JP2015182392A - Molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a latex capable of achieving an aqueous coating composition capable of obtaining a coating film excellent in balance between adhesiveness and moist heat resistance without containing chlorine.SOLUTION: There is provided a molded body which comprises a substrate, a primer layer (A) formed on the substrate and one or more layers (T) formed on the primer layer (A), wherein tetrahydrofuran solubles in the primer layer (A) contain 14 to 50 mass% of components derived from an alicyclic monomer unit, the primer layer (A) has a chlorine concentration of 300 ppm or less and the scores of the cross-cut adhesion test after the wet heat test of the molded body is 2 to 5.

Description

  The present invention relates to a molded body.

  Plastic materials used for vehicular bumpers, vehicular moldings, etc. generally have poor paint wettability and poor adhesion. In particular, when the plastic material (hereinafter sometimes referred to as “base material”) is a polypropylene resin or the like, the adhesiveness between the top coating material and the material is poor because it is chemically inert. For this reason, conventionally, the primer is generally applied before the top coating is applied. As these primers, various solvent-type primers have been studied and used. In recent years, an aqueous primer that does not use an organic solvent has been proposed and partially used in consideration of the environment.

  As such an aqueous primer, Patent Document 1 discloses an aqueous chlorinated polyolefin resin, an aqueous alkyd resin, and an aqueous novolac type epoxy resin. Patent Document 2 discloses an aqueous chlorinated polyolefin resin, an aqueous polyurethane resin, an aqueous epoxy resin and an organic strong base and / or a salt thereof. Patent Document 3 discloses an aqueous primer obtained by adding a curing agent such as an oxazoline curing agent or an epoxy curing agent to an aqueous polyolefin resin, an aqueous acrylic resin, or an aqueous polyurethane resin.

JP 2001-139875 A JP 2004-002801 A Japanese Patent Laid-Open No. 06-336568

  In the molded body described above, the primer described above is required to have excellent adhesion to both the topcoat and the substrate in order to bring the topcoat and the substrate into close contact. In particular, when the molded body is used for a vehicle bumper, a vehicle mall, or the like, there may be a problem that the coating film is peeled off between the primer and the base material when the vehicle collides or receives an external impact. . From such a viewpoint, the coating film and the substrate are required to have high adhesion without peeling off.

  Further, when used outdoors as a vehicle component, it is required to have excellent heat and humidity resistance.

  Furthermore, it is also required that corrosion of molding equipment such as a furnace can be suppressed by reducing the chlorine content of the molded body.

  The present invention has been made in view of the above-mentioned present situation, and has a high adhesion that the base material and the coating film do not peel off, is excellent in wet heat resistance, and can reduce the chlorine content. Is intended to provide.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have paid attention to the use of a copolymer latex containing an alicyclic monomer as an essential component for the primer layer used in the molded body. Invented the invention.

That is, the present invention is as follows.
[1]
A substrate;
A primer layer (A) formed on the substrate;
One or more layers (T) formed on the primer layer (A);
A molded body containing
The tetrahydrofuran-soluble component in the primer layer (A) contains 14 to 50% by mass of a component derived from an alicyclic monomer unit,
The primer layer (A) has a chlorine concentration of 300 ppm or less,
The molded body has a cross-cut adhesion test score of 2 to 5 after the wet heat test,
Molded body.
[2]
The primer layer (A) is formed by applying an aqueous coating composition on the substrate,
The aqueous coating composition comprises (a-1) an alicyclic monomer, (a-2) an ethylenically unsaturated carboxylic acid monomer, and (a-3) the component (a-1) and (a -2) The molded article according to [1], comprising a copolymer latex (a) obtainable by copolymerization with another monomer copolymerizable with the component.
[3]
The molded body according to [1] or [2], wherein the base material contains a polyolefin resin.
[4]
The molded body according to any one of [1] to [3], wherein the layer (T) includes a base coating layer and a clear coating layer.
[5]
Any one of [1] to [4], wherein the number average molecular weight of the component derived from the alicyclic monomer unit contained in the tetrahydrofuran-soluble component in the primer layer (A) is 5,000 to 100,000. The molded product according to 1.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the molded object which has the high adhesiveness which a base material and a coating film do not peel, is excellent in wet heat resistance, and can reduce chlorine content.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as this embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  The molded body of this embodiment includes a base material, a primer layer (A) formed on the base material, and one or more layers (T) formed on the primer layer (A). And the tetrahydrofuran soluble part in a primer layer (A) contains 14-50 mass% of components derived from an alicyclic monomer unit, and the chlorine concentration of a primer layer (A) is 300 ppm or less. The molded body is a molded body having a score of 2 to 5 in a cross-cut adhesion test after the wet heat test.

  The primer layer (A) can be obtained, for example, by drying an aqueous coating composition containing the copolymer latex (a).

  The copolymer latex (a) comprises (a-1) an alicyclic monomer, (a-2) an ethylenically unsaturated carboxylic acid monomer, and (a-3) (a-1) component and ( a-2) It can be obtained by copolymerizing another monomer copolymerizable with the component (however, (a-1) component + (a-2) component + (a-3) component = 100. 0 parts by mass).

  (A-1) By using an alicyclic monomer, it is possible to improve the adhesion, water resistance, moisture resistance, and heat and moisture resistance of the molded article of this embodiment.

  (A-1) The alicyclic monomer may have an alicyclic structure and can be polymerized with other monomers. Examples of the component (a-1) include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, And dicyclopentenyloxyethyl (meth) acrylate. Among these, isobornyl (meth) acrylate is preferable. These may be used alone or in combination of two or more.

  (A-1) Component as (a-1) component, (a-2) component and (a-3) component (hereinafter referred to as all monomer units) in a total amount of 100.0 parts by mass Is preferably 25.0-90.0 parts by mass, more preferably 30.0-85.0 parts by mass. (A-1) The lower limit of the ratio of a component is the said range, and can improve further the adhesiveness, water resistance, moisture resistance, and heat-and-moisture resistance of the molded object of this embodiment. (A-1) The upper limit of the ratio of a component is the said range, and can improve the adhesiveness of a molded object, water resistance, moisture resistance, and heat-and-moisture resistance further.

  (A-2) By having an ethylenically unsaturated carboxylic acid monomer, the storage stability can be improved with respect to the component (a) that can be used in the molded article of the present embodiment. Examples of the component (a-2) include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid, and ethylenically unsaturated dicarboxylic acid monomers such as itaconic acid, maleic acid, and fumaric acid. Can be mentioned. These may be used alone or in combination of two or more.

  The proportion of the component (a-2) in the total monomer total amount of 100.0 parts by mass is preferably 0.1 to 5.0 parts by mass, more preferably 0.1 to 4.5 parts by mass. Part, more preferably 0.1 to 4.0 parts by weight, and still more preferably 0.3 to 4.0 parts by weight.

  (A-2) The storage stability of the aqueous coating composition which can be used as a raw material of the molded object of this embodiment can be improved because the lower limit of the ratio of a component is the said range. (A-2) The upper limit of the ratio of a component is the said range, and can improve the adhesiveness of a molded object, water resistance, moisture resistance, and heat-and-moisture resistance.

