KR102573493B1 - Kit for coating on a metal substrate and coated metal product - Google Patents

Abstract

The present invention relates to a metal material coating kit and a metal product, and more specifically to a modified acrylic resin; methylbenzene; at least one ketone-based solvent selected from 2-butanone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; and methanol; a first agent comprising; A first polymer containing PVC, a second polymer containing an adipate-based compound, a plasticizer, a stabilizer, a heat stabilizer, an antioxidant, a UV stabilizer, an inorganic filler, and a lubricant containing a second agent; and a resin coating agent comprising an acrylate compound-styrene-acrylonitrile copolymer; It relates to a metal material coating kit comprising a and a metal product manufactured using the same.

Description

Metal material coating kit and metal product {KIT FOR COATING ON A METAL SUBSTRATE AND COATED METAL PRODUCT}

The present invention relates to a metal material coating kit and a metal product.

An acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as 'ASA resin') is a styrene-based terpolymer resin widely used in the industry. ASA resin has excellent mechanical properties, including acrylic rubber with no ethylenically unsaturated group instead of butadiene rubber, and has weather resistance, aging resistance, chemical resistance, stiffness, impact resistance, and processability. ASA resin has various uses and is widely used in automobiles, miscellaneous goods, electrical/electronic parts, building materials, automobile interior and exterior materials, ship interior and exterior materials, leisure products, and gardening products.

However, ASA resin has the disadvantage of cracking or discoloration and deterioration of physical properties when exposed to various solvents or chemicals, and it is difficult to use for steel/plastic co-extrusion applications due to the low adhesive layer between the substrate and the coating process. there is. In particular, when the metal tube is double-extruded with the ASA resin, the metal tube and the ASA resin may not adhere to each other, and after a certain period of time, the ASA resin cracks or peels off. As the size of the final product increases, the cracking phenomenon may occur severely.

Therefore, it is necessary to develop a coating process and material capable of improving the adhesion between the metal tube and the ASA resin to enable a co-extrusion process and improving the stability of the ASA resin coating when the ASA resin is coated on the metal tube.

Korean Registered Patent Publication No. 10-2478502

An object of the present invention is to meet the above technical problems, to provide excellent adhesion performance between the second agent and the metal material, and to provide excellent compatibility with the heat-stable first agent and the resin (eg ASA resin) of the resin coating, It is to provide a metal material coating kit including a resin coating agent for a resin film on a metal material and a second agent, which is a thermoplastic elastomer having excellent high heat resistance characteristics, and capable of a co-extrusion process.

Another object of the present invention is to provide a metal product coated with a metal material coating kit, uniform film formation of a resin film by a co-extrusion process, and improved adhesion and thermal stability.

As a means for achieving the above object, the metal material coating kit of the present invention includes a modified acrylic resin; methylbenzene; at least one ketone-based solvent selected from 2-butanone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; and a first agent comprising methanol; A first polymer containing PVC, a second polymer containing an adipate-based compound, a plasticizer, a stabilizer, a heat stabilizer, an antioxidant, a UV stabilizer, an inorganic filler, and a lubricant containing a second agent; and a resin coating agent including an acrylate compound-styrene-acrylonitrile copolymer.

The composition of the present invention, the first agent is a modified acrylic resin 1% to 20% by weight, methylbenzene 10% to 40% by weight, ketone solvent 10% to 30% by weight; and 10% to 40% by weight of methanol, and the methylbenzene:mass ratio of the ketone-based solvent may be 1:1.5 to 1:4.

In the configuration of the present invention, the modified acrylic resin is one selected from the group consisting of an epoxy-modified styrene acrylic resin, an epoxy-modified acrylic resin, a polyester-modified acrylic resin, a silicone-modified acrylic resin, a polycarbonate-modified acrylic resin, and a fluorine-modified acrylic resin Or it may be one containing two or more kinds.

According to the configuration of the present invention, the first agent may further include 0.1% to 10% by weight of a polyester-modified urethane resin, an acrylic-modified urethane resin, or both.

The configuration of the present invention, the modified acrylic resin is one or two or more acrylate monomers selected from the group consisting of methyl methacrylate, hydroxyl ethyl methacrylate, cyclohexyl methacrylate and isobutyl methacrylate may include

According to the configuration of the present invention, the second agent comprises 40% to 70% by weight of the first polymer including the PVC, 10% to 30% by weight of the second polymer, and 1% to 10% by weight of the plasticizer. 1% to 10% by weight of the stabilizer, 0.1% to 5% by weight of the heat-resistant stabilizer, 0.01% to 2% by weight of the antioxidant, 0.01% to 1% by weight of the UV stabilizer, 5% to 5% by weight of the inorganic filler 20% by weight, and 0.01% to 2% by weight of the lubricant may be included.

In the configuration of the present invention, the heat-resistant stabilizer includes one or two or more selected from the group consisting of a phenol-based heat-resistant stabilizer, a sulfur-based heat-resistant stabilizer, and a phosphate-based heat-resistant stabilizer, and the phenol-based heat-resistant stabilizer is 2-tert-butyl- 4-methoxyphenol, 2-tert-butyl-4,6-dimethoxyphenol, 3,5-di-tert-butyl-4-hydroxytoluene, 4-hydroxymethyl-2,6-di-tert- Butylphenol, 2,4,6-tri-tert-butylphenol, 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 4,4'-butylidene-bis(6- tert-butyl-m-cresol), 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 2, 2'-dihydroxy-3,3'-bis(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane, 4,4'-methylene-bis(2,6-di-tert-butylphenol ), d,l-α-tocopherol (vitamin E), 2,6-bis(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methylphenol, 3-(4-hydroxy- 3,5-di-tert-butylphenyl)propionic acid n-octadecyl, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2 ,4,6-(1H,3H,5H)-trione, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)benzylbenzene , 1,3,5-tris(4-hydroxy-3,5-di-tert-butylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione, tetrakis [Methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, decamethylenecarboxylic acid disalicyloylhydrazide, N,N'-bis[3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 2,2'-oxyamide-bis-ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl ) Propionate, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3-methyl -4-hydroxy-5-tert-butylbenzyl) sulfide, 4,4'-butylidene-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)-2-laurylthioether , 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-bis(octylthio)-1,3,5-triazine and 2,4-bis(4-hydride) It may contain one or two or more selected from the group consisting of oxy-3,5-di-tert-butylanilino)-6-(n-octylthio)-1,3,5-triazine.

