JPH07103257B2 - Polyolefin-based bead molding method Surface decoration coating method for foams - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface decoration coating method for a polyolefin bead molding foam.

[0002]

2. Description of the Related Art Polyolefin-based bead molding foams have a small specific gravity and are considered to have many uses in terms of their physical properties. In recent years, due to problems such as resource recycling, thermosetting properties of urethane foam moldings and the like have been considered. Demand is increasing in place of foam moldings. However, due to the molding method, it is unavoidable that the foamed foam produced from the molding machine will have an uneven pattern on the entire surface of the foamed beads, and the decorative finish as various final products. In order to do so, a considerable number of steps are required. For example, when the surface of the foam is treated by polishing or heat melting so that it looks smooth at first glance, so-called bare holes and fine small holes remain. Many processes such as painting, painting of an intermediate coating containing a filler, polishing, and top coating are required. For this reason, it takes a great deal of time to finish the foam by decoration, and the present situation is that it is given up halfway.

Further, if the general coating is performed without smoothing the uneven surface, there is a problem that the cosmetic value in appearance is halved.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted various studies and experiments in consideration of such technical situation and as a result, have found that a specific silicone oil; at least one of metal powder, mica and pearl foil; Polyolefin-based bead molding method When a coating film is formed on a foam using a top-coat decorative coating material containing a coloring pigment and a binder component selected from specific resin components, a polyolefin-based bead molding method is used. The inventors have found that a coating film having an extremely excellent decorative appearance and protective property can be formed in a simple process by utilizing the pattern of expanded bead particles on the surface of the material of the method foam, and have completed the present invention.

That is, the present invention provides (a) a chlorinated polyolefin resin, (b) an acrylic resin, (c) an acrylated or vinylated alkyd resin, and (d) a polyisocyanate and a polyol resin which is reactively cured therewith. The main component of the binder is at least one component selected from, and (A) a silicone oil having a number average molecular weight of 5,000 or more and containing methylchlorosilane as a main component in the solid content of 0.1 to 3
% By weight, (B) at least one of metal powder, mica, and pearl foil in solid content of 0.5 to 20% by weight, and (C)
A top-coating decorative coating containing a coloring pigment in an amount of 0 to 20% by weight in solid content is applied to the surface of a polyolefin-based bead molding foam and dried and cured to form a pattern of the foamed bead particles on the surface of the foam. The present invention relates to a surface decoration coating method for a polyolefin-based bead molding foam, which is characterized by being exposed.

In the present invention, the polyolefin-based bead molding foam is a foam molding machine (mainly a chain type) in which beads of olefin homopolymers such as ethylene, propylene and butylene, or copolymers mainly of these are used. Is foamed and molded into a molded body of various shapes. In the present invention, the expansion ratio of the foam is not particularly limited, but is usually about 5 to 100 times, preferably about 10 to 50 times.

In the method of the present invention, the foam to be used may have a surface shape substantially as it is taken out from the molding machine without being subjected to deformation processing by mechanical treatment such as polishing, but under the condition that the surface shape is not impaired. With chrome-sulfuric acid treatment, which is usually performed on the surface of polyolefin,
Treatment such as corona treatment may be performed. If there is an unnecessary portion called a burr in some cases, it may be removed by a suitable method such as cutting.

According to the method of the present invention, when a release agent that inhibits adhesion of the coating film is attached to the surface of the polyolefin bead molding foam, a method such as wiping with a solvent such as toluene is used. Therefore, it is desirable to remove the release agent in order to prevent a decrease in the adhesiveness between the foam and the adhesion primer (hereinafter simply referred to as a primer) or the paint.

The top decorative paint used in the present invention is (a)
Chlorinated polyolefin resin, (b) acrylic resin,
At least one component selected from (c) an acrylated or vinylated alkyd resin, and (d) a polyisocyanate and a polyol resin that is reactively cured therewith, is used as the main component of the binder, and (A) methylchlorosilane is the main component. 0.1 to 3% by weight of silicone oil having a number average molecular weight of 5000 or more in the solid content, and (B) at least one of metal powder, mica and pearl foil in the solid content of 0.5 to 20% by weight and (C ) The content of the coloring pigment in the solid content is 0 to 20% by weight.

