JP2009155500A - Antifouling paint composition and antiadhesive body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifouling paint composition capable of forming a film excellent in antifouling property and excellent also in adhesion to a substrate, and to provide an antiadhesive body sufficiently protected from grease. <P>SOLUTION: The antifouling paint composition includes a fluororesin prepared by copolymerizing a fluoroolefin and a hydroxyl group-containing vinyl monomer, a silicone-modified acrylic resin prepared by copolymerizing a silane compound and a hydroxyl group-containing acrylic monomer, and an organic solvent. In the composition, the silicone-modified acrylic resin is 11-20 pts.mass and the organic solvent is 100-300 pts.mass, respectively, based on 100 pts.mass of the fluororesin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antifouling coating composition and an adhesion preventing body.

  A coating composition for imparting antifouling properties to a substrate such as a metal plate, film or wood is known. As such a coating composition, one containing a fluorine-based resin is generally known.

For example, a coating composition containing a fluorinated copolymer having a predetermined structure and a curing agent (see, for example, Patent Document 1), and an antifouling property obtained by dissolving a fluorinated copolymer having a predetermined structure in an organic solvent. Composition for fluorine resin coating (for example, see Patent Document 2 or 3), antifouling agent having thermally dissociable fluorine-containing protecting group, resin for coating containing crosslinkable functional group, curing agent and / or curing catalyst, A coating composition comprising an antifouling adhesive having a hydrophilic polyether group having a terminal fluoroalkylation (see, for example, Patent Document 4) ), A resin composition for thermally crosslinkable paints containing a fluorine-containing monomer (see, for example, Patent Document 6), a functional group-containing synthetic resin, and a functional group-containing liquid polydialkylsiloxane or functional group-containing liquid fluoropolymer. Coating composition comprising an antifouling component, an ether (e.g., Patent Document 7 refer), and the like.
JP-A-5-17535 JP-A-6-264020 JP-A-6-248222 JP-A-8-337771 JP-A-9-302328 JP-A-10-195373 International Publication No. 2004/066658 Pamphlet

However, although the coating compositions described in Patent Documents 1 to 7 show a temporary effect on water repellency and antifouling properties, they cannot be said to have sufficient antifouling properties particularly against fat stains.
For this reason, it is necessary to wash | clean regularly the adhesion prevention body to which the said coating composition was provided.

  Further, the functional group-containing liquid polydialkylsiloxane in the coating composition described in Patent Document 7 has insufficient adhesion to the substrate because the main chain is a silane chain. That is, when applied to a predetermined substrate to form a film, the film itself becomes strong, but the adhesion to the substrate is poor.

  The present invention has been made in view of the above circumstances, and an antifouling coating composition capable of forming a film having excellent antifouling properties and excellent adhesion to a substrate, and fat stains are sufficiently suppressed. It aims at providing an adhesion prevention body.

  The inventors of the present invention have intensively studied to solve the above problems, and surprisingly, the above problems can be solved by using a fluorine-based resin having a predetermined structure and a silicone-modified acrylic resin having a predetermined structure. As a result, the present invention has been completed.

  That is, the present invention includes (1) a fluorine-based resin copolymerized with a fluoroolefin and a hydroxyl group-containing vinyl monomer, a silicone-modified acrylic resin copolymerized with a silane compound and a hydroxyl group-containing acrylic monomer, and an organic solvent. The antifouling paint composition contains 11 to 20 parts by mass of the silicone-modified acrylic resin and 100 to 300 parts by mass of the organic solvent with respect to 100 parts by mass of the fluororesin.

  In the present invention, (2) the fluoroolefin is tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 3,3,3-trifluoropropylene, pentafluoropropylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride and The antifouling paint composition according to the above (1), which is at least one selected from the group consisting of perfluoroalkyl vinyl ethers.

  In the present invention, (3) hydroxyl group-containing vinyl monomer is hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxycarboxylic acid vinyl ester, hydroxycarboxylic acid allyl ester, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, N-hydroxyalkyl acrylamide, and The antifouling paint composition according to the above (1), which is at least one selected from the group consisting of N-hydroxyalkylmethacrylamide.

  In the present invention, (4) the silane compound is tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxy. Silane, diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p- Styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypro Rumethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyl Trimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl- Butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3- Chloropropyltrimethoxysilane The above (1), which is at least one selected from the group consisting of 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and 3-isocyanatopropyltriethoxysilane. The antifouling coating composition.

  In the present invention, (5) hydroxyl group-containing acrylic monomer is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, The antifouling paint composition according to the above (1), which is at least one selected from the group consisting of 2-hydroxy-3-phenoxypropyl acrylate and 2-hydroxy-3-phenoxypropyl methacrylate.

  The present invention resides in (6) the antifouling coating composition according to the above (1), wherein the molecular weight of the fluororesin is from 5,000 to 15,000.

