JP5513723B2 - Oil-cleaning resin composition and functional interior member - Google Patents

Description

  The present invention relates to a resin composition that easily cleans oil and a functional interior member having a coating film of the resin composition formed on the surface thereof.

  Residential materials, especially those that easily adhere to oil, such as kitchen components, are representative of inorganic materials such as tiles, hydrophilic materials such as glass, and Teflon (registered trademark) as materials that can easily remove oil. Water repellent and oil repellent materials are used.

In addition, as a surface treatment for kitchen parts used in environments where oils are likely to adhere, such as range hoods, oil stains can be easily removed by applying hydrophilic coating and floating the oil stains with a large amount of water. (Refer to Patent Documents 1 and 2) or water-repellent coating so that oil stains can be easily wiped off (see Patent Documents 3 and 4).
JP 2000-199637 A JP 2006-292326 A JP-A-10-57732 Japanese Patent Laid-Open No. 10-9630

In order to make the surface easy to remove oil by applying hydrophilic coating or water repellent coating as described above, the current situation is that both general hydrophilic coating and water repellent coating have advantages and disadvantages. For example, in hydrophilic coating, an inorganic hydrophilic material in which an inorganic compound mainly composed of Al ₂ O ₃ , SiO _2, or MgO typified by water glass is baked is often used. However, since these need to be treated at a high temperature, the base material to be coated is limited to metals, ceramics and the like, and there is also a drawback that cracks are likely to occur in the coating film. Further, the formed coating film has a large surface roughness, and when the dirt is clogged in the gaps between the irregularities, it becomes difficult to remove the dirt only by wiping with water, and it is necessary to wash with a large amount of water. In addition to inorganic hydrophilic materials, there are organic hydrophilic materials whose main purpose is antifouling and antifogging functions, in which hydrophilic groups are introduced into acrylic polyols, and in which inorganic materials are hybridized. It has been difficult to achieve both wiping and removing properties of oil and chemical resistance that can withstand actual use.

  On the other hand, the water-repellent coating includes fluorine-based and silicone-based materials, and can generally form a coating film with good slipperiness, so that it is excellent in wiping workability of solid-based stains. However, there is a problem that fluid dirt such as oil is difficult to remove completely because it spreads and spreads. Furthermore, the water-repellent coating film has the property that when water is applied to the area where the oil is attached, the oil will sink under the water, and when wiping with water, the oil will spread thinly and leave an oil film. There is also a problem that it is difficult to completely remove the oil.

  This invention is made | formed in view of said point, and it aims at providing the resin composition which can form the coating film which can wipe off oil easily and has high chemical resistance. In addition, it is an object of the present invention to provide a functional interior member having excellent oil removability.

The easily removable resin composition according to the present invention includes (1-A) an acrylic polyol having a hydrophilic group, (1-B) Mw 50000 or less , and an acrylic polyol other than the (1-A) component ; (1-C) a resin containing at least one selected from organometallic compounds and basic organic silane compounds and (1-D) at least one curing agent selected from polyisocyanate and amino resin as at least a constituent component In the resin composition, the component (1-A) is in the range of 10 to 60% by mass and the component (1-B) is in the range of 10 to {(24/57) × 100} % by mass. In addition, the (1-A) component contains (A) 30 to 70% by mass of (meth) acrylic acid alkyl ester monomer having 3 or less carbon atoms in the alkyl group, and (B) 4 or more carbon atoms in the alkyl group. (Meta) a 5 to 40% by mass of alkyl alkyl ester monomer, 10 to 40% by mass of monomer having (C) amide group, and (D) hydroxyalkyl ester monomer of (meth) acrylic acid at a rate of 10 to 30% by mass, It contains a polymerization composition (α) obtained by copolymerizing (A) to (D), and (E) a surfactant having an active hydrogen group.

  According to the present invention, the wiping performance can be improved by the hydrophilic (1-A) resin component, and the chemical resistance can be improved by the (1-B) component that improves the crosslinking density. Therefore, the oil can be easily wiped off only by wiping without requiring a large amount of water, and a film having high chemical resistance can be formed.

  In the present invention, Mw (weight average molecular weight) was measured with a differential refractometer using a high-speed GPC device “HLC-8220GPC” manufactured by Tosoh Corporation. Further, “(meth) acrylic acid alkyl ester monomer” means that either an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer may be used.

  In the present invention, the basic organic silane compound as the (1-C) component is a silane compound having a nitrogen-containing heterocyclic group in its structure.

  By using a silane compound having a nitrogen-containing heterocyclic group in the structure in this way, a film having a high surface hardness can be obtained.

  Moreover, the functional interior member according to the present invention is characterized in that the above resin composition is formed on the surface, and a film excellent in easy oil removal and chemical resistance is formed on the surface. A functional interior member can be obtained.

  And when this functional interior member is a kitchen member, it is easy for oil stains to adhere to the kitchen member, but because the surface of the kitchen member has a film with excellent oil removability and chemical resistance, Oil can be easily removed using a cleaning agent exhibiting alkalinity or acidity.

  According to the present invention, oil can be easily wiped off by simply wiping without requiring a large amount of water, and a film having high chemical resistance can be formed. It is possible to form a functional interior member having a surface excellent in properties and chemical resistance.

  Hereinafter, the best mode for carrying out the present invention will be described.

  The easily washable resin composition according to the present invention improves the crosslink density with acrylic polyol (1-A) having a hydrophilic group, which is a resin component that imparts hydrophilicity and improves oil wiping properties. And an acrylic polyol (1-B) having an Mw of 50000 or less, which is a resin component that enhances chemical resistance, and at least one selected from an organometallic compound and a basic organosilane compound for improving the curing reactivity of the resin composition Essential components are (1-C) and at least one of polyisocyanate and amino resin (1-D), which are curing agents for the resin composition.

