JP2005350605A - Ultraviolet-curing type sealer for inorganic material, method for forming sealer coating film for inorganic material, method for producing coated product and coated product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an ultraviolet-curing type sealer for an inorganic material. <P>SOLUTION: The ultraviolet-curing type sealer for an inorganic material comprises an epoxy acrylate-based unsaturated compound (A), an unsaturated compound (B) containing two or more unsaturated groups radical-polymerizable by ultraviolet irradiation in one molecule except the compound (A), a silane coupling agent (C), an ultraviolet polymerization initiator (D) and a polyisocyanate (E) as essential components. The method for producing a product coated with the ultraviolet-curing type sealer for an inorganic material comprises a process for coating and impregnating an inorganic material with the ultraviolet-curing type sealer for an inorganic material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to an ultraviolet curable sealer for inorganic materials, a method for forming a sealer coating film for inorganic materials, a method for producing the same, and a coated product. More specifically, the present invention provides an inorganic material coated product that improves the strength of the inorganic material and is excellent in top coat coating suitability (such as top coat adhesion).

Inorganic materials include calcium silicate boards, asbestos cement boards, lightweight cellular concrete boards, wood chip cement boards, pulp cement boards, etc., and these materials are used as, for example, building materials, civil engineering materials, and industrial materials. In recent years, inorganic materials such as outer wall materials and roof materials using the above materials tend to be reduced in weight in order to improve the workability of houses. As a result, the weakness of the base material is a problem.
As countermeasures against such problems, there are known a method of undercoating with an acrylic emulsion paint (Patent Document 1) and a method of impregnating a water-dispersible polyisocyanate into an inorganic material (Patent Document 2).

JP 2000-140751 JP 2002-146340 A

  The one described in Patent Document 1 is a method in which a photocurable clear is applied to an inorganic decorative board that has been pre-coated with an acrylic emulsion paint. The acrylic emulsion paint is a so-called lacquer type (a type in which a film is formed without a curing reaction) in which a film is formed by volatilization of water to form a film. In addition, the reinforcing effect on the inorganic decorative board is inferior, and the film performance (moisture resistance, water resistance, etc.) is lowered when exposed to rain for a long time, and the adhesion with the top coat film is inferior. there were.

  The one described in Patent Document 2 is that water-dispersible polyisocyanate is impregnated in an inorganic material, and the impregnated polyisocyanate reacts with moisture to form a polymer, and is chemically bonded to a hydroxyl group or the like contained in the inorganic material. This is a so-called curing type sealer coating that reinforces the inorganic material, but it takes time to cure, moisture tends to remain in the cured inorganic material, and polyisocyanate and moisture There is a problem that a by-product (carbon dioxide gas, etc.) generated by the reaction is easily trapped in the inorganic material, and an inorganic decorative board excellent in durability for a long time cannot be obtained.

  An object of this invention is to provide the inorganic material coating product excellent in the reinforcement effect of an inorganic decorative board, coating-film performance (moisture resistance, water resistance, etc.), long-term adhesiveness with top coat film, etc.

The ultraviolet curable sealer for inorganic materials according to the present invention contains an epoxy acrylate unsaturated compound (A) and two or more unsaturated groups capable of radical polymerization by ultraviolet irradiation in one molecule other than the compound (A). An unsaturated compound (B), a silane coupling agent (C), and an ultraviolet polymerization initiator (D) are contained as essential components.
The ultraviolet curable sealer for inorganic materials according to the present invention further contains polyisocyanate (E).

The method for forming a sealer coating film for an inorganic material according to the present invention is characterized in that the ultraviolet curable sealer for an inorganic material is coated on an inorganic material, impregnated, and then irradiated with ultraviolet rays.
The method for producing a coated product according to the present invention is a method for producing a product coated with an ultraviolet curable sealer for an inorganic material, and the step of coating and impregnating the ultraviolet curable sealer for an inorganic material on an inorganic material It is characterized by including.
The coated product according to the present invention is manufactured by the above-described method.