  The present invention provides (7) the antifouling agent according to the above (1), in which the fluorine-based resin and the silicone-modified acrylic resin are bonded to the crosslinking agent at the hydroxyl group of each other and cured by adding the crosslinking agent. Present in a paint composition.

  The present invention is the above (7), wherein (8) the crosslinking agent is an isocyanate crosslinking agent, and the fluorine-based resin and the silicone-modified acrylic resin are bonded to the isocyanate crosslinking agent at each hydroxyl group to form a urethane bond. It exists in the coating composition for antifouling of description.

  The present invention provides (9) an antifouling coating composition according to any one of the above (1) to (6) and an isocyanate-based cross-linking agent on the surface of a substrate and cured to thereby prevent the antifouling. It exists in the adhesion prevention body in which the film | membrane which has dirtiness is formed.

  In addition, as long as the objective of this invention is met, the structure which combined said (1)-(9) suitably is also employable.

The antifouling coating composition of the present invention comprises a fluororesin copolymerized with a fluoroolefin and a hydroxyl group-containing vinyl monomer, a silicone-modified acrylic resin copolymerized with a silane compound and a hydroxyl group-containing acrylic monomer, and an organic A solvent, and with respect to 100 parts by mass of the fluororesin, by setting the silicone-modified acrylic resin to 11 to 20 parts by mass and the organic solvent to 100 to 300 parts by mass, it is possible to prevent adhesion of dust to the substrate. The grease stain on the substrate can be sufficiently suppressed. Therefore, regular cleaning becomes unnecessary.
Further, it is possible to form a film having excellent adhesion to the substrate and excellent light resistance of the film itself.

  Here, the reason why the antifouling coating composition is excellent in antifouling properties and adhesiveness is not clear, but by using a fluororesin having a predetermined structure, water repellency and antifouling properties are improved, It is considered that the adhesiveness to the substrate is improved by using a silicone-modified acrylic resin having a predetermined structure excellent in compatibility with the fluorine-based resin. However, the factor is not limited to this.

In the antifouling coating composition of the present invention, when the fluoroolefin is the above compound, the antifouling property against dust adhesion is particularly improved.
Further, when the hydroxyl group-containing vinyl monomer is the above compound, a fluorine resin having a hydroxyl group can be easily obtained.
Furthermore, when the silane compound is the above compound, the water repellency and antifouling property against oil stains are particularly improved.
Furthermore, when the hydroxyl group-containing acrylic monomer is the above compound, a silicone-modified acrylic resin having a hydroxyl group can be easily obtained.

In the antifouling coating composition, the molecular weight of the fluororesin is preferably 5000 to 15000.
In this case, the fluorine-based resin is easily dissolved in the organic solvent. Therefore, it becomes easy to apply the antifouling coating composition to the substrate.
In addition, when the antifouling coating composition is applied to a substrate to form a film, fat contamination of the substrate can be reliably suppressed, and the adhesion of the film to the substrate is further improved.

In the antifouling paint composition, by adding a crosslinking agent, the fluorine-based resin and the silicone-modified acrylic resin are bonded to the crosslinking agent at the hydroxyl group of each other and cured, The antifouling coating composition that does not contain has excellent storability because its own curing is suppressed.
If a crosslinking agent is added, a film having excellent strength can be formed as necessary.
In addition, since a urethane bond is formed when a crosslinking agent is an isocyanate type crosslinking agent, a flexible and strong film | membrane can be formed.

Since the antifouling body of the present invention is provided with the antifouling coating composition and the isocyanate-based cross-linking agent on the surface of the substrate and cured, a film having antifouling properties is formed. Can be prevented, and oil stains can be sufficiently suppressed. Therefore, regular cleaning becomes unnecessary.
In addition, the adhesion between the film of the adhesion preventing body and the substrate is excellent, and the light resistance of the film itself is also excellent.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In addition, the overlapping description is abbreviate | omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. Furthermore, “(meth) acryl” in the present specification means “acryl” and “methacryl” corresponding thereto, and “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. means.

  The antifouling coating composition according to the present embodiment comprises a fluororesin copolymerized with a fluoroolefin and a hydroxyl group-containing vinyl monomer, a silicone-modified acrylic resin copolymerized with a silane compound and a hydroxyl group-containing acrylic monomer, And an organic solvent.

According to the antifouling coating composition according to the present embodiment, it is possible to prevent dust from adhering to the substrate and to sufficiently suppress fat stains on the substrate. Therefore, regular cleaning becomes unnecessary.
Further, it is possible to form a film having excellent adhesion to the substrate and excellent light resistance of the film itself.

Here, the blending ratio of the fluororesin, the silicone-modified acrylic resin, and the organic solvent is such that the silicone-modified acrylic resin is 11 to 20 parts by mass and the organic solvent is 100 to 300 parts by mass with respect to 100 parts by mass of the fluororesin. Part.
Moreover, it is preferable that 11-15 mass parts of silicone modified acrylic resins and 150-250 mass parts of organic solvents are contained with respect to 100 mass parts of fluororesin.