  (A-3) A component is not specifically limited, The monomer which has polymerizable unsaturated groups other than (a-1) component and (a-2) component is mentioned. Examples of the component (a-3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl. Linear chains such as (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, etc. Or (meth) acrylate containing a branched alkyl group; vinyl aromatic compounds such as styrene and α-methylstyrene; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy Propyl (meth) acrylate, hydride Polymerizable unsaturated monomers containing hydroxyl groups such as hydroxyalkyl (meth) acrylates such as xylbutyl (meth) acrylate, allyl alcohol, and ε-caprolactone modified products of the above hydroxyalkyl (meth) acrylates; containing polyoxyalkylene groups Polymerizable unsaturated monomer; (meth) acrylamide-alkanesulfonic acid such as 2-acrylamido-2-methylpropanesulfonic acid; sulfonic acid group such as sulfoalkyl (meth) acrylate such as 2-sulfoethyl (meth) acrylate (2-acryloyloxyethyl) acid phosphate, (2-methacryloyloxyethyl) acid phosphate, (2-acryloyloxypropyl) acid phosphate, (2-methacryloyloxypropiate) ) Polymerizable unsaturated monomer containing a phosphate group such as acid phosphate; Alkoxyalkyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; Perfluoroalkyl (meta ) Acrylate, N, N-diethylaminoethyl (meth) acrylate; (meth) acrylamide, (meth) acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; (Meth) acrolein, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), acetoacetoxyethyl (meth) acrylate, acetoacetoxyallyl Polymerizable unsaturated monomers containing a carbonyl group such as stealth and diacetone (meth) acrylamide; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, Polymerizable unsaturated monomers containing an epoxy group such as 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allylglycidyl ether; isocyanate ethyl (meth) acrylate, polymerizable unsaturated monomers containing isocyanate groups such as m-isopropenyl-α, α-dimethylbenzyl isocyanate; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-meta Polymerizable unsaturated monomers containing alkoxysilyl groups such as liloyloxypropyltriethoxysilane; polymerizable unsaturated monomers containing epoxy groups or polymerizable unsaturated monomers containing hydroxyl groups and unsaturated Reaction products with fatty acids: allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate , Pentaerythritol Tiger (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1 -Compounds having two or more polymerizable unsaturated groups in one molecule such as trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene; 1,3-butadiene, isoprene, 2-chloro Conjugated diene monomers such as -1,3-butadiene; vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and the like. These may be used alone or in combination of two or more.

  The proportion of the component (a-3) in the total monomer total amount of 100.0 parts by mass is preferably 5.0 to 74.9 parts by mass, more preferably 11 to 69.9 parts by mass. Yes, more preferably 11 to 69.7 parts by mass.

  The tetrahydrofuran-soluble component in the primer layer (A) contains 14 to 50% by mass of components derived from the alicyclic monomer unit. When the content of the component derived from the alicyclic monomer unit is in the above range, adhesion, water resistance, moisture resistance, and heat and moisture resistance can be improved. In addition, content of the component derived from the alicyclic monomer unit in tetrahydrofuran soluble part can be calculated | required based on the method as described in the Example mentioned later. And as a suitable method of making content of the component derived from the alicyclic monomer unit in tetrahydrofuran soluble content into the said range, the method of using (a) component is mentioned, for example. Examples of such a method include a method using an aqueous coating composition containing the component (a). The content of the component derived from the alicyclic monomer unit in the tetrahydrofuran-soluble component is, for example, within the scope of the present application, increasing the component (a-1) and increasing the amount of the component (a). By decreasing the number average molecular weight of the component derived from the alicyclic monomer unit contained in the tetrahydrofuran soluble component, the component tends to increase, and (a-1) the component is decreased. There is a tendency to reduce the amount by increasing the number average molecular weight of the component derived from the alicyclic monomer unit contained in the tetrahydrofuran-soluble component.

  The number average molecular weight of the component derived from the alicyclic monomer unit contained in the tetrahydrofuran-soluble component in the primer layer (A) is preferably 5,000 to 100,000, more preferably 5,000 to 90,000, still more preferably. Is 5000-80000. When the number average molecular weight is in the above range, the adhesion, water resistance, moisture resistance, gasohol resistance, storage stability, and heat and moisture resistance of the molded body can be further improved. The number average molecular weight can be controlled by a known method, for example, by adjusting the amount of the chain transfer agent.

  The molecular weight distribution (ratio of weight average molecular weight / number average molecular weight) of the component derived from the alicyclic monomer unit contained in the tetrahydrofuran-soluble component in the primer layer (A) is preferably 1.5 to 10.0. More preferably, it is 1.7-9.0, More preferably, it is 1.8-8.0. When the molecular weight distribution is in the above range, the adhesion, water resistance, moisture resistance, gasohol resistance, storage stability, and heat and moisture resistance of the molded body can be further improved. The molecular weight distribution can be controlled by a known method, for example, by adding the chain transfer agent in a plurality of times.

  A chain transfer agent can be used for the polymerization for obtaining the component (a). Examples of chain transfer agents include dimers of nucleus-substituted α-methylstyrene such as α-methylstyrene dimer; n-butyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, and n-lauryl mercaptan. And the like; mercaptans such as tetramethylthuradium disulfide and tetraethylthuradium disulfide; halogenated derivatives such as carbon tetrachloride and carbon tetrabromide; 2-ethylhexyl thioglycolate and the like. Among these, mercaptans are preferable. These may be used alone or in combination of two or more.

  The amount of the chain transfer agent used is preferably 0.10 to 2.50 parts by mass, more preferably 0.15 to 2.50 parts by mass with respect to the total monomer total amount of 100.00 parts by mass. . By controlling the amount of the chain transfer agent within the above range, it becomes easier to control the number average molecular weight of the component (a), and the adhesion, water resistance, moisture resistance, gasohol resistance, and storage stability of the molded product. In addition, the moisture and heat resistance can be further improved.

  A method for adding the chain transfer agent is not particularly limited, and a known method can be adopted. For example, batch addition, batch addition, continuous addition and the like can be mentioned.

  The glass transition temperature of the component (a) is preferably −1 to 55 ° C. By setting the glass transition temperature of the component (a) within the above range, the adhesion, water resistance, moisture resistance, and moisture heat resistance of the molded body can be further improved. The glass transition temperature here can be measured according to ASTM D3418-97.

  Examples of the method for producing the component (a) include a method of emulsion polymerization, a method of dispersing a solution-polymerized copolymer in water, and the like. Among these, the emulsion polymerization method is preferable. In emulsion polymerization, a monomer mixture may be further added to the emulsion polymerization system. For example, a method may be mentioned in which a part of the monomer mixture is collectively charged into an emulsion polymerization system in advance and then the remaining monomer mixture is charged continuously or intermittently. Moreover, the method of charging a monomer mixture continuously or intermittently from the beginning may be sufficient. These polymerization methods may be used individually by 1 type, and may use 2 or more types together. In emulsion polymerization, for example, a method of performing polymerization with a radical initiator in the presence of an emulsifier in an aqueous medium may be employed.

  In the step of adding the monomer mixture, a so-called power feed method in which the composition of the monomer mixture continuously changes can be used.

  (A) As a number average particle diameter of a component, Preferably it is 40 nm-500 nm, More preferably, it is 50 nm-450 nm, More preferably, it is 50 nm-400 nm. By adjusting the number average particle diameter within the above range, the adhesion, water resistance, moisture resistance, storage stability, and heat and moisture resistance of the molded body can be further improved.

