JP2010229383A - Graffiti-proof paint composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a graffiti-proof paint composition useful for preventing graffiti on the concrete surface of buildings and constructions and painted surfaces etc. <P>SOLUTION: This graffiti-proof paint composition contains an organopolysiloxane (a) containing a Si-C bond and a hydrolyzable silyl group, an organopolysiloxane (b) containing no hydrolyzable silyl group and a glass flake pigment (c), and the usage ratios of component (a) and component (b) are in the range of 50-99.9 mass% for component (a) and 0.1-50 mass% for component (b) based on the total mass of both and the content of component (c) is in the range of 0.1-30 pts.mass to 100 pts.mass of the total of component (a) and component (b). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a coating composition useful for preventing graffiti on a concrete surface or a painted surface of a building or a structure.

  In recent years, the graffiti by spray paint etc. has increased mainly on the concrete surface and painted surface of buildings, and the appearance of these aesthetics is increasing. In addition, since such graffiti cannot be easily removed, a great amount of labor and cost are required for removal. Therefore, in order to prevent graffiti from sticking, it is proposed to form a pollution-preventing coating by applying a paint containing silicone oil or wax to the surface of these structures or by applying a reactive silicone resin paint. (For example, see Patent Documents 1 to 3).

  Patent Document 4 proposes a method of spreading a surface treatment agent containing a specific organopolysiloxane on the surface of a coating film of an automobile or the like to form a film that can easily remove attached dirt components.

  However, such reactive silicone resin-based paints and surface treatment agents have poor graffiti prevention performance over time, and when coated thickly with roller coating or brush coating, cracks occur in the coating film over time at room temperature drying. There was a problem.

JP-A-6-182290 JP 9-94524 A JP-A-10-216619 JP 2005-97527 A

  The object of the present invention is to provide a graffiti-preventing coating film that is excellent in sustainability of performance without causing cracks in the formed film even when thickly applied by roller coating or the like on the concrete surface or painted surface of a building or structure. It is to provide a coating composition that can be formed.

  The present invention contains an organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group, an organopolysiloxane (b) containing no hydrolyzable silyl group, and a glass flake pigment (c). The proportion of component (a) and component (b) used is within the range of 50 to 99.9% by mass of component (a) and 0.1 to 50% by mass of component (b) based on the total mass of both. The graffiti-preventing paint composition, wherein the content of component (c) is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass in total of component (a) and component (b), And a coating method comprising applying the coating composition to a surface to be coated.

  According to the present invention, a specific amount of glass flake pigment is blended with a specific polysiloxane component, so that the formed film is cracked even when thickly applied by roller coating or the like to the concrete surface or painted surface of a building or structure. A graffiti-preventing coating film can be formed without generation. In addition, the formed coating film has excellent durability for preventing graffiti, and can contribute to maintaining aesthetics for a long time. Furthermore, since a glittering feeling is imparted, the difference between the painted part and the unpainted part can be easily understood and the unpainted part can be clarified.

  As the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group used in the present invention, conventionally known ones can be used without limitation, and as a production method thereof, for example, a Si—C bond in a molecule can be used. And a method of hydrolyzing and condensing an organohalosilane containing silane and alkoxylating with an alcohol; a method of hydrolyzing and condensing an organoalkoxysilane containing a Si—C bond in the molecule, and the like.

  Specifically, as these methods, various conditions can be adopted using an organosilane compound containing at least one selected from organosilane compounds containing Si—C bonds represented by the following formulas (1) to (3) as raw materials. It hydrolyzes and condenses.

In the above formulas (1) to (3), R ¹ is the same or different and is a substituted or unsubstituted hydrocarbon group or a polymerizable unsaturated group, and X is the same or different and is a hydroxyl group, an alkoxy group, Represents a halogen atom.

Specific examples of R ¹ are the same or different, and are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, i -Pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, i-heptyl group, n-octyl group, i-octyl group, n-nonyl group, n-decyl group, n-octadecyl group, etc. Alkyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl group such as benzyl group, phenethyl group and phenylpropyl group; 3-chloropropyl group; Halogenated alkyl group such as 3,3,3-trifluoropropyl group; vinyl group, allyl group, i-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl A cycloalkenyl group such as 2-cyclohexylenyl group, 3-cyclohexylenyl group, 2-vinylcyclohexyl group, 3-vinylcyclohexyl group, 4-vinylcyclohexyl group, 2-vinylphenyl group, 3-vinylphenyl group, 4- Polymerizable unsaturated groups such as vinylphenyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 3-allyloxypropyl group, 3- (meth) acryloyloxypropyl group; aminoethyl group, Examples thereof include aminoalkyl groups such as 3-aminopropyl group; glycidoxyalkyl groups such as 3-glycidoxypropyl group.

  On the other hand, X may be the same or different and may be methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, tert-butoxy group, n-pentyloxy group, i- Examples thereof include alkoxy groups such as a pentyloxy group, n-hexyloxy group, i-hexyloxy group and phenoxy group; halogens such as chlorine, bromine and fluorine;

  Specific examples of the organosilane compounds represented by the above formulas (1) to (3) include monoalkoxysilanes such as trimethylmethoxysilane; dialkoxysilanes such as dimethyldimethoxysilane and diphenyldimethoxysilane; methyltrimethoxysilane, methyl And trialkoxysilanes such as triethoxysilane and phenyltrimethoxysilane; organohalosilanes such as dimethyldichlorosilane and trimethylchlorosilane; and the like.

  In the present invention, the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group is generally composed mainly of an organosilane compound represented by the formula (1) and / or the formula (2). An organopolysiloxane having a three-dimensional structure is preferable. Moreover, in order to adjust the hardness of a coating film, a flexibility, bending resistance, etc., the organosilane compound represented by Formula (3) and / or Formula (4) can also be mixed suitably as a raw material.

