JP2010037397A - Antifouling coating composition, coating film containing antifouling coating composition, method for forming coating film, and coated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means for improving antifouling property, stain removing property and antifouling durability without impairing touch or texture of a material, such as leather. <P>SOLUTION: The antifouling coating composition contains a phosphorylcholine analog group-containing polymer and an aqueous coating material or a solvent-based coating material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antifouling coating composition, a coating film containing the antifouling coating composition, a method for forming the coating film, and a coated article. More specifically, an antifouling coating composition capable of improving the antifouling property, dirt removing property and antifouling durability without impairing the touch and texture of a material such as leather, and a coating containing the antifouling coating composition. The present invention relates to a film, a method for forming the coating film, and a coated article.

  In general, dirt in genuine leather, synthetic leather, etc. used indoors often adheres to the surface of sebum, protein, carbon, sand or a mixture thereof. Therefore, there is a demand for a technique for preventing the adhesion of dirt and a technique for easily removing the dirt even if the dirt is attached.

Examples of the surface treatment technique for preventing the above-described dirt from adhering include the techniques described in Patent Documents 1 and 2. Patent Document 1 discloses a technique for forming an antifouling film using an aqueous fluororesin dispersion, and Patent Document 2 discloses a technique for forming a film mainly composed of an acrylic silicon compound on the outermost layer. Has been.
JP-A-8-283654 JP 2007-191820 A

  However, the techniques described in Patent Documents 1 and 2 are excellent in antifouling performance, but on the other hand, the influence on touch and texture cannot be avoided. There was a problem that it was not possible to maintain the tactile sensation.

  Then, an object of this invention is to provide the means which can improve antifouling property, stain | pollution | contamination property, and antifouling durability, without impairing the tactile feeling and texture of materials, such as leather.

  In view of the above problems, the present inventors have made extensive studies. In this series of studies, a study was carried out to incorporate a phosphorylcholine-like group-containing polymer having a characteristic of high hydrophilicity into the paint used for the surface treatment of the material. As a result, surprisingly, when a coating composition containing a polymer containing a phosphorylcholine-like group is applied, the antifouling property and dirt removing property of the material surface are improved without substantially impairing the original feel and texture of the material. I found. Furthermore, it has been found that by applying the coating composition, the antifouling durability of the material, which is a more practical characteristic, is improved, and the present invention has been completed.

  That is, the present invention is an antifouling coating composition containing a phosphorylcholine-like group-containing polymer and a water-based or solvent-based coating.

  ADVANTAGE OF THE INVENTION According to this invention, the antifouling coating composition which can improve antifouling property, stain | pollution | contamination removal property, and antifouling durability can be provided, without impairing the touch feeling and texture of materials, such as leather.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following forms.

  The present invention is an antifouling coating composition containing a phosphorylcholine-like group-containing polymer and a water-based or solvent-based coating.

  Conventionally, by applying a fluorine-based polymer or silicone-based polymer as a water / oil repellent agent to the surface of the material, the surface free energy is lowered to exhibit water / oil repellency on the surface of the material, preventing the adhesion of dirt components and dirt. Removability has been realized. However, since the coating film on the surface of the material becomes hydrophobic, these surface treatments impair the original moist feeling of the material, and there has been a problem of achieving both antifouling property and tactile feeling / texture.

  On the other hand, the present invention specifically relates to an antifouling paint composition in which a phosphorylcholine-like group-containing polymer (hereinafter also simply referred to as “PC polymer”) is dissolved and mixed in a water-based paint or a solvent-based paint. I will provide a. The mechanism by which the antifouling property of the material is manifested in the present invention is presumed as follows. That is, since the PC polymer used in the present invention is hydrophilic, the coating film formed from the coating material containing the PC polymer becomes hydrophilic. Therefore, lipophilic substances that cause dirt such as sebum and protein are less likely to adhere to the coating surface. Even if dirt adheres, for example, when the surface of the coating film is wiped off with a wet cloth, moisture enters between the lipophilic substance and the coating film to float the dirt, and the dirt can be easily removed. .

  Further, the phosphorylcholine-like group in the PC polymer is presumed to have a 6-membered cyclic structure that easily incorporates free water. Therefore, when the antifouling paint composition of the present invention is used, it is considered that a moist feel is maintained over a long period of time, and both the antifouling property as described above and the maintenance of the original feel and texture of the material are compatible.