Examples of the polyolefin in the above (a) chlorinated polyolefin resin include homopolymers of olefins such as ethylene, propylene and butylene, and copolymers thereof. The chlorinated polyolefin resin includes Chlorinated products of these may be used. The chlorine content may be usually 10 to 40% by weight, and if it is less than 10%, it is difficult to form a coating material in view of solubility and crystallinity, and if it exceeds 40%, stability is deteriorated, which is not preferable. These resins are generally commercially available, and commercially available products include, for example, HARDREN 11L and HARDREN 15-L.
L B (Toyo Kasei Kogyo Co., Ltd.), SUPERCHLON 832L
(Sanyo Pulp Industry Co., Ltd. ) and the like. It is also possible to use a modified product of this. As the modified product, there is one in which a functional group such as a carboxyl group, a hydroxyl group, an epoxy group or the like is introduced, and the modification stage may be before or after chlorination. Commercially available products of these modified resins or resin solutions include Acridic 57-693 (manufactured by Dainippon Ink and Chemicals, Inc.), Supercron 224H (OH content 1.7%, manufactured by Sanyo Kokusaku Pulp Co., Ltd.). ), Hardlen B1
3 (containing OH group and epoxy group) (manufactured by Toyo Kasei Co., Ltd.) and the like. When using a resin containing a functional group such as a hydroxyl group or an epoxy group, it is preferable to use a compound that reacts with the functional group and crosslinks as a curing agent in order to improve the physical properties. For example, non-volatile polyisocyanate adducts for resins with hydroxyl groups (eg tolylene diisocyanate and hexamethylene diisocyanate trimer adducts)
It is desirable to use a curing agent composed of a component that reacts with an epoxy group such as a polyamide resin at room temperature in a resin having an epoxy group. With respect to the resin having a hydroxyl group, the compounding amount of the curing agent is such that the molar ratio of NCO: OH group is about 1: 0.6 to 1.5, preferably 1: 0.8 to 1.
It may be about 2 and, for a resin having an epoxy group, the active amino group is 0.5 to 1.3 equivalents, preferably about 0.6 to 1.2 equivalents to the epoxy group. It should be so.

As the acrylic resin (b), a polymer of a monomer containing a (meth) acrylic acid ester, which is suitable for paints, may be used. The proportion of the (meth) acrylic acid ester monomer in the acrylic resin is not particularly limited, but is usually about 25 to 100% by weight, preferably 30 to 9% by weight based on the total amount of the monomers.
It may be about 8% by weight. As the (meth) acrylic acid ester, for example, an ester of acrylic acid and / or methacrylic acid with an alcohol having an alkyl group having 1 to 6 carbon atoms, a cycloalkyl alcohol, an aromatic alcohol, an alcohol containing a hydroxyl group, or the like is used. be able to. Other monomers to be copolymerized include aromatic vinyl monomers such as styrene, vinyl esters such as vinyl acetate,
Monomers having unsaturated groups such as α, β unsaturated mono- or dicarboxylic acids are used. These monomers are hydroxyl groups,
It may have a functional group such as a carboxyl group or an epoxy group. Also, a silyl group, an alkoxysilyl group, or the like can be introduced at the terminal or side chain of the copolymer. The copolymer resin having these functional groups can be used in combination with a curing agent that reacts and crosslinks with the functional groups to increase the physical properties of the coating film. As such a curing agent, in the moisture-curable coating,
Organotin compounds such as dibutyltin dilaurate, acidic phosphoric acid esters such as dibutyl phosphate, amines such as ethanolamine, organic acids such as paratoluene sulfonic acid, methyl orthoformate and the like can be used alone or in combination, and a hydroxyl group can be used. The above-mentioned polyisocyanate adduct can be used for the resin having, and various epoxy curing agents can be used for the resin having the epoxy group. The amount of the curing agent blended is about 0.1 to 5% by weight with respect to the resin solid content in the moisture-curable coating, and the same as in the above (a) for the resin having a hydroxyl group and the resin having an epoxy group. do it. In addition, an acrylic resin modified with a chlorinated polyolefin resin can also be used, and this modified resin has good adhesion to the material. Solvents for acrylic resins include toluene, xylene, butyl acetate,
There are methyl isobutyl ketone and the like, which can be appropriately mixed and used. Commercially available products of the resin include solid resins and those polymerized and copolymerized by solution polymerization. For example, Acridic A157, Acridic A801,
Acridic CL-408, Acridic 56-8
34 (manufactured by Dainippon Ink and Chemicals, Inc.), Zemlac Y
Examples include C3623 and various other types (manufactured by Kaneka Corporation).