According to the configuration of the present invention, the mass ratio of the phenol-based heat-resistant stabilizer to the sulfur-based heat-resistant stabilizer is 1:0.1 to 1:1, and the sulfur-based heat-resistant stabilizer is 2-mercaptobenzimidazole, N,N'-diphenylthio Urea, tetramethylthiuram disulfide, N-oxydiethylene-2-benzothiazolyl sulfenamide, N-cyclohexyl-2-benzothiazolyl sulfenamide, cyclohexylamine salt of 2-mercaptobenzothiazole, N ,N-diisopropyl-2-benzothiazolesulfenamide, 2-(N,N-diethylthiocarbamoylthio)benzothiazole, tetraethylthiuramdisulfide, dibenzothiazyldisulfide, diethyldity Zinc carbamate, zinc ethylphenyldithiocarbamate, zinc di-n-butyldithiocarbamate, dilaurylthiodipropionate, dilaurylthiodi-1,1'-methylbutyrate, dimyristyl-3 One or two selected from the group consisting of 3'-thiodipropionate, laurylstearylthiodipropionate, distearylthiodipropionate, distearylthiodibutyrate and dioctadecyldisulfide Including the above, the phosphate-based heat stabilizer is 1 selected from the group consisting of phenyl diisodecyl phosphate, diphenyl isodecyl phosphate, triphenyl phosphate, trinonyl phenyl phosphate, calcium acetylacetonate, dioctyltin maleate and phosphate It may include a species or two or more species.

In the composition of the present invention, the stabilizer is in the group consisting of calcium stearate, ricinoleic acid calcium salt, zinc stearate and zinc ricinoleate The antioxidant includes one or two or more selected from the group consisting of hindered phenol, hindered amine, and diphenyl disulfide, and the lubricant includes chlorinated paraffin, wax, fatty acid It may include one or two or more selected from the group consisting of esters, fatty acid amides, ethylene bis steamides, and fatty acid amides.

According to the configuration of the present invention, the inorganic filler includes at least one shape of beads, flakes, filaments, fibers, plates, and powders, and the inorganic filler includes particles having an average size of 0.1 μm to 50 μm, and the The inorganic filler may further include particles surface-treated with an organic acid.

In the configuration of the present invention, the inorganic filler is stainless steel, silicon carbide, graphene, graphite, tartanium carbide, aluminum nitride, precipitated calcium carbonate, kaolin, aluminum silicate, silica, alumina, titanium dioxide, satin white , dolomite, mica, aluminum flakes, bentonite, rutile, magnesium hydroxide, gypsum, sheet silicates, talcum, calcium silicate; and oxides, nitrides, hydroxides and carbides of titanium, zirconium or hafnium; It may be one containing one or two or more selected from the group consisting of.

In the configuration of the present invention, the second polymer is polydi (2-ethylhexyl) glycol adipate (polydi (2-ethlhexyl) giycoladipate), poly (neopentyl glycol adipate) (poly (neopentyl glycol adipate)) and poly (1,2-propylene glycol adipate) (poly (1,2-propylene glycol adipate)), and the plasticizer is a metal perchlorate, citrate, polycyclopentadiene , hydrogenated terphenyl, polypropylene oxide, phosphoric acid ester, trimellitate, phthalate, benzoate, fatty acid ester alcohol, dimer acid ester, glutalate, dibutyl sebacate, dioctyl sebacate, diisopropyl As sebacate, acrylic acid ester, epoxidized fatty acid ester, epoxidized soybean oil, polyester, adipic acid, phthalate, azerato, dioctyl phthalate, (di)acetylated monoglyceride, diethyl 1,4-cyclohexanedicarboxylate It may contain one or two or more selected from the group consisting of latex, dioctyl terephthalate, and 1,2-cyclohexane dicarboxylic acid diisononyl ester.

As a means for achieving the above object, the metal product of the present invention, as manufactured by the metal coating kit, includes a metal material; a first layer formed by coating a first agent on the metal material; and a second layer formed on the first layer by double-extruding the metal material coated with the first layer, the second agent, and the resin coating agent, and a resin film layer formed on the second layer. can include

In the configuration of the present invention, the metal material coated with the first layer is first heated at a temperature of 120 ° C to 300 ° C using a high-frequency heater, followed by double extrusion, and after double extrusion, at a temperature of 80 ° C to less than 150 ° C. It may be prepared by heating the car.

In the configuration of the present invention, the hardness (Rockwell surface hardness) of the second layer is 80 or more, the thermal expansion coefficient of the second layer is 50 ppm / ° C or less, and the thermal expansion coefficient (CTE) of the metal material and the second layer ) may be less than ± 20 ppm / ° C.

In the configuration of the present invention, the thickness of the first layer is 0.5 μm to 50 μm, the thickness of the second layer is 0.5 μm to 200 μm, and the thickness of the resin film layer is 0.5 μm to 2000 μm.

The present invention includes a second agent, which is an elastic material that is compatible with a resin coating agent (eg, ASA resin) and has excellent heat resistance, and a first agent that is an adhesive capable of attaching the second agent to a metal material, A metal material coating kit having improved thermal stability and adhesion may be provided.

The present invention can provide a metal material coating kit capable of forming a resin film on a metal material by co-extrusion (eg, double extrusion or triple extrusion) at a high temperature (eg, 180 ° C. or higher).

The present invention can provide a metal product with improved adhesion and stability between the metal material and the resin film by offsetting the thermal expansion coefficient between the metal material and the resin film (eg ASA resin film) using the metal material coating kit of the present invention.

Hereinafter, various embodiments of the present invention will be described in detail. And, in describing the embodiments of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. In addition, terms to be described later are terms defined in consideration of functions of the present invention, which may vary according to the intention or custom of a user or operator. Therefore, the definition should be made based on the contents throughout this specification.

Hereinafter, the metal coating kit and the metal product of the present invention will be described in detail with reference to Examples. However, the present invention is not limited to these examples.

According to one embodiment, a metal material coating kit is a kit for surface treatment of a metal material or formation of a resin film, and includes a first agent used as a surface treatment agent for improving surface adhesive or adhesion; A second agent for controlling the thermal properties to improve the adhesiveness or stability of the resin film; And a resin coating agent; may include.

According to an embodiment, the metal material may be a metal thin film, a metal stick (eg, a tube, a rod, or a polygonal tube), a metal plate, or a metal film, but is not limited thereto. For example, the metal material may include metal (eg, aluminum, copper, iron, titanium, magnesium, etc.), alloy (eg, copper alloy, aluminum alloy, iron alloy, titanium alloy, magnesium alloy), stainless steel (eg, austenite-based). It may be Ferrite-based, Martensite-based, Duplex-based), steel, etc., but is not limited thereto. For example, steel, steel, copper (e.g. copper foil), AZ91, AM60, ZK51, ZK61, AZ31, AZ61, ZK60, SUS 304, SUS 310, SUS 316, SUS 321, STS 410, STS 430, STS 304, It may be STS 631 or the like, but is not limited thereto.

According to one embodiment, the surface roughness (Ra) of the metal material is 0.5 μm or more, 1.0 μm or more, 1.6 μm or more, 2.0 μm or more; 5.0 μm or less, 4.0 μm or less, or 3.0 μm or less (the minimum and maximum values can be selected from the values mentioned here). By adjusting the surface roughness of the metal material, film formation and adhesion by the first agent may be improved.

According to one embodiment, the first agent may include a modified acrylic resin and a solvent. According to one embodiment, the modified acrylic resin is 1% to 20% by weight of the first agent; 5% to 20% by weight; 10% to 18% by weight; or 12% to 18% by weight. When included within the above range, an acrylic one-component adhesive for adhesiveness may be provided, and adhesiveness and thermal stability may be improved.