  By applying the antifouling paint composition of the present invention to the material surface and drying, a coating film containing a predetermined amount of PC polymer is formed on the material surface. As a result, functions such as hydrophilicity of the PC polymer, reduction of dirt adhesion, improvement of dirt removal, improvement of antifouling durability of the material, and maintenance of touch and texture can be imparted to the material surface. .

  Hereinafter, the components constituting the antifouling coating composition of the present invention will be described in detail.

[Phosphorylcholine-like group-containing polymer]
The PC polymer used in the present invention is preferably a copolymer represented by the following chemical formula [I].

In the chemical formula [I], m is 30 to 70 mol%, n is 70 to 30 mol%, and m + n = 100 mol%, and L is a linear or branched alkyl group having 4 to 22 carbon atoms. , A linear or branched fluorine-containing alkyl group having 4 to 22 carbon atoms, or a group represented by — (R ¹ —O) _p —R ² , wherein R ¹ has 2 to 4 carbon atoms. R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and p is an integer of 2 to 16.

  The PC polymer comprises a monomer represented by the following chemical formula [II] (2-methacryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate, hereinafter simply referred to as “MPC”) and a methacrylate ester. It can be obtained by polymerization.

  The MPC has a structure represented by the following chemical formula [II].

  Among the methacrylic acid esters, examples of the monomer in which L is a linear or branched alkyl group having 4 to 22 carbon atoms include, for example, n-butyl (meth) acrylate, 2-ethylhexyl ( Examples include (meth) acrylate, n-dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octadecyl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, and behenyl (meth) acrylate. It is done.

  Examples of the monomer in which L is a linear or branched fluorine-containing alkyl group having 4 to 22 carbon atoms among the methacrylic acid esters include, for example, perfluorooctylethyl (meth) acrylate, 1H , 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 2,2,2-trifluoro-1-trifluoromethylethyl (meth) acrylate .

Furthermore, among the methacrylic acid ester, L is ^- (R 1 _-O) Examples of monomers as the group represented by p -R ² are, for example, 2-hydroxyethyl (meth) acrylate, 2- Examples include hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate.

  These other monomers may be used alone or in combination of two or more.

  The bonding form of the copolymer formed from the PC monomer and the other monomer may be a block or random.

By appropriately selecting L in the chemical formula [I], the solubility of the copolymer represented by the chemical formula [I] in the paint can be controlled. For example, in the case of a water-based paint using water as a solvent, L is preferably an alkyl group. In the case of a solvent-based paint using toluene, DMF or the like as a solvent, L is an alkyl group or-(R ¹ -O). A group represented by _p— R ² is preferred.

  Among the alkyl groups used in L, a 2-ethylhexyl group, an n-dodecyl group, an n-octadecyl group, or a behenyl group is more preferable, and an octadecyl group is more preferable from the viewpoint of the texture and feel of the coated article.

  Among the fluorine-containing alkyl groups used in L, perfluorooctylethyl groups are more preferable from the viewpoint of the texture and feel of the coated article.

Furthermore, among the groups represented by — (R ¹ —O) _p —R ² used for L, from the viewpoint of the texture and feel of the coated article, a polyethylene glycol group (R ¹ = ethylene group, R ² = hydrogen atom) , P = 2 to 8), polypropylene glycol group (R ¹ = isopropylene group, R ² = hydrogen atom, p = 6 to 16), polypropylene glycol group (R ¹ = isopropylene group, R ² = hydrogen atom, p = 9-16) is more preferable.

  In order to enhance antifouling durability, m in the chemical formula [I] is more preferably 30 to 50 mol%, and n in the chemical formula [I] is more preferably 70 to 50 mol% (provided that m + n = 100 mol%).

  The PC polymer is produced by polymerizing a monomer mixture of the MPC and other monomers by a conventionally known method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or the like. Can do. Among these, during polymerization, the inside of the polymerization system is set to an atmosphere of an inert gas such as nitrogen, carbon dioxide, or helium, preferably radicals under polymerization conditions of a polymerization temperature of 0 to 100 ° C., preferably a polymerization time of 10 minutes to 48 hours. A polymerization method is preferred. In this radical polymerization, a conventionally known radical polymerization initiator can be used.