The (c) acrylated or vinylated alkyd resin is an alkyd resin modified with natural semi-drying oil, modified with natural drying oil, or modified with fatty acids thereof, and has a short oil length of 28 to 45%. For medium oily unsaturated alkyd resin,
A (meth) acrylic acid ester; an aromatic vinyl monomer such as styrene or vinyltoluene; or a vinyl monomer such as vinyl acetate graft-polymerized can be used.
These resins are usually naphthenic acid, octylic acid, 2-
Co, Pb, Zn, such as ethylhexyl acid and octenoic acid,
A so-called metal dryer such as Mn salt can be added to dry and cure. The compounding amount of these metal dryers is 0.01 to 0.
It may be about 5% by weight. Examples of commercially available products of these resins include Styresol 4250 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

In the combination of (d) the polyisocyanate and the polyol resin which is cured by reaction therewith, the polyisocyanate is a polyisocyanate adduct,
For example, tolylene diisocyanate, a trimer adduct such as hexamethylene diisocyanate, or the like can be used,
As the polyol resin which is reactively cured with polyisocyanate, a polyester resin having at least two hydroxyl groups in one molecule; castor oil, castor oil modified product, alkyd resin modified with coconut oil, semi-drying oil and the like can be used. Examples of commercially available products of such polyols resins, Desmophen 600 (manufactured by Sumitomo Bayer Co.), Burnock D6-43 9 (80% nonvolatile, solvent xylene, MIB
K) (manufactured by Dainippon Ink and Chemicals, Inc.) and the like, and as a commercially available product of polyisocyanate, Sumidule N-7
5 (Sumitomo Bayer Co., Ltd.), Coronate L (Nippon Polyurethane Co., Ltd.) and the like.

The polyisocyanate and the polyol resin may be blended in such a ratio that the NCO / OH ratio is usually 0.8 to 1.2.

The component (A) to be added to the top decorative coating used in the present invention is a silicone oil containing methylchlorosilane as a main component and having a number average molecular weight of 5000 or more. By adding this silicone oil, the decorative coating film can form a clear pattern along the boundary of the beads on the surface of the expanded beaded particle layer of the base material. Such a clear pattern is an effect that cannot be seen on other materials such as a wood surface and a metal surface. It is necessary that the number average molecular weight of the silicone oil is 5000 or more, and if it is less than that, it is not effective, and those having a number average molecular weight of 100,000 to 1,000,000 are particularly desirable for pattern formation.
Further, the silicone oil is a polysiloxane containing methylchlorosilane as a main component, and one obtained by using 80% by weight or more of methylchlorosilane as a monomer component is preferably used. As other monomer components,
For example, phenylchlorosilane can be used. Further, those partially modified with an amino group, an epoxy group or the like can be used, but an unmodified one is preferable. The amount of silicone oil added is 0.1 to 0.1% in the solid content of the top decorative paint.
3% by weight. If the addition amount is less than 0.1%, the pattern effect is small, and if it exceeds 3%, the tendency of repelling becomes strong, which is not preferable. The optimum addition rate is somewhat affected by the foaming ratio of the raw material, but 0.4 to 1.2% gives the most preferable result. Commercial products of such silicone oil include
TRS10N (Wacker), Shin-Etsu Silicone KP3
10 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Resin content 100
%, The viscosity is too high and it is difficult to handle, so it is usually diluted with an approximately equal amount of a solvent such as toluene or xylene.

The component (B) is also an essential component for the top-coating decorative paint used in the present invention. Metal powders of aluminum, copper, brass and the like (including flakes); foils of natural or synthetic mica; and natural or At least one component selected from the synthetic pearl foil is used. The metallic powder in the form of foil or scale has a greater decorative effect than that of spherical or irregular shape. Non-leafing type is preferable although surface-treated one is also included. The particle size is preferably between 1 and 100 microns. As aluminum foil, there are commercial products such as Alpaste 1200N (manufactured by Toyo Aluminum Co., Ltd.) and Iriodin (manufactured by Merck). The blending amount of these components is
It is 0.5 to 20% by weight in the solid content of the top decorative paint. If the blending amount is less than 0.5%, the metallic effect is small, and if the blending amount exceeds 20%, it is unnecessary and economically disadvantageous.

