferably 100 μm or less, still more preferably 10 μm or less. Is.

The blending ratio of the pigment is appropriately determined depending on the color development property, the hiding property, etc. of the coating film.

The wetting agent is blended with the pigment to moisten the pigment described above. Examples of the wetting agent include alcohol. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol and the like, which have 1 or more and 4 or less carbon atoms. Examples of monohydric alcohols such as ethylene glycol, glycerin, and diethylene glycol are polyhydric alcohols having 2 or more and 4 or less carbon atoms. A monohydric alcohol is preferable, and propanol is more preferable. The wetting agent can be used alone or in combination.

The blending ratio of the wetting agent is, for example, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 100 parts by mass or more, still more preferably 200 parts by mass or more, based on 100 parts by mass of the pigment. Further, for example, it is 1,000 parts by mass or less, preferably 500 parts by mass or less, and more preferably 300 parts by mass or less.

When the blending ratio of the wetting agent is at least the above lower limit, the pigment can be sufficiently moistened and the pigment can be efficiently dispersed in the two-component curable coating composition. On the other hand, when the blending ratio of the wetting agent is not more than the above-mentioned upper limit, the drying property of the coating film (that is, the property that the drying described later can be easily carried out) can be kept good.

The filler is a stress relaxation agent that relaxes the stress applied to the coating film when the coating film is stressed. Examples of the filler include oxides such as silica, alumina, titania, zirconia, zinc oxide, iron oxide, and mica, carbides such as silicon carbide, and nitrides such as silicon nitride. Preferred are oxides, more preferably silica, and even more preferably colloidal silica.

The filler may be of an acidic or alkaline type, for example, such that the suspension exhibits acidic or alkaline when suspended in water by surface treatment. Preferably, the filler includes an acidic type.

As the filler, for example, a commercially available product may be used. Examples of the filler include Snowtex series (acidic type colloidal silica, manufactured by Nissan Chemical Industries, Ltd.).

The average particle size of the filler is, for example, 1 nm or more, preferably 10 nm or more, and for example, 100 nm or less, preferably 50 nm or less.

The blending ratio of the filler is the active ingredient (solid content), and is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts by mass, based on 100 parts by mass of the total amount of the trialkoxysilane and the silicone oil. It is more than parts by mass, and is, for example, 1,000 parts by mass or less, preferably 300 parts by mass or less, and more preferably 100 parts by mass or less. The blending ratio of the filler is the active ingredient (solid content), and is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass, based on the two-component curable coating composition. The above, and for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less. The mixing ratio of the filler in the active ingredient (solid content) is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 50% by mass or less, based on the coating film (solid content). , Preferably adjusted to 40% by mass or less.

When the blending ratio of the filler is equal to or higher than the above lower limit, the stress applied to the coating film can be reliably relaxed. On the other hand, if the blending ratio of the filler is not more than the above upper limit, the shape retention of the coating film can be maintained.

3. 3. Component of liquid B 3-1. Trialkoxysilane Trialkoxysilane is a trifunctional silane compound and is contained in the liquid B as a monomer component forming a binder in the cured coating film in the two-component curable coating composition. Examples of the trialkoxysilane include alkyltrialkoxysilane, alkenyltrialkoxysilane, and aryltrialkoxysilane.

Examples of the alkyltrialkoxysilane include methyltrimethoxysilane (CH ₃ Si (OCH ₃ ) ₃ ), methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, and methyltripentoxysilane. , Methylalkoxysilanes such as methyltrihexoxysilanes, such as ethyltrialkoxysilanes such as ethyltrimethoxysilane, ethyltriethoxysilane, eg n-propyltrimethoxysilane, n-propyltriethoxysilane and the like. Examples thereof include trialkoxysilane.

Examples of the alkenyltrialkoxysilane include vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane.

Examples of the aryltrialkoxysilane include phenyltrialkoxysilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, and phenyltriisopropoxysilane.

Examples of the trialkoxysilane include alkyltrialkoxysilane, more preferably methylalkoxysilane, and even more preferably methyltrimethoxysilane.