  In the present invention, the component (1-A) includes (A) an alkyl group (meth) acrylic acid alkyl ester monomer having 3 or less carbon atoms, and (B) an alkyl group having 4 or more carbon atoms (meth) acrylic. Acid alkyl ester monomer, monomer having (C) amide group, (D) acrylic polymerization composition (α) copolymerized with hydroxyalkyl ester monomer of (meth) acrylic acid, and (E) surface activity having active hydrogen group It is prepared containing an agent.

  In the component (1-A), the alkyl group (meth) acrylic acid alkyl ester monomer (A) having an alkyl group having 3 or less carbon atoms includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and the like. Specific examples can be given.

  Examples of the (meth) acrylic acid alkyl ester monomer (B) having 4 or more carbon atoms in the alkyl group include butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and dicyclopentadienyl (meth). Specific examples include acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, and the like.

  In the component (1-A), the monomer (C) having an amide group is for improving the hydrophilicity of the cured film, and includes (meth) acrylamide, dimethyl (meth) acrylamide, dimethylaminopropyl acrylamide, diacetone acrylamide. N-methylolacrylamide and the like can be mentioned as specific examples.

  In the (1-A) component, the (meth) acrylic acid hydroxyalkyl ester monomer (D) having reactivity with the polyisocyanate or amino resin of the (1-D) component is a (meth) acrylic acid ester having a hydroxyl group. And a glycol-based adduct of (meth) acrylic acid ester or a vinyl ether having a hydroxyl group.

  Examples of the (meth) acrylic acid ester having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Can be mentioned.

  The glycol-based adduct of the (meth) acrylic acid ester includes mono (meth) acrylates composed of at least one of polyethylene glycol, polypropylene glycol, tetramethylene glycol, and the like and ε-caprolactone. Additives can be mentioned. Commercially available products of this glycol-based adduct include “Blemmer AET series”, “APT series”, “AE series”, “AEP series”, “Blemmer AP-400”, “AP-550” manufactured by NOF Corporation. ”,“ AP-800 ”,“ Blemmer PEP series ”,“ PET series ”,“ PPT series ”,“ PP series ”,“ MA series ”manufactured by Nippon Emulsifier Co., Ltd., Daiichi Kogyo Seiyaku Co., Ltd. “New Frontier NF Series”, “Placcel FM Series”, “FA Series” manufactured by Daicel Chemical Industries, Ltd., and the like can be mentioned.

  Examples of the vinyl ether having a hydroxyl group include hydroxyalkyl vinyl ethers such as 4-hydroxybutyl vinyl ether and cyclohexane dimethanol monovinyl ether, and hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether and cyclohexane dimethanol monoallyl ether.

  In the component (1-A), the surfactant (E) having an active hydrogen group is reactive with the polyisocyanate and amino resin of the component (1-D) and improves the hydrophilicity of the cured film. , Anionic, cationic, nonionic and amphoteric surfactants. Specific examples of the active hydrogen group include a hydroxyl group, a carboxyl group, an amino group, an amide group, a phosphate group, and a sulfonyl group.

  Furthermore, as the surfactant (E) having an active hydrogen group, those having an Mw of 2000 or more are preferable. If it is less than Mw2000, it may be difficult to obtain sufficient oil wiping properties. Although the upper limit of a weight average molecular weight (Mw) is not specifically limited, It is desirable that it is Mw 20000 or less practically.

  Specific examples of the anionic surfactant containing an active hydrogen group include castor oil monosulfate, castor oil monophosphate, sorbitan fatty acid ester sulfate, sorbitan fatty acid ester phosphate, polyoxyalkylene glycerol ether monosulfate, polyoxyalkylene glycerine ether monoester. Examples thereof include phosphate, perfluoroalkyl ester phosphate and the like.

  Specific examples of the active hydrogen group-containing cationic surfactant include dialkanolamine salts, polyoxyalkylene alkylamine ether salts, polyoxyalkylene alkyl ammonium salts, polyoxyalkylene dialkanol amine ether salts, and the like. .

  Specific examples of the active hydrogen group-containing amphoteric surfactant include N, N-di (β-hydroxyalkyl) N-hydroxyethyl-N-carboxyalkylammonium betaine, N, N-di (polyoxyethylene) -N -Alkyl-N-sulfoalkylammonium betaine, perfluoroalkyl betaine, etc. can be mentioned.

  Specific examples of the nonionic surfactant containing an active hydrogen group include polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyglycerin fatty acid ester and the like.

  In the (1-A) component, the acrylic polymerization composition (α) is obtained by copolymerizing the (A) component, the (B) component, the (C) component, and the (D) component. As the polymerization method, any polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization and the like can be used. Among them, the monomers (A) to (D) and the surfactant (E) are used. A solution polymerization method is preferred in which is dissolved in a solvent and polymerized in the presence of a polymerization initiator as necessary.

  Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t-hexyl peroxyneodecanate, and t-butyl peroxybivalate, and 2,2-azobis. Examples thereof include azo compounds such as -iso-butyronitrile, 2,2-azobis-2,4-dimethylvaleronitrile, and 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile.

  This polymerization initiator can be used alone or in combination of two or more, and the amount used is not particularly limited, but each monomer of components (A) to (B) A range of about 0.01 to 5.0 parts by mass with respect to a total of 100 parts by mass is generally preferred.

  Examples of the solvent include ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester organic solvents such as methyl acetate, ethyl acetate, and butyl acetate, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. Polar solvents, alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbon-based organic solvents such as toluene, xylene, “Sorvesso 100” (manufactured by Exxon Chemical), n-hexane, cyclohexane, methyl Aliphatic hydrocarbon / alicyclic hydrocarbon organic solvents such as cyclohexane, “Loose”, “Mineral Spirit EC” (both manufactured by Shell), cellosolve organic solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, tetrahydro Emissions, may be mentioned ether-based organic solvent such as dioxane, n- butyl carbitol, carbitol organic solvents such as iso- amyl carbitol. Of course, these solvents can be used alone or in combination of two or more.

