JP2008184521A - Primer and coating method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a primer that exhibits excellent adhesion to a plastic material and excellent interlayer adhesion to a coating film functioning as a substrate in recoating, and a coating method using the primer. <P>SOLUTION: The primer comprises a chlorinated polyolefin resin (A) having a chlorine content of 5-50 mass% and a weight-average molecular weight of 1,000-100,000, a blocked polyisocyanate compound (B), a diol (C) having a weight-average molecular weight of 120-1,000 and a curing catalyst (D), where the contents of the components (A), (B), (C) and (D) are 50-90 mass%, 50-10 mass%, 0.5-12 mass% and 0.01-1.5 mass%, respectively, based on the total mass of the resin solid contents of the components (A) and (B). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

 The present invention relates to a primer excellent in adhesion to a plastic material, particularly a polyolefin material, and excellent in adhesion to a surface coating film during non-sand recoating (repainting), and a coating method using the same.

Polyolefin molded products are often used as members for automobile outer panels and home appliances, and recently, recycled polyolefin molded products have also been reused. Primer containing chlorinated polyolefin in order to improve the adhesion between the top coat and the molded polyolefin product when using a two-component topcoat containing a polyisocyanate compound as the overcoated paint for a molded polyolefin product Is used. However, when recycled products of polyolefin products that have been included in polyolefin molded products up to now (for example, styrene butadiene rubber, isoprene rubber, etc.) or polyolefin molded products in which the hydroxyl group-containing polyolefin is reduced or not added at all are reused. Has the disadvantage of insufficient adhesion to polyolefin materials.

In addition, when repair coating is performed after applying a primer and a top coat to a polyolefin molded product, normally, the coating film is sanded to remove dust, blisters, etc., and then the primer and top coat are repainted on that part ( Recoated). At this time, the entire surface of the coating film to be repainted is not polished (non-sand), and the primer and the top coating are repainted on the unpolished coating film. In such a case, the interlayer adhesion between the lower layer coating film and the repainted primer was insufficient.

By applying directly to the molded product of difficult-to-adhere polyolefin material without applying a primer, it gives excellent adhesion, and also has high gloss appearance, weather resistance, solvent resistance, and coating workability 2 As the liquid coating composition, (A) a chlorinated polyolefin resin having a chlorine content of 10 to 50% by mass, (B) an acrylic-modified chlorinated polyolefin resin, and (C) a weight average molecular weight of 2,000 to 50,000, An acrylic resin and / or polyester resin having a hydroxyl value of 10 to 90 mgKOH / g and (D) an isocyanate compound are essential components, and the ratio of isocyanate equivalent to hydroxyl equivalent is [isocyanate equivalent] / [hydroxyl equivalent] = 0.5. /1.0 to 1.2 / 1.0, and the component (A) in the total mass (solid content) of the component (A), the component (B) and the component (C) is 3 to 3. 0 wt%, (B) component is from 5 to 40 wt%, and coating compositions are known (C) component is 40 to 92 wt% (e.g., see Patent Document 1). However, since the function as a primer and the function as a top coat are used in combination, adhesion to a molded product of polyolefin material is not sufficient, and there is a problem of pot life in a two-component paint.

In addition, it can be directly applied to polyolefin-based molded products without the need for pre-treatment processes such as primer coating, and it has excellent paint storage stability, as well as adhesion, hot water resistance, and gasoline resistance. As a coating resin composition capable of forming an excellent coating film, (1) an acetoacetoxy group-containing monomer in the presence of 5 to 50 parts by weight of a chlorinated polyolefin resin having a chlorine content of 15 to 50% by weight And a polymer having an acetoacetoxy group in the side chain obtained by polymerization or copolymerization with other monomers that can be copolymerized as required, and (2) an isocyanate compound as essential components. A resin composition for paint having good adhesion to a characteristic polyolefin-based material is known (see, for example, Patent Document 2). However, this resin composition for paint is a two-component paint and has a problem of pot life.

Moreover, as a primer for plastics having excellent adhesion to molded articles of polyolefin-based materials and recoat adhesion to coating films, the chlorine content is 16 to 22% by weight and the weight average molecular weight is 30,000 to 120,000. A blocked polyisocyanate (B) obtained by blocking a chlorinated polyolefin (A), an isocyanurate type aliphatic and / or alicyclic polyisocyanate with a dialkyl ester of malonic acid and an acetoacetate, and a polyol resin (C). A primer for plastics characterized by the above is known (for example, see Patent Document 3). However, although the adherence is good when a molded article or a coating film of a polyolefin-based material is sanded, there is a drawback that the recoat adhesion in the case of non-sanding is insufficient.