The blending ratio of the trialkoxysilane is, for example, 100 parts by mass or more, preferably 200 parts by mass or more, more preferably 300 parts by mass or more, still more preferably 500 parts by mass or more, based on 100 parts by mass of the silicone oil. Particularly preferably, it is 625 parts by mass or more, and more preferably 700 parts by mass or more, 750 parts by mass or more, 800 parts by mass or more, 850 parts by mass or more, 1000 parts by mass or more, and 1200 parts by mass or more. The mixing ratio of the trialkoxysilane is, for example, 200,000 parts by mass or less, preferably 5,000 parts by mass or less, more preferably 3,000 parts by mass or less, and further, with respect to 100 parts by mass of the silicone oil. Preferably, it is 1,500 parts by mass or less. The blending ratio of the trialkoxysilane is, for example, 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and for example, with respect to the two-component curable coating composition. , 80% by mass or less, preferably 50% by mass or less, more preferably 25% by mass or less. Further, the mixing ratio of the trialkoxysilane is such that the content ratio of the cured product of the trialkoxysilane in the coating film (solid content) is, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass. The above, for example, is adjusted so as to be 80% by mass or less, preferably 40% by mass or less. When the blending ratio of the trialkoxysilane is not less than the above lower limit and not more than the upper limit, the shape retention and fastness (strength) of the coating film can be reliably maintained.

3-2. Components Suitable for Liquid B Liquid Liquid B preferably further contains a catalyst, an alcohol, and an alkoxy group-containing siloxane oligomer.

Examples of the catalyst include acids and bases.

Examples of the acid include organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and p-toluenesulfonic acid, such as hydrochloric acid and sulfuric acid. Examples include inorganic acids such as nitric acid and phosphoric acid. Organic acids are preferable, and acetic acid and acrylic acid are more preferable.

Examples of the base include inorganic bases such as ammonia, sodium hydroxide, potassium hydroxide and calcium hydroxide, and organic bases such as tetramethylammonium hydroxide and guanidine.

As the catalyst, an acid is preferably used from the viewpoint of preventing the generation of a gel when the two liquids (liquid A and liquid B) are mixed at room temperature.

The mixing ratio of the catalyst is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, and for example, 10 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of trialkoxysilane. It is less than a part by mass. The mixing ratio of the catalyst is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, and for example, 5% by mass or less, preferably 5% by mass or less, based on the two-component curable coating composition. Is 2% by mass or less.

Alcohol is a hydrolysis reaction control agent that controls the equilibrium reaction because alcohol is produced by hydrolysis of the alkoxy group in trialkoxysilane and the above-mentioned hydrolysis is an equilibrium reaction. Examples of the alcohol include alcohols exemplified by the wetting agent, preferably monohydric alcohol, and more preferably methanol.

The blending ratio of the alcohol is, for example, 0.1 part by mass or more, preferably 1 part by mass or more, more preferably 2 parts by mass or more, and for example, 50 parts by mass with respect to 100 parts by mass of the trialkoxysilane. Parts or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. The mixing ratio of alcohol is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.4% by mass or more with respect to the two-component curable coating composition. Further, for example, it is 10% by mass or less, preferably 2% by mass or less, and more preferably 1% by mass or less.

When the blending ratio of the alcohol is equal to or higher than the above lower limit, the condensation reaction between the two liquids (liquid A and liquid B) and then coating can be controlled. On the other hand, if the blending ratio of the alcohol is equal to or less than the above upper limit, the degree of condensation can be sufficient to form a coating film during coating after mixing the two liquids.

The alkoxy group-containing siloxane oligomer is a non-adhesive auxiliary agent that assists the non-adhesiveness and water repellency of silicone oil in the coating film even when the coating film is rubbed. Further, the alkoxy group-containing siloxane oligomer is preferably contained in the liquid B. As a result, it is possible to effectively suppress a decrease in non-adhesiveness after the durability test of the coating film after rubbing.

Examples of the alkoxy group-containing siloxane oligomer include methyl-based silicone alkoxy oligomers and methylphenyl-based silicone alkoxy oligomers, and preferably methyl-based silicone alkoxy oligomers. Examples of the methyl silicone alkoxy oligomer include methyl trimethoxysilane and a methyl silicone methoxy oligomer produced from dimethyl dimethoxysilane.

As a method for producing an alkoxy group-containing siloxane oligomer, for example, an aqueous hydrochloric acid solution is added to methyltrimethoxysilane and stirred while cooling, followed by heating and stirring, and further by acid hydrolysis condensation to remove methanol under reduced pressure. There are methods and so on.

As the alkoxy group-containing siloxane oligomer, a commercially available product may be used. As the alkoxy group-containing siloxane oligomer, for example, X-40-9250 (manufactured by Shin-Etsu Chemical Co., Ltd.) is used.