  The number average particle diameter can be adjusted by using a method of adjusting the amount of the emulsifier used or a known seed polymerization method when it is produced by emulsion polymerization. As the seed polymerization method, a method such as an internal seed method in which a copolymer latex is polymerized in the same reaction system after producing a seed, or an external seed method using a separately produced seed can be appropriately selected and used.

  Examples of emulsifiers that can be used in emulsion polymerization include non-reactive emulsifiers such as anionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers and nonionic emulsifiers; and chemical structural formulas of emulsifiers having hydrophilic groups and lipophilic groups. Examples thereof include reactive emulsifiers such as anionic reactive emulsifier and nonionic reactive emulsifier into which an ethylenic double bond is introduced. A conventionally well-known thing can also be used for these.

  Examples of anionic emulsifiers that are non-reactive emulsifiers include non-reactive alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfones. Acid salt, naphthalenesulfonic acid formalin condensate, polyoxyethylene polycyclic phenyl ether sulfate, polyoxyethylene distyrenated phenyl ether sulfate, fatty acid salt, alkyl phosphate, polyoxyethylene alkylphenyl ether sulfate Etc.

  Examples of the cationic emulsifier that is a non-reactive emulsifier include alkyl ammonium salts such as dodecyl ammonium chloride, quaternary ammonium salts, and the like.

  Examples of amphoteric emulsifiers that are non-reactive emulsifiers include betaine ester type emulsifiers.

  Nonionic emulsifiers that are non-reactive emulsifiers include, for example, non-reactive polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyethylene distyrenated phenyl ether, sorbitan fatty acid ester , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide, polyoxyethylene alkylphenyl ether and the like.

  Examples of the anionic reactive emulsifier which is a reactive emulsifier include ethylenically unsaturated monomers having a sulfonic acid group, a sulfonate group or a sulfate ester group, and salts thereof, and a sulfonic acid group or an ammonium salt thereof. A compound having a group (ammonium sulfonate group or alkali metal sulfonate group) which is an alkali metal salt is preferable. Specific examples include, for example, alkylallylsulfosuccinate (for example, “Eleminol ™ JS-2”, “Eleminol ™ JS-5” manufactured by Sanyo Chemical Co., Ltd.); “Latemul ™ S” manufactured by Kao Corporation -120 "," Latemul (trademark) S-180A "," Latemuru (trademark) S-180 ", etc.); polyoxyethylene alkylpropenyl phenyl ether sulfate ester salt (for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) “AQUALON ™ HS-10”, “AQUALON ™ HS-1025”, etc.); α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-poly Oxyethylene sulfate ester salt (for example, “Adekaria Soap (trademark) SE-1025N” manufactured by Asahi Denka Kogyo Co., Ltd.); Ammonium = α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethylene (for example, “Aqualon (trademark) KH-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) can be used.

  As a nonionic reactive emulsifier which is a reactive emulsifier, for example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (for example, manufactured by Asahi Denka Kogyo Co., Ltd.) "Adekalia Soap (trademark) NE-20", "Adekalia Soap (trademark) NE-30", "Adekalia Soap (trademark) NE-40" and the like.); Polyoxyethylene alkylpropenyl phenyl ether (For example, “AQUALON ™ RN-10”, “AQUALON ™ RN-20”, “AQUALON ™ RN-30”, “AQUALON ™ RN-50” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., etc. And the like.

  The amount of the emulsifier is preferably 0.1 to 10.0 parts by mass, more preferably 0.1 to 8.0 parts by mass, with respect to the total monomer total amount of 100.0 parts by mass. More preferably, it is 0.1-6.0 mass parts. An emulsifier may be used individually by 1 type and may use 2 or more types together.

  The use amount of the non-reactive emulsifier is preferably 1.0 part by mass or less, more preferably 0.8 part by mass or less, and further preferably 0 with respect to the total monomer total amount of 100.0 parts by mass 0.7 parts by mass or less, more preferably 0.6 parts by mass or less. The use amount of the reactive emulsifier is preferably 0.1 to 10.0 parts by mass, more preferably 0.1 to 8.0 parts by mass with respect to 100.0 parts by mass of the total amount of all monomers. More preferably, it is 0.1 to 6.0 parts by mass. By making the usage-amount of an emulsifier into the said range, (a) component can improve the stability of superposition | polymerization, and also the adhesiveness of the molded object of this embodiment, water resistance, moisture resistance, and heat-and-moisture resistance. This can be further improved.

  The radical initiator is one that initiates addition polymerization of a monomer by radical decomposition in the presence of heat or a reducing agent, and both inorganic and organic initiators can be used. . Preferable initiators include, for example, peroxodisulfate, peroxide, azobis compound and the like. These may be used alone or in combination of two or more.

  Specific examples of the radical initiator include, for example, potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, 2,2-azobisbutyronitrile, cumene. A hydroperoxide etc. are mentioned. These may be used alone or in combination of two or more.

  The amount of the radical initiator used is preferably 0.1 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass with respect to 100.0 parts by mass of the total amount of all monomers. More preferably, it is 0.1-1.0 mass part. By making the usage-amount of a radical initiator into the said range, the heat-and-moisture resistance of a molded object can be improved further.

  Moreover, you may combine reducing agents, such as acidic sodium sulfite, ascorbic acid, its salt, erythorbic acid, its salt, and Rongalite with the above-mentioned radical initiator. That is, a so-called redox polymerization method can also be used.

  (A) As a polymerization temperature in the case of manufacturing a component, it is usually preferable that it is 40-100 degreeC. From the viewpoint of production efficiency and flexibility of the component (a) to be obtained, the polymerization temperature in the period from the start of polymerization to the end of addition of the monomer mixture is usually preferably 45 to 95 ° C, more Preferably it is 55-90 degreeC.

  A method of raising the polymerization temperature (so-called cooking step) can also be employed to increase the polymerization conversion rate of each monomer after the addition of all the monomers in the polymerization system. The polymerization temperature in such a process is preferably 80 to 100 ° C.

  (A) As a superposition | polymerization solid content density | concentration in the case of manufacturing a component, from a viewpoint of production efficiency and the particle diameter control at the time of emulsion polymerization, Preferably it is 10-60 mass%, More preferably, it is 15-55 mass%. . The polymerization solid content concentration here is the solid content concentration at the completion of the polymerization, and specifically, the solid content after drying with respect to the mass of the latex before drying (including non-solid components such as water). The ratio of the mass of

  In producing the component (a), various known polymerization regulators can be used at the time of emulsion polymerization or at the end of emulsion polymerization, if necessary. Examples of such a polymerization regulator include a pH regulator and a chelating agent.

  Examples of the pH adjuster include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium hydrogen carbonate, disodium hydrogen phosphate, amines such as monoethanolamine, dimethylethanolamine, triethanolamine, and triethylamine. It is done. Among these, amines such as ammonium hydroxide, monoethanolamine, dimethylethanolamine, triethanolamine, and triethylamine are preferable. These may be used alone or in combination of two or more.

  Examples of the chelating agent include sodium ethylenediaminetetraacetate.