In this case, the fluorine-based resin and the silicone-modified acrylic resin are easily dissolved uniformly in the organic solvent.
Therefore, it becomes easy to apply the antifouling coating composition to the substrate, and when applied to the substrate to form a film, the soiling of the substrate can be reliably suppressed, and the adhesion of the film to the substrate will be more excellent. .

  In addition, when the blending ratio of the silicone-modified acrylic resin is less than 11 parts by mass, the antifouling property against oily dirt becomes insufficient, and when it exceeds 20 parts by mass, the antifouling property against dust becomes insufficient.

Next, the fluorine resin will be described.
In the antifouling coating composition according to the present embodiment, a fluororesin having a predetermined structure is used in order to improve water repellency and antifouling properties.

  Such a fluororesin has a structure in which a fluoroolefin and a hydroxyl group-containing vinyl monomer are copolymerized. The polymerization method of the fluoroolefin and the hydroxyl group-containing vinyl monomer is not particularly limited, such as radical polymerization, cation polymerization, anion polymerization and the like.

The fluoroolefin is composed of tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 3,3,3-trifluoropropylene, pentafluoropropylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, and perfluoroalkyl vinyl ether. It is preferably at least one selected from the group.
In this case, the antifouling property against dust adhesion is particularly improved.

On the other hand, the hydroxyl group-containing vinyl monomer is selected from the group consisting of hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxycarboxylic acid vinyl ester, hydroxycarboxylic acid allyl ester, hydroxyalkyl (meth) acrylate, and N-hydroxyalkyl (meth) acrylamide. It is preferable that at least one selected.
In this case, a fluororesin having a hydroxyl group can be easily obtained.

  Examples of the hydroxyalkyl vinyl ether include hydroxyalkyl vinyl ethers having 4 to 10 carbon atoms. Specifically, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, hydroxybutyl vinyl ether, Hydroxyisobutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 2- (4-hydroxycyclohexylethyl) vinyl ether, 2,3-dihydroxypropyl vinyl ether, etc. .

  Examples of the hydroxyalkyl allyl ether include hydroxyalkyl allyl ether having 5 to 11 carbon atoms, specifically, hydroxyethyl allyl ether, hydroxypropyl allyl ether, hydroxybutyl allyl ether, hydroxyisobutyl allyl ether, hydroxyhexyl allyl ether. 4-hydroxycyclohexyl allyl ether, 2- (4-hydroxycyclohexylethyl) allyl ether, 2,3-dihydroxypropyl allyl ether, and the like.

  Examples of the hydroxycarboxylic acid vinyl ester include a hydroxycarboxylic acid vinyl ester having 4 to 10 carbon atoms, and specifically, a hydroxyvinyl acetate, a hydroxypropanoate, a hydroxybutanoate, a hydroxyhexanoate, 4-hydroxy Examples include cyclohexyl vinyl acetate.

  Examples of the hydroxycarboxylic acid allyl ester include hydroxycarboxylic acid allyl esters having 5 to 11 carbon atoms, specifically, allyl hydroxyacetate, allyl hydroxypropanoate, allyl hydroxybutanoate, allyl hydroxyhexanoate, 4-hydroxy Examples include cyclohexyl allyl acetate.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxyalkyl (meth) acrylates having 5 to 8 carbon atoms. Specifically, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate Etc.

  Examples of N-hydroxyalkyl (meth) acrylamide include hydroxyalkyl (meth) acrylamide having 5 to 8 carbon atoms, specifically, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide etc. are mentioned.

  In the copolymerization of the fluoroolefin and the hydroxyl group-containing vinyl monomer, another monomer may be mixed and copolymerized.

  Examples of the other monomer include alkyl vinyl ether, alkyl allyl ether, carboxylic acid vinyl ester, carboxylic acid allyl ester, α-olefin, alkyl (meth) acrylate, N-alkyl (meth) acrylamide and the like. In addition, these may be used individually by 1 type and may be used in mixture of 2 or more types.

  Examples of the alkyl vinyl ether include alkyl vinyl ethers having 4 to 10 carbon atoms. Specific examples include ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, hexyl vinyl ether, cyclohexyl vinyl ether, cyclohexyl ethyl vinyl ether, and 2-ethylhexyl vinyl ether. Can be mentioned.

  Examples of the alkyl allyl ether include alkyl allyl ethers having 5 to 11 carbon atoms, and specifically include ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, hexyl allyl ether, cyclohexyl allyl ether, cyclohexyl ethyl. Examples include allyl ether and 2-ethylhexyl allyl ether.

  Examples of the carboxylic acid vinyl ester include carboxylic acid vinyl esters having 4 to 10 carbon atoms, and specific examples include vinyl acetate, vinyl propanoate, vinyl butanoate, vinyl hexanoate, and cyclohexyl vinyl acetate.