  Specific examples of the organosilane compound represented by the above formula (4) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraphenoxysilane; tetrahalosilanes such as tetrachlorosilane, and the like. Can be mentioned.

  Moreover, the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group is produced by using a bifunctional organosilane compound represented by the formula (2) as a main component. An organopolysiloxane having a linear structure may be used.

  In the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group, the alkoxy group bonded to the silicon atom as the hydrolyzable silyl group, that is, the alkoxysilyl group is caused by moisture or moisture in the air. It is known that it is hydrolyzed to become silanol, and the condensation reaction between silanols proceeds at room temperature.

  In order for the coating film of the composition of the present invention to exhibit stain resistance or stain removability with respect to hydrophilic or hydrophobic stain components, an organo group containing a Si—C bond and a hydrolyzable silyl group is used. The polysiloxane (a) preferably has a methyl group as a substituent, and the organopolysiloxane (a) has a methyl group concentration of 20 mol% or more, preferably 40 mol% or more.

  In this specification, the methyl group concentration of the organopolysiloxane (a) can be calculated based on the following formula.

Methyl group concentration (mol%) of organopolysiloxane (a) = (n2 / n1) × 100
n1: Total number of moles of substituent R ¹ in the organosilane compounds of the above formulas (1), (2), (3) and (4), n2: Number of moles of methyl group in substituent R ¹ The organopolysiloxane (a) containing a -C bond and a hydrolyzable silyl group contains an organopolysiloxane (a1) containing a benzene ring structure in order to improve crack resistance of the formed coating film. It is desirable that the organopolysiloxane (a1) has a benzene ring concentration of 20 mol% or more, preferably 20 to 70 mol%.

  The benzene ring concentration of the organopolysiloxane (a1) can be calculated based on the following formula.

Concentration of benzene ring (mol%) of organopolysiloxane (a1) = (n3 / n1) × 100
n1: the total number of moles of the substituent R ¹ in the organosilane compounds of the above formulas (1), (2), (3) and (4), n3: the number of moles of the benzene ring in the substituent R ¹ .

  As a compounding quantity of the said organopolysiloxane (a1), it is 5-80 mass% with respect to the organopolysiloxane (a) containing a Si-C bond and a hydrolyzable silyl group, Preferably it is 5-70 mass%. This is desirable from the standpoint of cracking resistance and drying properties of the formed coating film.

  Furthermore, in the present invention, the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group improves the effect of easily removing attached dirt, so that an organopolysiloxane skeleton having a three-dimensional structure and It is desirable to contain an organopolysiloxane (a2) that contains a linear organopolysiloxane skeleton in the molecule.

  Examples of the linear organopolysiloxane skeleton include a structure represented by the following formula (5).

In the formula (5), j represents an integer of ² to 1,000, R ² is the same or different and represents a substituted or unsubstituted hydrocarbon group, and the hydrocarbon group is a saturated group, May be the same or different, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n- Pentyl group, i-pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, i-heptyl group, n-octyl group, i-octyl group, n-nonyl group, n-decyl group, n- Alkyl groups such as octadecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group, phenethyl group and phenylpropyl group; 3 Halogenated alkyl groups such as chloropropyl group and 3,3,3-trifluoropropyl group, aminoalkyl groups such as aminoethyl group and 3-aminopropyl group; glycidoxyalkyl groups such as 3-glycidoxypropyl group In particular, a methyl group is preferable.

  Examples of the method for producing the organopolysiloxane (a2) containing both the organopolysiloxane skeleton having a three-dimensional structure and the linear organopolysiloxane skeleton in the molecule include (1) alkoxy group and polymerization in the molecule. A method of reacting an organopolysiloxane having a three-dimensional structure containing a polymerizable unsaturated group with a linear organopolysiloxane containing Si-H groups at both ends, or (2) an alkoxy group in the molecule And a method of reacting an organopolysiloxane having a three-dimensional structure containing a Si—H group with a linear organopolysiloxane containing a polymerizable unsaturated group at both ends.

  Examples of the polymerizable unsaturated group include a vinyl group, an allyl group, an i-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group and the like; a 2-cyclohexylenyl group, a 3-cyclohexylenyl group, Cycloalkenyl groups such as 2-vinylcyclohexyl group, 3-vinylcyclohexyl group, 4-vinylcyclohexyl group; vinylphenyl groups such as 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group; 2-allylphenyl Group, 3-allylphenyl group, allylphenyl group such as 4-allylphenyl group; 3-allyloxypropyl group, 3- (meth) acryloyloxypropyl group, among others, vinyl due to reactivity with Si-H group A group is desirable.

  In the reactions (1) and (2) above, simple metals such as Ni, Rh, Pd, and Pt and compounds thereof in the presence of an organic solvent such as hexane, pentane, toluene, xylene, etc., if necessary, in accordance with conventional methods The hydrosilylation reaction can be performed using the complex as a catalyst.

  In the reactions (1) and (2) above, in order to minimize the amount of unreacted linear organopolysiloxane and obtain the desired compound without gelation, The functional group (polymerizable unsaturated group or Si-H group) of the organopolysiloxane having a three-dimensional structure is excessive with respect to the functional group (Si-H group or polymerizable unsaturated group) of siloxane. It is desirable to make it.

  As a compounding quantity of the said organopolysiloxane (a2), it is 1-60 mass% with respect to the organopolysiloxane (a) containing a Si-C bond and a hydrolyzable silyl group, Preferably it is 3-50 mass%. It is desirable from the viewpoints of soil removability and curability (touch drying property).