  The blending ratio of the components (A) to (D) is (A) 30 to 70% by mass, (B) 5 to 40% by mass, (C) 10 to 40% by mass, and (D) 10 to 30%. The range of mass% is preferable (total of 100 mass%). When the component (A) and the component (B) are more than this range or less, the chemical resistance of the film may be lowered. When the amount of the component (C) exceeds this range, the oil wiping property is improved, but the chemical resistance may be lowered. When the amount is small, the oil wiping property may be lowered. If the amount of the component (D) exceeds this range, the polymerization cannot be stably performed, and it becomes difficult to stably synthesize the resin. If the amount of the component (D) is small, the oil wiping property decreases. At the same time, the crosslink density decreases, so that chemical resistance may also decrease.

  Moreover, the compounding quantity of (E) component is although it does not specifically limit, The range of 5-20 mass% is preferable in (1-A) component (except a solvent). When the blending amount of the component (E) is less than this range, the oil wiping property tends to decrease, and conversely, when it is large, the coating hardness and chemical resistance such as alkali resistance tend to decrease. .

  In the present invention, the above (1-B) component is a component having a role of improving the crosslink density and improving the chemical resistance of the film, and is an acrylic polyol having an Mw of 50,000 or less. An acrylic polyol having an Mw of 50,000 or less can be used without particular limitation. For example, commercially available products such as “LR2629” manufactured by Mitsubishi Rayon Co., Ltd. with Mw16000, “A814” manufactured by Dainippon Ink Industries, Ltd. of Mw30000, Dainippon Ink Industries, Ltd. “A817” or the like can be used. From the viewpoint of compatibility and curability, the range of Mw 10000 to 30000 is particularly suitable.

  An acrylic polyol obtained by polymerizing an unsaturated monomer mixture selected from a hydroxyl group-containing unsaturated monomer, an acid group-containing unsaturated monomer, and other unsaturated monomers can also be used. The hydroxyl group-containing unsaturated monomer is not particularly limited. For example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, “Plexel FM1” (ε-caprolactone-modified hydroxyethyl methacrylate) manufactured by Daicel Chemical Industries, Ltd. ), Polyethylene glycol monoacrylate or monomethacrylate, polypropylene glycol monoacrylate or monomethacrylate, and the like.

  The acid group-containing unsaturated monomer is not particularly limited, and examples thereof include carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and maleic acid.

  The other unsaturated monomer is not particularly limited, and examples thereof include acrylic monomers or acrylic monomers having an ester group such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, and lauryl of acrylic acid or methacrylic acid; vinyl Vinyl alcohol ester monomers of alcohol and carboxylic acids such as acetic acid and propionic acid; unsaturated hydrocarbon monomers such as styrene, α-methylstyrene, vinyl naphthalene, butadiene, isoprene; acrylonitrile, methacrylonitrile, etc. Nitrile monomers of acrylamide; acrylamide monomers such as acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, and diacetoneacrylamide.

  The oil easy-cleaning resin composition of the present invention comprises the (1-A) component and the (1-B) component as resin components that form a coating matrix, and the (1-A) component and the (1- The blending ratio of the component B) is in the resin composition (excluding the solvent), the component (1-A) is in the range of 10 to 60% by mass, and the component (1-B) is in the range of 10 to 60% by mass. It is set to do. When the (1-A) component is less than this range, the oil wiping property is lowered, and when it is more, the chemical resistance such as alkali resistance is lowered. Further, when the (1-B) component is less than this range, chemical resistance such as alkali resistance is lowered, and conversely, when it is more, the oil wiping property is lowered.

  In the present invention, the above (1-C) component is a component that acts as a urethane curing catalyst and enhances reactivity, and is selected from at least one of an organometallic compound and a basic organosilane compound.

  Examples of the organometallic compound include dioctyl tin bis (2-ethylhexyl maleate), dioctyl tin oxide or a condensate of dibutyl tin oxide and silicate, dibutyl tin dioctate, dibutyl tin dilaurate, dibutyl. Tin distearate, dibutyltin diacetylacetonate, dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (2-ethylhexylmaleate), dibutyltin bis (oleylmaleate) ), Stanas octoate, tin stearate, di-N-butyltin laurate oxide, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zincs, cobalt naphthenate, calcium octylate, naphthenic acid Copper, tetra (2-ethylhexyl) titanate, etc. It can, they may be used alone or in combination of two or more thereof.

The basic organic silane compound is an organic silane compound having at least one group selected from an amino group (NH _2- ), a mono-substituted amino group, a di-substituted amino group, and a nitrogen-containing heterocyclic group. is there. For example, as mono-substituted amino group, N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N-pentylamino group, N-hexylamino group, N-cyclohexylamino group, N-phenylamino group can be exemplified, and examples of the di-substituted amino group include N, N-dimethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-dibutylamino group. N, N-dipentylamino group, N, N-dihexylamino group, N, N-dicyclohexylamino group, N, N-diphenylamino group and the like. The nitrogen heterocyclic group refers to a heterocyclic compound containing a nitrogen atom as a constituent element of a ring, and usually a three-membered ring to a ten-membered ring is common. In the present invention, when an organic silane compound having a nitrogen-containing heterocyclic group is used as the catalyst of the (1-C) component, an effect of increasing the surface hardness of the coating can be obtained. Examples of the nitrogen-containing heterocyclic group include pyridine, imidazole, pyrrole, triazine, triazole, indole, and tetrazole. Among them, imidazole is preferable from the viewpoint of compatibility and stability.