Examples of the color pigment as the component (C) include carbon black, cyanine blue, cyanine green,
It is desirable to use red iron oxide, iron oxide yellow, red or yellow organic pigment, etc., which has as large coloring power as possible and can impart or correct color tone while maintaining the metallic luster of the component (B). . The blending amount is 0 to 20% by weight in the solid content of the top decorative paint. Generally 2
If it exceeds 0%, the metallic effect is impaired and the gloss is impaired, which is not preferable.

The top decorative paint used in the present invention may further contain a dehydrating agent, a suspending agent, a pigment dispersant, and
Various paint additives such as color separation inhibitor, anti-skinning agent, curing accelerator, etc., solvent, diluent, small amount of organic / inorganic filler, etc. can be blended in the same amount as usual paint do it.

As a method for producing the top-coat decorative coating, a general method may be used, and a method such as dissolution, stirring or dispersion may be used in accordance with a conventional method. Depending on the difficulty of dispersion of the color pigment, a part of the binder to be used and the pigment are used as a dispersant, various additives (for example, an antifoaming agent, an anti-settling agent, a dehydrating agent if necessary), a roll mill, a sand mill, If necessary, glass beads or steel beads may be added using a high-speed stirrer and dispersed for the required time, and after filtration, the remaining components such as silicone oil may be added. Metal powder,
Mica, pearl foil and the like may be added to the paint after being dispersed with a part of the solvent used in advance by a stirrer or the like.

The decorative coating material used in the present invention may have a solid content concentration of about 20 to 65% by weight, and may have an appropriate viscosity by using a resin and a solvent and a diluent depending on the film forming agent. It may be diluted before use. As such a solvent and a diluent, for example, toluene, xylene, methyl isobutyl ketone, butyl acetate, ethylene glycol monoethyl ether acetate and the like can be used solvents which are used for ordinary solvent type paints, and an isocyanate curing agent is used. Except in the case, butanol, ethylene glycol monoethyl ether and the like, the decorative coating method of the present invention that can also use solvents for solvent-based paints, depending on the type of the binder resin component, generally, a primer is applied in advance, After this is dried, an intermediate paint (which may be omitted) and a top decorative paint are applied. Since the decorative paint using the chlorinated polyolefin resin of (a) above or the acrylic resin modified with the chlorinated polyolefin resin of (b) as the binder component has good adhesion to the material, It is also possible to directly apply the coating without the primer after performing the above-mentioned pretreatment, and the coating process can be simplified.

As the primer, a mixture of a material, an intermediate coat / top coat and a binder having good adhesion may be used. The binder component is not particularly limited, but a solution or dispersion of a chlorinated polyolefin having a chlorine content of 10 to 40% by weight or a modified product thereof can be used as is commonly used. Further, if necessary, additives such as a filler, a curing agent, a curing accelerator, etc. can be added thereto. As the solvent, toluene or a solvent mainly containing this is usually used. When polyisocyanate is used as the curing agent, a solvent such as butyl acetate or ethylene glycol monoethyl ether acetate is added to dissolve the whole system. As the modified product, a product having a hydroxyl group, a carboxyl group or an epoxy group introduced or a product obtained by copolymerizing a small amount of an unsaturated group having these groups can be used. However, normally, an unmodified chlorinated polyolefin resin may be used. These resins are generally commercially available, and examples of commercially available products include Hardlen 1
1L, Hardren 15-L L B (Toyo Kasei Kogyo Co., Ltd.), SUPERCHLON 832L has (Sanyo Pulp Industry Co., Ltd.), etc., it has been dissolved and diluted with a solvent typically such as toluene, a solid resin It can also be used by dissolving it in a solvent. The primer is usually a solution having a solid content of about 5 to 20% by weight, or in a state of being emulsified with water or water containing a solvent by an appropriate means, using a general coating method such as brush, roller or spraying. It suffices to paint and air dry or evaporate the solvent at a temperature below the softening point of the material to dry. Further, since a polyolefin resin having a low chlorine content has a strong tendency to be crystallized, it is desirable to preliminarily heat it at 80 to 90 ° C. for several hours to make it an amorphous state before use.