The blending ratio of the alkoxy group-containing siloxane oligomer is, for example, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 25 parts by mass with respect to 100 parts by mass of the silicone oil. Further, for example, it is 1,000 parts by mass or less, preferably 500 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 50 parts by mass or less. The blending ratio of the alkoxy group-containing siloxane oligomer is, for example, 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.4% by mass, based on the two-component curable coating composition. % Or more, more preferably 0.5% by mass or more, and for example, 5.0% by mass or less, preferably 3.0% by mass or less, more preferably 1.0% by mass or less. The blending ratio of the alkoxy group-containing siloxane oligomer is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, based on the coating film (solid content). Yes, and it is adjusted so that it is, for example, 50% by mass or less, preferably 40% by mass or less.

When the blending ratio of the alkoxy group-containing siloxane oligomer is at least the above lower limit, the non-adhesiveness and water repellency of the silicone oil in the coating film can be reliably assisted even if the coating film is rubbed. On the other hand, if the blending ratio of the alkoxy group-containing siloxane oligomer is not more than the above upper limit, a good coating film state can be maintained.

3-3. Other Components in Solution B Solution B preferably contains trialkoxysilane (trifunctional silane compound) as a silane compound, dialkoxysilane (bifunctional silane compound), and / or tetraalkoxy. It is substantially free of silane (a tetrafunctional silane compound). In other words, the liquid B may contain a small amount of dialkoxysilane and / or tetraalkoxysilane to the extent that the effect of the present invention is not impaired. Dialkoxysilanes and / or tetraalkoxysilanes may be contained as impurities in trialkoxysilanes. Specifically, the liquid B contains dialkoxysilane in an amount of, for example, 1 part by mass or less, preferably 0.1 part by mass or less, more preferably 0.01, based on 100 parts by mass of trialkoxysilane. Permissible with a content ratio of parts by mass or less. Further, the liquid B contains tetraalkoxysilane in an amount of, for example, 1 part by mass or less, preferably 0.1 part by mass or less, more preferably 0.01 part by mass or less, based on 100 parts by mass of trialkoxysilane. The content ratio of is acceptable.

4. Preparation of two-component curable coating composition Then, in order to prepare a two-component curable coating composition, liquid A and liquid B are prepared, respectively.

For example, water, silicone oil, and oxyalkylene group-containing group-modified silicone oil are mixed and mixed to prepare solution A. Alternatively, water, silicone oil, oxyalkylene group-containing group-modified silicone oil, pigment, wetting agent, and filler are mixed and mixed to prepare solution A. Liquid A preferably comprises only water, a silicone oil, an oxyalkylene group-containing group-modified silicone oil, a pigment, a wetting agent, and a filler.

To mix each of the above components, for example, a stirrer such as a homomixer, an ultrasonic homogenizer, a bead mill, or a disper is used. These are used alone or in combination as appropriate.

Separately from solution A, solution B composed of trialkoxysilane is prepared. Preferably, a trialkoxysilane, a catalyst, an alkoxy group-containing siloxane oligomer, and an alcohol are mixed and mixed to prepare a liquid B. Liquid B preferably comprises only trialkoxysilane, a catalyst, an alkoxy group-containing siloxane oligomer, and an alcohol.

As a result, a two-component curable coating composition in which liquid A and liquid B are prepared respectively is prepared.

Then, the liquid A and the liquid B are blended so that each component has the above-mentioned blending ratio. Specifically, the blending ratio of the liquid B to the total amount of the liquid A and the liquid B is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 16% by mass. More preferably, 17% by mass or more, 18% by mass or more, 19% by mass or more, and 20% by mass or more are preferable. When the blending ratio of the liquid B is not less than the above lower limit, a sufficiently cured coating film can be formed, and in addition, a decrease in non-adhesiveness after the durability test can be effectively suppressed. The blending ratio of the liquid B to the total amount of the liquid A and the liquid B is, for example, 75% by mass or less, preferably 50% by mass or less. When the blending ratio of the liquid B is not more than the above upper limit, it is possible to prevent the liquid A from becoming excessively small, sufficiently promote the hydrolysis of the trialkoxysilane by the water of the liquid A, and the silicone of the liquid A. Since the blending amount of the oil can be surely secured, the coating film can exhibit sufficient non-adhesiveness.

The blending ratio of the liquid A is the balance of the blending ratio of the liquid B described above.

Then, the solution A and the solution B are stirred and mixed. The stirring time is not particularly limited, and is, for example, 0.1 hour or more, preferably 1 hour or more, and for example, 24 hours or less.