According to one embodiment, the modified acrylic resin is one selected from the group consisting of an epoxy-modified styrene acrylic resin, an epoxy-modified acrylic resin, a polyester-modified acrylic resin, a silicone-modified acrylic resin, a polycarbonate-modified acrylic resin, and a fluorine-modified acrylic resin. Or two or more may be included. Preferably, it may be an epoxy-modified styrene acrylic resin, an epoxy-modified acrylic resin, and a silicone-modified acrylic resin in consideration of thermal stability.

According to one embodiment, the modified acrylic resin is one or two or more acrylate monomers selected from the group consisting of methyl methacrylate, hydroxyl ethyl methacrylate, cyclohexyl methacrylate, and isobutyl methacrylate, or These polymers may be included. For example, the silicone-modified acrylic resin contains 10% to 40% by weight of a silicone acrylate monomer (e.g., preferably 10% to 15% by weight), 30% to 70% by weight of an acrylate monomer, and 10% by weight of an organic solvent. It may be prepared by polymerizing a mixture of 0.5 wt% to 5 wt% of an initiator and 0.5 wt% to 30 wt%. Here, the organic solvent is not particularly limited, but may be selected from butyl acetate, xylene, and the like. The initiator is not particularly limited, but aromatic ketones such as acetophenone, benzophenone, xanthone, benzoin compounds and the like; tertiary amines such as triethanolamine, methyldiethanolamine and 4-dimethylaminobenzophenone; acylphosphorous compounds including triorganobenzoyldiarylphosphine oxide, triorganobenzoyldiorganophosphonate and triorganobenzoyldiarylphosphine sulfide; benzoyl peroxide; azoisobutylonitrile; etc. can be selected.

According to one embodiment, the solvent is an organic solvent and may include an aromatic hydrocarbon-based solvent, a ketone-based solvent, and alcohol. The solvent is the balance of the first agent, 99% to 80% by weight, or 90% to 80% by weight; or 90% to 84% by weight. When it is within the above range, it is uniformly applied on the metal material and adhesion between the second agent and the metal material can be improved. For example, 10 wt% to 40 wt% of an aromatic hydrocarbon-based solvent and 10 wt% to 30 wt% of a ketone-based solvent in the first agent in consideration of adhesiveness and thermal stability; and 10% to 40% by weight of alcohol.

According to one embodiment, the mass ratio (w / w) of the aromatic hydrocarbon-based solvent (eg, methylbenzene): the ketone-based solvent of the solvent is 1: 1.5 to 1: 4; 1:1.5 to 1:3; or 1: 1.5 to 1: 2.5; When included within the above mass ratio range, uniform surface treatment, adhesiveness, and thermal stability by the first agent may be improved.

According to one embodiment, the aromatic hydrocarbon-based solvent may include one or two or more selected from the group consisting of benzene, toluene, xylene, mesitylene, and methyl benzene. According to one embodiment, the ketone-based solvent includes one or two or more selected from the group consisting of 2-butanone (ie, methyl ethyl ketone), acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone can do. According to one embodiment, the alcohol may be selected from alcohols having 1 to 3 carbon atoms. Preferably, the solvent may include methylbenzene, 2-butanone and methanol. More preferably, the first agent may include 25% to 35% by weight of methylbenzene, 15% to 25% by weight of a ketone solvent, and 25% to 35% by weight of methanol. This can improve uniform surface treatment, adhesion and thermal stability by the first agent.

According to one embodiment, the first agent may further include a polyester-modified urethane resin, an acrylic-modified urethane resin, or both. It is the balance or 0.1% to 10% by weight of the first agent; 0.1% to 8% by weight; 0.5% to 5% by weight; or 1% to 3% by weight. When included within the above range, adhesiveness and thermal stability by the first agent may be improved.

According to one embodiment, the second agent is a first polymer containing polyvinyl chloride (PVC), a second polymer containing an adipate-based compound, a plasticizer, a stabilizer, a heat-resistant stabilizer, an antioxidant, a UV stabilizer, Inorganic fillers and lubricants may be included. The second agent is a thermoplastic polymer elastomer with excellent heat resistance in a high-temperature coating or extrusion process, and realizes the formation of a resin film by a high-temperature co-extrusion process by lowering the difference in thermal expansion coefficient between the metal material and the resin coating agent (or resin film layer) , the stability of the resin film can be secured. That is, by forming an intermediate layer (eg, a second layer) between the thin film by the first agent and the resin film in the coating of the metal material, it can provide a bumper role during thermal expansion between the resin film layer and the metal material at high temperature.

According to one embodiment, the first polymer containing the PVC is 40% to 70% by weight of the second agent; 45% to 60% by weight; or 50% to 55% by weight. When included within the above range, it is possible to provide elasticity and flexibility to the intermediate layer (eg, the second layer) by the second agent, and to provide a resin matrix that provides excellent compatibility with a resin film (eg, ABS resin).

According to one embodiment, the second polymer may be kneaded and compounded with the first polymer to improve hardness and heat resistance. The second polymer is 10% to 30% by weight of the second agent; 15% to 25% by weight; or 15% to 20% by weight; can be When included within the above range, compatibility with the components of the second agent is excellent, and elasticity, flexibility, and hardness of the second agent can be improved.

According to one embodiment, the second polymer is polydi (2-ethylhexyl) glycol adipate (polydi (2-ethlhexyl) giycoladipate), poly (neopentyl glycol adipate) (poly (neopentyl glycol adipate)) and poly It may include one or two or more selected from the group consisting of (1,2-propylene glycol adipate) (poly (1,2-propylene glycol adipate)). Preferably, it may be polydi(2-ethlhexyl)giycoladipate and poly(neopentyl glycol adipate).

According to one embodiment, the molecular weight (Mw) of the second polymer is 1000 to 100,000; 5,000 to 100,000; 10,000 to 100,000; 10,000 to 95,000; or 50,000 to 95,000 (g/mol). When included within the above molecular weight range, elasticity and flexibility of the second agent may be improved, and excellent processability may be provided.

According to one embodiment, the plasticizer is 1% to 10% by weight of the second agent; 2% to 8% by weight; or 5% to 8% by weight. When included within the above range, processability, elasticity, and flexibility of the second agent may be improved, and compatibility of a resin film (eg, ABS resin) may be improved in a metal material coating process.

According to one embodiment, the plasticizer is a metal perchlorate of alkali metal, alkaline earth metal, aluminum, zinc, lanthanum or cerium metal perchlorate; aromatic oil; cyclic olefins such as citrate and polycyclopentadiene; poly alpha olefins; hydrogenated terphenyls or other terpene derivatives; polypropylene oxide, phosphoric acid ester; trimellitate; phthalates; benzoate; fatty acid ester alcohol; dimer acid ester; grtarayto; sebacates such as dibutyl sebacate, dioctyl sebacate, and diisopropyl sebacate; acrylic acid ester; epoxidized fatty acid esters; epoxidized soybean oil; Polyester; polyethers such as adipic acid, phthalate, and azereto; as dioctyl phthalate; (di) acetylated monoglyceride; diethyl 1,4-cyclohexanedicarboxylic acid (diethylester); dioctyl terephthalate; And 1,2-cyclohexane dicarboxylic acid diisononyl ester (1,2-cyclohexane dicarboxylic acid diisononyl ester); may include one or two or more selected from the group consisting of. Preferably selected from (di)acetylated monoglyceride, 1,4-cyclohexanedicarboxylicacid (diethylester) and dioctyl terephthalate It can be.