  The aqueous coating composition containing the component (a) contains the component (a). The molded article obtained from such an aqueous coating composition is excellent in adhesion, water resistance, moisture resistance, gasohol resistance, storage stability, and heat and moisture resistance.

  The aqueous coating composition preferably further comprises (b) an aqueous polyurethane resin. By including the component (a) and the component (b), the gasohol resistance of the molded body is further improved. When the aqueous coating composition contains the component (a) and the component (b), the total content of the component (a) and the component (b) is 100% by mass in terms of solid content, and the content of the component (a) is 10 to 80. The content of component (b) is 20 to 90% by mass. When the content of the component (a) is 10% by mass or more, the adhesion, water resistance, moisture resistance, and heat and moisture resistance of the molded body are further improved. (A) Gasohol resistance of a molded object further improves that content of a component is 80 mass% or less.

  As the component (b), for example, a polyfunctional isocyanate compound, a polyol having two or more hydroxyl groups in one molecule, and a hydrophilization having both a hydroxyl group and a carboxylic acid group such as dimethylolpropanediol or dimethylolbutanediol. The urethane prepolymer obtained by reacting the agent in the presence of an excess of isocyanate group in the presence of a catalyst such as dibutyltin dilaurate is carboxylated with an organic base such as amines or an inorganic base such as potassium hydroxide or sodium hydroxide. After neutralizing the acid, it is made aqueous by adding ion-exchanged water, and further, a urethane dispersion having a high molecular weight with a chain extender; after synthesizing a urethane prepolymer not containing a carboxylic acid, carboxylic acid, sulfonic acid, Chain extension using a diol or diamine with a hydrophilic group such as ethylene glycol , Neutralized with the basic substance and water-further urethane dispersion was a high molecular weight by using a chain extender as needed; emulsifier include urethane dispersion or the like obtained in combination if necessary.

  Examples of the polyfunctional isocyanate compound include 1,6-hexane diisocyanate, lysine diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and the like. And polyfunctional isocyanate compounds such as adducts, burettes, and isocyanurates, and the like.

  Examples of the polyol include a polyester polyol, a polyether polyol, and a polycarbonate polyol.

  Examples of chain extenders include diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, flange methanol, diethylene glycol, triethylene glycol, and tetraethylene glycol, and ethylene oxide and propylene oxide. A polyether diol compound obtained by addition polymerization of tetrahydrofuran, etc .; a polyester having a terminal hydroxyl group, obtained from the above diol compound and a dicarboxylic acid such as (anhydrous) succinic acid, adipic acid, or (anhydrous) phthalic acid, and their anhydrides Diols; polyhydric alcohols such as trimethylolethane and trimethylolpropane; aminoalcohols such as monoethanolamine, diethanolamine, and triethanolamine; ethylenediamine, Ropi diamine, butylene diamine, hexamethylene diamine, phenylene diamine, toluene diamine, xylene diamine, diamine compounds such as isophoronediamine; water, ammonia, hydrazine, and a dibasic acid hydrazide.

  As the component (b), a commercially available urethane dispersion can be used. Examples of such commercially available products include "Superflex (trademark) 150", "Superflex (trademark) 420", "Superflex (trademark) 460" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), "Bihydrol ( (Trademark) VP LS2952 (manufactured by Sumika Bayer Urethane Co., Ltd.), "VONDIC (trademark) 2260", "VONDIC (trademark) 2220", "Hydran (trademark) WLS210", "Hydran (trademark) WLS213" (above, DIC Corporation) Product), “NeoRez (trademark) R9603” (manufactured by Avicia), and the like.

  In addition to the above-described components, the aqueous coating composition can be appropriately mixed with other aqueous resins and the like as necessary. Examples of the other aqueous resin include an aqueous acrylic resin, an acrylic emulsion, an amino resin emulsion, and an aqueous epoxy resin. In addition, these aqueous resins may be used as a pigment dispersant described later.

  Aqueous coating compositions can be added to other formulations usually added as paints (eg, thickeners, pigments, pigment dispersants, antifoaming agents, inorganic fillers, surfactants, neutralizers, stabilizers, thickeners). Agent, surface conditioner, leveling agent, ultraviolet absorber, antioxidant, conductive carbon, conductive filler, conductive filler such as metal powder, organic modifier, plasticizer, etc.) if necessary be able to.

  Examples of the thickener include associative nonionic urethane thickener, alkali swelling thickener, bentonite which is an inorganic intercalation compound, and the like.

  Examples of pigments include inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, and bitumen, and organic pigments such as azo pigments, anthracene pigments, perylene pigments, quinacridone pigments, indigo pigments, and phthalocyanine pigments. Colored pigments; Body pigments such as talc and precipitated barium sulfate; Conductive pigments such as whiskers coated with conductive carbon and antimony-doped tin oxide; Metals or alloys such as aluminum, copper, zinc, nickel, tin, and aluminum oxide And non-colored or colored metallic luster materials.

  Examples of the pigment dispersant include an aqueous acrylic resin; an acidic block copolymer such as “BYK-190” manufactured by Big Chemie; a styrene-maleic acid copolymer; “Surfinol (trademark) GA” manufactured by Air Products, Examples thereof include acetylenic diol derivatives such as “Surfinol (trademark) T324”; water-soluble carboxymethylcellulose acetate butyrate such as “CMCAB-641-0.5” manufactured by Eastman Camicar. By using these pigment dispersants, a stable pigment paste can be prepared.

  Examples of the antifoaming agent include “Surfinol (trademark) 104PA” and “Surfinol (trademark) 440” manufactured by Air Products.

  Silica etc. are mentioned as an inorganic filler.

  The aqueous coating paint composition can be produced by mixing the components described above. In particular, when producing an aqueous coating composition containing a pigment, a method of preparing an aqueous coating composition by preparing a pigment dispersion paste containing a pigment and a pigment dispersant in advance and adding other components thereto is preferable. This method has an advantage of excellent production efficiency.

  In the present embodiment, the primer layer (A) may be a coating film obtained by coating such an aqueous coating composition on the surface of a substrate.

  The chlorine concentration of the primer layer (A) is 300 ppm or less. When the chlorine concentration of the primer layer (A) is 300 ppm or less, corrosion of the furnace when the molded body is incinerated can be prevented.

  Examples of base materials include polyolefin resins such as polypropylene (PP) and polyethylene (PE), acrylonitrile styrene (AS), acrylonitrile butadiene styrene (ABS), polyphenylene oxide (PPO), vinyl chloride (PVC), and polyurethane. Examples thereof include resin materials such as (PU) and polycarbonate (PC), and molded products thereof. Among these, those containing polyolefin resin are preferable.

  Examples of the one or more layers (T) include a top coat layer. The layer (T) preferably includes a base coating layer and a clear coating layer. The top coat layer can be formed by coating with, for example, a one-pack melamine baking paint, a two-pack urethane paint, a one-pack lacquer paint, a glitter paint, or a high solid clear paint. The clear layer is included in the top coat layer.

  The base coating layer can be formed by applying a base paint. Examples of the base paint include those containing an aqueous resin, a pigment, and water. In the base paint, the aqueous resin is generally dissolved or dispersed in water, and the pigment is dispersed in water. The base coating material may contain a hydrophilic organic solvent as a solvent, but it is preferable that the content of water in the total solvent is 51 to 100% by mass.