Depending on the foaming ratio of the material and the like, even if a primer and a top-coating decorative paint are used, if the paint is inhaled or if it is necessary to increase the physical properties such as the feeling of flesh and the impact resistance of the coated product, It is desirable to apply an intermediate coating material between the two. As the intermediate coating material, a coating material containing a relatively large amount of an inorganic filler is suitable. The intermediate coating composition may be solvent-based or water-dispersed, but water-dispersed is particularly preferable. As the solvent, solvent-based paints can use the same solvents as those used in the above-mentioned top-coat decorative paint, and water-dispersed paints use deionized water, as well as ether alcohol-based, alcohol-based, etc. solvents. It is also possible to use those to which is added. As the binder, it is possible to use an epoxy resin-curing agent-based two-component paint, an acrylic rubber one-component paint, or the like. Bisphenol type polyglycidyl ether is suitable as the epoxy resin, and polyamide or polyamidoamine is suitable as the curing agent, which may be emulsified or water-solubilized by a suitable method. Acrylic rubber is a monomer such as 2-ethylhexyl acrylate that has a low glass transition point and a large elongation when made into a polymer and various acrylic acid esters, methacrylic acid esters, styrene, vinyl acetate, etc. It is suitable to use an emulsion copolymer with the body, which has a relatively higher elongation than a general acrylic copolymer when formed into a coating film. When an acrylic rubber emulsion is used, the impact resistance of the formed decorative coating is good. Commercial products of these resins,
Commercially available paints made from these materials include, for example, Epicoat 1001 (manufactured by Ciel Sekiyu KK) for epoxy resins, Aquatoto (Toto Kasei Co., Ltd.) for emulsified epoxy resins, and Aqua for polyamide resins. Tote (Toto Kasei Co., Ltd.) and various water-based epoxy resin paints such as hydroepoxy (manufactured by Takashi Kubo Paint Co., Ltd.)
The acrylic rubber emulsion resins include Boncoat 3625 and 3665 (both Dainippon Ink and Chemicals, Inc.), and the acrylic rubber-based water-based paints include Dan water (Nippon Paint Co., Ltd.).

Examples of the inorganic filler to be added to the intermediate coating include silica, calcium carbonate, kaolin, talc, mica powder, etc.
The amount may be about 30 to 150 parts by weight with respect to 00 parts by weight.

The solid content of the intermediate coating composition is usually 30 to
It may be about 70% by weight, preferably about 40 to 70% by weight. The intermediate coating may be usually applied by a general method such as spray coating, brush coating, roller coating,
After coating, it may be dried at room temperature or forcedly dried at a temperature of 80 ° C. or lower. The number of times of application may be one or more, and the total dry film thickness may be usually about 30 to 800 μm, preferably about 50 to 300 μm.

In the method of the present invention, as described above, after forming a primer coating film, an intermediate coating film, etc., if necessary,
Apply the above-mentioned top coat paint.

The method of applying the top-coating decorative coating is not particularly limited, and it may be applied by a general method such as spray coating, brush coating, roller coating, etc. Usually, once or twice coating is sufficient. It is appropriate that the dry film thickness is about 30 to 100 μm. The drying method may be room temperature drying or forced drying at a temperature of about 40 to 80 ° C. as in the case of the above-mentioned intermediate coating material.

By forming the decorative coating film as described above, the original pattern having a beautiful decorative effect can be obtained along the bead boundary pattern of the foam by utilizing the pattern on the surface of the substrate while maintaining the adhesion to the substrate. A decorative coating film having a beautiful metallic appearance can be obtained in a simple process.

According to the surface decoration coating method of the present invention, a beautiful decorative effect can be exerted along the bead boundary pattern of the polyolefin bead molding foam even when the primer and the intermediate coating material are applied. The reason for this is not fully understood, but it is because a relatively large amount of metallic pigments and coloring pigments are aggregated on the boundary surface of the beads due to the relationship between the uneven surface pattern of the substrate and the surface tension of the paint, and then the pattern is formed by drying. It can be estimated that

[0029]

EFFECTS OF THE INVENTION According to the decorative coating method for a polyolefin bead molding foam according to the present invention, the decorative coating film having a unique and beautiful metallic appearance by making use of the pattern on the surface of the substrate while maintaining the adhesion to the substrate. Can be obtained in a simple process. A beautiful metallic appearance that makes use of such a pattern on the surface of the substrate is obtained when the same paint is applied to other materials such as ordinary plastic plates, metals, wood products, paper products, inorganic materials in the same process. This is not seen, and it is a unique effect obtained only when the above-mentioned specific top-coat decorative paint is used with a polyolefin-based bead molding foam as a material. Further, according to the method of the present invention, such an effect can be obtained not only when the decorative coating is spray-coated, but also when the brush coating or the roller coating is performed. Further, this effect is not impaired even when an intermediate coating material is used.