JP 2005-139336 A JP-A-8-311397 Japanese Patent Laid-Open No. 2002-121462

The present invention has excellent adhesion to plastic materials, particularly polyolefin materials, and excellent interlaminar adhesion to a coating film used as a base in recoating (repainting), particularly a urethane resin-based top coating film. It is an object of the present invention to provide a primer and a coating method using the primer.

As a result of intensive studies to solve the above problems, the present inventor has added a low molecular weight diol and a curing catalyst to a composition containing a specific chlorinated polyolefin resin and a blocked polyisocyanate compound. Thus, it has been found that recoat adhesion to a molded article or a coating film made of a plastic material such as a polyolefin-based material has been remarkably improved, and the present invention has been completed based on these findings.

That is, the present invention is a chlorinated polyolefin resin (A), a blocked polyisocyanate compound (B) having a chlorine content of 5 to 50% by mass and a weight average molecular weight of 1,000 to 100,000, and a weight average molecular weight of The diol (C) of 120 to 1,000 and the curing catalyst (D) are contained, and the content ratio of the above components is (A) with respect to the total mass of resin solids of the component (A) and the component (B). ) Component is 50-90% by mass, (B) component is 50-10% by mass, (C) component is 0.5-12% by mass, and (D) component is 0.01-
The primer is characterized by being 1.5% by mass.

The present invention also provides a method for coating a plastic molded product, characterized in that the above primer and top coating are sequentially applied to a plastic molded product, baked and cured, and a top coating film is formed. .
In addition, the present invention sequentially applies the primer and the top coat on a plastic molded product, and after baking and curing, further coats the primer and the top coat on the top coat film in sequence, and then bake and cure. The present invention provides a method for painting a plastic molded product.
In addition, the present invention is a molding characterized in that the primer and the top coating are sequentially applied to the top coating film of the molded product in which the top coating is applied and cured to form a top coating film, and is baked and cured. A method for painting products is provided.

In addition, the present invention provides a method for coating a molded product, wherein the top coat is a one-coat type two-component urethane resin paint.
Further, the present invention provides a method for coating a molded article, wherein the top coat film comprises two layers of a base coat film and a clear paint film, and at least the clear paint is a two-component urethane resin paint. It is to provide.
In the method for coating a molded product according to the present invention, the top coat film comprises three layers of a colored base coat film, a pearl base coat film, and a clear paint film, and at least the clear paint is a two-component urethane resin paint. A method for painting a molded article is provided.

By using the primer of the present invention, the adhesion of the primer coating to a plastic material, particularly a polyolefin material, is excellent, and the interlayer adhesion between the urethane resin-based top coating film and the primer coating film used as a base in recoating (repainting) An excellent coating film can be obtained.

The chlorinated polyolefin resin of the component (A) used in the present invention has a chlorine content of 5 to 50% by mass, preferably 15 to 35% by mass, and more preferably 18 to 25% by mass. If the chlorine content exceeds 50% by mass, the adhesion to plastic materials, particularly polyolefin materials and coatings, will be poor. If the chlorine content is less than 5% by mass, the solubility in the solvent will decrease. Therefore, a problem arises in storage stability.

The weight average molecular weight of the chlorinated polyolefin resin (A) is 1,000 to 100,000, preferably 5,000 to 90,000, more preferably 10,000 to 80,000. If the weight average molecular weight exceeds 100,000, a problem such as poor coating workability occurs. If the weight average molecular weight is less than 1,000, the resin itself has insufficient cohesive force, so that a normal coating film cannot be obtained. Occurs.
Examples of the chlorinated polyolefin resin (A) include a resin obtained by modifying a polymer resin having a polyolefin resin as a main skeleton with chlorine. As polyolefin resin, in addition to polyethylene resin, polypropylene resin, etc., modified polyolefin resin modified with maleic anhydride etc., hydroxyl group, carboxyl group, methacryloyl group, acryloyl group or epoxy group etc. in the molecular terminal or molecular chain Examples thereof include polyolefin polymer compounds.

Specific examples of the component (A) chlorinated polyolefin resin include chlorinated polyethylene resin, chlorinated polypropylene resin, chlorinated ethylene-propylene copolymer, chlorinated ethylene-vinyl acetate copolymer, and these chlorinated polyolefin resins. And the like modified by copolymerizing an acid anhydride such as maleic anhydride.
Moreover, a commercial item can be used for the (A) component chlorinated polyolefin resin. Examples of the commercially available products include Super Clone 773H, Super Clone 822, Super Clone 892L, Super Clone 832L, Super Clone E (above, manufactured by Nippon Paper Chemicals Co., Ltd.), HARDREN 14LLB, HARDREN CY9122, HARDREN HM-21, Hardren 13-MLJ (above, manufactured by Toyo Kasei Kogyo Co., Ltd.) and the like.