According to one embodiment, the stabilizer is 1% to 10% by weight of the second agent; 1% to 8% by weight; 1% to 5% by weight; or 2% to 3% by weight. When contained within the above range, it is possible to provide appropriate viscosity to the second agent and improve bonding with the first agent.

According to one embodiment, the stabilizer is from the group consisting of calcium stearate, ricinoleic acid calcium salt, zinc stearate and zinc ricinoleate. One or two or more selected species may be included. Preferably, it may be calcium stearate.

According to one embodiment, the heat-resistant stabilizer is 0.1% to 5% by weight of the second agent; 0.1% to 3% by weight; 0.1% to 2.5% by weight; 0.5% to 2.5% by weight; or 1% to 2% by weight. When included within the above range, the thermal properties of the second agent are effectively controlled (eg, reduction in the thermal expansion coefficient difference between the metal material and the resin film) without deteriorating compatibility between the second agent and the resin film (eg, ABS resin), and the resin The stability of the film can be imparted.

According to one embodiment, the heat-resistant stabilizer is a high heat-resistant stabilizer, and may include, for example, one or two or more selected from the group consisting of a phenol-based heat-resistant stabilizer, a sulfur-based heat-resistant stabilizer, and a phosphate-based heat-resistant stabilizer. Preferably, it may be a mixture of the phenol-based heat-resistant stabilizer and the sulfur-based heat-resistant stabilizer. For example, the mass ratio of the phenol-based heat-resistant stabilizer to the sulfur-based heat-resistant stabilizer is 1:0.1 to 1:1; 1:0.3 to 1:1; or 1:0.5 to 1:0.8. By applying the mass ratio, the thermal properties of the second agent are effectively controlled (eg, reduction in the thermal expansion coefficient difference between the metal material and the resin film) without degrading the compatibility between the second agent and the resin film (eg, ABS resin), and the resin The stability of the film can be imparted. For example, it may preferably be a mixture of the phenol-based heat-resistant stabilizer, the sulfur-based heat-resistant stabilizer, and the phosphate-based heat-resistant stabilizer. For example, the mass ratio of the phenol-based heat-resistant stabilizer to the sulfur-based heat-resistant stabilizer to the phosphate-based heat-resistant stabilizer is 1:0.1 to 1:0.1 to 1; 1 : 0.3 to 1 : 0.3 to 1; or 1:0.5 to 0.8:0.5 to 0.8. By applying the mass ratio, the thermal properties of the second agent are effectively controlled (eg, reduction in the thermal expansion coefficient difference between the metal material and the resin film) without degrading the compatibility between the second agent and the resin film (eg, ABS resin), and the resin The stability of the film can be imparted.

According to one embodiment, the phenolic heat-resistant stabilizer is 2-tert-butyl-4-methoxyphenol, 2-tert-butyl-4,6-dimethoxyphenol, 3,5-di-tert-butyl-4- Hydroxytoluene, 4-hydroxymethyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2,2'-methylene-bis(4-ethyl-6-tert -butylphenol), 4,4'-butylidene-bis(6-tert-butyl-m-cresol), 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 4,4 '-bis(2,6-di-tert-butylphenol), 2,2'-dihydroxy-3,3'-bis(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane, 4 ,4'-methylene-bis(2,6-di-tert-butylphenol), d,l-α-tocopherol (vitamin E), 2,6-bis(2-hydroxy-3-tert-butyl-5 -Methylbenzyl)-4-methylphenol, 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionic acid n-octadecyl, 1,3,5-tris(4-tert-butyl-3 -Hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H, 3H,5H)-trione, 1,3,5-trimethyl-2,4,6-tris( 3,5-di-tert-butyl-4-hydroxyphenyl)benzylbenzene, 1,3,5-tris(4-hydroxy-3,5-di-tert-butylbenzyl)-s-triazine-2 ,4,6-(1H,3H,5H)-trione, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, decamethylenecarboxylic acid di Salicyloylhydrazide, N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 2,2'-oxyamide-bis-ethyl- 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide, 4,4'-butylidene-bis(2-methyl-4 -Hydroxy-5-tert-butylphenyl)-2-laurylthioether, 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-bis(octylthio)- 1,3,5-triazine and 2,4-bis(4-hydroxy-3,5-di-tert-butylanilino)-6-(n-octylthio)-1,3,5-triazine It may include one or two or more selected from the group consisting of.

According to one embodiment, the sulfur-based heat-resistant stabilizer is 2-mercaptobenzimidazole, N, N'-diphenylthiourea, tetramethylthiuram disulfide, N-oxydiethylene-2-benzothiazolyl sulfenamide , N-cyclohexyl-2-benzothiazolylsulfenamide, cyclohexylamine salt of 2-mercaptobenzothiazole, N,N-diisopropyl-2-benzothiazolesulfenamide, 2-(N,N- Diethylthiocarbamoylthio)benzothiazole, tetraethylthiuramdisulfide, dibenzothiazyldisulfide, zinc diethyldithiocarbamate, zinc ethylphenyldithiocarbamate, di-n-butyldithiocarbamic acid Zinc, dilaurylthiodipropionate, dilaurylthiodi-1,1'-methylbutyrate, dimyristyl-3,3'-thiodipropionate, laurylstearylthiodipropionate, distea It may include one or two or more selected from the group consisting of arylthiodipropionate, distearylthiodibutyrate, and dioctadecyldisulfide.

According to one embodiment, the phosphate-based heat stabilizer is selected from the group consisting of phenyl diisodecyl phosphate, diphenyl isodecyl phosphate, triphenyl phosphate, trinonyl phenyl phosphate, calcium acetylacetonate, dioctyltin maleic phosphate and phosphoric acid salts. One type or two or more types may be included.

According to one embodiment, the antioxidant is 0.01% to 2% by weight of the second agent; 0.01% to 1.5% by weight; 0.01 wt % to 1 wt %; 0.05% to 2% by weight; 0.1% to 2% by weight; 0.2% to 1% by weight; 0.2% to 0.5% by weight; can be When included within the above range, it is possible to improve stability by preventing deterioration of the film.