[0030]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples.

In each of the production examples, a usual method such as dissolution, stirring, dispersion, etc. was adopted as the method for producing the coating material.
Depending on the difficulty of dispersion of the color pigment, a part of the binder to be used and the required pigment are used together with a dispersant and various additives (for example, a defoaming agent, an antisettling agent, a dehydrating agent if necessary), a roll mill, a sand mill. Using a high-speed stirrer, etc., glass beads and steel beads were added, if necessary, and dispersed for a required time. After filtration, the remaining components such as silicone oil were added. The metal powder and pearls were previously dispersed in a part of the solvent used with a stirrer under relatively simple conditions and added to the paint. The intermediate water-based paint is emulsified using only a high-speed stirrer,
Pigment dispersion was performed. In the case of a two-pack type paint, a curing agent was added at a predetermined ratio just before use to stir and homogenize, and then coating was performed. All compounding amounts are parts by weight.

Production Example 1 Waterborne epoxy resin intermediate coating paint A Aquatote 205 (manufactured by Tohto Kasei Co., Ltd., bisphenol A type epoxy resin emulsion, solid content 50%) 100 parts talc 30 parts Additive (precipitation inhibitor, antifoaming agents, anti-sagging agents) Aqua tote 8535 to more than 3 parts and intermediate coating a main agent (manufactured by Tohto Kasei Co., Ltd., a polyamide resin solid resin 50%) 6 0 parts water (60 ° C.) 20 parts data Le KU 30 parts or more with the intermediate coating material A curing agent Production Example 2 Water-based acrylic rubber intermediate coating material B Boncoat 3625 (manufactured by Dainippon Ink and Chemicals, Inc., acrylic rubber emulsion resin solid content 60%) 100 parts Calcium carbonate 30 parts titanium oxide 8 parts Cal Bo carboxymethyl cellulose 6% aqueous solution of 6 parts of additives (preservatives, dispersing agents, antifoaming agents, anti-settling agent, etc.) 2 parts aqueous ammonia 25%) 2 parts or more as the intermediate coating B Production Example 3 Top coating decorative coating A HARDREN B13 (Toyo Kasei Co., Ltd. chlorinated polyolefin resin xylene solution solid content 30%) 100 parts Alpaste NL-1200N (Toyo Corporation) Aluminum Co., Ltd., aluminum foil 5 parts Cyanine Green 2 parts Shin-Etsu Silicone KP310B (Shin-Etsu Chemical Co., Ltd., silicone oil 50% xylene solution with a molecular weight of about 100,000 to 500,000) 0.6 parts Xylene 12 parts Additives ( Dispersant, antifoaming agent) 0.5 part or more is the main component of decorative paint A.

Sumidur N75 (manufactured by Sumitomo Bayer Co., Ltd., hexamethylene diisocyanate trimer adduct) 2 parts Ethylene glycol monoethyl ether acetate 8 parts The above is the decorative coating A curing agent.

Production Example 4 Top coat decorative paint B (acrylic lacquer type) Acridic A157 (manufactured by Dainippon Ink and Chemicals, Inc., acrylic resin 50% toluene butanol solution) 100 parts Alpaste NL1200N 6 parts Bengara 2 parts carbon Black 0.2 parts Silicone TRS10N (Wacker, silicone oil having a molecular weight of 100,000) 0.8 parts Additives (dispersant, suspending agent, antifoaming agent) 1 part Xylene 15 parts The above is the decorative paint B.

Production Example 5 The above is the main component of decorative paint C.