The blocked polyisocyanate compound of component (B) used in the present invention is obtained by non-releasing an isocyanate group of a polyisocyanate compound having two or more isocyanate groups in one molecule with a blocking agent. When the blocking agent is dissociated, the blocked polyisocyanate compound is expected to react with the (C) component diol, but basically plays a role in increasing the affinity with the top coat film. .

As the polyisocyanate compound, various polyisocyanates can be used without particular limitation as long as they are conventionally used for paint applications. As such polyisocyanate, various polyisocyanates, such as aromatic polyisocyanate and aliphatic or alicyclic polyisocyanate, can be used, for example. Examples of such polyisocyanates include toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), and 2-isocyanate. Preferable examples include ethyl-2,6-diisocyanate caproate (LTI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), hydrogenated xylene diisocyanate (HXDI) and the like. The polyisocyanate may be used in the form of a burette type, adduct type, isocyanurate type or the like as a prepolymer. From the viewpoint of weather resistance, it is preferable to use an aliphatic polyisocyanate. Polyisocyanate may be used individually by 1 type, or may be used as a mixture thereof.

As the blocking agent for the polyisocyanate compound, an appropriate one is selected depending on the dissociation temperature, and examples include oxime, active methylene compound, malonic acid dialkyl ester, acetoacetate ester, ε-caprolactam, β-diketone and the like.
The blocked polyisocyanate compound may be used alone or as a mixture thereof.
In the present invention, the content ratio of the component (A) and the component (B) is 50 to 90% by mass of the component (A) with respect to the total mass of the resin solids of the component (A) and the component (B). B) A component is 50-10 mass%. Preferably, the component (A) is 60 to 80% by mass and the component (B) is 40 to 20% by mass.
Here, each content rate of said (A) component and (B) component says content rate of each resin solid content of (A) component and (B) component. In addition, resin solid content says the heating residue measured by the method described in JISK5601-1-2.

  When the component (A) is less than 50% by mass, the adhesion of the primer coating to the plastic material decreases, and when the component (A) exceeds 90% by mass, the top coating film and the primer coating Adhesion is reduced. When the component (B) is less than 10% by mass, the adhesion between the top coating film and the primer coating is reduced, and when the component (B) exceeds 50% by mass, the primer coating on the plastic material Adhesion is reduced.

The diol of the component (C) used in the present invention improves the wettability of the chlorinated polyolefin resin to the plastic material, and when recoating, the wet top coat film, particularly the urethane resin base top coat film, is used as a base. It plays a role to improve the sex and adhesion. In particular, when an unreacted isocyanate compound remains in the vicinity of the interface with the primer in the lower urethane resin-based topcoat film in contact with the primer, a diol having a low molecular weight has high mobility. It is considered that there is a high possibility of moving inside to the vicinity of the interface and reacting with an unreacted isocyanate compound, and the effect of improving the interlayer adhesion between the primer coating and the top coating during recoating is remarkable.

(C) The weight average molecular weight of the diol of a component is 120-1,000, Preferably it is 120-800. When the weight average molecular weight of the diol of the component (C) is less than 120, the storage stability of the primer is lowered due to the decrease in solubility in the main aromatic solvent, which is not preferable. When the weight average molecular weight exceeds 1,000, the effect of improving the adhesion to the upper coating film of the lower layer, particularly the urethane resin-based upper coating film is not observed.
Specific examples of the low molecular weight diol of component (C) include dipropylene glycol, triethylene glycol, hydrogenated bisphenol A, and the like. Further, as the low molecular weight diol of the component (C), a diol that is a reaction product of an excess amount of a diol and a dibasic acid, a lactone adduct such as caprolactone, or the like can be used. Diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol, pentanediol, hexanediol, heptanediol, octanediol, butylethylpropanediol, cyclohexanediol, and cyclohexanedimethanol. And phenyldimethanol. Dibasic acids include dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, hexahydroterephthalic acid, maleic acid and fumaric acid Examples thereof include acids and acid anhydrides thereof. Moreover, it may be modified with a monoglycidyl compound such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, sec-butylphenol glycidyl ether, or neodecanoic acid glycidyl ester containing a monoglycidyl group.

In this invention, the content rate of (C) component is with respect to the total mass of the resin solid content of (A) component and (B) component,
It is 0.5-12 mass%, Preferably it is 1-10 mass%, Most preferably, it is 1.5-8 mass%. When the content ratio of the component (C) is less than 0.5% by mass, the adhesion of the primer coating to the top coating film, particularly the urethane resin-based top coating film, which is the base is insufficient, and the content exceeds 12% by mass. Is unfavorable because the storage stability of the primer is reduced due to a decrease in compatibility with the chlorinated polyolefin resin which is the main component (A).
In addition, the content rate of (C) component is a content rate of the active ingredient of (C) component, and an active ingredient means the component which does not contain a solvent etc. when diluted with a solvent etc. here.