  INDUSTRIAL APPLICABILITY According to the present invention, a coated inorganic product excellent in performance such as a reinforcing effect, moisture resistance, and water resistance of an inorganic material can be obtained by irradiating a specific sealer impregnated in the inorganic material with ultraviolet rays. Since a cured sealer coating can be formed in a short time after the sealer coating, it is economical, and since no by-product due to the ultraviolet curing reaction is generated, it does not affect the deterioration of the inorganic material.

The ultraviolet curable sealer for inorganic materials of the present invention will be described below.

  The epoxy acrylate unsaturated compound (A) used in the sealer of the present invention is synthesized by reacting an epoxy compound such as epichlorohydrin with acrylic acid or methacrylic acid.

  Specific examples of the epoxy acrylate include bisphenol A-type epoxy (meth) acrylate synthesized by reaction of bisphenol A, epichlorohydrin, and (meth) acrylic acid, and reaction of bisphenol S, epichlorohydrin, and (meth) acrylic acid. Synthesized bisphenol S type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate synthesized by reaction of bisphenol F, epichlorohydrin and (meth) acrylic acid, phenol novolac, epichlorohydrin and (meth) acrylic acid Phenol novolac-type epoxy (meth) acrylate synthesized by the reaction can be mentioned.

  The epoxy (meth) acrylate unsaturated compound (A) has an average number of 1 or more, preferably 2 or more (meth) acryloyl groups in one molecule, and a number average molecular weight of 900 to 5000, preferably 970 to 2000. belongs to.

  The unsaturated compound (B) used in the sealer of the present invention is an unsaturated compound (B) containing an unsaturated group which can be radically polymerized by irradiation with two or more ultraviolet rays in one molecule (hereinafter referred to simply as “ Abbreviated as “unsaturated compound (B)”), which is an unsaturated compound other than the compound (A).

  The unsaturated compound (B) includes a monomer or an oligomer. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Multifunctional (meth) acrylic acid esters of polyhydric alcohols such as (meth) acrylate: diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethyl Lenglycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dibutylene glycol di (meth) acrylate, tributylene glycol di (meth) ) Acrylates, di (meth) acrylates of polyalkylene glycols such as tetrabutylene glycol di (meth) acrylate, and the like. These can be used alone or in combination of two or more.

  Among the unsaturated compounds (B) described above, poly (alkylene glycol) di (meth) acrylates are particularly preferable because they are excellent in impregnation with inorganic materials.

  The silane coupling agent (C) used in the sealer of the present invention has a hydrolyzable group (preferably a lower alkoxyl group) that directly bonds to one or more silicons in average in one molecule.

  Specific examples of the silane coupling agent (C) include γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxy Propyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ- Aminopropyltrimethoxy Examples thereof include silane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane. These can be used alone or in combination of two or more.

Among these, when an ultraviolet curable coupling agent containing an unsaturated group in the molecule is used as an essential component, it chemically bonds with other unsaturated compounds by ultraviolet irradiation, and also has a hydrolyzable silane group and an inorganic material. As a result, chemical properties such as moisture resistance and water resistance are improved, and there is an advantage that a strong inorganic material coated product having excellent long-term adhesion can be obtained.
The ultraviolet polymerization initiator (D) used in the sealer of the present invention has the above-mentioned epoxy acrylate unsaturated compound (A), unsaturated compound (B) and silane coupling agent (C) (has an unsaturated group). The unsaturated group contained in the case) promotes the radical polymerization reaction during ultraviolet irradiation, and conventionally known ones can be used without particular limitation.

  Specific examples of the ultraviolet polymerization initiator (D) include benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, and benzyl dimethyl ketal. Moreover, as a brand name, for example, Irgacure (made by Ciba Geigy, trade name), Darocur (made by MERUCK, trade name), KAYACURE (made by Nippon Kayaku Co., Ltd., trade name) Tinuvin (made by BASF, trade name), DAIDO UV (manufactured by Daido Kasei Co., Ltd., trade name). These can be used alone or in combination of two or more.