  In addition, the basic organic silane compound used as the catalyst of the (1-C) component may contain a carboxylic acid in order to slightly suppress the reaction rate. Examples of the carboxylic acid for suppressing the reaction include aromatic carboxylic acids such as benzoic acid and phthalic acid.

  The blending amount of the (1-C) component is not particularly limited, but when the (1-C) component is an organometallic compound, 0.001 to 0.00 in the resin composition (excluding the solvent). It is desirable to set it to be contained in the range of 1% by mass. In the case of a basic organic silane compound, it is set to be contained in the range of 0.05 to 10% by mass in the resin composition (excluding the solvent). It is desirable to do. In any case, if the (1-C) component is less than these ranges, the oil wiping property may be reduced, and if it is large, the pot life (pot life) as a paint is remarkably short. There is a risk.

  In the present invention, the (1-D) component is at least one of a polyisocyanate and an amino resin used as a curing agent component, and both can react with a hydroxyl group in the resin to form a cured film. Is.

  Examples of the polyisocyanate include aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4 (or 2,6) -diisocyanate, 4 Cyclic aliphatic diisocyanates such as 4,4'-methylenebis (cyclohexyl isocyanate) and 1,3- (isocyanatomethyl) cyclohexane; Aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate; Organic polyisocyanate itself such as triisocyanate or higher polyisocyanate such as isocyanate, or each of these organic polyisocyanates Isocyanate and polyhydric alcohol, an adduct of low molecular weight polyester resin or water, etc., or cyclic polymer between the organic diisocyanates described above (e.g., isocyanurates), and the like biuret type adducts. Among these, hexamethylene diisocyanate isocyanurate is particularly preferred. Moreover, these can be used individually by 1 type or in mixture of 2 or more types.

  When polyisocyanate is used as the curing agent component of (1-D), the blending amount of polyisocyanate is not particularly limited, but the isocyanate group (NCO) contained in the polyisocyanate is the above (1 More preferably, the equivalent ratio of NCO / OH to the hydroxyl group (OH) in the resin of component (A) or (1-B) is in the range of 0.2 to 2.0. It is usually appropriate to select it to be in the range of .5 to 1.5.

  Moreover, said amino resin can be used as a hardening | curing agent component similarly to polyisocyanate, and melamine resin, benzoguanamine resin, glycoluril resin, urea resin etc. are contained in amino resin. Of these, melamine resins and benzoguanamine resins are common.

  Of these melamine resins and benzoguanamine resins, those alkylated are preferred. Other types such as imino type and methylol type can easily react with imino type melamine resin or methylol type melamine resin even if the partial hydrolysis condensate of alkoxysilane compound is treated with silane coupling agent. Since storage stability falls, it is not preferable. Of the alkyl etherified melamine resins, melamine resins substituted with methoxy groups and / or butoxy groups are preferred. In addition to the effect of paint storage stability, the melamine resin becomes hydrophobic, so when the film is formed, the melamine resin is unevenly distributed in the upper layer of the film, and the cross-linking density of the surface layer is increased. Can be prevented from penetrating into the interior of the coating, and the stain resistance is improved. The melamine resin substituted with a methoxy group and / or a butoxy group refers to a melamine resin etherified with an i-butyl group or an N-butyl group alone or with a butyl group and a methyl group.

  When an amino resin is used as the curing agent component of (1-D), the amount of the amino resin is not particularly limited, but it is contained in the resin composition (excluding the solvent) in the range of 10 to 50% by mass. It is desirable to set so as to. When the amino resin as the (1-D) component is less than this range, curing may be insufficient and chemical resistance such as alkali resistance may be deteriorated. On the other hand, when there are more amino resins as a (1-D) component than this range, there exists a possibility that the wiping off property of oil may fall.

  The resin composition of the present invention can be obtained by blending the above components (1-A) to (1-D), and this resin composition is applied to the surface of a substrate. By curing, it is possible to obtain a functional interior member or the like in which a film easily washed with oil is formed on the surface of the substrate.

  The application method of the resin composition is not particularly limited, and any method can be adopted, but spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, brush coating, A method such as sponge coating can be suitably used. Moreover, it is not limited only to apply | coating, For example, a resin composition is shape | molded into a sheet form, this is laminated | stacked on the surface of a base material, or a resin composition is sprayed on the inner surface of a metal mold | die. A film is formed, and when the substrate is molded with this mold, the resin composition coating is laminated on the substrate, or the nonwoven fabric is impregnated with the resin composition and molded with a press or the like. There is also a method of laminating on the surface of the substrate.

  Also, the curing method is not particularly limited, and is arbitrarily selected from room temperature (room temperature standing) to high-temperature baking according to the desired cured film performance, the heat-resistant temperature of the base material, productivity, and the like. It is something that can be done.

  Also, the film thickness of the film is not particularly limited. Usually, the film thickness may be about 1 to 100 μm. However, since the easy removal of oil is reduced by the surface irregularities of the base material, the film is as smooth as possible. Therefore, it is preferable to form the film with a film thickness of 10 to 50 μm by a general coating method.

  The substrate is not particularly limited, and an inorganic substrate, an organic substrate, or the like can be used. Examples of the inorganic base material include aluminum, iron, stainless steel, galvanized steel sheet, glass, enamel, ceramics such as ceramics, slate, and alumina. Examples of the organic base material include polycarbonate, acrylic resin, ABS resin, vinyl chloride resin, epoxy resin, FRP and other plastic materials and sheets. In addition, those coated with an organic film may be used as a base material. Examples of the organic film include acrylic, polyester, urethane, epoxy, melamine, silicon, and fluorine films. When these coatings are formed by application of a paint, the paint system is not particularly limited, such as a solvent system, an aqueous system, or a solventless system. In order to improve the adhesion between these coatings and the substrate, surface treatment such as solvent degreasing, alkali degreasing, and polishing may be performed on the substrate, and an acrylic, epoxy, or silicon primer is used as an underlayer. You may make it apply | coat to a base material.