  The aqueous resin constitutes a vehicle in the obtained coating film. The aqueous resin here includes water-soluble resins, water-dispersible resins, emulsion resins and the like.

  The aqueous resin is not particularly limited as long as it can be dissolved or dispersed in water. For example, as the resin forming the matrix, for example, an acrylic resin, a polyurethane resin, or the like is preferable.

  Examples of the acrylic resin include a copolymer of an acrylic monomer and another ethylenically unsaturated monomer. Examples of acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N -Dimethylmethacrylamide, N, N-dibutylacrylamide, N, N-dibutylmethacrylamide, ring-opening adduct of caprolactone of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (meth) acrylic acid of polyhydric alcohol Examples include esters. Examples of other ethylenically unsaturated monomers include styrene, α-methylstyrene, itaconic acid, maleic acid, vinyl acetate and the like.

  The polyurethane resin is not particularly limited as long as it is a commonly used aqueous urethane resin, but a urethane dispersion is preferable. Examples of the polyurethane resin include those obtained by reacting a polyol with an isocyanate to extend the chain. As this polyol, polyester, polyether, acrylic, etc. having a hydroxyl group are preferable. The above polyurethane resin can be made water-based by a method of emulsifying using a surfactant or a method of forcibly emulsifying the polyurethane resin having a carboxyl group in water after neutralizing with a amine or ammonium. A polyurethane dispersion is preferred.

  A commercially available product can be used as the dispersion of the polyurethane resin. Examples of such commercially available products include “Takelac ™ XW-75”, “Takelac ™ W165”, “Takelac W166”, “Takelac ™ A170”, “Takelac ™ X35” (any Manufactured by Takeda Pharmaceutical Co., Ltd.), "NeoRez (trademark) R9649", "NeoRez (trademark) R966", "NeoRez (trademark) R972" (all manufactured by Abycia), "DALTON (trademark) VTW6465 / 36" (Sorusia) Commercial products such as “Superflex (trademark) series 110”, “Superflex (trademark) series 150”, “Superflex (trademark) series 460S” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

  Examples of the crosslinking agent include amino resins, block polyisocyanates, and polycarbodiimide compounds. Of these, amino resins are preferred.

  Examples of the amino resin include di-methylol melamine, tri-methylol melamine, tetra-methylol melamine, penta-methylol melamine, hexa-methylol melamine, and alkyl etherified products thereof (the alkyl group includes a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, isobutyl group, etc.), urea-formaldehyde condensate, urea-melamine cocondensate and the like.

  Examples of the blocked polyisocyanate include polyfunctional isocyanate compounds blocked with a blocking agent such as alcohol, tertiary amine, lactam, and oxime. It does not specifically limit as polyfunctional isocyanate, What was mentioned above can also be used.

  Examples of the polycarbodiimide compound include compounds having at least two carbodiimides (—N═C═N—) in the molecule.

  In the base paint, the ratio of the resin forming the matrix and the crosslinking agent is 100 parts by mass in total of the resin forming the matrix and the crosslinking agent, preferably 50 to 90 parts by mass of the resin forming the matrix, and the crosslinking agent. Is 10 to 50 parts by mass, more preferably 60 to 85 parts by mass of the resin forming the matrix and 15 to 40 parts by mass of the crosslinking agent. The crosslinking degree in a coating film improves further that a crosslinking agent is 10 mass parts or more. On the other hand, when the crosslinking agent is 50 parts by mass or less, the storage stability of the coating composition is further improved and the curing rate can be moderately suppressed, so that the appearance of the coating film is further improved.

  The aqueous resin contained in the base paint can be made aqueous by adjusting the acid value and neutralizing an acid group such as a carboxyl group with a basic substance. Examples of the basic substance include amine compounds. Of the amine compounds, diethanolamine, dimethylethanolamine, triethanolamine and the like are preferable. As the solvent, water is usually the main component, but an organic solvent can be used in combination as necessary.

  Examples of the pigment contained in the base paint include aluminum flake pigment, metal oxide-coated alumina flake pigment, metal oxide-coated silica flake pigment, graphite pigment, interference mica pigment, colored mica pigment, metal titanium flake pigment, and stainless steel flake pigment. , Plate-like iron oxide pigments, metal-plated glass flake pigments, metal oxide-coated plated glass flake pigments, hologram pigments, flake pigments such as cholesteric liquid crystal polymers, titanium oxide, colored pigments and extender pigments.

  The base paint may appropriately contain conventionally known additives in addition to the water-based resin and pigment described above.

  The clear paint generally contains an acrylic resin. The clear coating material preferably contains an acrylic resin having a hydroxylalkyl group in the side chain and a polyisocyanate.

  The clear paint has a diluted paint, that is, a solid content ratio at the time of painting of generally 52% by mass or more, and preferably 55% by mass or more. In the present specification, the solid content ratio at the time of coating means that after the above-mentioned resin and solvent are stirred and mixed, immediately after # 4 at a temperature of 20 ° C. in accordance with JIS K-5600-2-2-2-3. It means the solid content when the viscosity measured with a Ford cup is about 20 seconds. The solid content rate at the time of coating is the amount of residue when heated at 105 ° C. for 3 hours in accordance with JIS K-5601-1-2.

  The solid content can be adjusted within this range, for example, by setting the weight average molecular weight of the acrylic resin used for the clear coating within the range described below.

  The clear paint is preferably a two-component type. Examples of the two-pack type include a two-pack type paint of an acrylic resin compound (main agent) and a polyisocyanate compound (curing agent).

The acrylic resin used for the clear coating can be obtained, for example, by polymerizing the radical polymerizable monomer exemplified for the above base coating. As an acrylic resin, what has a monomer represented by either of following formula (1)-(3) is preferable. Thereby, the coating film excellent in the glittering appearance can be obtained.
(In the formula, R represents H or CH _{3. A} represents a number of 3 or 4.)
(In the formula, R represents H or CH ₃ ; b represents an average number of 2 to 5)
(In the formula, R represents H or CH _3. C represents a number of 1 to 10.)

  The weight average molecular weight of the acrylic resin used for the clear coating is preferably 4500 to 8000. The weight average molecular weight here can be measured by gel permeation chromatography (GPC; mobile phase tetrahydrofuran, calibration curve polystyrene).

  Even if the acrylic resin having a hydroxyloxy group different from the hydroxylalkyl group described above, for example, an acrylic resin obtained by polymerizing 2-hydroxylethyl methacrylate, if the solid content at the time of coating is low, the second The orientation of the glitter pigment in the base coating film is not disturbed. Examples of such an acrylic resin include a high molecular weight acrylic resin having a weight average molecular weight exceeding 8000.

  The acrylic resin used for the clear coating preferably has a hydroxyl value of 90 to 180 (KOHmg / g). When the hydroxyl value is 180 (KOHmg / g) or less, the proportion of hydroxyl groups remaining without crosslinking reaction can be reduced, and as a result, deterioration in water resistance and the like can be further suppressed. When the hydroxyl value is 90 (KOHmg / g) or more, the crosslink density increases, so that the film cohesive force does not decrease, and the chemical resistance and solvent resistance can be further improved. The hydroxyl value here can be measured by the acetic anhydride-pyridine method.