  Examples of the carboxylic acid allyl ester include carboxylic acid allyl esters having 5 to 11 carbon atoms, and specific examples include allyl acetate, allyl propanoate, allyl butanoate, allyl hexanoate, allyl cyclohexyl acetate, and the like.

  Examples of the α-olefin include α-olefins having 2 to 8 carbon atoms, and specific examples include ethylene, propylene, butylene, isobutylene, 1-hexene, and styrene.

  Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having 5 to 8 carbon atoms, and specifically, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexylmethyl (meth) ) Acrylate and the like.

  Examples of N-alkyl (meth) acrylamides include alkyl (meth) acrylamides having 5 to 8 carbon atoms. Specifically, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl ( And (meth) acrylamide.

The blending ratio of the fluoroolefin is preferably adjusted to be 40 to 80 mol%, and more preferably adjusted to 45 to 70 mol% with respect to the entire fluororesin.
On the other hand, the blending ratio of the hydroxyl group-containing vinyl monomer is preferably adjusted to be 20 to 60 mol%, more preferably 30 to 55 mol% with respect to the entire fluororesin. preferable.
In addition, when other monomers are included, the blending ratio of the other monomers is preferably adjusted to be 30 to 70 mol% with respect to the whole fluororesin, and is 40 to 60 mol%. It is more preferable to adjust so that it may become.

The hydroxyl value (mgKOH / g) of the fluororesin is preferably 50 to 120.
In this case, the antifouling property against dust adhesion is further improved. The hydroxyl value is a value measured using xylene as a solvent in accordance with JIS K0070-1992.

The fluorine-based resin preferably has a molecular weight of 5,000 to 15,000.
In this case, the fluorine-based resin is easily dissolved in the organic solvent. Therefore, it becomes easy to apply the antifouling coating composition to the substrate.
In addition, when the antifouling coating composition is applied to a substrate to form a film, fat contamination of the substrate can be reliably suppressed, and the adhesion of the film to the substrate is further improved.

Next, the silicone-modified acrylic resin will be described.
In the antifouling coating composition according to the present embodiment, a silicone-modified acrylic resin that is excellent in compatibility with a fluorine-based resin is used in order to improve the adhesion to the substrate.

  Further, since the silicone-modified acrylic resin has a hydroxyl group (hydroxy group) as will be described later, the fluorine-based resin and the silicone-modified acrylic resin are bonded by adding a crosslinking agent described later. Thereby, the formed film becomes stronger.

  The silicone-modified acrylic resin is obtained by polymerizing an acrylic monomer and a silane compound by a known method. In addition, the polymerization method of an acryl-type monomer and a silane compound is not specifically limited, such as radical polymerization, cationic polymerization, anionic polymerization.

The acrylic monomer is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate. It is preferable that it is at least one.
In this case, a silicone-modified acrylic resin having a hydroxyl group can be easily obtained.

The above silane compounds are tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane. , Hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldi Toxisilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxy Silane, 3-merca It is preferably at least one selected from the group consisting of ptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and 3-isocyanatopropyltriethoxysilane.
In this case, the water repellency and antifouling property against oil stains are particularly improved.

In addition, also in the said silicone modified acrylic resin, you may mix and copolymerize the other monomer mentioned above.
Such other monomer is synonymous with the other monomer in the fluororesin described above.

60-240 are preferable and, as for the hydroxyl value (mgKOH / g) of a silicone modified acrylic resin, 100-180 are more preferable.
In this case, the strength of the film is further improved. The hydroxyl value is a value measured using xylene as a solvent in accordance with JIS K0070-1992.

The silicone-modified acrylic resin preferably has a molecular weight of 5,000 to 20,000.
In this case, the silicone-modified acrylic resin is easily dissolved in the organic solvent. Therefore, it becomes easy to apply the antifouling coating composition to the substrate.
In addition, when the antifouling coating composition is applied to a substrate to form a film, fat contamination of the substrate can be reliably suppressed, and the adhesion of the film to the substrate is further improved.

Next, the organic solvent will be described.
Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, esters, ethers, ketones, amides, sulfonate esters, acetates, and the like. In addition, these may be used individually by 1 type and may be used in mixture of 2 or more types.

  Examples of the aliphatic hydrocarbons include hexane and cyclohexane.

  Examples of aromatic hydrocarbons include benzene, toluene, xylene, and the like.

Examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, octanol, nonanol, benzyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol (degree of polymerization _{3 to} 100), CF ₃ CH _2. OH, F (CF ₂ ) ₂ CH ₂ OH, (CF ₃ ) ₂ CHOH, F (CF ₂ ) ₃ CH ₂ OH, F (CF ₂ ) ₄ C ₂ H ₅ OH, H (CF ₂ ) ₂ CH ₂ OH , H (CF ₂ ) ₃ CH ₂ OH, H (CF ₂ ) ₄ CH ₂ OH, ethylene glycol acetate, diethylene glycol acetate and the like.