The (D) component curing catalyst used in the present invention is not particularly limited as long as it promotes the reaction between the reactive component contained in the overcoat film as a base and the (C) component diol, and is used particularly for urethane resins. Preferred is a catalyst. When the top coat film used as the base is a urethane resin-type paint film, the reaction between the unreacted isocyanate of the urethane resin-type top coat film used as the base and the hydroxyl group of the primer layer of the recoat is promoted, and the adhesion during non-sand recoat is improved. improves.

Specific examples of the (D) component curing catalyst include tin compounds and zinc compounds. Examples of tin compounds include tin halides such as tin chloride and tin bromide, organotin compounds such as dibutyltin diacetate and dibutyltin dilaurate, and zinc compounds include zinc halides such as zinc chloride and zinc bromide, Examples thereof include zinc salts of organic acids such as zinc octylate and zinc laurate. One kind of tin compound or zinc compound as a curing reaction catalyst may be used, or two or more kinds may be used in combination, or may be used in combination with another curing reaction catalyst.

In this invention, the content rate of (D) component is 0.01- with respect to the total mass of the resin solid content of (A) component and (B) component.
The amount is 1.5% by mass, preferably 0.02 to 1.0% by mass, and particularly preferably 0.05 to 0.8% by mass. When the ratio of the component (D) is less than 0.01% by mass, the effect of promoting the curing reaction is not sufficiently exhibited,
When the amount exceeds 1.5% by mass, the recoat adhesion is considered to be excessively hardened, which is not preferable.
In addition, the content rate of (D) component is a content rate of the active ingredient of (D) component, and an active ingredient means the component which does not contain a solvent etc. when diluted with a solvent etc. here.

The primer of this invention can use a low molecular weight liquid epoxy resin, a color pigment, an extender pigment, an organic solvent, and various additives as needed. Examples of the color pigment include organic pigments such as azo lake pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, yellow lead, yellow iron oxide, Examples thereof include inorganic pigments such as bengara and titanium dioxide. Examples of extender pigments include kaolin and talc.

The organic solvent is not particularly limited as long as it can dissolve each component, but preferably does not react with an isocyanate compound. For example, aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform and carbon tetrachloride, dibutyl ether, Examples include ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and esters such as ethyl acetate, n-propyl acetate, and n-butyl acetate. These solvents may be used alone or in combination of two or more. The blending method of each component, the luster pigment, the color pigment, the organic solvent, various additives, and the resin addition method are not particularly limited and can be performed by various methods, and the mixing order and the addition order are various. Can be done in order.

As a suitable coating method using the primer of the present invention, the primer is heated as necessary, adjusted to a desired viscosity by adding an organic solvent, air spray, airless spray, electrostatic air spray, Although painting can be performed using a commonly used coating machine such as a flow coater or a dipping type coating machine, or a brush, air spray coating is preferred. The dry coating thickness of the primer coating is preferably 2 to 15 μm, particularly preferably 4 to 10 μm.

After the primer of the present invention is applied, it is preferable to apply the top coat paint wet on wet without baking. The top coat may be a one-coat type paint, a two-coat type paint, or a three-coat type paint, but the paint that forms the uppermost coating layer is a two-pack type urethane resin paint. It is preferable that The urethane resin-based topcoat paint is not particularly limited as long as the coating film is formed by the reaction between the polyol and the isocyanate compound.

As the one-coat type top coat, a solid paint or a metallic paint may be used. The dry coating thickness of the top coating is preferably 15 to 40 μm, more preferably 20 to 35 μm. As the two-coat type paint, a combination of a colored base coat paint such as a metallic base coat paint or a pearl-like base coat paint and a clear paint is common, and the dry coat thickness of the base coat paint is preferably 10 to 20 μm. The dry coating thickness of the paint is preferably 20 to 40 μm, and more preferably 25 to 35 μm. As the three-coat type paint, a combination of a colored base coat paint, a pearl-like base coat paint, and a clear paint is common, and the dry coat thickness of the colored base coat paint is preferably 5 to 15 μm. The thickness is preferably 5 to 15 μm, and the dry coating thickness of the clear coating is preferably 20 to 40 μm, more preferably 25 to 35 μm. When these paints are reapplied, wet-on-wet in an uncured state is preferred.

Baking and drying conditions for the urethane resin-based topcoat are preferably 20 to 150 ° C. for 5 minutes to 3 days, and more preferably 80 to 140 ° C. for 10 to 30 minutes.
Examples of the molded product to which the primer of the present invention is applied include molded products made of polyolefin materials such as polyethylene and polypropylene, and plastic materials containing polyolefin. Furthermore, the present invention can be applied to molded products made of plastic materials such as ABS resin, PC resin, and nylon.