  In the present invention, the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group includes “SR2406”, “SR2410”, “SR2420”, “SR2416”, “SR2402”, “AY42-161”. (Toray Dow Corning Silicone Co., Ltd.), FZ-3704, FZ-3511 (Nihon Unicar Co., Ltd.), KC-89S, KR-500, X-40- 9225 "," X-40-9246 "," X-40-9250 "," KR-217 "," KR-9218 "," KR-213 "," KR-510 "," X-40-9227 " , “X-40-9247”, “X-41-1053”, “X-41-1056”, “X-41-1805”, “X-41-1810”, “X-40-265” 1 "," X-40-2308 "," X-40-9238 "," X-40-2239 "," X-40-2327 "," KR-400 "," X-40-175 "," Commercial products such as “X-40-9740” (manufactured by Shin-Etsu Chemical Co., Ltd.) are also applicable.

  In the present invention, the organopolysiloxane (b) containing no hydrolyzable silyl group does not substantially hydrolyze itself, and is added to improve the coating workability and make the formed coating film uniform. It is what is done. The organopolysiloxane (b) containing no hydrolyzable silyl group is, for example, a linear polysiloxane represented by the following formula (6) or the following formula (8) and / or from the viewpoint of coating workability: Mention may be made of cyclic polysiloxanes.

  As said linear polysiloxane compound, the compound represented by the following Formula (6) can be mentioned.

R ³ is the same or different and represents a substituted or unsubstituted hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl. Group, n-pentyl group, i-pentyl group, n-hexyl group, alkyl group such as i-hexyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group; aryl group such as phenyl group; benzyl group, phenylpropyl group An aralkyl group such as an aminoalkyl group such as an aminoethyl group and a 3-aminopropyl group; a glycidoxyalkyl group such as a 3-glycidoxypropyl group and the like. Groups, in particular methyl groups, are preferred. Y represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms or a polyoxyalkylene group represented by the following formula (7). When Y is an alkyl group, for example, an n-hexyl group, i -Hexyl group, n-heptyl group, i-heptyl group, n-octyl group, i-octyl group, n-nonyl group, n-decyl group and the like, among which an alkyl group having 6 to 9 carbon atoms is preferable. . k1 represents an integer of 1 to 8, and k2 represents an integer of 1 to 8. In the compound represented by the above formula (6), it is desirable that both k1 and k2 are 1 because the coating workability of the composition of the present invention is excellent.

^{_{-O- (CHR 4 -CH 2 -O)}} k3 -R 41 (7)
k3 represents an integer of 1 to 20, preferably 2 to 20, and R ⁴ represents a methyl group or a hydrogen atom. R ⁴¹ represents hydrogen or a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, particularly preferably hydrogen or a methyl group.

  In the linear organopolysiloxane compound represented by the above formula (6), by introducing a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms or a polyoxyalkylene group as Y, hydrophilicity / hydrophobicity of the compound The degree of the property can be controlled, and it is useful for improving the compatibility with the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group and various components described later, and the adhesion of the formed coating film. Can do.

  Examples of the cyclic polysiloxane compound that can be used as the organopolysiloxane (b) include compounds represented by the following formula (8).

R ⁵ is the same or different and represents a substituted or unsubstituted hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl. Group, n-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; phenyl group and other aryl groups; benzyl group and phenylpropyl group An aralkyl group such as an aminoalkyl group such as an aminoethyl group and a 3-aminopropyl group; a glycidoxyalkyl group such as a 3-glycidoxypropyl group and the like. Groups, in particular methyl groups, are preferred. l represents an integer of 3 to 10. Specific examples of suitable cyclic polysiloxane compounds include methylcyclopolysiloxanes such as decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, and dodecamethylcyclohexasiloxane. The above exemplified compounds may be used singly or in combination.

  In the present invention, the organopolysiloxane (a) containing the Si—C bond and the hydrolyzable silyl group and the organo containing no hydrolyzable silyl group from the viewpoints of graffiti prevention, painting workability, drying properties, etc. The proportion of polysiloxane (b) used is such that the amount of component (a) is 50 to 99.9% by mass, preferably 60 to 90% by mass, based on the total mass of component (a) and component (b). The amount of (b) needs to be in the range of 0.1 to 50% by mass, preferably 10 to 40% by mass. If the amount of the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group is less than 50% by mass, the anti-graffiti properties and finish are inferior. Tend to decrease.

The glass flake pigment (c) used in the present invention is usually scaly particles having an average particle diameter of 5 to 300 μm and an average thickness of 0.5 to 20 μm, mainly composed of SiO ₂ , and ZnO or B ₂ O. ₃ and other components may be included in some amounts. The surface is desirably coated with a metal oxide or metal-plated, and any known metal species can be used without particular limitation, for example, Ti, Fe, Zn, Sn, Zr, Au, Ag Cu, Ni, Al and the like.

  Content of the said glass flake pigment (c) is 0.1-30 mass parts with respect to a total of 100 mass parts of the above-mentioned component (a) and component (b), Preferably it is the range of 0.5-25 mass parts. Is within. When the content of the glass flake (c) is less than 0.1 parts by mass, the crack resistance of the formed coating film becomes insufficient. On the other hand, when the content exceeds 30 parts by mass, the finish is lowered, which is not preferable.

  The composition of the present invention preferably further contains an organosilicate compound (d). Thereby, there is an advantage that the surface of the formed coating film is hydrophilically modified with rain water or the like over time, and is less likely to become dirty. Examples of the organosilicate compound (d) that can be used for such purpose include a linear compound represented by the following formula (9).

Wherein, ^{R 6} are the same or different, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 1 to 100. Examples of the hydrocarbon group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, i-pentyl group, Alkyl groups such as n-hexyl group, i-hexyl group and n-octyl group, and aryl groups such as phenyl group are preferred. In particular, R ⁶ is preferably an alkyl group having 1 to 4 carbon atoms. As the organosilicate compound (d), those having an average degree of condensation of 2 to 15 are suitable. By weight fraction of the silica remaining as silica when the organosilicate compound (d) is baked at 900 ° C. Preference is given to organosilicate compounds which have been condensed until they are in the range of 20 to 60% by weight. In addition to the linear condensate represented by the above formula (9), the organosilicate compound (d) may contain a condensate having a branched or cyclic structure. The organosilicate compound (d) is contained in an amount of 20% by mass or less, preferably 1 to 15% by mass with respect to the coating composition.