Zemlac ZT118Z (Kanefuchi Chemical Industry Co., Ltd., solid content 18% organic tin-containing xylene solution) 11 parts The above is the decorative coating C curing agent Production Example 6 Top coat decorative coating D (vinyl alkyd type) Styresol 4250 (Dainippon Ink and Chemicals, Inc., vinyl alkyd resin 50% xylene solution) 100 parts Alpaste NL1200N 4 parts Shin-Etsu Silicone KP310B (Shin-Etsu Chemical Co., Ltd., 50% xylene silicone oil with a molecular weight of about 100,000 to 500,000) Solution) 0.4 part Cobalt naphthenate 6% 0.4 part Additive (antifoaming agent) 0.3 part Xylene 20 parts The above is designated as decorative coating D.

[0037] Production Example 7 topcoat decorative paint E (polyester urethane) BURNOCK D 6-43 9 (Dainippon Ink and Chemicals, nonvolatile content 80% solvent xylene, MIBK) 100 parts ALPASTE NL1200N 6 parts Cyanine Green 3 parts Carbon black 0.1 part Shin-Etsu Silicone KP310B (Shin-Etsu Chemical Co., Ltd., silicone oil with a molecular weight of about 100,000 to 500,000, 50% xylene solution) 0.5 part Butyl acetate 15 parts Additives (dispersant, suspending agent) , Color separation preventing agent, antifoaming agent, dibutyltin dilaurate) 1.2 parts Coronate L (polyurethane is manufactured by Nippon Polyurethane Co., Ltd., solid content: 75%) 80 parts 80 parts ethylene glycol monoethyl 10 parts or more of ether acetate is used as the decorative coating E curing agent.

Examples 1 to 7 and Comparative Examples 1 to 6 As a material, a bead-molded polypropylene foam (trade name: Eperan PP (Kanefuchi Chemical Co., Ltd.) (foaming ratio 30 times or 15 times) 40 mm thick plate Was wiped with toluene and cleaned, and the coating interval was 24 for multi-layer coating.
Ford cup 20 seconds at room temperature (however, 25 hours for intermediate paint)
The viscosity was adjusted to ˜30 seconds and spray coating was performed. The coating amount is 100 g / m ^{2 for the} primer and 300 g for the intermediate coating.
/ M ² , and the topcoat was 120 g / m ^{2 for the} decorative paint (both were converted to paint), and the number of times of coating was once.

The coated finished product is left at rest for 1 day at 4 ° C at 4 ° C.
After standing for 8 hours, the state of the coating film and the decorative effect are observed, and the adhesion is determined according to JIS K5400-1991 paint test method 8.5.
1. According to the above, a grid pattern with a space of 2 mm was prepared and a peeling test was performed using cellophane tape. The evaluation criteria were as follows: ⊚ is excellent, adhesiveness is 10 points, ◯ is good, adhesiveness is 6 to 8 points, Δ is slightly bad, adhesiveness is 2 to 4 points, and x is poor and adhesiveness is 0 points.

Table 1 shows the coating process and evaluation results of Examples 1 to 7 and Comparative Examples 1 to 6.

[0041]

[Table 1]

The coated plate according to Example 7 has particularly good impact resistance and is suitable for applications where impact resistance is required.

Claims (3)

[Claims] 1. A chlorinated polyolefin resin,
At least one component selected from (b) an acrylic resin, (c) an acrylated or vinylated alkyd resin, and (d) a polyisocyanate and a polyol resin that is reactively cured with the polyisocyanate is used as the main component of the binder, A) 0.1 to 3% by weight of a solid content of silicone oil containing methylchlorosilane as a main component and having a number average molecular weight of 5000 or more, (B)
A polyolefin-based bead molding is applied to a top-coat decorative coating containing at least one of metal powder, mica, and pearl foil in a solid content of 0.5 to 20% by weight, and (C) a coloring pigment in a solid content of 0 to 20% by weight. A method for coating a surface decoration of a polyolefin-based bead molding foam, which comprises exposing the surface of a foam to a surface and then curing the foam to reveal a pattern of the expanded bead particles. 2. A top coat decorative paint containing a chlorinated polyolefin resin having a chlorine content of 10 to 40% by weight and containing a functional group consisting of at least one of a hydroxyl group and an epoxy group, and a curing agent as a binder component. The method of claim 1. 3. The method according to claim 1, wherein an adhesion primer is applied, an intermediate coating material containing an acrylic rubber emulsion and an inorganic filler as a main component is applied, and then a top coating material is applied.