  Examples of the radical polymerization initiator include 2,2′-azobis (2-amidinopropyl) dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2 -(5-methyl-2-imidazolin-2-yl) propane) dihydrochloride, 2,2'-azobisisobutyramide dihydrate, 2,2'-azobisisobutyronitrile (AIBN), peroxy Ammonium sulfate, potassium persulfate, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxydiisobutyrate, lauroyl peroxide, 2,2 ′ -Azobis (2,4-dimethylvaleronitrile), t-butylperoxyneodecanoate, etc. are mentioned. These radical polymerization initiators may be used alone or in combination of two or more. Further, various redox accelerators may be used in combination with the polymerization initiator. As for the usage-amount of a polymerization initiator, 0.01-5 mass parts is preferable with respect to 100 mass parts of monomers or monomer mixture compositions.

  The weight average molecular weight of the PC polymer is preferably 10,000 to 1,000,000, more preferably 20,000 to 400,000, from the viewpoint of miscibility with the paint and the friction durability of the finished paint. More preferably, it is 30,000-200,000. In the present invention, as the weight average molecular weight, a value measured by the method of Examples described later is adopted.

[Water-based paint or solvent-based paint]
The antifouling paint composition of the present invention contains a water-based paint or a solvent-based paint.

  Examples of the water-based paint include emulsion oil paint, emulsion lacquer, or synthetic resin emulsion paint.

  Examples of the emulsion oil paint include those obtained by emulsifying linseed oil, enamel oil, tung oil and the like with water.

  As said emulsion lacquer, what emulsified nitrocellulose with water is mentioned, for example.

  Examples of the synthetic resin emulsion paint include, for example, resin emulsion (polyvinyl acetate emulsion, polystyrene / polybutadiene emulsion, polyacryl emulsion, polyacryl / silicon emulsion, polyvinyl chloride emulsion, polyvinyl chloride / polychloride And vinylidene emulsions, polybutadiene / polyacrylonitrile emulsions, polyurethane emulsions, etc.).

  Examples of the solvent-based paints include, for example, alkyd resin paints, amino alkyd resin paints, vinyl resin paints, room temperature drying acrylic resin paints, baking dry acrylic resin paints, tar epoxy epoxy resins Paints, varnish / enamel epoxy resin paints, one-component polyurethane resin paints, multi-component polyurethane resin paints, unsaturated polyester resin paints, and chlorinated rubber paints.

  As these paints, those produced according to a known production method can be used, or those commercially available as water-based paints or solvent-based paints can be used as they are. A commercially available coating composition (coating component) diluted with an appropriate amount of solvent can also be used.

  The PC polymer used in the present invention has particularly good affinity with a polyurethane resin-based paint. Polyurethane resin-based paints are generally paints that form a coating film by a reaction between polyisocyanate and a polyol compound, and there are one-pack type and multi-pack type. Moreover, the kind of solvent also has an aqueous type and a solvent type. The PC polymer used in the present invention has good affinity with any of these polyurethane resin paints.

  The content of the PC polymer in the antifouling coating composition of the present invention is preferably 100% by mass based on the total solid content of the antifouling coating composition from the viewpoint of more effectively expressing the effects of the present invention. It is 0.1-30 mass%. The content is more preferably 1 to 20% by mass, and still more preferably 1 to 10% by mass. When the content of the PC polymer is less than 0.1% by mass, the antifouling property may not be exhibited. When content of the said PC polymer exceeds 30 mass%, the film thickness of a coating film may become insufficient.

  In addition, various components can be added to the antifouling coating composition of the present invention. For example, known substances generally used as paint additives, such as fluororesins, fluororesin powders, silicone oils, desiccants such as metal dryers, dispersants such as phosphates, plasticizers, Antifoaming agent, thickener, anti-settling agent, leveling agent, antiseptic, antifungal agent, antioxidant, UV absorber, antioxidant, flame retardant, wetting agent, antifreezing agent, film-forming aid, color Anti-separation agent, rheology adjusting agent, various catalysts, various metal chelates such as aluminum chelate and titanium chelate, anti-skinning agent, pH adjusting agent and the like can be appropriately added within a range not impairing the effects of the present invention.

  Next, the manufacturing method of the antifouling paint composition of this invention is demonstrated. However, the technical scope of the present invention is not limited to the following.