According to one embodiment, the antioxidant may include one or two or more selected from the group consisting of hindered phenols, hindered amines, and diphenyl disulfide. For example, the hindered phenol is BHT, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), pentaerythritol tetrakis[3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate], 3,3',3",5,5',5"-hexa-tert-butyl-α,α',α"-(mesitylene-2,4,6 -triyl)tri-p-cresol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris[(4-tert-butyl -3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (3 ,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, calcium diethylbis[{3, 5 -Screw(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]phosphonate, bis(2,2'-dihydroxy-3,3'-di-tert-butyl-5,5'- Hindered phenolic antioxidants such as dimethylphenyl)ethane, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl)-4-hydroxyphenyl]propionamide, etc. For example, the antioxidant may be "IRGANOX 1010" from Ciba (now part of BASF) (Germany) and "NAUGARD 445" from Chemtura Europe, Ltd (UK). In order to ensure the compatibility of the antioxidant, the molecular weight (M _W ) may be 200 to 2,000 (g/mol).

According to one embodiment, 0.01% to 1% by weight of the second agent of the UV stabilizer; 0.01% to 0.8% by weight; 0.01% to 0.5% by weight; 0.05% to 1% by weight; 0.1% to 0.5% by weight; or 0.2% to 0.3% by weight. When included within the above range, it is possible to effectively suppress ultraviolet degradation (ultraviolet degradation) causing the formation of microcracks (eg, cracks), exfoliation, and yellowing of the second agent. According to one embodiment, the UV stabilizer may include an organic UV stabilizer, an inorganic UV stabilizer, or both ultraviolet (UV) light stabilizers. For example, the organic UV stabilizer is triazine, benzotriazole, benzoxazinone, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl)oxy phenols (eg ^Tinuvin® 1577), 2,2,6,6-tetramethylpiperidinyl derivatives (Tinuvin 123 (BASF) or Hostavin 3058 (Clariant)).

According to one embodiment, the lubricant is to lower the viscosity of the melt, extrusion and injection load in the extrusion process, 0.01% to 2% by weight of the second agent; 0.01% to 1.5% by weight; 0.01% by weight to 1; 0.01% to 0.5% by weight; 0.1% to 0.5% by weight; or 0.2% to 0.5% by weight. When included within the above range, adhesion with the first agent is well achieved in the co-extrusion process, and a uniform resin film (eg, ABS resin) can be formed.

According to one embodiment, the inorganic filler is 5% to 20% by weight of the second agent; 5% to 15% by weight; or 10% to 15% by weight. When included within the above range, it is possible to prevent appearance defects due to excessive use and to improve elasticity and flexibility. In addition, the bumper function can be activated during thermal expansion between the metal material and the resin film.

According to one embodiment, the inorganic filler includes at least one shape of beads, flakes, fibers, filaments, plates, and powders, and the inorganic filler has a thickness of 0.1 μm to 50 μm; 0.1 μm to 35 μm; 0.1 μm to 30 μm; 0.1 μm to 20 μm; 0.3 μm to 20 μm; It may include particles having an average size of 0.5 μm to 10 μm. Here, the size may be length, thickness, diameter, radius, etc. according to the shape of the particle, and may be, for example, an average particle diameter.

According to one embodiment, the inorganic filler may be selected from organic acids, silanes (eg, alkyl silanes), amino acids, carboxylic acids, It may be surface-treated with at least one or two or more selected from the group consisting of polyamines, ammonia based compounds, and quaternary ammonium compounds. Preferably, it may include particles surface-treated with an organic acid. For example, the organic acid is oxalic acid, malic acid, maleic acid, malonic acid, formic acid, lactic acid, acetic acid, picolinic acid, citric acid, succinic acid, tartaric acid, glutaric acid, glutamic acid, glycolic acid, propionic acid, fumaric acid, salicylic acid, pimelin It may include one or two or more selected from the group consisting of acid, benzoic acid, butyric acid, aspartic acid, sulfonic acid, and phthalic acid. Preferably, the surface-treated particles with the organic acid is 0.01 to 5 parts by weight based on 100 parts by weight of the particles; 0.01 parts by weight to 2 parts by weight; Alternatively, 0.1 part by weight to 1 part by weight of an organic acid may be included.

According to one embodiment, the inorganic filler is a metal; metalloid; oxides, nitrides, hydroxides, carbides, carbonates, silicates, hydrates, dioxides, phosphates and peroxides of metals, metalloids or both; It may include at least one or more of a mineral and an alloy. For example, at least one oxide or nitride selected from among silicon, aluminum, gallium, tin, cobalt, cerium, iron, barium, germanium, magnesium, nickel, copper, zinc, vanadium, calcium, titanium, manganese, zirconium, and hafnium. , hydroxides and carbides; It may include one or two or more selected from the group consisting of. For example, the inorganic filler is stainless steel, silicon carbide, graphene, graphite, tartanium carbide, aluminum nitride, precipitated calcium carbonate, kaolin, aluminum silicate, silica, alumina, ceria, zirconia, titania, barium titania, germania, mangania, magnesia, titanium dioxide, satin white, dolomite, mica, aluminum flakes, bentonite, rutile, magnesium hydroxide, gypsum, sheet silicates ), talcum, calcium silicate; And titanium, zirconium or hafnium oxides, nitrides, hydroxides and carbides; may include one or more selected from the group consisting of.

According to one embodiment, the resin coating agent may include an acrylate compound-styrene-acrylonitrile copolymer, and may further include a residual amount of a solvent and an additive. The acrylate compound-styrene-acrylonitrile copolymer is 1% to 99% by weight of the resin coating agent; 10% to 95% by weight; 30% to 90% by weight; 50% to 90% by weight; 70% to 90% by weight; or 80% to 90% by weight. When included within the above range, compatibility and adhesion with the second agent are good, and poor appearance and deterioration in stability after the co-extrusion process can be prevented.

According to one embodiment, the resin coating agent may further include a residual amount or 1% to 99% by weight of a solvent. ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, and propylene glycol ethyl propyl ether; propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, and butoxybutyl alcohol; butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate; butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, and butoxybutyl propionate; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether; Aromatic hydrocarbons, such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylmethylpropionate, 2-hydroxy-2-methylethylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate , Butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methoxymethylacetate, methoxyethylacetate, methoxyacetate propyl, methoxybutylacetate, ethoxymethylacetate, ethoxyethylacetate, ethoxyacetatepropyl, ethoxyacetatebutyl, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methoxymethylpropionate, 2-methoxypropionic acid Ethyl, 2-methoxypropylpropionate, 2-methoxybutylpropionate, 2-ethoxymethylpropionate, 2-ethoxyethylpropionate, 2-ethoxypropylpropionate, 2-ethoxybutylpropionate, 2-butoxymethylpropionate , 2-butoxyethylpropionate, 2-butoxypropylpropionate, 2-butoxybutylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-methoxypropylpropionate, 3-methoxybutylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, 3-ethoxypropylpropionate, 3-ethoxybutylpropionate, 3-propoxymethylpropionate, 3-propoxyethylpropionate, 3-propoxypropylpropionate, 3 -Esters such as butyl propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and pyran; And γ-butyrolactone may include one or more selected from cyclic esters.

According to one embodiment, the resin coating agent may further include other additives such as dyes as needed, but this document does not specifically mention them.