  The polyisocyanate used in the clear coating is not particularly limited as long as it is a compound having two or more isocyanate groups. Examples of the polyisocyanate include aromatic polyisocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate and metaxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate and the like. Alicyclic polyisocyanates; the above monomers and multimers such as the above buret type, nurate type, and adduct type.

  The polyisocyanate is preferably a multimer from the viewpoint of curability, and is preferably selected according to the performance of the obtained coating film. From the viewpoint of weather resistance, it is more preferable not to use an aromatic polyisocyanate, and it is more preferable to use an aliphatic polyisocyanate or an alicyclic polyisocyanate.

  A commercially available product may be used as the polyisocyanate. Examples of such commercially available products include “Sumijoule (trademark) N3200-90CX” and “Sumijoule (trademark) N3500” (both manufactured by Sumitomo Bayer Urethane Co., Ltd.), “Duranate (trademark) 24A90PX” and “Duranate ( Trademark) THA-100 "(all manufactured by Asahi Kasei Chemicals)," Takenate (trademark) D165N-90CX "," Takenate (trademark) D170N "(all manufactured by Takeda Pharmaceutical Company Limited), and the like. In the two-component curable high solid paint, the equivalent ratio of the NCO group of the polyisocyanate to the OH group of the acrylic resin (NCO / OH) is preferably 0.8 to 2.0. When the equivalent ratio is 0.8 or more, coating film performance such as scratch resistance and solvent resistance is further improved. Moreover, the softness | flexibility of the coating film obtained further improves because an equivalent ratio is 2.0 or less, and generation | occurrence | production of a crack can be suppressed further.

  The flow-down viscosity of the clear coating is preferably 15 to 25 seconds, more preferably 15 to 20 seconds. When the flow-down viscosity is in the above range, paint atomization at the time of coating becomes good, so that an excellent appearance can be obtained. The falling viscosity can be measured according to JIS K5600-2-2-3. For example, after setting the paint temperature to 20 ° C., it can be measured using a # 4 Ford cup in accordance with the regulations.

  The clear coating is further blended with additives such as coloring pigments, extender pigments, modifiers, UV absorbers, leveling agents, dispersants, antifoaming agents, etc., as long as they do not impair their transparency. It is possible.

  The method of applying the aqueous coating composition or the top coating to the base material is not particularly limited, and for example, spray coating such as air spray or airless spray, bell coating, disk coating, curtain coating, shower coating, brush coating, etc. The method etc. which apply | coat and dry the obtained primer layer after that are mentioned. The primer layer may be dried by either natural drying or forced drying, but forced drying is preferred from the viewpoint of coating efficiency. Examples of forced drying include warm air drying, near infrared drying, and electromagnetic wave drying. The drying temperature is selected within a temperature range in which the base material is not thermally deformed. Usually, the material temperature is preferably 110 ° C. or lower, more preferably 100 ° C. or lower. The drying time usually depends on the drying temperature and the wind speed in the drying furnace, and is appropriately set in consideration of energy efficiency.

  The dry film thickness of the coating film (for example, primer layer) obtained from the aqueous coating composition is preferably 5 to 30 μm. When the dry film thickness is 5 μm or more, a continuous uniform film can be obtained. Water resistance etc. improve further because a dry film thickness is 30 micrometers or less.

  Next, a step of forming one or more layers (T) by applying a top coat on the primer layer (A) obtained from the aqueous coating composition is performed. The method for applying the top coating is not particularly limited, and it can be applied by the same method as that for the aqueous coating composition. The dry film thickness (film thickness of the layer (T)) of the top coat is preferably 5 to 50 μm. When the dry film thickness is 5 μm or more, a continuous uniform film tends to be obtained. When it is 50 μm or less, water resistance and the like tend to be further improved.

  Moreover, the score of the cross-cut adhesion test after the wet heat test is 2-5 in the molded body of this embodiment. The cross-cut adhesion test after the wet heat test is a cross-cut test in accordance with JIS K-5400 after the molded body is allowed to stand for 10 days in an atmosphere of 80 ° C. and 80% humidity. Is evaluated with 1 to 5 points. In detail, it can measure based on the method as described in an Example. In addition, when the score of the cross-cut adhesion test after the wet heat test of the molded body is 2 to 5, sufficient physical properties that can be practically used outdoors as a molded body can be exhibited in a balanced manner. Moreover, the score of the cross-cut adhesion test after the wet heat test of the molded body can be controlled by controlling, for example, the physical properties and various blending amounts of the component (a) in the molded body. For example, within the scope of the present embodiment, (a-1) increase the component and chain transfer agent, (a-2) decrease the component and emulsifier, glass transition temperature, number average molecular weight, number average particle size, etc. It can be raised by making it smaller.

  The molded body of the present embodiment can be suitably used as a member for automobiles or the like in which polyolefin resin is used as a material. Such a molded body has a high practical value.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded. Unless otherwise specified, the content and the like are based on mass standards.

[Production Example 1]
In a reaction vessel equipped with a stirrer, a reflux condenser, a dripping tank, and a thermometer, 140 parts by mass of water as an initial charge and Aqualon KH10 (polyoxyethylene-1- (allyloxymethyl) shown in Table 1 as a polymerization initial raw material Alkyl ether sulfate ammonium salt: 100% solids / Daiichi Kogyo Seiyaku Co., Ltd.) 0.1 parts by mass, polystyrene seed latex (10% solids) 5.0 parts by mass with a number average particle size of 18 nm, The temperature in the reaction vessel was sufficiently stirred at 75 ° C. Subsequently, the monomer mixture shown in Table 1 was continuously added from the dropping tank to the reaction vessel over 3 hours and 30 minutes. On the other hand, after 1 minute from the start of the addition of the monomer mixture, the addition of an aqueous mixture consisting of 91 parts by weight of water, 0.3 parts by weight of ammonium peroxodisulfate, and 0.1 parts by weight of “AQUALON KH10” was started. The polymerization reaction was started. This aqueous mixture was continuously added over 3 hours and 29 minutes. After the addition of the aqueous mixture, the temperature in the reaction vessel was raised to 80 ° C., and the polymerization reaction was continued for 90 minutes to increase the polymerization conversion rate. The polymerization conversion rate when the polymerization reaction was completed was 95% or more. Then, it cooled to room temperature. After cooling, the reaction product was filtered with a 200 mesh filter to remove aggregates. After filtration, 25% ammonium hydroxide was added to adjust the pH to 9.0 to obtain a latex containing a copolymer. This latex was filtered using a 325 mesh filter to obtain a copolymer latex L1. About the obtained copolymer latex L1, the number average molecular weight, molecular weight distribution, glass transition temperature, and number average particle diameter were measured by the following methods. Table 1 shows the evaluation results of the physical properties of the copolymer latex L1.

[Production Examples 2-12, 14-25]
Copolymer latexes L2 to L12, L14 in the same manner as in Production Example 1 except that the composition of the initial polymerization raw material, the monomer mixture, and the aqueous mixture was changed to the conditions described in Tables 1 and 2. -L25 was produced. The evaluation results of each physical property of these copolymer latexes are shown in Tables 1 and 2.