Recoating (repainting) in the present invention is, for example, a method in which the primer of the present invention and the topcoat paint are sequentially applied to a molded product in which a topcoat paint is applied and cured to form a topcoat paint film, and is baked and cured. Examples include a method in which the primer of the present invention and the top coat are sequentially applied to a plastic molded article, and after baking and curing, re-coating is performed when there is a problem with adhesion of dust or a coating film. In this case, after removing the dust, the primer is applied again without sanding the entire top coat film, and the primer and the top coat are sequentially applied and baked in the same manner as the first time. In addition, recoating (repainting) can provide a coating film with excellent adhesion by sequentially coating and baking the primer and the topcoating paint, even if the topcoating film as a base is partially peeled off. .

Examples of the coated article obtained by the coating method of the present invention include structures, metal products, plastic products, rubber products, and the like. More specifically, automobiles, automotive parts (for example, parts such as bodies, bumpers, spoilers, mirrors, wheels, interior materials, etc., of various materials), metal plates such as steel plates, motorcycle parts, motorcycle parts , Road materials (eg, guardrails, traffic signs, noise barriers, etc.), tunnel materials (eg, side walls, etc.), ships, railway vehicles, aircraft, musical instruments, home appliances, building materials, containers, office supplies, sports equipment And toys.

Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. The present invention is not limited to these examples. Hereinafter, unless otherwise specified, “part” and “%” mean “part by mass” and “% by mass”, respectively. Moreover, in Tables 1-6, the unit of the numerical value which shows the compounding quantity of each component is a mass part.
In the examples and comparative examples, each item was evaluated by the following method.

<Evaluation method of paint and coating film>
(Primer storage stability)
The primer was stored at 40 ° C. for 10 days, and its state was evaluated according to the following criteria.
○: No abnormality is observed.
Δ: Slight separation is observed.
X: Remarkable separation is observed.

(Primer painting workability)
A commercially available black polypropylene plate (length 70 mm, width 150 mm, thickness 3 mm) was wiped with isopropyl alcohol to remove dirt and dust adhering to the object to be coated. Next, adjust the viscosity of the primers shown in Tables 2 and 3 to 11 seconds with Ford Cup # 4 (20 ° C) using xylene, and paint with air spray. Sex was evaluated.
○: Can be painted without abnormality.
×: The paint cannot be applied due to the aggregation of the paint, or the thread is pulled during the painting and the paint cannot be applied normally.

(Adhesion of first coat)
In the above manner, on the primer coating film coated on the commercially available black polypropylene plate so as to have a dry coating thickness of 6 to 8 μm, in a wet-on-wet manner, a dilution solvent (butyl acetate / xylene = 70/30 (mass ratio) mixed solvent) Air-coating the top coating with viscosity adjusted so that the viscosity of the coating is 12 seconds in a Ford Cup # 4 (25 ° C.) and left at room temperature for 5 minutes. Then, it was kept at 90 ° C. for 20 minutes and dried. The dry coating thickness of the top coat is 25 μm for the 1-coat type, 15 μm for the 2-coat type base paint, 10 μm for the 3 coat-type colored base coat paint, and 3 μm for the pearl base coat paint. In the case of 8 μm and in the case of a clear paint, it was 30 μm, and all coatings including the 2-coat type and the 3-coat type were performed wet on wet. In order to use the obtained coated plate for the test, it was allowed to stand at room temperature for 60 minutes, and was cut into 11 vertical and horizontal cuts with a cutter knife, and peeled off with cellophane tape so that 100 squares could be obtained at 2 mm intervals in the coating film. The state was evaluated according to the following criteria.

○: The coating film does not peel off (100/100 in cross-cut notation)
Δ: State where the coating film is partially peeled (90 to 99/100 in crosscut notation)
X: State in which the coating film is peeled off (0 to 89/100 in cross-cut notation)
When peeling is recognized in the coating film, it is confirmed whether the peeling site is an interlayer between the material and the primer coating film or an interlayer between the primer coating film and the top coating film.

(Adhesion between the first overcoating and recoating overcoating)
In the above-described manner, on the commercially available black polypropylene plate, on the primer coating coated so as to be 6 to 8 μm, in a wet-on-wet, diluted solvent (butyl acetate / xylene = 70/30 (mass) In the mixed solvent), the viscosity of the top coating was adjusted to 12 seconds with a Ford Cup # 4 (25 ° C.) by air spraying, left at room temperature for 5 minutes, and then 100 ° C. Held for 40 minutes and dried. The dry coating thickness of the top coat is 25 μm for the 1-coat type, 15 μm for the 2-coat type base paint, 10 μm for the 3 coat-type colored base coat paint, and 3 μm for the pearl base coat paint. In the case of 8 μm and in the case of a clear paint, it was 30 μm, and all coatings including the 2-coat type and the 3-coat type were performed wet on wet. This coated plate is allowed to stand at room temperature for 24 hours. In the same manner as in the first time, the primer and the top coat are wet-on-wet by air spraying, left at room temperature for 5 minutes, and then at 80 ° C. for 20 minutes. Dried.