  The present composition further comprises a siloxane macromonomer (e1), a hydrolyzable silyl group-containing polymerizable unsaturated monomer (e2), a hydroxyl group-containing polymerizable unsaturated monomer (e3), and, if necessary, these and It is desirable to contain an acrylic resin (e) obtained by copolymerization of another polymerizable unsaturated monomer (e4) that can be copolymerized from the viewpoint of crack resistance and adhesion of the formed coating film.

  Examples of the siloxane macromonomer (e1) include one-end or both-end vinyldimethylpolysiloxane, one-end or both-end vinylpolysiloxane in which the methyl group of the side chain is partially substituted with a phenyl group, one-end or both-end (meta ) Acryloyloxypropyldimethylpolysiloxane, and one or both terminal (meth) acryloyloxypropylpolysiloxanes in which the methyl group of the side chain is partially substituted with a phenyl group.

  Examples of the hydrolyzable silyl group-containing polymerizable unsaturated monomer (e2) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and γ- (meth) acryloyloxypropyltrimethoxysilane. Vinyltriacetoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, and the like.

  Examples of the hydroxyl group-containing polymerizable unsaturated monomer (e3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. C2-C8 hydroxyalkyl ester of acrylic acid or methacrylic acid; monoester of polyether polyol such as polyethylene glycol, polypropylene glycol, polybutylene glycol and unsaturated carboxylic acid such as (meth) acrylic acid; Vinyl ether, allyl alcohol, hydroxyalkyl ester of (meth) acrylic acid, (poly) alkylene glycol mono (meth) acrylate, etc. and lactones (for example, ε-caprolactone, γ-vale Adducts with poly (rolactone); monoethers of polyether polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and the like, and hydroxyl-containing unsaturated monomers such as 2-hydroxyethyl (meth) acrylate; α, β-unsaturated carboxylic acids And adducts of monoepoxy compounds such as Cardura E10 (manufactured by Shell Chemical Co., Ltd.) and α-olefin epoxides; glycidyl (meth) acrylate and acetic acid, propionic acid, pt-butylbenzoic acid, fatty acids and the like Adducts with monobasic acids; monoesters or diesters of acid anhydride group-containing unsaturated compounds such as maleic anhydride and itaconic anhydride and glycols such as ethylene glycol, 1,6-hexanediol and neopentyl glycol Compound; hydroxyethyl vinyl Hydroxyalkyl vinyl ethers such as ether, 3-chloro-2-hydroxypropyl (meth) hydroxyl group-containing monomers containing chlorine such as acrylate, allyl alcohol - can be exemplified Le like.

  Examples of the other polymerizable unsaturated monomer (e4) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, and 2-carboxypropyl (meth). Carboxyl group-containing unsaturated monomers such as acrylate and 5-carboxypentyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( Butyl (meth) acrylate (n-, i-, t-), hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, (meth ) Lauryl acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate C1-C18 alkyl ester or cycloalkyl ester of acrylic acid or methacrylic acid; acrylic acid or methacrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate C2-C18 alkoxyalkyl esters of acids; chain alkyl vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, t-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, octyl vinyl ether; cyclopentyl vinyl ether; Cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; Aryl vinyl ethers such as phenyl vinyl ether and trivinyl phenyl ether Aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; Allyl ethers such as allyl glycidyl ether and allyl ethyl ether; Vinyl acetate, vinyl propionate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, isocaproic acid Vinyl esters such as vinyl, vinyl pivalate, vinyl caprate, and beova monomer (manufactured by Shell Chemical Co.); propenyl esters such as isopropenyl acetate and isopropenyl propionate; olefinic compounds such as ethylene, propylene, butylene, and vinyl chloride; Vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) a Relate, nitrogen-containing alkyl (meth) acrylates such as Nt-butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) Acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl ( Polymerizable amides such as (meth) acrylamide; aromatic nitrogen-containing monomers such as 2-vinylpyridine, 1-vinyl-2-pyrrolidone and 4-vinylpyridine; polymerizable nitriles such as acrylonitrile and methacrylonitrile; glycidyl (meth) Acrylate , Polymerizable glycidyl compounds such as allyl glycidyl ether; allyl monomers such as diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, diallyl tetrabromophthalate, pentaerythritol-diallyl ether, allyl glycidyl ether; perfluorobutyl ethyl (meta ) Acrylate, perfluoroisononylethyl (meth) acrylate, perfluoroalkyl (meth) acrylate such as perfluorooctylethyl (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4- Tandiol diacrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, hydroxyisocyanurate tri (meth) acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, glycerol allyloxy di (meth) ) Acrylate, 1,1,1-tris (hydroxymethyl) ethanedi (meth) acrylate, 1,1,1-tris (hydroxymethyl) (Meth) acrylates of polyhydric alcohols such as tritri (meth) acrylate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, diallyl isophthalate, pentaerythritol diallyl ether, divinylbenzene Etc.

  The proportion of the monomers used can be varied over a wide range depending on the desired physical properties, but the siloxane macromonomer (e1) is 1 to 40% by mass, preferably 2 based on the total amount of the monomer mixture. ˜25 mass%, hydrolyzable silyl group-containing polymerizable unsaturated monomer (e2) is 5 to 50 mass%, preferably 10 to 40 mass%, and hydroxyl group-containing polymerizable unsaturated monomer (e3) is 1 to 40 mass%. The range of 10 to 30% by mass and the other polymerizable unsaturated monomer (e4) is preferably 0 to 93% by mass, and preferably 5 to 78% by mass.

The copolymerization of the above monomer mixture is usually carried out in an organic solvent in the presence of about 0.01 to about 8 parts by weight of a polymerization initiator per 100 parts by weight of the total amount of monomers. At a normal pressure or optionally under a pressure of up to about 30 kg / cm ² G.