While the solution A and the solution B are being stirred, the silanol group is produced by hydrolysis of the alkoxyryl group (Si—OR) contained in the trialkoxysilane, and the produced silanol group is partially derived from the silanol group. The formation of a siloxane (-Si-O-Si-) oligomer by the condensation reaction proceeds.

As a result, a coating composition composed of a two-component curable coating composition is prepared.

The coating composition is then applied to the object.

Objects include products that require non-adhesiveness and water repellency, such as rollers, molds, plates (plate members), chutes, hoppers, cooking utensils, and the like.

Examples of the roller include a drying roller, a coating roller, a transfer roller, a bonding roller, a crimping roller, a guide roller, a roller for applying a pattern to a siding material (outer wall material), a papermaking roller, a printing roller and the like.

Examples of the mold include a protective material manufacturing mold, a rubber tire manufacturing mold, an automobile parts manufacturing mold, a urethane molding mold, a hot melt adhesive molding mold, a solid hot melt adhesive extrusion mold, and the like. ..

Examples of the plate include a plate used in the step of bonding a non-woven fabric and a water-absorbent polymer material to which a hot melt can adhere, a resin pellet sliding plate, and the like.

Examples of the hopper include a food measuring instrument hopper and a powder input hopper.

Examples of cooking utensils include grills, pots, frying pans, grill plates, and the like.

Examples of the method of applying the paint to the object include a spray coating method, a dispenser method, a brush coating, and a spatula coating. Preferably, the spray coating method is mentioned.

As a result, a coating film prepared from the two-component curable coating composition is formed.

The coating is then dried and fired.

The drying temperature is, for example, 50 ° C. or higher, preferably 100 ° C. or lower, and the drying time is, for example, 1 minute or longer, preferably 10 minutes or longer, for example 120 minutes or shorter, preferably 60 minutes or shorter. .. For example, under the above conditions, the coating film and the object are put into a dryer, for example.

The firing temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 150 ° C. or higher, particularly preferably 200 ° C. or higher, and for example, 280 ° C. or lower. , Preferably 250 ° C. or lower. The firing time is, for example, 10 minutes or more, preferably 20 minutes or more, and for example, 120 minutes or less, preferably 60 minutes or less.

By the above-mentioned drying, the alkoxy group in the trialkoxysilane is hydrolyzed to form a silanol group, the alkoxysilyl group and the silanol group are dealcoholized to form a siloxane bond, and the silanol groups are dehydrated and condensed. As the reaction for forming a siloxane bond proceeds, the curing reaction of the trialkoxysilane proceeds. Further, water and a wetting agent (preferably alcohol) derived from solution A, a catalyst and alcohol derived from solution B, alcohol generated by the above-mentioned hydrolysis reaction, and water and alcohol generated by the condensation reaction are removed. Will be done.

In addition, the above-mentioned firing promotes the above-mentioned curing reaction.

The thickness of the coating film thus obtained is, for example, 1 μm or more, preferably 20 μm or more, and for example, 200 μm or less, preferably 80 μm or less.

5. Effect The coating film obtained from the above-mentioned two-component curable coating composition has high non-adhesiveness and good appearance. Therefore, it is possible to impart high non-adhesiveness and good appearance to the object.

Further, if the oxyalkylene group in the oxyalkylene group-containing group-modified silicone oil is polyoxyethylene, a hydrophilic segment can be reliably formed in the oxyalkylene group-containing group-modified silicone oil, so that the oxyalkylene group-containing group The modified silicone oil can act as a surfactant in the silicone oil in the aqueous phase.

Further, in the two-component curable coating composition, since the silicone oil and the oxyalkylene group-containing group-modified silicone oil are both contained in the solution A, the oxyalkylene group-containing group-modified silicone oil disperses the silicone oil in the solution A. The properties are improved in advance, whereby a stable coating composition can be obtained.

Further, in this two-component curable coating composition, if the kinematic viscosity of the silicone oil at 25 ° C. is 500 mm ² / s or more, it is possible to suppress a decrease in non-adhesiveness after the durability test of the coating film.

Further, if the liquid B contains an alkoxy group-containing siloxane oligomer, it is possible to effectively suppress a decrease in non-adhesiveness after the durability test of the coating film.