In order to use the obtained coated plate for the test, it was allowed to stand at room temperature for 60 minutes, and was cut into 11 vertical and horizontal cuts with a cutter knife, and peeled off with cellophane tape so that 100 squares could be obtained at 2 mm intervals in the coating film. The state was evaluated according to the following criteria.
○: The coating film does not peel off (100/100 in cross-cut notation)
Δ: State where the coating film is partially peeled (90 to 99/100 in crosscut notation)
X: State in which the coating film is peeled off (0 to 89/100 in cross-cut notation)

Resin Production Example 1 (Production of Diol Resin Solution)
A glass 2 L flask equipped with a thermometer and a stirrer was charged with 561 parts of 1,6 hexanediol and 347.1 parts of adipic acid, gradually heated to 140 ° C. and then heated to 190 ° C. over 3 hours. The temperature was raised to. After maintaining the temperature at 190 ° C. for 2 hours and proceeding with the esterification reaction, the temperature was raised to 210 ° C. over 2 hours, and the esterification reaction was carried out until the resin acid value became 1 or less. The obtained resin was cooled, 91.9 parts of xylene was added, and a diol resin solution C-1 having a weight average molecular weight of 330 and a resin solid content (active ingredient) of 90% by mass was obtained.

Resin production examples 2-4 (production of diol resin solution)
Resin synthesis was performed using the raw materials shown in Table 1 in the same manner as in Resin Production Example 1, and diol resin solutions C-2 to C-4 shown in Table 1 were obtained. However, the raw material “Cardura E-10” in Table 1 is a versatile acid monoglycidyl ester (manufactured by Japan Epoxy Resin Co., Ltd.).

Primer production example 1
In a dispersion container, a chlorinated polypropylene resin solution (trade name “Hardren CY9122” manufactured by Toyo Kasei Kogyo Co., Ltd., maleic anhydride-modified chlorinated polypropylene resin, chlorine content 22 mass%, weight average molecular weight 50,000-60,000, Resin solid content 20%) 525 parts, Tyco CR-90 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) 99 parts, Pigment Black FW200 beads (carbon black, manufactured by Degussa Co., Ltd.) 0.1 part and TSY-1 ( 0.9 part of yellow pigment (manufactured by Toda Pigment Co., Ltd.) is added and dispersed until the particle size is 15 μm or less. When the desired particle size is reached, the dispersion is stopped and blocked polyisocyanate (trade name “Desmodur BL3175”, manufactured by Sumitomo Bayer Urethane Co., Ltd., HDI isocyanurate blocked with MEK oxime, containing NCO amount 11.2% 60 parts), 5 parts of Diol C-1 produced in Resin Production Example 1, 0.9 part of dibutyltin dilaurate and 309.1 parts of xylene were taken out and stirred sufficiently. Table 2 Primer P-1 of Primer Production Example 1 shown in FIG.

Primer production examples 2 to 17
Primers P-2 to P-17 shown in Table 2 and Table 3 were obtained in the same manner as Primer Production Example 1.

The meanings of the trade names or abbreviations shown in the table are as follows.
1): Taipei CR-90: Titanium oxide, manufactured by Ishihara Sangyo Co., Ltd. 2): Acicular conductive titanium oxide: Conductive titanium oxide, manufactured by Ishihara Sangyo Co., Ltd. 3): Pigment Black FW200 beads: Carbon black, Degussa 4): PRINTEX L: Conductive carbon black, manufactured by Degussa Co., Ltd. 5): TSY-1: yellow pigment, manufactured by Toda Pigment Co., Ltd. 6): Hardren CY9122: manufactured by Toyo Kasei Kogyo Co., Ltd. Maleic anhydride-modified chlorinated polypropylene resin, chlorine content 22 mass%, weight average molecular weight 50,000-60,000, heating residue 20 mass%

7): Super Clone 892L: manufactured by Nippon Paper Chemical Co., Ltd., maleic anhydride-modified chlorinated polypropylene resin, chlorine content 22% by mass, weight average molecular weight 60,000 to 70,000, heating residue 20% by mass
8): Death module BL3175: manufactured by Sumitomo Bayer Urethane Co., Ltd., HDI isocyanurate blocked with MEK oxime, 11.2% by mass of NCO content, 75% by mass of heating residue
9): Death module BL3272MPA: manufactured by Sumitomo Bayer Urethane Co., Ltd., HDI isocyanurate blocked with ε-caprolactam, content of NCO 10.2% by mass, heating residue 72% by mass
10): Death module BL4265SN: manufactured by Sumitomo Bayer Urethane Co., Ltd., IPDI isocyanurate blocked with MEK oxime, NCO content 8.9% by mass, heating residue 65% by mass