According to one embodiment, the metal product of the present invention is manufactured with a metal material coating kit according to one embodiment of the present invention, the metal product includes a metal material; a first layer formed by coating the first agent on the metal material; a second layer on the first layer; and a resin coating layer on the second layer.

According to one embodiment, the first layer may be formed by applying (or coating) the first agent on the metal material. For example, spray coating (eg, ultrasonic spray), spin coating, extrusion, and the like may be used. For example, the first layer may be an adhesive layer that stably bonds the second layer and the metal material and has excellent thermal stability.

According to one embodiment, the thickness of the first layer, 0.5 ㎛ to 50 ㎛; 0.5 μm to 30 μm; 0.5 μm to 20 μm; Or it may be 1 μm to 10 μm. When it is included within the above thickness range, it is uniformly applied on the metal material and the stability of the resin film can be maintained while improving the adhesion with the second agent.

According to an embodiment, after applying (or coating) the first agent on the surface of the metal material, the first agent may be heated, which will be described in more detail below. According to an embodiment, the second layer formed on the first layer and the second layer formed on the second layer by air-extruding (eg, double extrusion) the second agent and the resin coating agent on the metal material coated with the first layer in an extruder. The formed resin film layer can be formed.

According to one embodiment, the metal material coated with the first layer is heated to 120 ° C to 300 ° C using a high-frequency heater; 150 °C to 250 °C; Alternatively, it may be heated to a temperature of 180 °C to 200 °C. Also, 1 minute to 12 hours at the above temperature; 5 minutes to 10 hours; Alternatively, it may be heated (or maintained) for 10 minutes to 5 hours. Next, the heat-treated metal material coated with the first layer may be double-extruded with a second agent and a resin coating agent. For example, the temperature (eg, processing temperature of ASA) in the double extrusion process may be the same as or higher than the first heating temperature. For example, 180 ° C or higher; or 180 °C to 250 °C. Next, the metal material coming out of the extruder after double extrusion has a temperature of 80 ° C to less than 150 ° C; 80 °C to 140 °C; 80 °C to 120 °C; 80 °C to 100 °C; or at least 10 minutes at a temperature of 90° C. to 100° C.; more than 30 minutes; 1 hour to 12 hours; 1 hour to 10 hours; Alternatively, secondary heating (eg, maintenance) may be performed for 2 to 5 hours. The first heating temperature may be higher than the second heating temperature. By applying the above-mentioned primary heating and secondary heating, the formation of a uniform film and the coextrusion process of the resin film can be smoothly performed. Moreover, it is possible to secure film stability by preventing peeling and cracking of the resin film.

According to one embodiment, according to one embodiment, the thickness of the second layer is 0.5 ㎛ to 200 ㎛; 1 μm to 200 μm; 2 μm to 150 μm; 5 μm to 100 μm; 10 μm to 90 μm; or 20 μm to 60 μm, and the thickness of the resin film layer is 0.5 μm or more; 0.5 μm to 2,000 μm; 1 μm to 2,000 μm; 5 μm to 1,000 μm; 10 μm to 900 μm; 20 μm to 800 μm; 30 μm to 700 μm; 30 μm to 500 μm; 40 μm to 300 μm; 40 μm to 200 μm; 40 μm to 100 μm; Or it may be 40 μm to 60 μm. The first layer, the second layer and the resin film layer may have the same or different thicknesses. For example, the thickness ratio of the first layer: the second layer: the resin coating layer is 1:1 to 20:1 to 200; 1:1 to 5:5 to 100; or 1:1 to 3:10 to 50. When included within the thickness ratio range, the adhesion of the second layer by the first layer may be improved, and compatibility between the second layer and the resin coating layer and a buffer function during thermal expansion may be improved.

According to one embodiment, the second layer may have high hardness and excellent heat resistance while having flexibility and elasticity. The hardness of the second layer is 80 or more; 85 or higher; or 95 or greater. Here, the hardness may be Rockwell Superficial Hardness (standard measurement method applied, based on 15 N, 30 N, or 45 N).

According to one embodiment, the thermal expansion coefficient of the second layer, 50 ppm / ℃ or less; 30 ppm/° C. or less; up to 25 ppm/°C or greater than 0 to 50 ppm/°C (20°C to 100°C). According to one embodiment, the difference between the coefficient of thermal expansion (CTE) of the metal material and the second layer is ± 20 ppm / ℃ or less; ± 10 ppm/°C or less; ± 5 ppm/° C. or less; or ± 2 ppm/° C. or less; ± 1 ppm/°C or less (20°C to 100°C); may be Due to the thermal expansion coefficient value or the difference in thermal expansion coefficient, it is possible to manufacture a metal product by a high-temperature co-extrusion process of the resin coating layer, and it is possible to improve the adhesion stability of the resin coating layer.

Example

Preparation Example 1

The first agent was prepared by mixing methylbenzene (34% by weight), 2-butanone (20% by weight), methanol (30% by weight) and a modified acrylic polymer (16% by weight, silicone-modified acrylic resin).

The second agent is PVC 52.8% by weight, second polymer 20% by weight (polydi (2-ethylhexyl) glycol adipate; _MW 95,000), plasticizer 7.5% by weight (polycyclopentadiene), stabilizer 2.5% by weight (lysi oleic acid calcium salt), high heat-resistant stabilizer 1.5% by weight (2-mercaptobenzimidazole), antioxidant 0.25% by weight (2,2'-methylenebis (4-methyl-6-tert-butylphenol), UV stabilizer It was prepared by compounding 0.3% by weight (benzotriazole), 15% by weight (aluminum nitride) of an inorganic filler and 0.15% by weight (chlorinated paraffin) of a lubricant.

Preparation Example 2

A first agent and a second agent were prepared in the same manner as in Preparation Example 1, except that 2-tert-butyl-4-methoxyphenol was used as a high heat-resistant stabilizer.

Preparation Example 3

The first agent was prepared in the same manner as in Preparation Example 1 except that 2-tert-butyl-4-methoxyphenol: 2-mercaptobenzimidazole: phenyldiisodecyl phosphate (1: 0.1: 0.5 mass ratio) was applied as a high heat-resistant stabilizer. and a second agent were prepared.

Production Example 4

A first agent and a second agent were prepared in the same manner as in Preparation Example 1, except that titania surface-coated with picolinic acid (0.1% by weight) was applied as the inorganic filler.

(Example 1)

Production of metal pipe coating products

A metal product was produced by co-extruding the first agent and the second agent of Production Example 1 into a metal pipe using an ASA resin (single component).

A metal tube (stainless steel, KS (JIS) 301, coefficient of thermal expansion: 16.9 to 17.0 x 10 ⁻⁶ /° C. (20° C. to 100° C.) was prepared.

In the extruder system, the metal tube was transported using an extractor, washed, and spray-coated with a first agent (adhesive). Next, the metal tube was preheated to a temperature of 120° C. or higher using a high-frequency heater and inserted into a mold. A second (intermediate layer) extruder and an ASA resin extruder were connected to the extrusion mold, and the middle layer and the ASA resin layer were double-extruded at 180° C. or higher, which is the processing temperature of the ASA resin.