  The antifouling coating composition of the present invention can be produced by stirring and mixing a PC polymer and a water-based or solvent-based coating. The PC polymer may be directly mixed with a water-based paint or a solvent-based paint, but from the viewpoint of more uniformly dissolving and dispersing the PC polymer in the paint, a solution in which the PC polymer is dissolved in the solvent is used as the paint. It is more preferable to mix with.

  When mixing the PC polymer and the water-based paint, specific examples of the solvent for dissolving the PC polymer include, for example, water; methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec- Hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-un Decyl alcohol, trime Lunonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl carbinol, diacetone alcohol, cresol, etc. Monoalcohol solvents; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2 , 4,2-ethylhexanediol-1,3, polyhydric alcohol solvents such as diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, Tyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso- Ketone solvents such as butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol; ethyl ether, iso-propyl ether, n-butyl ether, n-hexyl ether, 2- Ethyl hexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethyl ethere , Ether solvents such as propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, acetic acid Ethyl, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxy acetate Butyl, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate , Methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol acetate Monoethyl ether, Propylene glycol monopropyl ether, Propylene glycol monobutyl ether, Dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, Diacetic acid glycol, Methoxytriglycol acetate, Ethyl propionate, n-Butyl propionate , Iso-amyl propionate, diethyl oxalate Ester solvents such as di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N- Nitrogen-containing solvents such as dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydro And sulfur-containing solvents such as thiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in admixture of two or more.

  When mixing the PC polymer and the solvent-based paint, specific examples of the solvent for dissolving the PC polymer include, in addition to the above-mentioned solvents, for example, n-pentane, iso-pentane, n-hexane, iso- Aliphatic hydrocarbon solvents such as hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n Examples include aromatic hydrocarbon solvents such as -propyl benzene, iso-propyl benzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propyl benzene, n-amylnaphthalene, and trimethylbenzene. These solvents can also be used alone or in admixture of two or more.

  Among the above-mentioned solvents, water, ethanol, iso-propanol, or a water / iso-propanol mixed solvent is preferable when using a water-based paint from the viewpoint of uniform miscibility and coating film leveling. When using a solvent-based paint, iso-propanol, iso-propanol / N, N-dimethylformamide mixed solvent, iso-propanol / methyl ethyl ketone mixed solvent, iso-propanol / methyl-n-butyl ketone mixed solvent, n-propanol / Toluene mixed solvent or iso-propanol / toluene mixed solvent is preferable.

  When the PC polymer is dissolved in a solvent, the concentration is preferably 1 to 50% by mass. If it is this range, PC polymer can melt | dissolve and disperse | distribute in a coating material more uniformly.

  The temperature when mixing and stirring the PC polymer and the water-based paint or solvent-based paint is preferably 4 to 60 ° C., and the mixing and stirring time is preferably 0.5 to 8 hours.

  A coating film can be formed by applying and drying the antifouling coating composition of the present invention. It is preferable that the coating film includes a layer containing the antifouling coating composition on at least the outermost layer. In this case, the coating film may have a single layer structure or a multilayer structure. When at least the outermost layer of the coating film contains the antifouling coating composition of the present invention, that is, contains the PC polymer, it is difficult for dirt to adhere, and even if dirt adheres to the surface, it can be easily wiped off and removed. And a coating film in which the feel and texture of the substrate are hardly impaired.

  When the coating film has a multilayer structure, layers other than the outermost layer are not particularly limited, and examples thereof include a base coat layer and a color coat layer. Moreover, the layer structure which piled up the coating film formed from the antifouling paint composition of this invention may be sufficient.

  Application of the antifouling paint composition of the present invention can be carried out by various methods. For example, a spray coating method, a dipping coating method, a spin coating method, a knife coating method, a gravure coating method, a flow coating method, a roll coating method, an application method, a brush coating, or a dipping method may be employed. Among these, a spray coating method, a knife coating method, a gravure coating method, or an application method is preferable. The drying method is not particularly limited, and for example, room temperature curing drying, baking curing drying, ultraviolet curing drying, electron beam curing drying, and the like can be employed.

  Although there is no restriction | limiting in particular in the film thickness of the coating film formed from the antifouling coating composition of this invention, 1-30 micrometers is preferable from a viewpoint of durability and a tactile sense, and 5-25 micrometers is more preferable. If the film thickness is less than 1 μm, the durability may decrease. Further, when the film thickness exceeds 30 μm, the tactile sensation may be deteriorated.