6. Modification Example In the above-described embodiment, the coating film is formed of a single layer, but the coating film can be formed as a plurality of layers. For example, first, a first two-component curable coating composition (two-component curable coating composition for a base layer) is applied to an object to prepare a base layer, and then a second two-component curable coating composition is placed on the base layer. The two-component curable coating composition (two-component curable coating composition for the top layer) is applied to prepare the top layer. Thereby, a coating film composed of a base layer and a top layer can also be formed. Then, the coating film is dried and fired.

The first two-component curable coating composition and the second first two-component curable coating composition may be, for example, the same or different from each other, and are preferably different from each other.

When the coating film is formed of a plurality of layers, the liquid A and the liquid B are blended in the above-mentioned blending ratios to prepare the first two-component curable coating composition, while the liquids A and B are mixed. A second two-component curable coating composition is prepared by blending at the above-mentioned blending ratio or a blending ratio other than the above-mentioned blending ratio. The blending ratios of the liquid A and the liquid B for preparing the second two-component curable coating composition are not restricted by the blending ratio described above, and the coating film exerts the above-mentioned effects. Further, the mixing ratio of water to trialkoxysilane, the mixing ratio of trialkoxysilane to silicone oil, and the like are not restricted in the preparation of the second two-component curable coating composition.

In one embodiment described above, both the silicone oil and the oxyalkylene group-containing group-modified silicone oil are contained in the liquid A, but the present invention is not limited thereto. For example, both the silicone oil and the oxyalkylene group-containing group-modified silicone oil may be contained in the liquid B, or one of them may be contained in the liquid A and the other may be contained in the liquid B. Further, the silicone oil and the oxyalkylene group-containing group-modified silicone oil may be contained in each of the liquid A and the liquid B (that is, a part of the silicone oil and a part of the oxyalkylene group-containing group-modified silicone oil). The balance of the silicone oil and the balance of the oxyalkylene group-containing group-modified silicone oil contained in the liquid A may be contained in the liquid B).

That is, the present invention includes the following aspects 1 to 9.

Aspect 1: The liquid A contains a silicone oil and an oxyalkylene group-containing group-modified silicone oil. In the first aspect, the liquid B does not contain either a silicone oil or an oxyalkylene group-containing group-modified silicone oil. In addition, aspect 1 corresponds to one embodiment described above.

Aspect 2: The liquid A contains a silicone oil and an oxyalkylene group-containing group-modified silicone oil, and the liquid B contains an oxyalkylene group-containing group-modified silicone oil. In the second aspect, the oxyalkylene group-containing group-modified silicone oil is distributed into the liquid A and the liquid B.

Aspect 3: The liquid A contains a silicone oil, and the liquid B contains an oxyalkylene group-containing group-modified silicone oil.

Aspect 4: The liquid A contains a silicone oil and an oxyalkylene group-containing group-modified silicone oil, and the liquid B contains a silicone oil. In aspect 4, the silicone oil is distributed into liquids A and B.

Aspect 5: Liquid A contains a silicone oil and an oxyalkylene group-containing group-modified silicone oil, and solution B contains a silicone oil and an oxyalkylene group-containing group-modified silicone oil. In aspect 5, the silicone oil is distributed into liquids A and B. The oxyalkylene group-containing group-modified silicone oil is distributed into liquids A and B.

Aspect 6: The liquid A contains a silicone oil, and the liquid B contains a silicone oil and an oxyalkylene group-containing group-modified silicone oil. In aspect 6, the silicone oil is distributed into liquids A and B.

Aspect 7: The liquid A contains an oxyalkylene group-containing group-modified silicone oil, and the liquid B contains a silicone oil.

Aspect 8: The liquid A contains an oxyalkylene group-containing group-modified silicone oil, and the liquid B contains a silicone oil and an oxyalkylene group-containing group-modified silicone oil. In aspect 7, the oxyalkylene group-containing group-modified silicone oil is distributed into liquids A and B.

Aspect 9: Liquid B contains a silicone oil and an oxyalkylene group-containing group-modified silicone oil. In the ninth aspect, the liquid A does not contain either a silicone oil or an oxyalkylene group-containing group-modified silicone oil.

In addition, as long as the effects of the present invention are not impaired, additives such as surfactants, dispersants, and leveling agents other than defoamers, thickeners, and oxyalkylene group-containing group-modified silicone oils can be added to solution A and / or It can also be added to the solution B in an appropriate ratio.

Examples and comparative examples are shown below, and the present invention will be described in more detail. The present invention is not limited to Examples and Comparative Examples. In addition, specific numerical values such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are the compounding ratios corresponding to those described in the above-mentioned "Form for carrying out the invention". Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, and parameters. be able to. In addition, unless otherwise specified in the following description, "part" and "%" are based on mass.