  Examples of the esters include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, methyl 2-hydroxypropionate, and ethyl 2-hydroxypropionate. Propyl 2-hydroxypropionate, butyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl ethoxyacetate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, benzyl acetate, ethyl benzoate, diethyl carbonate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, Acid propylene, ethyl lactate.

  Examples of ethers include dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, die Lenglycol dipropyl ether, diethylene glycol dibutyl ether, tetrahydrofuran, crown ether, benzyl ethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, acetic acid Examples include diethylene glycol monobutyl ether.

  Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 2-heptanone, 2-octanone, and 3,3-dimethyl-2. -Butanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, isophorone and the like.

  Examples of amides include N, N-dimethylformamide, N, N-diethylformamide, N-methylformamide, N-methylacetamide, acetamide, N-methylpyrrolidone and the like.

  Examples of the sulfonic acid esters include dimethyl sulfoxide.

  Examples of acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, Propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate, 3-methoxybutyl Acetate, 3-methyl-3- Butoxy butyl acetate and the like.

Among these, it is preferable to use an aromatic hydrocarbon.
In particular, aromatic hydrocarbons having a boiling point of 120 to 210 ° C. such as toluene and xylene are more preferable.
In this case, since the fluororesin can be easily dissolved, it can be easily applied to the substrate by a method such as spraying described later.

  The antifouling coating composition according to this embodiment is obtained by dissolving the above-described fluorine-based resin and silicone-modified acrylic resin in an organic solvent.

The viscosity of the antifouling coating composition is preferably 50 to 150 cps.
In this case, the handling is easy and the film to be formed is easily uniform.

Here, the antifouling coating composition preferably contains a synthetic resin.
Examples of the synthetic resin include polyether polyol.
In this case, the polyether polyol suppresses bleeding of the antistatic agent.

  Polyether polyols include polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxypropylene glycol, polyethylene-polyoxyethylene glycol graft polymer, polyhydric alcohol ethylene oxide adduct, polyhydric alcohol propylene oxide adduct, polyhydric acid Examples include adducts of alcohol ethylene oxide and propylene oxide. In addition, these may be used individually by 1 type and may be used in mixture of 2 or more types.

The blending ratio of the synthetic resin is preferably 5 to 25% by mass, more preferably 7 to 22% by mass, and still more preferably 9 to 19% by mass.
In this case, the antifouling property against dust adhesion is further improved.

It is preferable that the antifouling coating composition contains a filler (filler).
Examples of the filler include silica, fluorine-based powder, titanium oxide, talc, graphite, plastic filler, and glass powder. In addition, these may be used individually by 1 type and may be used in mixture of 2 or more types.
Among these, it is more preferable to use fluorine-based powder or glass-based powder.

  When the antifouling coating composition containing the filler is applied to the substrate on which the image is drawn, the gloss on the surface of the film disappears, so that the reflection of light is suppressed and the image becomes difficult to see.

The particle diameter of the filler is preferably 30 to 80 μm.
Further, when a film is formed, the surface of the filler is preferably exposed from the film.
In this case, adhesion of dust, gum, pressure-sensitive adhesive sheet and the like and fat stains can be more sufficiently suppressed, and a matte effect can be exhibited.

The blending ratio of the filler is preferably 2 to 30% by mass and more preferably 3 to 25% by mass with respect to the total solid content of the antifouling coating composition.
When the mixing ratio of the filler is less than 2% by mass, the matting effect tends to be insufficient as compared with the case where the mixing ratio is within the above range. When the mixing ratio exceeds 30% by mass, Compared with the case where the ratio is within the above range, the surface becomes whitish and the image tends to be difficult to recognize.

The antifouling coating composition preferably contains an ultraviolet absorber.
In this case, light resistance is improved.
Examples of such UV absorbers include benzophenone UV absorbers, benzotriazole UV absorbers, triazine UV absorbers, hindered amine UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, and nickel complex salts. An ultraviolet absorber etc. are mentioned. In addition, these may be used individually by 1 type and may be used in mixture of 2 or more types.

The antifouling coating composition preferably contains an antistatic agent.
In this case, the antifouling property against dust adhesion is further improved.
As such an antistatic agent, known ones can be used. For example, Baytron S V2 (manufactured by HC STACK), ORMECON NW-D102MT (manufactured by Nissan Chemical Industries), Nopcostat HS (San Nopco) ), Sanconol 0862-20R (manufactured by Sanko Chemical Industries), Sanconol N-0220R (manufactured by Sanko Chemical Industries), Sanconol PEO-20R (manufactured by Sanko Chemical Industries), SE ECON-801 (manufactured by Enex), CIL -312 (manufactured by Nippon Carlit Co., Ltd.). In addition, these may be used individually by 1 type and may be used in mixture of 2 or more types.

  In addition to these, the antifouling coating composition includes additives such as an antifoaming agent, a viscosity modifier, a leveling agent, a dispersant, a wetting agent, a lubricant, an antiseptic, a pH adjuster, and a flame retardant. It may be included.