  The coated article of the present invention includes a coating film formed using the antifouling coating composition of the present invention on the outermost surface of an object to be coated. The material of the article to be coated in the present invention is not particularly limited. For example, it can be applied to all materials such as cement-based substrates such as concrete, mortar, slate; metals such as steel, aluminum and stainless steel; glass; wood; plastics; tiles; Examples of the coated article having such a material and having the coating film of the present invention include, for example, vehicle parts, home appliances, building members, furniture, tableware, shoes, bags, leather accessories, leather clothing, Or the raw material for handicrafts etc. are mentioned.

  Among these, the coating film in the present invention is more preferably formed on the surface of natural leather or a leather-like base material because it can make use of the touch and texture of leather.

  The leather to be coated may be either natural leather or a leather-like base material, and various leathers can be used. Examples of the leather include natural leather, or leather-like base materials such as artificial leather, synthetic leather, and vinyl leather. Examples of animals derived from natural leather include cattle, sheep, goats, pigs, horses, kangaroos and deer.

  The natural leather or synthetic leather having the coating film of the present invention can be processed into various leather products. For example, interior parts of buildings; automobile seats, headrests, armrests, steering, door linings, ceiling linings, aircraft seats, cabin linings, railcar seats, ship seats, etc .; sofas, living chairs Leather furniture such as boots, pumps, men's business shoes, sports shoes, safety shoes; leather bags such as school bags, handbags, shoulder bags, pouches, Boston bags, rucksacks; skirts, coats , Pants, jackets, rider suits, ski wear, gloves, hats and other leather apparel; wallets, belts, watch bands, notebooks, harnesses, book covers and other leather accessories; and handicraft materials. In addition, the manufacturing method of these leather products may be a method of cutting and sewing the leather having the coating film of the present invention, or may be a method of coating after forming the leather product.

  The present invention will be described in further detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. The weight average molecular weight was measured by gel permeation chromatography (GPC, standard substance: polymethyl) using chloroform / ethanol = 6/4 (volume ratio, containing 0.5 mass% lithium bromide) as an eluent. Methacrylate) was used to detect the refractive index.

(Synthesis Example 1: Synthesis of Polymer 1)
MPC 28.53 g, octadecyl methacrylate (hereinafter also simply referred to as “C18MA”) 45.03 g, perfluorooctylethyl methacrylate (hereinafter also simply referred to as “FMA”) 6.43 g (monomer composition molar ratio, MPC / C18MA) / FMA = 40/55/5) was dissolved in 320 g of n-propanol and placed in a four-necked flask, and nitrogen was blown in for 30 minutes. Thereafter, 1.0 g of azobisisobutyronitrile was added at 60 ° C. to carry out a polymerization reaction for 24 hours. The polymerization solution was dropped into 3 liters of diethyl ether with stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 68.5 g of powder. The weight average molecular weight evaluated by GPC was 30,000. This is polymer 1.

(Synthesis Example 2: Synthesis of Polymer 2)
16.14 g of MPC, propylene glycol monomethacrylate (L in the chemical formula [I] is a group represented by — (CH ₂ —CH (CH ₃ ) —O) _p —H, where p is 9 63.13 g (hereinafter also simply referred to as “PPGMA”), 0.73 g of FMA (monomer composition molar ratio, MPC / PPGMA / FMA = 40/55/5) 0.73 g -Dissolved in 320 g of propanol, placed in a four-necked flask, and blown with nitrogen for 30 minutes. Thereafter, 0.5 g of azobisisobutyronitrile was added at 60 ° C. to carry out a polymerization reaction for 24 hours. The polymerization solution was added dropwise to 3 liters of hexane while stirring, and the deposited precipitate was filtered and vacuum dried at room temperature for 48 hours to obtain 60.7 g of powder. The weight average molecular weight evaluated by GPC was 130,000. This is polymer 2.

Example 1
Polymer 1 which is a PC polymer was dissolved in water to obtain an aqueous solution having a concentration of 7.5% by mass. Next, with respect to the aqueous polyurethane resin-based paint (manufactured by Union Pet Co., Ltd.), the obtained aqueous solution is an amount such that the content of the PC polymer is 0.1% by mass with respect to the total solid content of the composition. Added. After the addition, the mixture was stirred and mixed to prepare an antifouling paint composition. After that, using the natural leather (size: A4 size) coated with the base (base coat and color coat), spraying the antifouling coating composition on the base coat, then baking and curing at 80 ° C. for 90 sec. did. This coating and baking curing operation was repeated twice to form a coating film. The film thickness after drying was 10 to 20 μm.