  The acrylic resin (e) obtained as described above has a number average molecular weight of 1,000 to 100,000, preferably 3,000 to 50,000. The number average molecular weight is HLC8120GPC manufactured by Tosoh Corporation, detector: differential refractometer, column: columns G4000XL, G3000XL, G2500XL, G2000XL manufactured by Tosoh Corporation, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 cc / It is a measured value under the condition of minutes.

  The acrylic resin (e) is desirably contained in an amount of 80% by mass or less, preferably 5 to 70% by mass with respect to the coating composition.

  The composition of the present invention may further comprise a silane coupling agent, a curing catalyst, an RTV rubber, a dehydrating agent, an organic solvent, a color pigment, colloidal silica, a resin particle, a surface conditioner, a viscosity conditioner, an ultraviolet absorber, an optical Additives such as stabilizers, antioxidants, surfactants, film-forming aids, thickeners; crosslinking agents such as isocyanate compounds and melamine resins can be appropriately blended.

  Among these, examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N Amino group-containing silane coupling agents such as β (aminoethyl) γ-aminopropylmethyldimethoxysilane; glycidyl group-containing silane couplings such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane Agent; Mercapto group-containing silane coupling agent such as γ-mercaptopropyltrimethoxysilane; Vinyl group-containing silane coupling agent such as vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane; γ- (meth) Acryloyl Trimethoxysilane, .gamma. (meth) acryloyloxy propyl triethoxysilane, .gamma. (meth) acryloyloxy propyl, such as dimethoxymethyl silane (meth) acryloyl group-containing silane coupling agent.

  The silane coupling agent is desirably contained in an amount of 10% by mass or less, preferably 0.5 to 5% by mass with respect to the coating composition from the viewpoint of graffiti prevention and drying properties.

  The curing catalyst is preferably an organometallic curing catalyst, such as diacetyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, diacetyltin dioctoate, tin octylate, dibutyltin diacetate, dibutyltin. Organotin compounds such as dioctoate; aluminum trimethoxide, aluminum tris (acetylacetonate), aluminum tri-n-butoxide, aluminum tris (acetoacetate ethyl), aluminum diisopropoxy (acetoacetate ethyl), aluminum acetylacetonate, etc. Organic aluminum compounds: titanium tetra (monoethyl ethoxide), titanium tetra (monoethyl ethoxide), titanium tetra (monobutyl ethoxide) Organic titanium compounds such as titanium tetrakis (acetylacetonate) and tetranormal butyl titanate; zirconium tetra (monomethyl ethoxide), zirconium tetra (monoethyl ethoxide), zirconium tetra (monobutyl ethoxide), zirconium normal propyrate, zirconium Organic zirconium compounds such as normal butyrate and zirconium tetrakis (acetylacetonate); Organic zinc compounds such as zinc naphthenate; Organic cobalt compounds such as cobalt octylate and cobalt naphthenate; Trimethyl borate, Triethylborate, Tritriborate Boric acid compounds such as boric acid esters such as propyl, tributyl borate, triphenyl borate, tri (4-chlorophenyl) borate, trihexafluoroisopropyl borate ; And the like, which may be used either alone or in combination.

  The curing catalyst is desirably contained in an amount of 10% by mass or less, preferably 0.5 to 7% by mass with respect to the coating composition, from the viewpoint of crack resistance and drying property of the coating film to be formed.

  As the UV absorber, an organic UV absorber and an inorganic UV absorber can be used. As the organic UV absorber, phenyl salicylate, p-octylphenyl salicylate, 4-t-butylphenyl salicylate can be used. Salicylic acid derivatives such as silicate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. Benzophenone series; benzotriazole series such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and other (hydroxyphenyltriazine series, oxalic anilide, cyanoacrylate, etc.) compounds, etc. For example, inorganic UV absorbers Fine titanium oxide particles, zinc oxide particles, fine particles of iron oxide and the like. Examples of the light stabilizer include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl). -5-chlorobenzotriazole, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy- 2,2,6,6-tetramethylpiperidine polycondensate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, bis- (2,2 ', 6 , 6'-Tetramethyl-4 Piperidinyl) Sebate - DOO, 4-benzoyloxy -2,2', 6,6'-tetramethyl piperidine, and the like.

  The said ultraviolet absorber and / or light stabilizer may be used independently, can also be selected suitably and can be used in combination.

  In the present invention, the graffiti-preventing coating film can be formed by applying the coating composition obtained as described above to the surface to be coated.

  The coating method of the coating composition can be applied using a coating means known per se, for example, using a roller, air spray, airless spray, lysine gun, universal gun, brush, iron, etc. . The coating amount is usually adjusted to be 1 to 100 μm, preferably 5 to 70 μm in terms of dry film thickness.

  The formed coating film can be dried by any of heat drying, forced drying, or room temperature drying depending on the type of paint used.

  Examples of the coated surface include various substrate surfaces and coated surfaces on which a coating film is formed. Examples of the substrate include metals such as iron, zinc, iron / zinc alloys, and aluminum; Inorganic base materials such as concrete, gypsum board, slate, siding material, porcelain tile wall surface, lightweight cellular concrete, mortar, brick, stone, and glass; plastic; leather; fiber and the like.

  In particular, when the surface to be coated is a concrete surface, it is desirable to apply the permeable water absorption inhibitor thereon and then apply the graffiti preventing coating composition of the present invention. In that case, it is desirable to apply the permeable water absorption inhibitor after drying the concrete surface so that the water content is 10% or less.