In the antifouling coating composition according to this embodiment, by adding a crosslinking agent, the fluorine-based resin and the silicone-modified acrylic resin are bonded (cured) to the crosslinking agent at each hydroxyl group to form a film. It has become a thing.
As a result, the antifouling coating composition containing no crosslinking agent is excellent in preservability because its own curing is suppressed.
On the other hand, if a crosslinking agent is added, a film having excellent strength can be formed as necessary.

  Examples of the crosslinking agent include isocyanate crosslinking agents, melamine crosslinking agents, urea resin crosslinking agents, polybasic acid crosslinking agents, and epoxy crosslinking agents.

  The isocyanate-based crosslinking agent includes a polyvalent isocyanate, and examples thereof include hexamethylene diisocyanate, isophorone diisocyanate, and isocyanurate-modified products, uretdione-modified products, biuret-modified products, and the like.

  Examples of the melamine-based crosslinking agent include butylated melamine, methylated melamine, epoxy-modified melamine, and alkyl etherified melamine.

  Examples of the urea resin-based crosslinking agent include methylated urea resins and butylated urea resins.

  Examples of the polybasic acid-based crosslinking agent include hexanedicarboxylic acid, undecane dicarboxylic acid, octadecane dicarboxylic acid, naphthalene dicarboxylic acid, trimellitic acid, and the like.

  Examples of the epoxy-based crosslinking agent include dicyclopentadiene dioxide.

Among these, it is preferable that the crosslinking agent is an isocyanate-based crosslinking agent, and that the fluorine-based resin and the silicone-modified acrylic resin are bonded to the isocyanate-based crosslinking agent at each hydroxyl group to form a urethane bond.
In this case, since a urethane bond is formed, a flexible and strong film can be formed.

The addition amount of the crosslinking agent is preferably 20 to 50 parts by mass and more preferably 40 to 50 parts by mass with respect to 100 parts by mass of the fluororesin.
In this case, the film is strengthened and the antifouling property against adhesion of dust is improved.

In addition, a reaction catalyst may be added in the crosslinking reaction between the fluorine-based resin and the silicone-modified acrylic resin and the crosslinking agent.
Examples of such a reaction catalyst include dibutyltin dilaurate and triethylamine for isocyanate crosslinking agents, and acidic catalysts for melamine crosslinking agents and urea resin crosslinking agents.
In addition, the mixture ratio of these reaction catalysts is 0.0001-5 mass parts with respect to 50 mass parts of crosslinking agents from a viewpoint of reaction rate adjustment.

Next, an anti-fouling body in which an antifouling film is formed by applying an antifouling coating composition and an isocyanate-based cross-linking agent to the surface of the substrate and curing with the cross-linking agent will be described.
FIG. 1 is a cross-sectional view showing an example of an adhesion preventing body according to the present embodiment.
As shown in FIG. 1, the adhesion preventing body 10 according to the present embodiment includes a base 1, a film 2 provided in a layer on the surface of the base 1, a base 1 and an image layer 3 sandwiched between the films 2, Is provided.

Hereinafter, the substrate 1, the film 2, and the image layer 3 will be described in more detail.
(Substrate)
In the adhesion preventing body 1 according to the present embodiment, the substrate 1 is made of metal such as film, wood, road sign, cement such as concrete mortar, plated steel plate such as glass, tile, guardrail, or coated steel plate.

The material of the film is a synthetic resin such as polyethylene, ethylene / vinyl acetate copolymer, polypropylene, polyvinylidene chloride, polyvinyl alcohol, polyester, nylon, polyvinyl chloride, polyacrylonitrile, polystyrene, styrene, polyurethane, acrylic or polycarbonate. Is mentioned.
In addition, examples of the metal include metals such as iron, copper, and aluminum.

In the case where the substrate 1 is a film, it is preferable that surface treatment such as blast treatment or corona treatment is performed on the surface of the film forming side.
In this case, since the surface of the film becomes uneven, the adhesion to the film is excellent.

(Image layer)
The image layer 3 is formed on the surface of the substrate 1.
Examples of the method for providing the image layer 3 include a screen printing method, an ink jet method, a transfer method, a roll coating method, and a spray method.

In the adhesion preventing body 10, an image such as a map, a pattern, a sign, or an image such as a character is formed on the image layer 3.
Such an image is drawn with a known dye or pigment.

Examples of the dye include natural dyes, synthetic dyes, fluorescent dyes, and examples of the pigment include inorganic mineral pigments, synthetic inorganic pigments, ceramic pigments and other inorganic pigments, insoluble dyes, azo pigments, polycyclic pigments, lakes, and the like. Examples thereof include organic pigments such as pigments.
The dye or pigment may be aqueous or oily.
Among these, since it is excellent in light resistance, it is preferable to use an inorganic pigment.