Topcoat paint production example 1 (2-coat urethane resin paint for 1 coat)
In a dispersion container, acrylic resin LB-9020 (BASF Coatings Japan Co., Ltd., heating residue 55% by mass, hydroxyl value 56 mgKOH / g) 45.5 parts, Tyco CR-90 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) ) 24 parts, 0.1 parts of Pigment Black FW200 beads (carbon black, manufactured by Degussa) and 0.6 parts of TSY-1 (yellow pigment, manufactured by Toda Pigment) have a particle size of 10 μm or less. Dispersed. When the desired degree of dispersion was reached, the dispersion was stopped, and the surface modifier Modaflow (manufactured by Monsanto Co., Ltd., acrylic copolymer, 100% by weight of heating residue) 0.2 part, xylene 10 parts and butyl acetate 13.2 parts Then, the mixture was thoroughly stirred with a disper to make it uniform, and a main component of a one-coat two-component top coat T-1 was prepared. As a curing agent, Sumidur N75 (manufactured by Sumitomo Bayer Urethane Co., Ltd., polyisocyanate resin, heating residue 75%, NCO content 16.5% by mass) was used. The mixture was mixed at a ratio of 4 and stirred to be uniform.

Top coat paint production example 2 (2 coat base coat paint)
Acrylic resin LB-9020 (BASF Coatings Japan Co., Ltd., heated residue 55 mass%, hydroxyl value 56 mg KOH / g) 45.5 parts, rheology control agent LC-0988 (BASF Coatings Japan Co., Ltd., inorganic System, 6 parts by weight of heating residue), aluminum flake pigment Alpaste TCR3040 (trade name, manufactured by Toyo Aluminum Co., Ltd., 80% by weight of heating residue, average particle diameter (D ₅₀ ) 17 μm, average thickness 0.8 μm ) 2.5 parts, Alpaste 6340NS (trade name, manufactured by Toyo Aluminum Co., Ltd., heating residue 71%, average particle size (D ₅₀ ) 13 μm, average thickness 0.29 μm) 3 parts, Death Module BL3175 (trade name) Manufactured by Sumitomo Bayer Urethane Co., Ltd., HDI isocyanurate blocked with MEK oxime, containing NC Amount 11.2 mass%, heating residue 75 mass%) 3.3 parts, surface modifier Modaflow (manufactured by Monsanto Co., Ltd., acrylic copolymer, heating residue 100 mass%) 0.2 parts, xylene 10 parts And 29.5 parts of butyl acetate were mixed and stirred with a disper for 10 minutes to make uniform, and a one-component two-coat metallic base coat paint T-2 was prepared.

Top coat paint production examples 3 to 4 (base coat paint for 2 coats)
In the same manner as in Topcoat Paint Production Example 2, metallic base coat paints T-3 to T-4 for 1-pack type 2-coat shown in Table 4 were prepared.

Topcoat paint production example 5 (base coat paint for 2 coats)
In the same manner as in Topcoat Production Example 2, the raw materials shown in Table 4 except for Sumidur N75 were mixed and stirred uniformly to prepare a main component of a two-component, two-coat metallic base coat T-5. As a curing agent, Sumidur N75 was mixed at a ratio of 96.5 parts of the main agent and 3.5 of the curing agent immediately before coating, and stirred to be uniform.

Top coat paint production example 6 (colored base coat paint for 3 coats)
In the same manner as in Topcoat Production Example 1, the pigments shown in Table 4 were dispersed, and the remaining raw materials excluding Sumidule N75 were added and taken out. The main agent was prepared. As a curing agent, Sumidur N-75 was mixed at a ratio of 96.5 parts of the main agent and 3.5 of the curing agent immediately before coating, and stirred to be uniform.

Top coat paint production example 7 (colored base coat paint for 3 coats)
In the same manner as in Topcoat Paint Production Example 6, the pigments shown in Table 4 were dispersed, the remaining raw materials were added and taken out, and stirred uniformly to prepare a one-component three-coat colored base coat coat T-7.

Top coat paint production example 8 (Pearl base coat paint for 3 coats)
A main component of pearl base coat coat T-8 for two-pack type three-coat was prepared in the same manner as in Topcoat Paint Production Example 5 except that the aluminum pigment was replaced with a pearl pigment. As a curing agent, Sumidur N-75 was mixed at a ratio of 96.5 parts of the main agent and 3.5 of the curing agent immediately before coating, and stirred to be uniform.

Topcoat paint production example 9 (Pearl base coat paint for 3 coats)
A pearl base coat coat T-9 for one-pack type 3 coat was prepared in the same manner as in the top coat production example 2 except that the pearl pigment was used instead of the aluminum pigment.