The permeable water absorption inhibitor is applied for the purpose of lowering the water permeability from the base material to the upper layer coating film, and any conventionally known one can be used without particular limitation. For example, the aforementioned organopolysiloxane (a ), An aqueous or organic solvent-type composition containing the alkylalkoxysilane represented by the formulas (1) to (3) and / or an oligomer thereof may be mentioned. The coating method can be performed using a coating means known per se, for example, using a roller, an air spray, an airless spray, a ricin gun, a universal gun, a brush, and the like. Its coating weight may be administered once per 30 to 200 g / ^{m 2,} it is desirable that preferably is adjusted to 50 to 150 g / ^{m 2.}

  Further, in the present invention, it is desirable to apply the graffiti-preventing coating composition after applying a water-based urethane resin-based paint or a water-based fluororesin-based paint to the surface to be coated.

  In this way, before applying the graffiti-preventing paint composition, by providing a coating film with water-based urethane paint or water-based fluororesin-based paint as a binder coat, in addition to imparting graffiti prevention properties, the aesthetics of the coated surface can be extended over a long period of time. Can be maintained across.

  For example, when the coated surface is a concrete surface, the so-called wet color phenomenon, in which the concrete surface is darkened by the application of the anti-graffiti paint composition of the present invention or other solvent-based paints, is suppressed by providing the binder coat as described above. There is an effect to.

  In addition, when the coated surface is a coated surface with a base material coated with a weak solvent-based paint, the above-mentioned binder coat is provided under the paint film with a graffiti-preventing paint to improve the solvent resistance. It has the effect of preventing coating defects such as chijimi and lifting caused by graffiti using lacquer sprays, etc., on coating films with low weak solvent paints.

  The painted surface with the above-mentioned weak solvent-based paint is, for example, a painted surface coated with a conventionally known weak solvent-based resin paint such as a weak solvent-based fluorine resin paint, a weak solvent-based acrylic silicon resin paint, or a weak solvent-based polyurethane resin paint. Can be.

  Here, the weak solvent generally means a solvent having a weak dissolving power and is not strictly distinguished, but has a boiling point selected from an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent. An example of the hydrocarbon solvent is 148 ° C. or higher.

  Specific examples thereof include mineral spirit, white spirit, mineral terpene, isoparaffin, solvent kerosene, aromatic naphtha, VM & P naphtha, and solvent naphtha. Examples of these commercially available products include “Solvesso 100”, “Solvesso 150”, “Solvesso 200”, “Essonaphtha No. 6” (manufactured by Esso Petroleum Corporation); “Swazol 1000”, “Swazol 1500” (and above, "Ipsol 100" (manufactured by Idemitsu Kosan Co., Ltd.); "HAWS", "LAWS" (manufactured by Shell Chemicals Japan Co., Ltd.); "A Solvent" (manufactured by Nippon Oil Co., Ltd.), etc. Can be mentioned.

  The water-based urethane resin-based paint used as the binder coat is not particularly limited as long as it contains a urethane component, and a conventionally known one such as an aqueous one-component urethane resin-based paint or aqueous two-component urethane resin-based paint is used. However, the use of an aqueous two-component urethane paint is suitable from the viewpoints of wet color suppression and solvent resistance. As the fluororesin-based paint, any conventionally known ones such as an aqueous one-part fluororesin-based paint and an aqueous two-part fluororesin-based paint can be used without particular limitation as long as the fluororesin component is included. The use of an aqueous two-component fluororesin-based paint is suitable from the viewpoints of wet color suppression and solvent resistance.

  The coating method can be performed using a coating means known per se, for example, using a roller, air spray, airless spray, brush, or the like. The coating amount is usually adjusted to be 15 to 100 μm, preferably 20 to 50 μm in terms of dry film thickness.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited only to these examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

Production Example 1 of Organopolysiloxane Containing Si-C Bond and Hydrolyzable Silyl Group
To a three-necked flask, 80 parts of methyltrimethoxysilane and 20 parts of dimethyldimethoxysilane were added, and 10 parts of 0.05N aqueous hydrochloric acid was added dropwise with stirring, followed by hydrolysis and condensation at 68 ° C. for 1 hour. This was heated to 120 ° C. to remove by-product methanol and filtered to obtain organopolysiloxane (A-1) containing a hydrolyzable silyl group.

Production Example 2
To a three-necked flask, 50 parts of methyltrimethoxysilane, 20 parts of dimethyldimethoxysilane and 30 parts of phenyltrimethoxysilane were added, and 10 parts of 0.05N hydrochloric acid was added dropwise with stirring, followed by hydrolysis and condensation at 68 ° C. for 1 hour. This was heated to 120 ° C. to remove by-product methanol and filtered to obtain organopolysiloxane (A-2) containing a hydrolyzable silyl group.

Production Example 3
To a three-necked flask, 85 parts of methyltrimethoxysilane and 15 parts of vinylmethyldimethoxysilane were added, and 15 parts of 0.05N aqueous hydrochloric acid was added dropwise with stirring, followed by hydrolysis and condensation at 68 ° C. for 2 hours. This was heated to 120 ° C. to remove byproduct methanol, and filtered to obtain organopolysiloxane (a).

  In another three-necked flask, 250 parts of organopolysiloxane (a), 125 parts of dimethylsiloxane oil having both ends Si—H groups (Note 1) as a component having a linear dimethylsiloxane skeleton, “CAT-PL-50T” (Note 2) 1.5 parts are added, hydrosilylation reaction is performed at 80 ° C. for 8 hours, this is subjected to reduced pressure treatment at 120 ° C. and 10 mmHg for 2 hours, filtered, and an organopolysiloxane skeleton having a three-dimensional structure and An organopolysiloxane (A-3) containing a linear dimethylpolysiloxane skeleton in the molecule and containing a hydrolyzable silyl group was obtained.

(Note 1) Dimethylsiloxane oil: H- [Me ₂ SiO] ₁₉ -Me ₂ Si-H as a main component.

  (Note 2) “CAT-PL-50T”: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., Pt-based catalyst.