  The image layer 3 includes dyes or pigments, synthetic resins, ultraviolet absorbers, antifoaming agents, viscosity modifiers, leveling agents, dispersants, wetting agents, lubricants, preservatives, pH adjusters, flame retardants, and the like. Additives may be included.

(film)
The film 2 is formed from above the image layer 3 of the substrate 1.
That is, after the image layer 3 is formed on the surface of the substrate 1, an antifouling coating composition containing the above-described fluorine-based resin and a silicone-modified acrylic resin is applied.
Here, examples of the application method include a screen printing method, an ink jet method, a transfer method, a roll coating method, a spray method, and an impregnation method.

  Then, by adding a crosslinking agent to the antifouling coating composition applied to the surface of the substrate 1, the antifouling coating composition is cured and the film 2 is formed.

Here, the thickness of the film 12 is preferably 5 to 1000 μm, and more preferably 20 to 1000 μm.
When the thickness is less than 5 μm, the durability tends to be inferior compared to the case where the thickness is within the above range, and when the thickness exceeds 1000 μm, the crack is compared with the case where the thickness is within the above range. May occur.

Since the antifouling body 10 is formed with the antifouling body 10, it is possible to prevent dust from adhering and to sufficiently prevent oil stains.
In addition, the adhesion between the film of the adhesion preventing body and the substrate is excellent, and the light resistance of the film itself is also excellent.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to embodiment mentioned above.

For example, the shape of the adhesion preventing body 10 according to the present embodiment is a plate shape, but may be a columnar shape or a triangular pyramid shape.
Further, the adhesion preventing body 10 according to the present embodiment includes a base body 1, a film 2 provided in a layered manner on the surface of the base body 1, and an image layer 3 sandwiched between the base body 1 and the film 2. The image layer 3 may not be provided.
Further, the substrate 1 may be transparent, and the image layer 3 may be formed on the back surface of the substrate 1.
Furthermore, a release paper may be pasted on the opposite side of the substrate 1 from the film 2 via an adhesive layer, or a metal foil may be pasted via an adhesive layer.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1
Fluorocarbon resin (trade name: Lumiflon LF200, manufactured by Asahi Glass Co., Ltd., hydroxyl value 52 mgKOH / g, 40% xylene solution) 100 parts by mass (solid content), silicone-modified acrylic resin (trade name: BYK-SILCLEAN3700, BIC Chemie) * Japan Co., Ltd.) 13 parts by mass (solid content) and 150 parts by mass of an organic solvent (xylene) were mixed to obtain an antifouling coating composition.

  And 46 mass parts of isocyanate type crosslinking agents (brand name; Coronate HX, Nippon Polyurethane Industry Co., Ltd.) were added to this, and the antifouling coating composition was spray-coated on an aluminum composite plate having a thickness of 3 mm. By applying and curing, a film was formed and an adhesion preventing body was obtained.

(Example 2)
Fluorine resin (trade name: Lumiflon LF906N, manufactured by Asahi Glass Co., Ltd., hydroxyl value 118 mgKOH / g, 35% xylene solution) 100 parts by mass (solid content) and silicone-modified acrylic resin 12 parts by mass (solid content) And 150 parts by mass of an organic solvent (xylene) were mixed to obtain an antifouling coating composition.

  Then, 43 parts by mass of an isocyanate-based cross-linking agent was added to this, and an antifouling coating composition was applied to an aluminum composite plate having a thickness of 3 mm by a spray coating method and cured to form a film and adhere The prevention body was obtained.

(Example 3)
An adhesion preventing body was obtained in the same manner as in Example 1 except that the amount of the silicone-modified acrylic resin was 3 parts by mass instead of 13 parts by mass.

(Comparative Example 1)
An adhesion preventing body was obtained in the same manner as in Example 1 except that the silicone-modified acrylic resin was not used.

[Evaluation methods]
1. Writing repellent property Each of the adhesion preventing bodies obtained in Examples 1 to 3 and Comparative Example 1 has an oil-based pen (trade name; oil-based magic ink, manufactured by Teranishi Chemical Co., Ltd.) or an aqueous pen (trade name; white board marker). Using Pentel), a straight line was drawn.
And the linear repelling condition was observed visually.
The writing repelling property was evaluated according to the following criteria. That is, も の indicates that the repellency is completely, 、 indicates that there is no repellency, and ◯ and Δ indicate intermediate points. Note that ◎ and ○ are practical ranges.
The obtained results are shown in Table 1.

2. Cloth removability A straight line was drawn on the surface of each of the adhesion preventing bodies obtained in Examples 1 to 3 and Comparative Example 1 using an oil pen or an aqueous pen.
And the operation which wipes it off with a nonwoven fabric (Brand name; Kimtex, Cressia Co., Ltd.) was repeated 10 times, and the residual state of the oil-based pen or the aqueous pen on the surface of the adhesion preventing body was visually observed.
The cloth removability was evaluated according to the following criteria. In other words, the oil pen or water-based pen that did not remain at all was marked with ◎, the remaining one was marked with ×, and the middle was marked with ◯ and Δ. Note that ◎ and ○ are practical ranges.
The obtained results are shown in Table 1.