The metal product was formed with a thickness of 1 μm for the first layer, 100 μm for the second layer, and 200 μm for the resin coating layer.

(Example 2)

A metal product was manufactured in the same manner as in Example 1 except for using the first and second agents of Preparation Example 2. The metal product was formed with a first layer of 1 μm, a second layer of 100 μm, and a resin coating layer of 200 μm.

(Example 3)

A metal product was manufactured in the same manner as in Example 1 except for using the first and second agents of Preparation Example 3. The metal product was formed with a first layer of 1 μm, a second layer of 100 μm, and a resin coating layer of 200 μm.

(Example 4)

A metal product was manufactured in the same manner as in Example 1 except for using the first and second agents of Preparation Example 4. The metal product was formed with a first layer of 1 μm, a second layer of 100 μm, and a resin coating layer of 200 μm.

(Comparative Example 1)

A metal product was manufactured by forming a resin coating layer on a metal pipe in the same manner as in Example 1, except that the first agent was not applied. The metal product was formed with a second layer of 100 μm and a resin coating layer of 200 μm.

(Comparative Example 2)

A metal product was manufactured by forming a resin coating layer on a metal pipe in the same manner as in Example 1, except that the second agent was not applied. The metal product was formed with a first layer of 1 μm and a resin film layer of 200 μm in thickness.

Measurement of Coefficient of Thermal Expansion (CTE)

It can be measured using a standard method known in the art. For example, the cured film of the second agent for evaluation was cut to a width of about 5 mm and a length of about 15 mm to obtain a test piece. About the test piece, thermomechanical analysis was performed by the tensile weighting method using the thermomechanical analyzer ("Thermo Plus TMA8310" by Rigaku). Specifically, after the test piece was mounted in the thermomechanical analyzer, the coefficient of thermal expansion was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5°C/min. Next, based on the second measurement result, the thermal expansion coefficient 　α (ppm/°C) in the range from 25°C (298K) to 150°C (423K) was calculated. The second samples of Production Examples 1 to 4 obtained thermal expansion coefficients of about 20 to 23 (ppm/°C).

High Thermal Storage test (HTS (High Thermal Storage test))

A high temperature storage test was performed using a standard method known in the art.

Specimens of the metal products of Examples 1 to 4 and Comparative Examples 1 to 2 were prepared and submitted to the HTS test (High Thermal Storage test). Basically, it was evaluated based on the 150 ° C. / 1000 h condition.

crack resistance test

Specimens of the metal products of Examples 1 to 4 and Comparative Examples 1 to 2 were prepared, and the test pieces were subjected to 1,000 cycles of -30 ° C. 30 minutes / (room temperature; 25 ° C.) / 150 ° C. 30 minutes as one cycle. After repetition, the appearance was visually observed and evaluated according to the following criteria.

The manufactured metal products were observed with the naked eye and an optical microscope for the state (peeling, cracks) of the resin coating film in the crack resistance test.

When the resin film was co-extruded using the first agent and the second agent according to the present invention, peeling, cracking, or cracking of the resin film did not occur in the manufactured metal product, but the products of Comparative Examples 1 and 2 were made of resin. The film was not uniform or the appearance was poor.

In addition, as a result of the high-temperature storage test and the crack resistance test, Examples 1 to 4 did not observe peeling, cracking, or cracking in appearance observation. That is, it has excellent cold/heat resistance stability. However, the products of Comparative Example 1 and Comparative Example 2 had many peeling parts in the high temperature storage test, and in the crack resistance test, cracking and peeling occurred in 4 cycles from -30 ° C. to room temperature.

That is, in Comparative Example 1, the adhesiveness of the intermediate layer was weak, and after a certain period of time, the resin film fell off and the ASA resin cracked. In Comparative Example 2, the double extrusion process of the ASA resin was performed on the metal tube using the adhesive of the first agent, but the number of thermal expansions of the two materials was different, so after a certain period of time, the resin film fell off and the ASA resin cracked. .

Therefore, the excellent adhesive performance by the first agent not only prevents peeling, cracks, and cracking of the resin film in a high-temperature environment (eg, high-temperature co-extrusion environment), but also relieves the difference in thermal expansion between the metal material and the resin film by the second agent. It is possible to evenly form a resin film and provide excellent stability of the resin film in a high-temperature environment (eg, a high-temperature co-extrusion environment).

The present invention, a first agent that can be utilized as an adhesive capable of stably bonding the second agent (eg, intermediate layer resin) and the metal material; and a second agent (eg, intermediate layer resin) that is compatible with the resin coating (eg, ASA resin) and has high heat resistance stability. In addition, the second agent (eg, intermediate layer resin) is a thermoplastic elastomer, and is compatible with a resin film (eg, ASA resin) and can provide high heat resistance stability. That is, it offsets the coefficient of thermal expansion between the gold material and the resin film (eg ASA resin), and forms a resin film (eg ASA resin) with excellent adhesion by a co-extrusion process (eg double or triple extrusion process). can be realized

Although the embodiments of the present invention have been described in more detail above, the present invention is not necessarily limited to these embodiments, and may be variously modified and implemented without departing from the technical spirit of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention, but to explain, and the scope of the technical idea of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The protection scope of the present invention should be construed according to the claims below, and all technical ideas within the equivalent range should be construed as being included in the scope of the present invention.

Claims (15)