The polyisocyanate (E) that can be used as necessary in the sealer of the present invention may be aromatic, aliphatic cyclic, aliphatic, or a combination of two or more of these, specifically Specifically, for example, tolylene diisocyanate, methylene bisphenyl isocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, lysine diisocyanate, xylene diisocyanate, Hexamethylene diisocyanate and its modified products, dicyclohexylmethane diisocyanate, isophorone diisocyanate, alcohols added based on these isocyanates, 2-3-mer of Aneto (oligomers) and the like. These can be used alone or in combination of two or more.
The blending ratio of each component constituting the sealer of the present invention is as follows.
The total amount of the epoxy acrylate unsaturated compound (A) and the unsaturated compound (B) is as follows.

  Epoxy acrylate unsaturated compound (A): 10 to 50% by weight, preferably 15 to 40% by weight. If it is less than 10% by weight, the material strengthening and top coat adhesion are inferior. On the other hand, if it exceeds 50% by weight, the impregnation property for inorganic materials is inferior.

  Unsaturated compound (B): 50 to 90%, preferably 60 to 85%. When the amount is less than 50% by weight, the impregnation property with respect to the inorganic material is inferior, and when it exceeds 90% by weight, the material reinforcement and the top coat adhesion are inferior.

The blending ratio of the silane coupling agent (C), the ultraviolet polymerization initiator (D) and the polyisocyanate (E) is 100 parts by weight in total of the epoxy acrylate unsaturated compound (A) and the unsaturated compound (B). On the other hand, it is as follows.
Silane coupling agent (C): 0.5 to 50 parts by weight, preferably 2 to 40 parts by weight. When the amount is less than 0.5 part by weight, the impregnation property to the inorganic material, the water resistance and the moisture resistance of the inorganic material are inferior, and when the amount exceeds 50 parts by weight, the above-described effect cannot be improved, and it is not economical.

  Ultraviolet polymerization initiator (D): 1 to 20 parts by weight, preferably 2 to 10 parts by weight. When the amount is less than 1 part by weight, the curability due to ultraviolet irradiation inside the inorganic material is inferior, and when the amount exceeds 20 parts by weight, the improvement in curability due to ultraviolet irradiation inside the inorganic material cannot be expected, and it is not economical. is there.

  Polyisocyanate (E): By blending this, there is an advantage that the sealer coating in the inorganic material internal direction that cannot be cured by ultraviolet irradiation can be cured. When blended, it is preferably blended at 20 parts by weight or less. If it exceeds 20 parts by weight, by-products due to curing increase, which is not preferable.

  The polyisocyanate (E) is preferably used by mixing with the blends (A) to (D) immediately before coating the inorganic material.

    In the sealer of the present invention, in addition to the above, various monofunctional monomers copolymerizable with the above oligomers and monomers as necessary (for example, other hydroxyl group-containing unsaturated monomers, carboxyl group-containing unsaturated monomers, alicyclic) Unsaturated monomers, styrene, glycidyl group-containing unsaturated monomers, other alkyl acrylates having 1 to 24 carbon atoms, etc.), hydrolysis reaction accelerators (acidic compounds, basic compounds, salts, etc.), leveling agents, etc. Can be blended. Further, extender pigments and colorants can be blended to such an extent that curability does not decrease.

    The sealer of the present invention is handled as a so-called 100% liquid which does not require a solvent, but can be used as an aqueous or organic solvent system using water or an organic solvent as needed.

    The forming method of the present invention is a method in which the ultraviolet curable sealer for an inorganic material is coated on an inorganic material, impregnated, and then irradiated with ultraviolet rays.

  Examples of the inorganic material on which the sealer is coated include calcium silicate material, asbestos cement material, lightweight cellular concrete material, wood chip cement material, and pulp cement material. Among these, a calcium silicate material is particularly preferable.