(Example 2)
The antifouling paint composition was prepared in the same manner as in Example 1 except that the PC polymer aqueous solution was added in such an amount that the content of the PC polymer was 1% by mass relative to the total solid content of the composition. Preparation and formation of a coating on the base coat of natural leather were carried out. The film thickness of the coated film after drying was 10 to 20 μm.

(Example 3)
The antifouling paint composition was prepared in the same manner as in Example 1 except that the PC polymer aqueous solution was added in such an amount that the content of the PC polymer was 3% by mass relative to the total solid content of the composition. Preparation and formation of a coating on the base coat of natural leather were carried out. The film thickness of the coated film after drying was 10 to 20 μm.

Example 4
The antifouling paint composition was prepared in the same manner as in Example 1 except that the PC polymer aqueous solution was added in such an amount that the content of the PC polymer was 5% by mass with respect to the total solid content of the composition. Preparation and formation of a coating on the base coat of natural leather were carried out. The film thickness of the coated film after drying was 10 to 20 μm.

(Comparative Example 1)
A coating film was formed on the base coat of natural leather in the same manner as in Example 1 except that the above water-based polyurethane resin-based paint was applied as it was. The film thickness of the coated film after drying was 10 to 20 μm.

(Comparative Example 2)
Instead of the PC polymer aqueous solution, a fluorine-based water / oil repellent (manufactured by Dainippon Ink & Chemicals, Inc., product number: TE-5A) was added in an amount of 5% by mass based on the total solid content of the composition. Except for the above, in the same manner as in Example 1, a coating composition was prepared and a coating film was formed on a base coating of natural leather. The film thickness of the coated film after drying was 10 to 20 μm.

(Example 5)
Using polymer 2 as the PC polymer, an IPA or NPA / toluene solution (20% by mass) was prepared. Next, with respect to the solvent-based polyurethane resin-based paint (solvent: N, N-dimethylformamide (DMF)), the PC polymer content is 5% by mass with respect to the total solid content of the composition. Of PC polymer solution was added. After the addition, the mixture was stirred and mixed to prepare an antifouling paint composition. Synthetic leather coated with a base (base coat and color coat) (manufactured by Komatsu Seiren Co., Ltd., size: A4 size) was used, and the antifouling coating composition was applied onto the base coat with an applicator and baked and cured. This coating and baking curing operation was repeated twice to form a coating film. The film thickness after drying was 10 to 20 μm.

(Example 6)
The antifouling paint composition was prepared in the same manner as in Example 5 except that the PC polymer solution was added in such an amount that the content of the PC polymer was 10% by mass relative to the total solid content of the composition. Preparation and formation of a coating on the base coat of synthetic leather were carried out. The film thickness of the coated film after drying was 10 to 20 μm.

(Example 7)
In the same manner as in Example 5, except that the PC polymer solution was added in such an amount that the content of the PC polymer was 30% by mass with respect to the total solid content of the composition, Preparation and formation of a coating on the base coat of synthetic leather were carried out. The film thickness of the coated film after drying was 10 to 20 μm.

(Example 8)
Using polymer 1 as the PC polymer, an IPA or NPA / toluene solution (20% by mass) was prepared. Next, the PC polymer solution was added to the solvent-based polyurethane resin-based paint so that the content of the PC polymer was 5% by mass with respect to the total solid content of the composition. After the addition, the mixture was stirred and mixed to prepare an antifouling paint composition. The antifouling coating composition was applied onto the base coating with an applicator using a synthetic leather (Komatsu Seiren Co., Ltd., size: A4 large) coated with the base (base coat and color coat), and baked and cured. This coating and baking curing operation was repeated twice, and a coating film was formed so that the film thickness after drying was 10 to 20 μm.

Example 9
The antifouling paint composition was prepared in the same manner as in Example 8 except that the PC polymer solution was added in such an amount that the content of the PC polymer was 30% by mass with respect to the total solid content of the composition. Preparation and formation of a coating on the base coat of synthetic leather were carried out. The film thickness of the coated film after drying was 10 to 20 μm.