Modified acrylic resin; methylbenzene; at least one ketone-based solvent selected from 2-butanone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; and a first agent comprising methanol;
a first polymer including PVC, a second polymer including an adipate compound, a second agent including a plasticizer, a stabilizer, a heat stabilizer, an antioxidant, a UV stabilizer, an inorganic filler, and a lubricant; and
a resin coating agent containing an acrylate compound-styrene-acrylonitrile copolymer;
Containing, a metal material coating kit. According to claim 1,
The first agent,
1% to 20% by weight of a modified acrylic resin;
10% to 40% by weight of methylbenzene;
10% to 30% by weight of a ketone solvent; and
10% to 40% by weight of methanol
including,
The methylbenzene: the mass ratio of the ketone solvent is 1: 1.5 to 1: 4,
Metallic coating kit. According to claim 1,
The modified acrylic resin includes one or more selected from the group consisting of an epoxy-modified styrene acrylic resin, an epoxy-modified acrylic resin, a polyester-modified acrylic resin, a silicone-modified acrylic resin, a polycarbonate-modified acrylic resin, and a fluorine-modified acrylic resin. To do, a metal material coating kit. According to claim 1,
The first agent further comprises a polyester-modified urethane resin, an acrylic-modified urethane resin, or both at 0.1% to 10% by weight, the metal material coating kit. According to claim 1,
The modified acrylic resin comprises one or two or more acrylate monomers selected from the group consisting of methyl methacrylate, hydroxyl ethyl methacrylate, cyclohexyl methacrylate and isobutyl methacrylate, a metal material coating kit. According to claim 1,
The second agent,
40% to 70% by weight of the first polymer containing the PVC;
10% to 30% by weight of the second polymer,
1% to 10% by weight of the plasticizer,
1% to 10% by weight of the stabilizer,
0.1% to 5% by weight of the heat-resistant stabilizer;
0.01% to 2% by weight of the antioxidant,
0.01% to 1% by weight of the UV stabilizer;
5% to 20% by weight of the inorganic filler, and
0.01% to 2% by weight of the lubricant
A metal material coating kit comprising a. According to claim 1,
The heat-resistant stabilizer includes one or two or more selected from the group consisting of a phenol-based heat-resistant stabilizer, a sulfur-based heat-resistant stabilizer, and a phosphate-based heat-resistant stabilizer,
The phenolic heat stabilizer is 2-tert-butyl-4-methoxyphenol, 2-tert-butyl-4,6-dimethoxyphenol, 3,5-di-tert-butyl-4-hydroxytoluene, 4- Hydroxymethyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 4 ,4'-butylidene-bis(6-tert-butyl-m-cresol), 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 4,4'-bis(2, 6-di-tert-butylphenol), 2,2'-dihydroxy-3,3'-bis(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane, 4,4'-methylene- Bis(2,6-di-tert-butylphenol), d,l-α-tocopherol (vitamin E), 2,6-bis(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4 -Methylphenol, 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionic acid n-octadecyl, 1,3,5-tris(4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl)-s-triazine-2,4,6-(1H, 3H,5H)-trione, 1,3,5-trimethyl-2,4,6-tris(3,5-di- tert-butyl-4-hydroxyphenyl)benzylbenzene, 1,3,5-tris(4-hydroxy-3,5-di-tert-butylbenzyl)-s-triazine-2,4,6-( 1H,3H,5H)-trione, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, decamethylene carboxylic acid disalicyloyl hydrazide , N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 2,2'-oxyamide-bis-ethyl-3-(3,5 -Di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6 -tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, 4,4'-butylidene-bis(2-methyl-4-hydroxy-5- tert-butylphenyl)-2-laurylthioether, 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-bis(octylthio)-1,3,5- 1 selected from the group consisting of triazine and 2,4-bis(4-hydroxy-3,5-di-tert-butylanilino)-6-(n-octylthio)-1,3,5-triazine A metal material coating kit comprising a species or two or more species. According to claim 7,
The mass ratio of the phenol-based heat-resistant stabilizer to the sulfur-based heat-resistant stabilizer is 1: 0.1 to 1: 1,
The sulfur-based heat stabilizer is 2-mercaptobenzimidazole, N, N'-diphenylthiourea, tetramethylthiuram disulfide, N-oxydiethylene-2-benzothiazolyl sulfenamide, N-cyclohexyl- 2-Benzothiazolylsulfenamide, cyclohexylamine salt of 2-mercaptobenzothiazole, N,N-diisopropyl-2-benzothiazolesulfenamide, 2-(N,N-diethylthiocarbamoylthio ) Benzothiazole, tetraethylthiuram disulfide, dibenzothiazyl disulfide, zinc diethyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc di-n-butyldithiocarbamate, dilaurylthiodi Propionate, dilaurylthiodi-1,1'-methylbutyrate, dimyristyl-3,3'-thiodipropionate, laurylstearylthiodipropionate, distearylthiodipropionate, Containing one or two or more selected from the group consisting of distearylthiodibutyrate and dioctadecyldisulfide;
The phosphate-based heat stabilizer is one or two or more selected from the group consisting of phenyl diisodecyl phosphate, diphenyl isodecyl phosphate, triphenyl phosphate, trinonyl phenyl phosphate, calcium acetylacetonate, dioctyltin maleate, and phosphate. A metal material coating kit comprising a. According to claim 1,
The stabilizer is one or two selected from the group consisting of calcium stearate, ricinoleic acid calcium salt, zinc stearate and zinc ricinoleate including more than
The antioxidant includes one or two or more selected from the group consisting of hindered phenols, hindered amines, and diphenyl disulfide,
The lubricant is a metal material coating kit comprising one or more selected from the group consisting of chlorinated paraffin, wax, fatty acid ester, fatty acid amide, ethylene bis steamide and fatty acid amide. According to claim 1,
The inorganic filler has a shape of at least one of beads, flakes, fibers, filaments, plates, and powders, the inorganic filler includes particles having an average size of 0.1 μm to 50 μm, and the inorganic filler is surface treated with an organic acid. Further comprising treated particles,
The inorganic filler is stainless steel, silicon carbide, graphene, graphite, tartanium carbide, aluminum nitride, precipitated calcium carbonate, kaolin, aluminum silicate, silica, alumina, titanium dioxide, satin white, dolomite, mica, aluminum flakes, bentonite, rutile, magnesium hydroxide, gypsum, sheet silicates, talcum, calcium silicate; and oxides, nitrides, hydroxides and carbides of titanium, zirconium or hafnium; A metal material coating kit comprising one or two or more selected from the group consisting of. According to claim 1,
The second polymer is polydi (2-ethlhexyl) giycoladipate, poly (neopentyl glycol adipate) and poly (1,2-propylene). Contains one or two or more selected from the group consisting of glycol adipate (Poly (1,2-propylene glycol adipate)),
The plasticizer is a metal perchlorate, citrate, polycyclopentadiene, hydrogenated terphenyl, polypropylene oxide, phosphate ester, trimellitate, phthalate, benzoate, fatty acid ester alcohol, dimer acid ester, glutarate, dibutyl sebacate (dibutyl sebacate), dioctyl sebacate, diisopropyl sebacate, acrylic acid ester, epoxidized fatty acid ester, epoxidized soybean oil, polyester, adipic acid, phthalate, azerato, dioctyl phthalate, (di)acetylated mono A metal material comprising one or two or more selected from the group consisting of glyceride, diethyl 1,4-cyclohexanedicarboxylate, dioctyl terephthalate, and 1,2-cyclohexane dicarboxylic acid diisononyl ester coating kit. A metal product manufactured with the metal coating kit of claim 1,
The metal product,
metal material;
a first layer formed by coating a first agent on the metal material; and
a second layer formed on the first layer and a resin coating layer formed on the second layer by double extruding the metal material coated with the first layer, the second agent, and the resin coating agent;
Including, metal products. According to claim 12,
A metal material coated with the first layer is first heated at a temperature of 120 ° C to 300 ° C using a high-frequency heater, followed by double extrusion, and manufactured by secondary heating at a temperature of 80 ° C to less than 150 ° C after double extrusion. phosphorus, metal products. According to claim 12,
The hardness (Rockwell surface hardness) of the second layer is 80 or more,
The thermal expansion coefficient of the second layer is 50 ppm / ° C or less,
The difference between the coefficient of thermal expansion (CTE) of the metal material and the second layer is ± 20 ppm / ℃ or less, the metal product. According to claim 12,
The thickness of the first layer is 0.5 μm to 50 μm,
The second layer has a thickness of 0.5 μm to 200 μm,
The thickness of the resin coating layer is 0.5 μm to 2,000 μm,
metal products.