  In the present invention, a functional interior member is not limited to a strict definition as an interior member, but can be wiped or touched, but installed in a place where it cannot be washed with a large amount of water. Examples thereof include, for example, a handle, a mirror door, switches, a table, a chair, a lighting fixture, and the like. Among these, a kitchen member is mentioned as an interior member to which oil is most easily adhered. Examples of the kitchen member include a range hood, a kitchen storage door, a kitchen counter, a sink, a hob, a kitchen board, a flooring around the kitchen, and a refrigerator.

Here, the oil stain is caused by the fact that the attached oil undergoes a peroxidation reaction, and the polar components increase in the oil molecules, causing the cohesive force and viscosity to increase and solidify, and the addition of unsaturated double bonds. The increase in molecular weight due to polymerization is also a factor. Specifically, for example, in kitchen components, unsaturated fatty acids such as linoleic acid contained in edible oil are oxidized according to the following reaction to become lipid peroxide (lipid hydroperoxide).
_{-CH 2 -CH = CH- + O 2} → -CH = CH (OOH) -
ROOH (hydroperoxide) → H ・ + ROO ・ (peroxide radical)
ROO ・ RH → ROOH + R ・
Lipid peroxide is decomposed into aldehydes, ketones, alcohols, and the like that cause odors, and if it is further oxidized, decomposed, and molecularly cleaved, it tends to cause acid corrosion. Further, the viscosity may increase due to polymerization, and the reaction product may be changed to a more complicated reaction product.

  In this way, oil stains such as lipid peroxide are likely to adhere to the surface of the kitchen member or the like, but it adheres by forming a film of the resin composition of the present invention on the surface of the substrate as described above. It is possible to easily remove oil stains by wiping with a cloth or the like without having to wash with a large amount of water, whether it is an early oil stain or a viscous oil. . Examples of oil stains that can be easily removed by forming a film of the resin composition of the present invention include edible oils used in the kitchen as described above. Oils and fats resulting from sebum and sweat can also be removed.

  In addition, the coating film formed on the surface of functional interior materials such as kitchen parts needs to be resistant to detergents, and is generally resistant to alkalis and alkalis (such as aqueous sodium carbonate) used in chemical resistance tests. In addition to acid resistance against chemicals (for example, oleic acid), there is also a need for durability against alkaline detergents containing citrus perfume ingredients specialized in removing oil stains that have been widely distributed in recent years. For example, D-limonene (orange peel component) is used as a citrus fragrance component, which has a structure similar to styrene, and when combined with a surfactant, alkali agent or solvent, it is more common than general alkaline chemicals. A general film having a very strong force to break the film and weak crosslinkability cannot withstand. Examples of detergents that contain orange peel components include “Kitchen Magiclin Deodorant Plus” (Kao), “Look Around Range” (Lion), “Orange Joy” (P & G) There is. On the other hand, the coating film formed from the resin composition of the present invention has high chemical resistance and has general alkali resistance and acid resistance, as well as durability against detergents containing D-limonene. And the coating is not destroyed by such a detergent.

  Next, the present invention will be specifically described with reference to examples.

<Synthesis Example 1 of (1-A) Component>
In a reaction vessel, 10 parts by mass of “Epan U105” as a surfactant of component (E), 211 parts by mass of MEK and 46 parts by mass of NMP as a solvent were charged, and the temperature was raised to 60 ° C.

  On the other hand, 45 parts by mass of MMA as the (meth) acrylic acid alkyl ester monomer having 3 or less carbon atoms in the alkyl group (A) and (meth) acrylic acid having 4 or more carbon atoms in the alkyl group (B) 10 parts by mass of IBMA as an alkyl ester monomer, 25 parts by mass of DMAA as a monomer having an amide group as component (C), and 20 parts by mass of 2-HEA as a hydroxyalkyl ester monomer of (meth) acrylic acid as component (D) A mixed monomer was prepared by mixing and further mixing 4.0 parts by mass of ABN-E as a polymerization catalyst.

  Then, the mixed monomer is dropped into the solvent containing the above surfactant at 60 ° C. over 3 hours, and the reaction is terminated after 3 hours to synthesize an acrylic polymerization composition (α), thereby obtaining an acrylic polyol. (1-A-1) component was obtained.

  The abbreviations and trade names of the above components are as shown below.

MMA: methyl methacrylate IBMA: isobutyl methacrylate DMAA: N, N-dimethylacrylamide 2-HEA: 2-hydroxyethyl acrylate MEK: methyl ethyl ketone NMP: N-methyl-2-pyrrolidone ABN-E: azobis-2-methylbutyronitrile (Japan) Hydrazine Industry Co., Ltd.)
Epan U105: Polyoxyethylene polyoxypropylene glycol ether Mw: 6400 (Daiichi Kogyo Seiyaku Co., Ltd.)
<Synthesis Example 2 of (1-A) Component>
(A) 35 parts by mass of component MMA, (B) 10 parts by mass of component IBM, (C) 35 parts by mass of component DMAA, (D) 2-HEA component An acrylic polyol (1-A-2) component was obtained in the same manner as in Synthesis Example 1 except that the blending amount of was changed to 20 parts by mass.

<Synthesis Comparative Example 1 of (1-A) Component>
(A) Component MMA content is 60 parts by mass, Component (B) IBMA content is 15 parts by mass, Component (C) DMAA content is 5 parts by mass, Component (D) 2-HEA An acrylic polyol (1-A-3) component was obtained in the same manner as in Synthesis Example 1 except that the blending amount of was changed to 20 parts by mass.