Topcoat paint production example 10 (clear paint)
Acrylic resin LB-9040 (manufactured by BASF Coatings Japan Co., Ltd., heating residue 55% by mass, hydroxyl value 78 mgKOH / g) 80 parts of surface conditioner Modaflow 0.2 part and butyl acetate 4.8 parts were mixed. The mixture was stirred and homogenized with a disper for 10 minutes to prepare a two-component clear paint T-10 main agent. As a curing agent, Sumidur N-75 was mixed at a ratio of 85 parts of the main agent and the curing agent 15 immediately before coating, and stirred to be uniform.

The meanings of the trade names or abbreviations shown in the table are as follows.
11): Iriodin 103WNT (Merck Co., Ltd., mica pigment)
12): Alpaste TCR3040: Aluminum pigment manufactured by Toyo Aluminum Co., Ltd., heating residue 80% by mass, average particle size (D ₅₀ ) 17 μm
13): Alpaste 6340NS (Toyo Aluminum Co., Ltd. aluminum pigment, heating residue 71 mass%, average particle diameter (D ₅₀ ) 13 μm
14): Sumidur N-75: manufactured by Sumitomo Bayer Urethane Co., Ltd., polyisocyanate resin, heating residue 75%, NCO content 16.5% by mass
15): Uban 122: manufactured by Mitsui Chemicals, Inc. Butylated melamine resin, heating residue 60% by mass
16): Modaflow: manufactured by Monsanto Co., Ltd., acrylic copolymer, heating residue 100% by mass

(Example 1)
Using P-1 as the primer and T-1 as the top coat, according to the paint and coating film evaluation methods described above, the storage stability of the primer, the primer workability, and the first top coat after the top coat And the adhesion test between the first overcoating and the recoating overcoating were conducted, and the evaluation results are shown in Table 5.

(Examples 2 to 12)
A test was conducted in the same manner as in Example 1 except that the top coat was changed to the combination shown in Table 5, and the evaluation results are shown in Table 5.
(Comparative Examples 1-5)
A test was conducted in the same manner as in Example 1 except that the top coat was changed to the combination shown in Table 6, and the evaluation results are shown in Table 6.

<Summary>
If the primer of this invention is in the range of this invention shown in a claim, as shown in Examples 1-12 of Table 5, the storage stability of a primer, coating workability | operativity, the 1st top coat film In addition, it is possible to obtain a coating film having excellent adhesion to the recoat film and excellent adhesion to the recoat film. In Examples 8 to 12 in Table 5, although the adhesion of the recoat coating film is somewhat lowered, it is at a level that causes no problem in practical use.
However, when the components (A) and (B) are outside the scope of the claims, the adhesion between the material and the primer decreases as shown in Comparative Example 1, or the primer and Adhesion of the topcoat is slightly lowered, and recoat adhesion is insufficient. Moreover, about (C) component and (D) component, when it becomes other than this invention, as shown in Comparative Examples 3-4, when (C) component increases, as shown in Comparative Example 5, the storage stability of a primer However, the recoat adhesion becomes insufficient.
From the above results, the primer of the present invention provides a coated article excellent in the storage stability of the primer, the coating workability, the adhesion between the material and the first overcoat film, and the recoat adhesion.

Claims (7)

Chlorinated polyolefin resin (A) having a chlorine content of 5 to 50 mass% and a weight average molecular weight of 1,000 to 100,000, a blocked polyisocyanate compound (B), having a weight average molecular weight of 120 to 1,000 The diol (C) and the curing catalyst (D) are contained, and the content ratio of the above components is such that the (A) component is 50 to 90 with respect to the total mass of the resin solids of the (A) component and the (B) component. % By mass, component (B) is 50-10% by mass, component (C) is 0.5-12% by mass, and component (D) is 0.01-
The primer characterized by being 1.5 mass%. A method for coating a plastic molded product, comprising: sequentially applying the primer according to claim 1 and a top coating to a plastic molded product, baking and curing the primer, and forming a top coating film. The primer according to claim 1 and the top coat are sequentially applied to a plastic molded article and baked and cured, and then the primer and top coat according to claim 1 are further applied to the top coat and baked and cured. A method of painting a plastic molded product characterized by: 3. Coating of a molded product characterized in that the primer and the top coating material of claim 1 are sequentially applied to the top coating film of the molded product in which the top coating material is applied and cured to form a top coating film, and then baked and cured. Method. The method for coating a molded article according to any one of claims 2 to 4, wherein the top coating is a one-coat type two-component urethane resin paint. The method for coating a molded article according to any one of claims 2 to 4, wherein the top coat film comprises two layers of a base coat film and a clear paint film, and at least the clear paint is a two-component urethane resin paint. The molded article according to any one of claims 2 to 4, wherein the top coat film comprises three layers of a colored base coat film, a pearl base coat film and a clear paint film, and at least the clear paint is a two-component urethane resin paint. How to paint.