The coating amount is 10 to 250 g / m by using a coating method such as brushing, spraying, roll coater, dipping, sponge roll, rubber roll, screen printing, etc., which has been conventionally known (including printing). ² , preferably 30 to 150 g / m ² .
The viscosity at the time of painting may be appropriately determined according to the coating means. For example, when a roller such as a sponge roll or a rubber roll is used, the viscosity obtained by IHS (using an Iwata Cup viscometer, measuring temperature 20 ° C.) The range is 1 to 30 seconds, preferably 2 to 20 seconds.
After coating, it is preferable to set so that the sealer sufficiently impregnates the inorganic material. Specifically, for example, it is in the range of 10 seconds to 1 hour, preferably 30 seconds to 10 minutes at room temperature (20 ° C.).

Conventionally known ultraviolet irradiation lamps such as halogen lamps, metal halide lamps and mercury lamps can be used for ultraviolet irradiation.
The ultraviolet irradiation amount varies depending on the type of the sealer, the type of lamp, the distance between the lamp and the sealer coating film, etc., but is usually in the range of 100 to 800 mj / cm ² , preferably 200 to 500 mj / cm ² .

  The inorganic material on which the sealer coating film is formed may be coated with a sanding sealer, if necessary, then polished, and then coated with a top coat.

  As the sanding sealer, it is particularly preferable to use a sanding sealer prepared by blending an extender pigment or the like with the ultraviolet curable sealer of the present invention so that the polishing operation can be easily performed. As extender pigments, conventionally known pigments can be used without particular limitation. Specific examples include magnesium silicate, barium sulfate, silica (silicon oxide), and the like.

The blending ratio of the extender pigment may be set as appropriate so that the curing by an ultraviolet ray irradiation is not substantially hindered and can be easily polished. 1 to 40 parts by weight, particularly 2 to 30 parts by weight is preferred.
Moreover, conventionally well-known things can be used as a sanding sealer other than the above. Specifically, UV curable sealers other than those of the present invention: Acrylic resin sealers, urethane resin sealers, polyester resin sealers, epoxy resin sealers, vinyl resin sealers, and other dry (lacquer type) sealers: containing hydroxyl groups Resin / (optionally blocked with a blocking agent such as alcohol) polyisocyanate curable sealer, hydroxyl group-containing resin / aminoplast curable sealer, epoxyamine curable sealer, epoxy acid curable sealer, hydrazide curable sealer And a curable sealer.

The sanding sealer is applied by a conventionally known coating (including printing) method such as brushing, spraying, roll coater, dipping, sponge roll, rubber roll, and screen printing. 250 g / ^{m 2,} preferably can be coated to be in the range of 30 to 150 g / ^{m 2.}
As the top coating material, a conventionally known top coating material can be used without particular limitation. Examples of the colored top coating include acrylic resin, urethane resin, vinyl chloride resin, fiber resin, silicone resin, polyester resin, alkyd resin, fluororesin, and two or more modified resins thereof. Or a blended resin can be used. The top coat can be either a lacquer type or a curable type.

  As the top coat, there are a case where a paint obtained by pigmenting the above resin-based paint is applied, and a case where a clear paint not containing a pigment is further applied thereon. In any case, the ultraviolet curable sealer of the present invention is applied. Can be used as a primer. Further, the top coating material may be in the form of a water-based, organic solvent-based or solvent-free coating.

The top coating is applied using a conventionally known coating (including printing) method such as brushing, spraying, roll coater, dipping, sponge roll, rubber roll, screen printing, and the coating amount is 20 to 300 g. / M ² , preferably 30 to 250 g / m ² .
The production method of the present invention is a method for producing a product coated with an ultraviolet curable sealer for inorganic materials, and the ultraviolet curable sealer for inorganic materials of the present invention is applied to the above inorganic material by the above-described coating method. Then, a coated product on which a sealer coating film is formed can be produced by impregnation.