First, each component used in each Example and each Comparative Example is described below.

(Silicone oil)
-KF-96-10cs: polydimethylsiloxane, kinematic viscosity (25 ° C): 10 mm ² / s, manufactured by Shin-Etsu Chemical Industry Co., Ltd.-KF-96-50cs: polydimethylsiloxane, kinematic viscosity (25 ° C): 50 mm ² / s , Shinetsu Kagaku Kogyo Co., Ltd. KF-96-100cs: polydimethylsiloxane, kinematic viscosity (25 ° C): 100 mm ² / s, Shinetsu Kagaku Kogyo Co., Ltd. KF-96-300cs: polydimethylsiloxane, kinematic viscosity (25 ° C) ): 300 mm ² / s, manufactured by Shinetsu Chemical Industry Co., Ltd., KF-96-500 cs: polydimethylsiloxane, kinematic viscosity (25 ° C.): 500 mm ² / s, manufactured by Shinetsu Chemical Industry Co., Ltd., KF-96-1000 cs: polydimethylsiloxane , Dynamic viscosity (25 ° C): 1,000 mm ² / s, manufactured by Shin-Etsu Chemical Industry Co., Ltd. KF-96-10,000 cs: Polydimethylsiloxane, kinematic viscosity (25 ° C): 10,000 mm ² / s, Shin-Etsu Chemical KF-96-100,000 cs manufactured by Kogyo Co., Ltd .: polydimethylsiloxane, kinematic viscosity (25 ° C): 100,000 mm ² / s, KF-96-100,000 cs manufactured by Shinetsu Chemical Industry Co., Ltd .: polydimethylsiloxane, kinematic viscosity (25 ° C): 500,000 mm ² / s, manufactured by Shinetsu Chemical Industry Co., Ltd. KF-96-1 million cs: polydimethylsiloxane, kinematic viscosity (25 ° C): 1,000,000 mm ² / s, Shinetsu Chemical Industry Co., Ltd. Made (Oxyalkylene group-containing group-modified silicone oil)
-KF-889: Oxyethylene group-containing group-modified silicone oil (side chain modified type), manufactured by Shin-Etsu Chemical Co., Ltd.-KF-6012: Oxyethylene-oxypropylene group-containing group-modified silicone oil (side chain modified type), KF-6016 manufactured by Shin-Etsu Chemical Co., Ltd .: oxyethylene group-containing group-modified silicone oil (side chain modified type), KF-6017 manufactured by Shin-Etsu Chemical Co., Ltd .: oxyethylene group-containing group-modified silicone oil (side chain modified type), KF-352A manufactured by Shin-Etsu Chemical Co., Ltd .: oxyalkylene group-containing group-modified silicone oil (side chain modified type), KF-353 manufactured by Shin-Etsu Chemical Co., Ltd .: oxyalkylene group-containing group-modified silicone oil (side chain modified type), Shin-Etsu Chemical Co., Ltd. ・ KF-6004: Oxyethylene group-containing group-modified silicone oil (both-terminal modified type), Shin-Etsu Chemical Co., Ltd. ・ KF-6020: Oxyalkylene group-containing group-modified silicone oil (side chain modified type), Shin-Etsu Chemical Co., Ltd. BY16-201: Oxyalkylene group-containing group-modified silicone oil (both-ended modified type), Toray Dow Corning Co., Ltd. SF8427: Oxyalkylene group-containing group-modified silicone oil (both-ended modified type), Toray・ SF8428: Oxyalkylene group-containing group-modified silicone oil (side chain-modified type), Toray Doukoning Co., Ltd. ・ FZ-2162: Oxyalkylene group-containing group-modified silicone oil (side chain-modified type), Toray -Made by Dow Corning-501W: Oxyalkylene group-containing group-modified silicone oil (side chain modified type), Toray-Dow Corning Co., Ltd.-L-7001: Oxyalkylene group-containing group-modified silicone oil (side chain modified type), Toray・ FZ-2110: Oxyalkylene group-containing group-modified silicone oil (side chain-modified type), Toray Dow-Conning Co., Ltd. ・ L-7002: Oxyalkylene group-containing group-modified silicone oil (side chain-modified type) , Toray Dow Corning, SH8400: Oxyalkylene group-containing group-modified silicone oil (side chain modified type), Toray Dow Corning, FZ-2203: Oxyalkylene group-containing group-modified silicone oil (ABn type), Toray・ KF-6028: Oxyethylene group-containing group-modified silicone oil (branched chain-modified type), Shin-Etsu Chemical Co., Ltd. ・ KF-6038: Oxyethylene group-containing group-modified silicone oil (both side chain-modified and alkyl) Modified type, dimethylsiloxane branched type), manufactured by Shin-Etsu Chemical Co., Ltd. -KF-6048: Oxyethylene group-containing group-modified silicone oil (side chain-modified / alkyl co-modified type, dimethylsiloxane linear type), manufactured by Shin-Etsu Chemical Co., Ltd. (pigment)
42-303A: Pigment, Cu (Cr, Mn) ₂ O ₄ , average particle diameter: 0.8 μm, manufactured by Tokan Material Technology Co., Ltd. 42-250A: Pigment, CoAl ₂ O ₄ , average particle diameter: 0. 8 μm, manufactured by Tokan Material Technology Co., Ltd. CR-50: pigment, TiO ₂ , average particle size: 0.25 μm, manufactured by Ishihara Sangyo Co., Ltd. TSY-155: pigment, α-FeOOH, average particle size: 0.6 μm, Toda Made by Kogyo Co., Ltd. ・ Iriodin163: Pearl mica pigment, average particle size: 20 to 180 μm, manufactured by Merck Co., Ltd. (wetting agent)
-2-Propanol: manufactured by Wako Pure Chemical Industries, Ltd. (filler)
-Snowtex O-40: colloidal silica suspension (average particle size: 20 to 25 nm), pH: 3, silica content: 40.5% by mass, manufactured by Nissan Chemical Co., Ltd.-Snowtex O: colloidal silica suspension ( Average particle size: 10 to 15 nm), pH: 3, silica content 20.4% by mass, manufactured by Nissan Chemical Co., Ltd. (trialkoxysilane)
-Methyltrimethoxysilane: manufactured by Wako Pure Chemical Industries, Ltd. (alcohol)
-Methanol: manufactured by Wako Pure Chemical Industries, Ltd. (catalyst)
-Acetic acid: manufactured by Wako Pure Chemical Industries (alkoxy group-containing siloxane oligomer)
-X-40-9250: Methyl-based silicone alkoxy oligomer, manufactured by Shin-Etsu Chemical Co., Ltd.