[Production Example 13]
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 140 parts by mass of water as an initial charge, and sodium dodecyl diphenyl ether disulfonate (50% by mass solid content) 0.2 as described in Table 1 as an initial polymerization raw material A mass part was added, and the temperature in the reaction vessel was maintained at 75 ° C. and sufficiently stirred. Subsequently, the monomer mixture shown in Table 1 was continuously added to the reaction vessel over 3 hours and 30 minutes. On the other hand, after 1 minute from the start of the addition of the monomer mixture, water 91 parts by mass, ammonium peroxodisulfate 0.3 part by mass, sodium dodecyl diphenyl ether disulfonate 0.4 part by mass, “AQUALON KH10” 0.4 part by mass The addition of the aqueous mixture consisting of parts was started to initiate the polymerization reaction. This aqueous mixture was continuously added over 3 hours and 29 minutes. Furthermore, 1.0 part by mass of t-dodecyl mercaptan was continuously added over 1 hour and 45 minutes after the lapse of 1 hour and 45 minutes from the start of addition of the mixture of monomers and the like. After the addition of the aqueous mixture, the temperature in the reaction vessel was raised to 80 ° C., and the polymerization reaction was continued for 90 minutes to increase the polymerization conversion rate. The polymerization conversion rate when the polymerization reaction was completed was 95% or more. Then, it cooled to room temperature. After cooling, the reaction product was filtered with a 200 mesh filter to remove aggregates. After filtration, 25% ammonium hydroxide was added to adjust the pH to 9.0 to obtain a latex containing a copolymer. This latex was filtered using a 325 mesh filter to obtain a copolymer latex L13. The evaluation results of each physical property of the copolymer latex L13 are shown in Table 1.

[Number average molecular weight, molecular weight distribution]
The latex prepared to pH 9 was dried at 105 ° C. for 3 hours and used as a sample. A 0.3 g sample was dissolved in 50 mL of tetrahydrofuran (THF), and then filtered using a membrane filter to obtain a measurement sample. About this, the weight average molecular weight (Mw) of polystyrene conversion and the number average molecular weight (Mn) of polystyrene conversion were measured by the gel permeation chromatography (The Tosoh Corporation make, "HLC-8120GPC"). From this measurement result, the molecular weight distribution (Mw / Mn) was calculated and obtained.

[Glass-transition temperature]
The latex adjusted to pH 9 was dried at 130 ° C. for 30 minutes to obtain a dried product. Using a differential scanning calorimeter (SII Nanotechnology, “DSC6220”), the temperature was increased from −120 ° C. to + 160 ° C. at a temperature increase rate of 20 ° C./min according to ASTM D3418-97. Thus, a differential scanning calorimetry curve was obtained, and a glass transition temperature was obtained.

[Number average particle size]
The latex adjusted to pH 9 was dried at 105 ° C. for 30 minutes to prepare a sample. The number average particle diameter was measured by a dynamic light scattering method using a light scattering photometer (model 6000, manufactured by CNN Wood) at an initial angle of 45 degrees and a measurement angle of 135 degrees.

[Production Example 26: Production of aqueous coating composition]
As shown in Table 3, in a container equipped with a stirrer, 30.00 parts by mass of latex L1, 20.00 parts by mass of “Superflex 150” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., aqueous polyurethane resin), pigment paste 27 .77 parts by mass, 19.28 parts by mass of deionized water, 0.72 parts by mass of antifoaming agent (“Dynol 604”, manufactured by Air Products), thickener (“ASE-60”, manufactured by Rohm and Haas) 1.44 parts by mass and 0.01 part by mass of dimethylethanolamine (manufactured by Kishida Chemical Co., Ltd.) were added dropwise in this order, and the desired aqueous coating composition A1 was obtained after stirring for 1 hour. The obtained aqueous coating composition A1 was subjected to a storage stability test by the following method. The results are shown in Table 3.

[Production Examples 27 to 54]
Aqueous coating compositions A2 to A29 were obtained in the same manner as in Production Example 26 except for the points shown in Tables 3 and 4. The results of these storage stability tests are shown in Tables 3 and 4.

[Production Example 55]
An aqueous solution similar to Example 1 except that acid anhydride-modified chlorinated polyolefin (manufactured by Nippon Paper Chemical Co., Ltd., “Supercron E-723”, chlorine content 19%) was used instead of copolymer latex L1. Coating composition A30 was prepared. The results of this storage stability test are shown in Table 4. In addition, the pigment dispersion paste used above was manufactured according to the following method.

[Production of pigment dispersion paste]
In a container equipped with a stirrer, an aqueous acrylic resin (solid content acid value: 50 KOH mg / g, weight average molecular weight: 30000, solid content rate: 30 mass%) 11.75 parts by mass, pigment dispersant (“Surfinol T324”, 2.07 parts by mass of Air Products), 1.61 parts by mass of antifoam (“Surfonol 440”, manufactured by Air Products), 38.5 parts by mass of deionized water, conductive carbon (“Carbon Black ECP600JD”, Lion 2.54 parts by mass of titanium oxide pigment (“Taypure-R960”, manufactured by DuPont) 37.64 parts by mass of silica (“Nipsil 50B”, manufactured by Nihon Silica Co.) 5.89 parts by mass in this order. After stirring for 1 hour, disperse with a 1.4L dynomill for laboratory use until a glide gauge is 20 μm or less, and a pigment dispersion paste Obtained. This pigment dispersion paste had a solid content of 52% by mass and a viscosity of 60 KU (20 ° C.). In addition, this solid content rate is the quantity of the residue when it heats at 105 degreeC for 3 hours based on JISK-5601-1-2.

[Storage stability]
After the obtained aqueous coating composition was stored in an incubator at 40 ° C. for 14 days, the presence or absence of thickening was visually confirmed and evaluated based on the following criteria.
○: There was no thickening compared to before the storage stability test.
(Triangle | delta): Although there was thickening compared with the storage stability test, it did not gelatinize.
X: Thickened and gelled as compared to before storage stability test.

[Production Example 56 Production of base paint]
(Preparation of aqueous acrylic resin X)
Into a reaction vessel equipped with a stirrer, thermometer, reflux tube, dropping funnel, nitrogen inlet tube, and heating device with thermostat, 27.0 parts by mass of 2-ethylhexyl glycol ether (EHG) was charged, and the reactants were stirred. The mixture was gradually heated to 110 ° C. While flowing nitrogen into the reaction vessel, 5.0 parts by mass of methacrylic acid (MAA), 8.0 parts by mass of 2-hydroxyacrylate (HEA), 30.0 parts by mass of methyl methacrylate (MMA), and ethyl acrylate under a nitrogen stream (EA) A monomer mixed solution consisting of 57.0 parts by mass and a solution consisting of 1.5 parts by mass of t-butylperoxyhexanate (TBPH) and 10.0 parts by mass of EHG as a radical polymerization catalyst are dropped over 3 hours. did. During the dropping, the liquid temperature in the reaction vessel was maintained at 110 ° C. A polymerization catalyst solution consisting of 0.5 parts by mass of TBPH and 5 parts by mass of EHG was added dropwise over 1 hour while maintaining the temperature at 110 ° C. after the completion of the addition.
Then, after aging for 1 hour while maintaining the reaction solution at 110 ° C., the solution temperature was lowered to 70 ° C., and 2 parts by mass of EHG and 30.0 parts by mass of 1-methoxy-2-propanol (MP) were added. Diluted. Subsequently, the solvent removal treatment was performed while maintaining the liquid temperature at 70 ° C. under reduced pressure, and MP was mainly distilled over about 2 hours, and the solvent removal treatment was performed when the fraction reached 25.0 parts by mass. finished.
The solid content of the resin after the solvent removal treatment in the reaction vessel was 67.5% by mass. The acid value of this product was 30 KOH mg / g, and the hydroxyl value was 39 KOH mg / g. Moreover, as a result of measuring by gel permeation chromatography by the styrene conversion method, the weight average molecular weight was 40000.
Next, while maintaining the internal temperature at 70 ° C., 5.0 parts by mass of dimethylethanolamine was added to the reaction vessel resin, and then 370.0 parts by mass of pure water was gradually added to the reaction vessel while stirring. The aqueous acrylic resin X was obtained by stirring. The solid content ratio of the aqueous acrylic resin X was 19% by mass.