<Synthesis Comparative Example 2 of (1-A) Component>
(A) Component MMA content is 30 parts by mass, Component (B) IBMA content is 5 parts by mass, Component (C) DMAA content is 45 parts by mass, Component (D) 2-HEA An acrylic polyol (1-A-4) component was obtained in the same manner as in Synthesis Example 1 except that the blending amount of was changed to 20 parts by mass.

<Synthesis Comparative Example 3 of (1-A) Component>
(A) Component MMA content is 50 parts by mass, Component (B) IBMA content is 20 parts by mass, Component (C) DMAA content is 25 parts by mass, Component (D) 2-HEA An acrylic polyol (1-A-5) component was obtained in the same manner as in Synthesis Example 1 except that the blending amount of was changed to 5 parts by mass.

<Synthesis Comparative Example 4 of (1-A) Component>
(A) 35 parts by mass of component MMA, (B) 10 parts by mass of IBMA component, (C) 15 parts by mass of DMAA component, (D) 2-HEA component (1-A-6) component was obtained in the same manner as in Synthesis Example 1 except that the blending amount of was changed to 40 parts by mass.

<Synthesis Comparative Example 5 of (1-A) Component>
(A) Component MMA content is 75 parts by mass, Component (B) IBMA content is 5 parts by mass, Component (C) DMAA content is 10 parts by mass, Component (D) 2-HEA An acrylic polyol (1-A-7) component was obtained in the same manner as in Synthesis Example 1 except that the blending amount of was changed to 10 parts by mass.

<Synthesis Comparative Example 6 of (1-A) Component>
(A) Component MMA content is 35 parts by mass, Component (B) IBMA content is 45 parts by mass, Component (C) DMAA content is 10 parts by mass, Component (D) 2-HEA An acrylic polyol (1-A-8) component was obtained in the same manner as in Synthesis Example 1 except that the blending amount of was changed to 10 parts by mass.

<Synthesis Comparative Example 7 of (1-A) Component>
In the reaction vessel, 211 parts by mass of MEK and 46 parts by mass of NMP were charged as solvents, and the temperature was raised to 60 ° C. (component (E) was not blended).

  On the other hand, 45 parts by mass of MMA as component (A), 10 parts by mass of IBMA as component (B), 25 parts by mass of DMAA as component (C), 20 parts by mass of 2-HEA as component (D), polymerization catalyst A mixed monomer was prepared by mixing 4.0 parts by mass of ABN-E.

  Then, the mixed monomer is dropped into the solvent containing the above surfactant at 60 ° C. over 3 hours, and the reaction is terminated after 3 hours to synthesize an acrylic polymerization composition (α), thereby obtaining an acrylic polyol. (1-A-9) component was obtained.

  Table 1 shows the composition of the acrylic polyols (1-A-1) to (1-A-9) obtained as described above. The weight average molecular weight (Mw), viscosity, nonvolatile content, and hydroxyl value are shown in Table 1.

  Using the acrylic polyols of the above (1-A-1) to (1-A-9), resin compositions were prepared as in the following Examples and Comparative Examples.

Example 1
As an acrylic polyol of (1-A) component, 27 parts by mass of the hydrophilic acrylic polyol (1-A-1) synthesized in Synthesis Example 1 described above, and an acrylic polyol of Mw 16000 as an acrylic polyol of (1-B) component Organotin catalyst (Mitsui Chemicals Polyurethane (Mitsui Chemicals Polyurethanes Co., Ltd.)) prepared by diluting a polyol ("LR2629" manufactured by Mitsubishi Rayon Co., Ltd .: solid content 55%) as an organometallic compound of 24 parts by mass and (1-C) component 1000 times in advance with methyl ethyl ketone. 4 parts by mass of “Formate TK-1” manufactured by Co., Ltd., and 5 parts by mass of polyisocyanate curing agent (“D-165N” manufactured by Mitsui Chemicals Polyurethanes Co., Ltd .: solid content 100%) as the (1-D) component. A resin composition was prepared by mixing 40 parts by mass of methyl ethyl ketone as a solvent and stirring for 5 minutes.

  Then, using a SUS304 test plate (manufactured by Nippon Test Panel Co., Ltd.) as a base material, the above hydrophilic resin composition was applied to the stainless steel base material by air spray so that the dry film thickness was 5 μm, and the temperature was 120 ° C. A painted plate was prepared by baking and drying at a temperature for 30 minutes.

( Reference Example 2)
As the (1-A) component, 64 parts by mass of the same hydrophilic acrylic polyol (1-A-1) as in Example 1, and as the (1-B) component, 24 masses of the same acrylic polyol “LR2629” as in Example 1. 4 parts by mass of the same organotin catalyst “Formate TK-1” as in Example 1 as the (1-C) component, and the same polyisocyanate curing agent “D-” as in Example 1 as the (1-D) component. A resin composition was prepared by mixing 7 parts by mass of “165N” and 40 parts by mass of methyl ethyl ketone as a solvent and stirring for 5 minutes. And the coated board was produced by coating this resin composition on a base material similarly to Example 1.

(Example 3)
A resin composition was prepared in the same manner as in Example 1 except that the hydrophilic acrylic polyol (1-A-2) synthesized in Synthesis Example 2 was used as the acrylic polyol of component (1-A). Further, a coated plate was produced in the same manner as in Example 1.

(Example 4)
Example 1 except that aminosilane ("KBM903" manufactured by Shin-Etsu Silicone Co., Ltd .: solid content 100%) previously diluted 100 times with methyl ethyl ketone was used as the basic organic silane compound of component (1-C). A resin composition was prepared in the same manner as in Example 1, and a coated plate was produced in the same manner as in Example 1.

(Example 5)
In addition to using imidazole silane (“IM-1000” manufactured by Nikko Metal Co., Ltd .: solid content 100%) as the basic organic silane compound of component (1-C), the blending amount was changed to 1 part by mass. Prepared a resin composition in the same manner as in Example 1, and produced a coated plate in the same manner as in Example 1.