(Example 1)
In a polypropylene container, 22.6 parts of water, 23.4 parts of 2-propanol, 0.4 parts of KF-889, 0.7 parts of KF-96-10cs, 9.6 parts of 42-303A, and , Snowtex O-40 was blended in 21.3 parts, and the mixture was stirred with a disper (TK HOMODISPER, manufactured by Plymix) for 30 minutes. Subsequently, the solution A was further dispersed for 30 minutes using a bead mill (DISPERMAT, manufactured by VMA-GETZMANN GMBA) to prepare 78.0 parts of the solution A.

Separately, 21.0 parts of methyltrimethoxysilane, 0.7 parts of methanol and 0.3 parts of acetic acid were mixed in a polypropylene container, and the mixture was stirred with a magnetic stirrer for 30 minutes to prepare 22.0 parts of solution B. ..

Then, the above-mentioned agents A and B were mixed in a glass container with a lid, and the mixture was stirred with a magnetic stirrer at 20 ° C. for 15 hours to prepare 100.0 parts of a coating composition.

Then, a flat plate test piece (thickness 1 mm, 60 mm × 90 mm, material aluminum) as an object was subjected to solvent degreasing treatment with methyl ethyl ketone, and then shot blasted using # 80 alumina particles.

Subsequently, the coating composition was applied to the flat plate test piece by air spray and dried at 80 ° C. for 30 minutes to prepare a coating film. Then, the coating film was further calcined at 250 ° C. for 30 minutes. The thickness (film thickness) of the coating film after firing was measured and found to be 30 μm.

(Example 2) to (Example 31), (Example 36) to (Example 76) , (Comparative Example 1) to (Comparative Example 3) and (Comparative Example 12) to (Comparative Example 15).
A coating composition was prepared in the same manner as in Example 1 except that the components of each of the solutions A and B were changed according to Tables 1 to 5 and 7 to 11, and then the coating film was applied. Made.

(Example 32)
First, a coating composition for a base layer was prepared according to the formulation of Example 18 shown in Table 3. Separately, a coating composition for the top layer was prepared according to the formulation shown in Example 32 shown in Table 6.