  The coated product of the present invention is a coated product manufactured by the above-described manufacturing method of the present invention. That is, the coated product of the present invention is a product obtained by laminating an inorganic material UV-curing sealer coating and a top coating on an inorganic material surface, and an inorganic material UV-curing sealer coating, a sanding sealer coating, an overcoating on the inorganic material surface. Laminated coating, UV curable sealer coating for inorganic materials, sanding sealer coating, top-coated colored coating laminated on inorganic material surface, UV curable sealer coating for inorganic materials, sanding on inorganic material surface It includes a laminate of a sealer coating, a top-coated colored coating, and a clear top-coated coating.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. Both parts and% are based on weight.

Example 1
30 parts of epoxy acrylate (a reaction product of 1 mol of EB-605 (trade name) manufactured by Daicel UCB Ltd. and 2 moles of acrylic acid), 70 parts of triethylene glycol diacrylate, Irgacure 819 (trade name, manufactured by Ciba Geigy) 1 part of UV polymerization initiator), 20 parts of γ-methacryloxypropyltrimethoxysilane and 5 parts of tolylene diisocyanate were blended to produce a sealer of Example 1.

Example 2
30 parts of epoxy acrylate (a reaction product of 1 mol of EB-605 (trade name) manufactured by Daicel UCB Ltd. and 2 moles of acrylic acid), 70 parts of tripropylene glycol diacrylate, Irgacure 819 (trade name, manufactured by Ciba Geigy) , UV polymerization initiator) 1 part, γ-methacryloxypropyltrimethoxysilane 20 parts, and tolylene diisocyanate 5 parts were blended to produce a sealer of Example 2.

Production Example of Sanding Sealer A 10 parts of magnesium silicate was blended with 100 parts of the sealer described in Example 1.

Example 3 (Example using the sealer of Example 1)
After removing dust and dust on the surface of the calcium silicate plate, preheating is performed so that the surface temperature is 40 ° C. or higher, and a sponge roll and a rubber roll are applied using the sealer of Example 1 so that the application amount is 60 g / m ^2. Then, setting was performed at 20 ° C. for 2 minutes, and irradiation was performed with a metal halide lamp at 260 mj / cm ² . Next, after lightly sanding with well 320 sandpaper, a top coating (urethane resin coating) was applied by spraying to a coating amount of 100 g / m ² and dried at 80 ° C. for 30 minutes to form a top coating film. .

As a result, it was good in peeling resistance (circle), cold-heat repetition test (circle), immersion peeling test (circle), 60 degreeC warm water half-immersion test (upper circle | round | yen, submerged part circle), moisture resistance test (circle), and frost damage test (circle).
Example 4 (Example 1 and Example using Sanding Sealer A)
After removing dust and dust on the surface of the calcium silicate plate, preheating is performed so that the surface temperature becomes 40 ° C. or higher, and a sponge roll and a rubber roll are applied so that the application amount is 60 g / m ² using the sealer of Example 1. Then, setting was performed at 20 ° C. for 2 minutes, and irradiation was performed with a metal halide lamp at 260 mj / cm ² . Next, sanding sealer A was used to coat with a sponge roll and a rubber roll so that the coating amount was 80 g / m ² , setting was performed at 20 ° C. for 2 minutes, and irradiation was performed with a metal halide lamp at 260 mj / cm ² . Next, after lightly sanding with well 320 sandpaper, a top coating (urethane resin coating) was applied by spraying to a coating amount of 100 g / m ² and dried at 80 ° C. for 30 minutes to form a top coating film. .

  As a result, it was good in peeling resistance (circle), cold-heat repetition test (circle), immersion peeling test (circle), 60 degreeC warm water half-immersion test (upper circle | round | yen, submerged part circle), moisture resistance test (circle), and frost damage test (circle).