(Example 6)
As the component (1-C), 4 parts by mass of an organotin catalyst ("Formate TK-1" manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) diluted 1000 times in advance with methyl ethyl ketone and imidazole silane (manufactured by Nikko Metal Co., Ltd.) A resin composition was prepared in the same manner as in Example 1 except that 1 part by mass of “IM-1000”: 100% solid content) was used in combination, and a coated plate was prepared in the same manner as in Example 1. .

(Comparative Example 1)
Using “Fressera R” manufactured by Matsushita Electric Works Co., Ltd., which is a silicone-based inorganic hydrophilic paint, the same stainless steel substrate as in Example 1 was applied by air spray so that the dry film thickness was 0.5 μm, and 150 A coated plate was prepared by baking and drying at a temperature of 10 ° C. for 10 minutes.

(Comparative Example 2)
Using “Fressera D” manufactured by Matsushita Electric Works, Ltd., which is a silicone-based inorganic water-repellent paint, it was applied to the same stainless steel substrate as in Example 1 with an air spray so that the dry film thickness was 1 μm, and 150 ° C. A coated plate was prepared by baking and drying at a temperature for 10 minutes.

(Comparative Example 3)
As the acrylic polyol of the (1-A) component, the synthesis was carried out except that the amount of the (C) component synthesized in the synthesis comparative example 1 was less than the range of claim 1 (1-A-3). A resin composition was prepared in the same manner as in Example 1, and a coated plate was produced in the same manner as in Example 1.

(Comparative Example 4)
As the acrylic polyol of the (1-A) component, it was carried out except that the amount of the (C) component synthesized in the above Comparative Example 2 was larger than the range of claim 1 (1-A-4). A resin composition was prepared in the same manner as in Example 1, and a coated plate was produced in the same manner as in Example 1.

(Comparative Example 5)
As the acrylic polyol of the (1-A) component, it was carried out except that the amount of the (D) component synthesized in the above Comparative Example 3 was less than the range of claim 1 (1-A-5). A resin composition was prepared in the same manner as in Example 1, and a coated plate was produced in the same manner as in Example 1.

(Comparative Example 6)
As the acrylic polyol of the (1-A) component, it was carried out except that (1-A-6), which was synthesized in the above-mentioned Synthesis Comparative Example 4 and the amount of the (D) component was larger than the range of claim 1, was used. A resin composition was prepared in the same manner as in Example 1, and a coated plate was produced in the same manner as in Example 1.

  In Comparative Example 6, the resin coating formed on the substrate surface using (1-A-6) was not evaluated because the coating itself was cloudy and the appearance was poor.

(Comparative Example 7)
As the acrylic polyol of the (1-A) component, it was carried out except that the amount of the (A) component synthesized in the above Comparative Example 5 was larger than the range of claim 1 (1-A-7). A resin composition was prepared in the same manner as in Example 1, and a coated plate was produced in the same manner as in Example 1.

(Comparative Example 8)
As the acrylic polyol of the (1-A) component, the procedure was carried out except that (1-A-8), which was synthesized in the above Comparative Example 6 and the amount of the (B) component was larger than the range of claim 1, was used. A resin composition was prepared in the same manner as in Example 1, and a coated plate was produced in the same manner as in Example 1.

(Comparative Example 9)
As (1-A) component acrylic polyol, the same procedure as in Example 1 was conducted except that (1-A-9), which was synthesized in Synthesis Comparative Example 7 above and (E) component was not used, was used. A resin composition was prepared, and a coated plate was produced in the same manner as in Example 1.

(Comparative Example 10)
(1-B) Acrylic polyol having a weight average molecular weight larger than the range of claim 1 and having an Mw of 54,000 (“AR3329” manufactured by Mitsubishi Rayon Co., Ltd .: solid content 50%) is used as the acrylic polyol of component (1-B). A resin composition was prepared in the same manner as in Example 1, and a coated plate was produced in the same manner as in Example 1.

(Comparative Example 11)
As the component (1-C), an epoxy silane that is not a basic organic silane compound (“KBM403” manufactured by Shin-Etsu Silicone Co., Ltd .: 100% solid content) was diluted 100 times with methyl ethyl ketone in advance and used. A resin composition was prepared in the same manner as in Example 1, and a coated plate was produced in the same manner as in Example 1.

(Comparative Example 12)
As the (1-A) component, 72 parts by mass of the same hydrophilic acrylic polyol (1-A-1) as in Example 1, and as the (1-B) component, 16 masses of the same acrylic polyol “LR2629” as in Example 1. 4 parts by mass of the same organotin catalyst “Formate TK-1” as in Example 1 as the (1-C) component, and the same polyisocyanate curing agent “D-” as in Example 1 as the (1-D) component. 165N ”and 40 parts by mass of methyl ethyl ketone as a solvent were mixed and stirred for 5 minutes to prepare a resin composition in which the amount of component (1-A) exceeds the range of claim 1. Thereafter, a coated plate was produced in the same manner as in Example 1.

(Comparative Example 13)
As the (1-A) component, 27 parts by mass of the same hydrophilic acrylic polyol (1-A-1) as in Example 1, and as the (1-B) component, 45 mass of the same acrylic polyol “LR2629” as in Example 1. 4 parts by mass of the same organotin catalyst “Formate TK-1” as in Example 1 as the (1-C) component, and the same polyisocyanate curing agent “D-” as in Example 1 as the (1-D) component. 7 parts by mass of “165N” and 40 parts by mass of methyl ethyl ketone as a solvent were mixed and stirred for 5 minutes to prepare a resin composition in which the amount of the (1-B) component was larger than the range of claim 1. Thereafter, a coated plate was produced in the same manner as in Example 1.