Then, the base layer coating composition was applied to the flat plate test piece by air spray. As a result, a wet-shaped base layer was formed. Subsequently, the coating composition for the top layer was applied to the flat plate test piece by air spray on the base layer of Example 18. As a result, a wet-shaped top layer was formed on the base layer.

Then, the base layer and the top layer were dried at 80 ° C. for 30 minutes to prepare a coating film. Then, the coating film was further calcined at 250 ° C. for 30 minutes. The thickness (film thickness) of the coating film after firing was measured and found to be 31 μm.

(Example 33) to (Example 35)
A coating film was prepared by treating in the same manner as in Example 32 except that the formulations of the coating composition for the top layer and the coating composition for the base layer were changed according to Table 6.

(Evaluation of coating film)
The following items were evaluated for the coating films of each Example and each Comparative Example. The results are shown in Tables 1 to 11.

1. 1. Appearance The appearance (smoothness) of the coating film was evaluated by visually observing the coating film according to the following criteria.

◯: The surface of the coating film was smooth.

Δ: The surface of the coating film was slightly uneven.

X: Repellent was observed on the coating film, and the surface was not smooth.

2. Non-adhesive (peeling)
(1) Tape peeling method The non-adhesiveness (peeling property) of the coating film was evaluated by the tape peeling method.

That is, first, a coating agent of a cloth adhesive tape (Nichiban Co., Ltd., No. 123, width 50 mm) composed of a sufu as a support and an adhesive having an adhesive strength of 4.74 (N / 10 mm) is applied. Was adhered (pressure-sensitive adhesive), and then the cloth adhesive tape was peeled off from the coating film. Then, the non-adhesiveness (peeling property (easy peeling property)) of the coating film was evaluated according to the following criteria.
⊚: The cloth adhesive tape could be peeled off from the coating film with almost no force.
◯: The cloth adhesive tape could be peeled off from the coating film with a slight force.
Δ: The cloth adhesive tape could be peeled off from the coating film with a moderate force.
X: The cloth adhesive tape could be peeled off from the coating film only with a large force.

(2) 180 degree peeling method (i) Tape peeling strength before sliding test 180 degree peeling method (JIS Z 0237: 2009, method 4), non-adhesiveness (peeling property) of the coating film ) Was evaluated.

That is, first, an adhesive of Nichiban's cellophane tape (registered trademark) product number CT405AP-18 (width 18 mm) is adhered (pressure sensitive adhesion), and then cellophane tape (distance 80 mm) is applied from the coating film at a speed of 300 mm / min. Then, it was peeled off at a peeling distance of 80 mm. Then, the non-adhesiveness (peeling property (easy peeling property)) of the coating film was evaluated as the peeling strength.

(Ii) Peeling strength of tape after sliding test Using RUBBING TESTER manufactured by Ohira Rika Kogyo Co., Ltd., wool felt was pressed against a coating film with a load of 1 kg to carry out a sliding test. Specifically, the non-adhesiveness after 5,000 sliding times was measured by measuring the peeling strength in the 180-degree peeling method described above.

3. 3. Robustness of coating film In the same test as "2. Non-adhesiveness (peeling property) (1) Tape peeling method" above, the coating film adhering to the tape after the test is visually observed and the coating film is coated. Strength (robustness) was evaluated according to the following criteria.

◯: The coating film did not adhere to the tape.

Δ: A part of the coating film was attached to the tape.

Claims (5)

A solution containing water and a solution B containing trialkoxysilane are contained.
The liquid A and / or the liquid B contains silicone oil and contains silicone oil.
The solution A and / or the solution B contains an oxyalkylene group-containing group-modified silicone oil modified with an oxyalkylene group-containing group containing an oxyalkylene group .
The silicone oil is an unmodified silicone oil,
The kinematic viscosity at 25 ° C. of the silicone oil, characterized in der Rukoto least 500 mm 2 / ^s, two-component curable coating composition. The two-component curable coating composition according to claim 1, wherein the oxyalkylene group is polyoxyethylene. The two-component curable coating composition according to claim 1 or 2, wherein both the silicone oil and the oxyalkylene group-containing group-modified silicone oil are contained in the liquid A. The two-component curable coating composition according to any one of claims 1 to 3 , wherein the liquid B further contains an alkoxy group-containing siloxane oligomer. A coating composition is prepared by mixing the liquid A and the liquid B in the two-component curing type coating composition according to any one of claims 1 to 4 , and the coating composition is applied to an object and cured. A coating film, which is obtained by allowing the coating film to be obtained.