Comparative Example 1
After removing dust and dust on the surface of the calcium silicate plate, preheat so that the surface temperature becomes 40 ° C. or higher, and use an aqueous sealer (trade name of Emulsion Sealer EP Sealer) so that the coating amount is 60 g / m ^2. The film was coated with a sponge roll and a rubber roll and dried at 100 ° C. for 5 minutes to form a sealer coating film. Next, after lightly sanding with well 320 sandpaper, a top coating (urethane resin coating) was applied by spraying to a coating amount of 100 g / m ² and dried at 80 ° C. for 30 minutes to form a top coating film. .

  As a result, it was bad in peeling resistance Δ, cold repetition test Δ, immersion peeling test Δ, 60 ° C. warm water half immersion test (upper Δ, submerged portion ×), moisture resistance test Δ, and frost damage test ×.

  Test methods described in Examples and Comparative Examples are as follows.

  Peeling resistance: 16 straight 4 × 4 mm squares are made by inserting five straight lines perpendicular to each other at intervals of 4 mm so as to reach the substrate with a sharp blade on the coating film of the test piece. The squares after the cellophane adhesive tape was adhered and peeled off were evaluated. ○ indicates that there is no cohesive failure of the material and no peeling of the coating is observed, △ indicates that cohesive failure of the material occurs, and a slight peeling is observed between the sealer and the topcoat, × indicates the material It shows a remarkable cohesive failure.

Cold heat repeat test: A 3 mm hole is made in the center of the test piece, left in an incubator at 80 ° C. ± 3 ° C. for 2 hours, and then left in an incubator at −20 ° C. ± 3 ° C. for 2 hours. About the coating film after a test, the same test as the said peeling resistance was performed, and evaluation was performed.
Immersion peeling test: A test piece is immersed in boiling water for 4 hours, dried at 60 ° C. ± 3 ° C. for 20 hours, further immersed in boiling water for 4 hours, and then dried at 60 ° C. ± 3 ° C. for 3 hours. About the coating film after a test, the same test as the said peeling resistance was performed, and evaluation was performed.

  60 ° C. warm water half-immersion test (upper portion, submerged portion): The test piece was left in a half-immersion state at a temperature of 60 ° C. ± 3 ° C. for 240 hours, and a test similar to the above-mentioned peeling resistance was performed for evaluation.

  Humidity resistance test: The specimen is left in a constant temperature and humidity chamber at a temperature of 50 ° C. ± 3 ° C. and a humidity of 95 ± 2% for 240 hours. About the coating film after a test, the same test as the said peeling resistance was performed and evaluated.

  Frost damage test: The cellophane adhesive tape adhesion test was performed after 50, 100, 200 cycles by the ASTM-B method to evaluate the adhesion due to the material cohesive failure and the above-mentioned peeling resistance of the sealer coating / coating. The evaluation is as follows. ○: No material cohesive failure in 200 cycles. Δ: No material cohesive failure at 100 cycles, but material cohesive failure at 200 cycles. X: Cohesive failure occurred in 50 cycles.

The ultraviolet curable sealer for an inorganic material of the present invention can be used for a coated product of an inorganic material having excellent impregnation properties and top coating adhesion to a substrate.

Claims (5)

Epoxy acrylate unsaturated compound (A), unsaturated compound (B) containing an unsaturated group capable of radical polymerization by irradiation with two or more ultraviolet rays in one molecule other than compound (A), silane coupling agent ( C), an ultraviolet curable sealer for inorganic materials, comprising an ultraviolet polymerization initiator (D) as an essential component. The ultraviolet curable sealer for inorganic materials according to claim 1, further comprising polyisocyanate (E). A method for forming a sealer coating film for an inorganic material, wherein the ultraviolet curable sealer for an inorganic material according to claim 1 or 2 is coated on an inorganic material, impregnated, and then irradiated with ultraviolet rays. A method for producing a product coated with an ultraviolet curable sealer for an inorganic material, comprising a step of coating and impregnating the ultraviolet curable sealer for an inorganic material according to claim 1 or 2 on an inorganic material. A manufacturing method of a characteristic painted product. A coated product produced by the method of claim 4.