(Comparative Example 14)
As component (1-B), 24 parts by mass of the same acrylic polyol “LR2629” as in Example 1, and as component (1-C), 4 parts by mass of the same organotin catalyst “Formate TK-1” as in Example 1. As the (1-D) component, 4 parts by mass of the same polyisocyanate curing agent “D-165N” as in Example 1 and 40 parts by mass of methyl ethyl ketone as the solvent were mixed and stirred for 5 minutes. A) A resin composition containing no component was prepared. Thereafter, a coated plate was produced in the same manner as in Example 1.

(Comparative Example 15)
As the (1-A) component, 27 parts by mass of the same hydrophilic acrylic polyol (1-A-1) as in Example 1, and as the (1-C) component, the same organotin catalyst as “Example 1 TK- 4 parts by mass of 1 ”, (1-D) component, 3 parts by mass of the same polyisocyanate curing agent“ D-165N ”as in Example 1, and 40 parts by mass of methyl ethyl ketone as a solvent are mixed and stirred for 5 minutes. Thus, a resin composition in which the component (1-B) was not arranged was prepared. Thereafter, a coated plate was produced in the same manner as in Example 1.

(Comparative Example 16)
As the (1-A) component, 27 parts by mass of the same hydrophilic acrylic polyol (1-A-1) as in Example 1, and as the (1-B) component, 24 masses of the same acrylic polyol “LR2629” as in Example 1. By mixing 5 parts by weight of the same polyisocyanate curing agent “D-165N” as in Example 1 and 40 parts by weight of methyl ethyl ketone as a solvent, as the (1-D) component, and stirring for 5 minutes, (1 -C) A resin composition containing no component was prepared. Thereafter, a coated plate was produced in the same manner as in Example 1.

(Comparative Example 17)
An SPCC test plate (manufactured by Nippon Test Panel Co., Ltd.) was used as a base material, and a metallic powder paint (“788 Line Nissin Powder Coat S 788-605 Metallic Silver Medium” manufactured by Takashi Kubo Paint Co., Ltd.)) was used on this SPCC base material. Was applied by electrostatic spraying so as to have a film thickness of 60 μm, and baked at a temperature of 180 ° C. for 15 minutes to prepare a powder-coated coated plate.

About the coating board produced in Examples 1 and 3-6, the reference example 2, and the comparative examples 1-17 as mentioned above, the wiping removal property of oil, coating-film hardness, and the chemical-resistance test of a coating film are tested. Evaluated in line. The evaluation method is as follows, and the results are shown in Tables 2 and 3.

(Evaluation method)
(1) Oil wiping removal property, viscous oil wiping removal property Oil wiping removal property evaluation method 0.1 g of Nissin Salad Oil (Nisshin Oilio Co., Ltd.) is applied to the surface of the coated plate, Using a cloth (100% cotton) folded up to a size of 50 mm x 80 mm, after performing 3 reciprocating wipes with a load of 500 g, the color difference (ΔEab) from before oil adhesion was measured with a color difference meter. The evaluation criteria were evaluated.

Evaluation method of wiping and removing property of viscous oil Apply 0.1g of sansic poppy oil (manufactured by Holbein Kogyo Co., Ltd.) on the surface of the coated plate, leave it for 24 hours after application, and then make it 50mm x 80mm Using a folded cloth (100% cotton), three-way wiping was performed with a load of 500 g. Thereafter, the color difference (ΔEab) before the oil adhesion was measured with a color difference meter in the same manner as described above, and evaluated according to the following criteria.
(Criteria)
Less than ΔEab 1: ○
ΔEab greater than 1 and less than 3: Δ
Greater than ΔEab 3: x
(2) Coating film hardness test The hardness of the coating film was measured by the pencil method according to JISK5600-5-4.
(3) Chemical resistance test As test solutions, 5% sodium hydrogen carbonate aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.), oleic acid (manufactured by Wako Pure Chemical Industries, Ltd.), “Kitchen Magiclin Deodorant Plus” ( Kao Corporation) was used. And the kitchen paper cut into 1cm □ is piled on the surface of the paint board, the test solution is dropped on the kitchen paper once a day, put on the watch glass and allowed to stand, and the appearance of the coating film after 7 days is It was evaluated according to the criteria.
(Criteria)
No change in appearance: ○
There is a trace as a frame where it was dripping: △
The coating reaches peeling: ×

  As can be seen in Tables 2 and 3, it was confirmed that the examples had excellent oil wiping properties and excellent chemical resistance.

Claims (4)

(1-A) an acrylic polyol provided with a hydrophilic group;
(1-B) Mw 50000 or less , (1-A) acrylic polyol other than the component ,
(1-C) at least one selected from an organometallic compound and a basic organosilane compound;
(1-D) at least one curing agent selected from polyisocyanates and amino resins;
A resin composition containing at least as a constituent component,
While containing (1-A) component in the range of 10 to 60% by mass and (1-B) component in the range of 10 to {(24/57) × 100} % by mass,
(1-A) component is
(A) 30-70 mass% of (meth) acrylic acid alkyl ester monomers having 3 or less carbon atoms in the alkyl group,
(B) 5 to 40% by mass of a (meth) acrylic acid alkyl ester monomer having 4 or more carbon atoms in the alkyl group,
(C) 10 to 40% by mass of a monomer having an amide group,
(D) 10 to 30% by mass of a hydroxyalkyl ester monomer of (meth) acrylic acid,
A polymerization composition (α) obtained by copolymerizing (A) to (D) at a ratio of
(E) a surfactant having an active hydrogen group.
An oil easy-cleaning resin composition characterized by that.   The resin composition according to claim 1, wherein the basic organic silane compound (1-C) is a silane compound having a nitrogen-containing heterocyclic group in the structure.   A functional interior member, wherein the resin composition according to claim 1 or 2 is formed on a surface.   It is a kitchen member, The functional interior member of Claim 3 characterized by the above-mentioned.