3. Tape Removability A straight line was drawn on the surface of each of the adhesion preventing bodies obtained in Examples 1 to 3 and Comparative Example 1 using an oil-based pen or an aqueous pen.
And the tape (made by Nichiban Co., Ltd.) was stuck on it and the removability at the time of peeling was observed visually.
The tape removability was evaluated according to the following criteria. In other words, the oil pen or water-based pen that did not remain at all was marked with ◎, the remaining one was marked with ×, and the middle was marked with ◯ and Δ. Note that ◎ and ○ are practical ranges.
The obtained results are shown in Table 1.

4). Dust adhesion Each of the adhesion preventing bodies obtained in Examples 1 to 3 and Comparative Example 1 was left for 1 week in a tunnel, and the adhesion of dust was visually observed.
The dust adhesion was evaluated according to the following criteria. In other words, ◎ indicates that the dust is extremely less attached, ◯ indicates that the dust is less adhered and the substrate is sufficiently recognized, and △ indicates that the dust is adhered but the substrate is recognized. Was marked with x. Note that ◎ and ○ are practical ranges.
The obtained results are shown in Table 1. Moreover, the photograph of the result of the dust adhesion test of the adhesion preventing body obtained in Example 1 is shown in FIG. 2, and the photograph of the result of the dust adhesion test of the adhesion preventing body obtained in Example 2 is shown in FIG. FIG. 4 shows a photograph of the result of the dust adhesion test of the adhesion preventing body obtained in Comparative Example 1.

From the result of Table 1, according to the adhesion prevention body of Examples 1-3 of this invention, in any of writing repellent property, cloth removal property, tape removal property, and dust adhesion property, it is compared with the adhesion prevention body of Comparative Example 1. Was also found to be excellent.
Therefore, according to the present invention, it was confirmed that a film having excellent antifouling property and excellent adhesion to a substrate can be formed.

FIG. 1 is a cross-sectional view showing an example of an adhesion preventing body according to the present embodiment. FIG. 2 is a photograph of the results of a dust adhesion test of the adhesion preventing body obtained in Example 1. FIG. 3 is a photograph of the results of the dust adhesion test of the adhesion preventing body obtained in Example 2. FIG. 4 is a photograph of the result of the dust adhesion test of the adhesion preventing body obtained in Comparative Example 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base | substrate 2 ... Film | membrane 3 ... Image layer 10 ... Adhesion prevention body

Claims (9)

A fluororesin obtained by copolymerizing a fluoroolefin and a hydroxyl group-containing vinyl monomer;
A silicone-modified acrylic resin obtained by copolymerizing a silane compound and a hydroxyl group-containing acrylic monomer;
An organic solvent,
With
The antifouling paint composition comprising 11 to 20 parts by mass of the silicone-modified acrylic resin and 100 to 300 parts by mass of an organic solvent with respect to 100 parts by mass of the fluororesin.   The fluoroolefin comprises tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 3,3,3-trifluoropropylene, pentafluoropropylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, and perfluoroalkyl vinyl ether. The antifouling coating composition according to claim 1, wherein the antifouling coating composition is at least one selected from the group.   The hydroxyl group-containing vinyl monomer is hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxycarboxylic acid vinyl ester, hydroxycarboxylic acid allyl ester, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, N-hydroxyalkyl acrylamide and N-hydroxyalkyl methacrylamide. The antifouling paint composition according to claim 1, wherein the antifouling paint composition is at least one selected from the group consisting of:   The silane compound is tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane. , Hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldi Toxisilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxy Silane, 3-merca 2. At least one selected from the group consisting of ptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane. The antifouling coating composition as described.   The hydroxyl group-containing acrylic monomer is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3- The antifouling paint composition according to claim 1, wherein the antifouling paint composition is at least one selected from the group consisting of phenoxypropyl acrylate and 2-hydroxy-3-phenoxypropyl methacrylate.   The antifouling coating composition according to claim 1, wherein the molecular weight of the fluororesin is 5,000 to 15,000.   2. The antifouling agent according to claim 1, wherein the fluorine-based resin and the silicone-modified acrylic resin are bonded to the crosslinking agent at a hydroxyl portion of each other and cured by applying a crosslinking agent. Coating composition. The crosslinking agent is an isocyanate-based crosslinking agent;
8. The antifouling coating composition according to claim 7, wherein the fluorine-based resin and the silicone-modified acrylic resin are bonded to the isocyanate-based crosslinking agent at a hydroxyl group to form a urethane bond.   A film having antifouling properties is formed by applying the antifouling coating composition according to any one of claims 1 to 6 and an isocyanate-based crosslinking agent to the surface of a substrate and curing the composition. An adhesion preventing body characterized by

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