Production and production example 4 of acrylic resin (B) having hydrolyzable silyl group, hydroxyl group and polysiloxane chain
A 4-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping device was charged with 81.8 parts of n-butyl acetate, heated under stirring, and maintained at 95 ° C. Next, at a temperature of 95 ° C., 20 parts of “Silaplane FM-0721” (Note 3), 30 parts of γ-methacryloyloxypropyltrimethoxysilane, 10 parts of 2-hydroxyethyl methacrylate, 40 parts of i-butyl methacrylate and polymerization A mixture comprising 4.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) as an initiator was added dropwise over 3 hours. After dropping, the mixture was aged at 95 ° C. for 2 hours to obtain an acrylic resin (B) having a hydrolyzable silyl group, a hydroxyl group and a polysiloxane chain having a solid content concentration of 55% and a number average molecular weight of 10,000.

  (Note 3) “Silaplane FM-0721”: trade name, manufactured by Chisso Corporation, methacryl group-containing siloxane macromonomer.

Production Examples 1 to 14 and Comparative Examples 1 and 2 of Graffiti Prevention Paint
Graffiti prevention paints (R-1) to (R-16) were produced by blending each component with the blending composition shown in Table 1 and stirring and mixing. In Table 1, (Note 4) to (Note 11) are as follows.

(Note 4) “Metashine 2015PSW1”: trade name, manufactured by Nippon Sheet Glass Co., Ltd., metal-plated glass flake pigment (Note 5) “Metashine 1020RS”: trade name, manufactured by Nippon Sheet Glass Co., Ltd., titanium oxide-coated glass flake pigment (Note 6) ) “Ethyl silicate 40”: trade name, manufactured by Colcoat, tetraethoxysilane condensate, average condensation degree 6, containing 40% by mass as SiO ₂ .
(Note 7) “Duranate TPA-90EK”: trade name, manufactured by Asahi Kasei Co., Ltd., isocyanurate of hexamethylene diisocyanate, non-volatile content 90%, isocyanate group content 21%
(Note 8) “TINUVIN 123”: trade name, manufactured by Ciba Specialty Chemicals, hindered amine light stabilizer (Note 9) “TINUVIN 405”: trade name, manufactured by Ciba Specialty Chemicals, hydroxyphenyl triazine UV absorber (Note 10) “MT-100SAS”: trade name, manufactured by Teika, fine particle titanium oxide (Note 11) “MZ-505S”: trade name, manufactured by Teika, fine particle zinc oxide.

Preparation of test coated plates Examples 15 to 28 and Comparative Examples 3 and 4
On a 150 x 70 x 0.8 mm chromate-treated aluminum plate, a two-component weak solvent-based fluororesin-based paint ("Serect F Mild"; trade name, manufactured by Kansai Paint Co., Ltd.) is used, and the dry film thickness is about 25 μm. The plate to be coated was dried for 24 hours under conditions of an air temperature of 23 ° C. and a relative humidity of 60%. On this, as shown in Table 2, the graffiti prevention paints (R-1) to (R-16) obtained in Examples 1 to 14 and Comparative Examples 1 and 2 are about 15 μm in dry film thickness using an applicator. The test piece was further coated for 14 days under conditions of an air temperature of 23 ° C. and a relative humidity of 60%, and subjected to the performance test described below. The evaluation test results are shown in Table 2.

Examples 29 to 42 and Comparative Examples 5 and 6
“EXERA 100” (manufactured by Kansai Paint Co., Ltd., penetrating water absorption inhibitor) was applied to a concrete plate of 150 × 70 × 10 mm with a brush so as to be 100 g / m ² , the temperature was 23 ° C., and the relative humidity was 60%. A plate to be coated was dried for 24 hours under the above conditions. As shown in Table 3, the graffiti-preventing paints (R-1) to (R-16) obtained in Examples 1 to 14 and Comparative Examples 1 and 2 are about 15 μm in dry film thickness using an applicator. The test piece was further coated for 14 days under conditions of an air temperature of 23 ° C. and a relative humidity of 60%, and subjected to the performance test described below. The evaluation test results are shown in Table 3.

Examples 43 to 55 and Comparative Examples 7 and 8
An aqueous two-component urethane paint (“Libermeister: (trade name, manufactured by Kansai Paint Co., Ltd.)) was applied to a 150 × 70 × 10 mm concrete plate with (applicator) so that the dry film thickness was 30 μm, and the temperature was 23 What was dried for 24 hours under the conditions of 60 ° C. and relative humidity was used as a coated plate, and as shown in Table 4, the graffiti-preventing paints obtained in Examples 1-14 and Comparative Examples 1-2 ( R-1) to (R-16) were coated with an applicator to a dry film thickness of about 15 μm, and further dried for 14 days under conditions of an air temperature of 23 ° C. and a relative humidity of 60% as test specimens. The results of the evaluation test are shown in Table 4.

Examples 56-63
On a 150 x 70 x 0.8 mm chromate-treated aluminum plate, a two-component weak solvent type fluororesin paint ("Seractect F Mild": trade name, manufactured by Kansai Paint Co., Ltd.) is used, and the dry film thickness is about 25 μm. And dried for 24 hours under conditions of an air temperature of 23 ° C. and a relative humidity of 60%, and further, an aqueous two-component urethane resin-based paint (“Libermeister”: trade name, manufactured by Kansai Paint Co., Ltd.) , Hydroxyl group-containing resin / polyisocyanate curing agent), aqueous one-component urethane resin-based paint (“Aqualetane”: trade name, manufactured by Kansai Paint Co., Ltd.), aqueous two-component fluororesin-based paint (fluorinated resin emulsion (“Lumiflon emulsion”): The product name, manufactured by Asahi Glass Co., Ltd.) and the polyisocyanate curing agent (“Bayhydr”: product name, manufactured by Bayer) are mixed immediately before use. Paint), aqueous one-component fluororesin-based paint (“Aqua Fluoro II”, trade name, manufactured by Kansai Paint Co., Ltd.) with an applicator so that the dry film thickness is 30 μm, and the temperature is 23 ° C. and the relative humidity is 60%. A plate to be coated was dried for 24 hours under the conditions. On this, as shown in Table 5, each graffiti prevention paint (R-4) to (R-5) obtained in Examples 4 and 5 was applied using an applicator so as to have a dry film thickness of about 15 μm. What was dried for 1 day under the conditions of an air temperature of 23 ° C. and a relative humidity of 60% was used as a test body, and subjected to a performance test described later. The evaluation test results are shown in Table 5.