(Comparative Example 3)
A coating film was formed on the base coat of synthetic leather in the same manner as in Example 5 except that the solvent-based polyurethane resin-based paint was applied as it was. The film thickness of the coated film after drying was 10 to 20 μm.

(Comparative Example 4)
A coating film was formed on the synthetic leather in the same manner as in Example 5 except that the silicone resin was added in an amount of 5% by mass with respect to the total solid content of the composition instead of the PC polymer solution. did. The film thickness of the coated film after drying was 10 to 20 μm.

(Evaluation 1: Antifouling property)
For soiling, artificial sebum composed of oleic acid, palmitic acid, trioleic acid, tripartymic acid, and tristearic acid, 12 kinds of JIS Z8901 test powder, 8 kinds of JIS Z8901 test powder, carbon black for JSTM pigment , As well as synthetic stains consisting of synthetic loess for JSTM pigments. After applying dirt on the surface of the material using a flat surface abrasion tester, the cloth was wiped off with a cloth (towel) containing water and a flat surface abrasion tester. The color was measured using a portable integrating sphere spectrophotometer (X-Rite, product number: SP64) before and after the stain was wiped off, and the color difference (ΔE) was evaluated.

  The dirt adhesion is evaluated by the color difference (ΔE) of the coating film before the dirt adheres (hereinafter also simply referred to as “initial stage”) and after the dirt adheres (before the dirt is wiped off). Evaluation was based on the color difference of the coating film between the initial stage and after the dirt was adhered and wiped off. In this evaluation, it shows that it is excellent in dirt adhesion and dirt removal property, so that (DELTA) E is a low value. The evaluation criteria are shown in Table 1 below. In addition, this test was repeated twice and the antifouling durability of the coating film was also evaluated.

(Evaluation 2: Touch)
The tactile sensation was scored by sensory evaluation with five panelists using a reference sample as favorite (10 points) -dislike (0 points). As the reference sample, 20 samples obtained by performing sensory evaluation of likes and dislikes by 60 people each in 6 countries in Japan, China, the United States, Germany, Italy, and France were used.

  The evaluation results of each Example and each Comparative Example are shown in Table 3 and Table 4 below.

  As is clear from the results of Tables 3 and 4 above, the antifouling coating composition of the present invention containing the PC polymer improves the antifouling property, stain removability, antifouling durability, and tactile sensation of the material. I understood. ADVANTAGE OF THE INVENTION According to this invention, the antifouling coating composition which can make the antifouling property and tactile feel of a raw material compatible by the coating to various materials without being restrict | limited to coating conditions can be provided.

Claims (10)

A polymer containing a phosphorylcholine-like group;
Water-based paint or solvent-based paint,
Antifouling paint composition containing The antifouling paint composition according to claim 1, wherein the phosphorylcholine-like group-containing polymer is a copolymer represented by the following chemical formula [I]:

In the chemical formula [I], m is 30 to 70 mol%, n is 70 to 30 mol%, and m + n = 100 mol%, and L is a linear or branched alkyl group having 4 to 22 carbon atoms. , A linear or branched fluorine-containing alkyl group having 4 to 22 carbon atoms, or a group represented by — (R ¹ —O) _p —R ² , wherein R ¹ has 2 to 4 carbon atoms. R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and p is an integer of 2 to 16.   The antifouling paint composition according to claim 1 or 2, wherein the phosphorylcholine-like group-containing polymer has a weight average molecular weight of 10,000 to 1,000,000.   The content of the phosphorylcholine-like group-containing polymer is 0.1 to 30% by mass with 100% by mass of the total solid content of the antifouling coating composition, according to any one of claims 1 to 3. Antifouling paint composition.   The antifouling paint composition according to any one of claims 1 to 4, wherein the water-based paint is a water-based polyurethane resin-based paint.   The antifouling paint composition according to any one of claims 1 to 4, wherein the solvent-based paint is a solvent-based polyurethane resin-based paint. A coating film comprising the antifouling paint composition according to any one of claims 1 to 6,
The said coating film is a coating film provided with the layer which contains the said antifouling coating composition in the outermost layer at least.   The method for forming a coating film according to claim 7, wherein the outermost layer is formed by a spray coating method, a knife coating method, a gravure coating method, or an application method.   A coated article having a coating film according to claim 7 or a coating film formed by the method according to claim 8.   The coated article according to claim 9, wherein the article to be coated is natural leather or synthetic leather.