Performance evaluation test (* 1) Graffiti prevention: A black lacquer spray (“acrylic lacquer spray”, manufactured by Campehapio Co., Ltd.) was scribbled on the coated surface of each specimen, and the degree of repellency was visually evaluated.
◎: It repels very well and it is impossible to identify what was written.
○: Repels, but can slightly identify graffiti.
Δ: Slightly recognizable, but the graffiti can be clearly identified.
X: Not repelled at all, and the graffiti can be clearly identified.

(* 2) Graffiti removability A black lacquer spray (“Acrylic Lacquer Spray”, manufactured by Campehapio Co., Ltd.) is scribbled on the coating surface of each specimen and dried for 24 hours under conditions of an air temperature of 23 ° C. and a relative humidity of 60%. Then, the state when wiped off with a solvent (a mixed solvent of toluene / ethyl acetate = 1/1) was visually evaluated.
◎: No trace of graffiti left,
○: Traces of graffiti remain slightly,
Δ: Traces of graffiti remain,
X: Graffiti cannot be removed at all.

(* 3) Crack resistance According to JIS K 5600-7-4 (wet and cold repeatability), immersed in water at 23 ° C for 18 hours, then subjected to a test at -20 ° C for 3 hours, and further at 50 ° C for 3 hours. did. This cycle was repeated for 10 cycles, and the state of the coating film after the test was visually evaluated.
○: crack is not recognized,
Δ: cracks are observed in a part of the coating film,
X: A remarkable crack is recognized by the coating film.

(* 4) Sustainability According to the accelerated weather resistance test of JIS K 5600-7-7 (xenon lamp method), after irradiation for 1000 hours, the above (* 1) graffiti prevention property was evaluated.
◎: It repels very well and it is impossible to identify what was written.
○: Repels, but can slightly identify graffiti.
Δ: Slightly recognizable, but the graffiti can be clearly identified.
X: Not repelled at all, and the graffiti can be clearly identified.

(* 5) Adhesiveness According to JIS K 5600-5-6 (cross-cut method), 25 squares (vertical 5 divisions × horizontal 5 divisions) having a size of 2 mm × 2 mm were prepared on each specimen. The cellophane adhesive tape was affixed to this, and it peeled off instantaneously and evaluated by measuring the peeling area of a coating film.
A: The area of peeling of the coating film is less than 5% of the total area,
○: The area of the peeling film is 5% or more and less than 15% of the total area,
(Triangle | delta): The area of peeling of a coating film is 15% or more of the whole area, and less than 35%,
X: The area of peeling of the coating film is 35% or more of the total area.
(* 6) Solvent resistance 2 ml of lacquer thinner was dropped on the coating film of each specimen using a dropper, and the coating film state of each specimen after drying the lacquer thinner was evaluated.
○: No abnormality in the coating film
Δ: Slight Chijimi is observed in the coating film,
X: Chijimi occurs in the coating film (lifting).

Claims (13)

An organopolysiloxane (a) containing a Si-C bond and a hydrolyzable silyl group, an organopolysiloxane (b) containing no hydrolyzable silyl group, and a glass flake pigment (c), and containing component (a) And component (b) is used in a range of 50 to 99.9% by mass of component (a) and 0.1 to 50% by mass of component (b) based on the total mass of both, The graffiti-preventing paint composition, wherein the content of c) is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass in total of component (a) and component (b). The graffiti prevention coating composition according to claim 1, wherein the organopolysiloxane (a) containing a Si-C bond and a hydrolyzable silyl group contains an organopolysiloxane (a1) containing a benzene ring structure. The organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group contains an organopolysiloxane skeleton having a three-dimensional structure and a linear organopolysiloxane skeleton in the molecule (a2). The graffiti prevention coating composition of Claim 1 or 2 containing). 4. The graffiti-preventing paint composition according to claim 1, wherein the glass flake pigment (c) is a glass flake pigment coated with a metal oxide or a glass flake pigment plated with a metal. The graffiti prevention coating composition according to any one of claims 1 to 4, further comprising an organosilicate compound (d). Siloxane macromonomer (e1), hydrolyzable silyl group-containing polymerizable unsaturated monomer (e2), hydroxyl group-containing polymerizable unsaturated monomer (e3), and other polymerizable unsaturated monomers copolymerizable therewith if necessary ( The anti-graffiti coating composition according to any one of claims 1 to 5, further comprising an acrylic resin (e) obtained by copolymerization of e4). The graffiti prevention coating composition according to any one of claims 1 to 6, further comprising a silane coupling agent. The graffiti prevention coating composition according to any one of claims 1 to 7, further comprising an organometallic curing catalyst. A coating method comprising applying the graffiti preventing coating composition according to any one of claims 1 to 8 to a surface to be coated. A coating method, comprising: applying a permeable water absorption inhibitor to a concrete surface, and then applying the graffiti preventing coating composition according to any one of claims 1 to 8. A coating method comprising applying a water-based urethane resin-based paint or a water-based fluororesin-based paint to a surface to be coated, and then applying the graffiti-preventing paint composition according to any one of claims 1 to 8. The coating method according to claim 11, wherein the water-based urethane resin-based paint and the water-based fluororesin-based paint are a water-based two-component urethane resin-based paint and a water-based two-component fluororesin-based paint, respectively. The coating method according to claim 11 or 12, wherein the surface to be coated is a painted surface in which a coating film made of a weak solvent-based paint is provided on a substrate.