(Preparation of aqueous acrylic resin Y)
A monomer mixture solution comprising 8.0 parts by mass of MAA, 15.0 parts by mass of HEA, 15.0 parts by mass of MMA, 52.0 parts by mass of EA, and 10.0 parts by mass of styrene (total 100.0 parts by mass) was used. The aqueous acrylic resin Y was obtained in the same manner and order as the aqueous acrylic resin X, except that the composition of the mixed solution dropped simultaneously with the monomer mixed solution was 10.0 parts by mass of EHG and 3.0 parts by mass of TBPH.
The solid content after solvent removal was 68% by mass. This had an acid value of 53 KOH mg / g and a hydroxyl value of 67 KOH mg / g. Moreover, as a result of measuring by gel permeation chromatography by the styrene conversion method, the weight average molecular weight was 27000.
In preparing the aqueous acrylic resin Y, the aqueous solution was maintained at an internal temperature of 70 ° C., 9.0 parts by weight of dimethylethanolamine (DMEA) was added to the resin component, and pure water 182.0 was stirred with stirring. Mass parts were gradually added into the reaction vessel, and forced stirring was performed. The solid content ratio of the aqueous acrylic resin Y was 30% by mass.

(Preparation of base paint)
In a container equipped with a stirrer, an aqueous acrylic resin X (70.0 parts by mass), an aqueous acrylic resin Y (200.0 parts by mass), a melamine resin (“XM2677”, manufactured by Nippon Cytec Co., Ltd .; 38.0 parts by mass), A 10% by mass DMEA aqueous amine solution (4.0 parts by mass) was added with stirring. Further, while continuing stirring, EHG (10.0 parts by mass), aluminum pigment (“aluminum paste 65-388”, manufactured by Toyo Aluminum Co., Ltd., 27.0 parts by mass) and dispersant (“BYK192”, manufactured by BYK Chemie, 0.7 parts by mass) was mixed in advance, and then urethane dispersion (“NeoRez R972”, manufactured by Avicia; 66.0 parts by mass), acidic phosphate ester (“JP508”, manufactured by Johoku Chemical Co., Ltd .; 0) 4 parts by mass) and a thickener (“ADEKA NOL UH752, manufactured by ADEKA; 2.5 parts by mass) and 350.0 parts by mass of water were added to obtain a base paint. The solid content rate was 19 mass%.

[Manufacture of clear paint]
(Manufacture of acrylic resin Z)
A reaction vessel equipped with a stirrer, thermometer, reflux tube, dropping funnel, nitrogen inlet tube and thermostat-equipped heating device was charged with 42.0 parts by mass of butyl acetate, and the reaction product was gradually heated to 125 ° C. It was. Then, under a nitrogen stream, 5.3 parts by mass of ethylhexyl acrylate, 45.1 parts by mass of t-butyl methacrylate, 10.0 parts by mass of styrene, 1.1 parts by mass of methacrylic acid, 38.5 parts by mass of hydroxybutyl acrylate, and polymerization A mixed monomer solution consisting of 12.0 parts by mass of t-butylperoxydiethylhexanate (TBPODEH) as an initiator was added dropwise using a dropping funnel over 3 hours with internal stirring. The internal temperature was 128 ° C., and a weak reflux state was maintained. Then, a solution prepared by dissolving 0.5 parts by mass of TBPODEH as a polymerization catalyst in 5 parts by mass of butyl acetate was dropped from the dropping funnel over 1 hour while stirring internally at an internal temperature of 128 ° C. Further, aging was performed while maintaining at 128 ° C. over 2 hours to obtain an acrylic resin Z.
The solid content of this product was 70% by mass, and the weight average molecular weight in terms of styrene by gel permeation chromatography was 6000. Moreover, the hydroxyl value (henceforth, OHV) by the acetic anhydride-pyridine method was 150 KOHmg / g. The solid content is measured according to JIS K-5601-1-2, and is the content of the solid content when the measurement sample is heated at 105 ° C. for 3 hours.

(Preparation of clear paint)
A mixed solvent (hereinafter, mixed solvent) containing acrylic resin Z (100.0 parts by mass), Solfit AC (an organic solvent made by Kuraray Co., Ltd.) and butyl acetate in a mass ratio of 3/2 in a stainless steel tank with a stirring blade. I .; 15 parts by mass) in order and stirred to obtain a uniform mixed state.
Subsequently, while stirring, the mixture solvent I (10.0 parts by mass) was mixed with “Tinuvin 292” (manufactured by Ciba Specialty Chemicals, hindered amine; 0.7 parts by mass) and “Tinuvin 384-2” (manufactured by Ciba Specialty Chemicals, A solution prepared by dissolving UV absorber; 1.4 parts by mass) was stirred, and then 0.7 parts by mass ("BYK310", manufactured by BYK Chemie, surface conditioner) and a surface conditioner ("BYKETOL SPECIAL"). ”, 2.8 parts by mass, manufactured by Big Chemie, surface conditioning agent), and 0.1 parts by mass of dibutyltin dilaurate (curing catalyst) were sequentially added and stirred to obtain a uniform mixed state. Subsequently, while stirring, the curing agent ("R-271", manufactured by Nippon Bee Chemical Co., polyisocyanate curing agent; solid content = 75 mass%, isocyanate group content (NCO%) = 16.5 mass %) 47.6 parts by mass was prepared to produce a stock clear paint.
Then, it diluted with the mixed solvent I (13.0 mass parts), and manufactured the clear coating material. The viscosity at this time is 20 seconds when measured using a # 4 Ford cup (manufactured by Ueshima Seisakusho) at a measurement temperature of 20 ° C. in accordance with JIS K-5600-2-2-2-3, and the solid content is It was 57 mass%.

[Production of substrate]
Unpainted bumper (mixture of polypropylene resin, ethylene rubber and talc) of automobile (Mazda's "Demio") is crushed and injection molded with Nissei Plastic Industry's injection molding machine "FC-120EF" A test piece of polypropylene resin (size: 70 mm × 70 mm × 3 mm) was prepared. The injection molding conditions were a cylinder temperature of 210 ° C., and the molding cycle was 60 seconds.

[Example 1]
The aqueous coating composition A1 was spray-coated (dry film thickness: 10 μm) on a polypropylene resin test piece washed with a neutral detergent, and dried at 80 ° C. for 30 minutes. After cooling, the base paint was applied to a dry film thickness of 15 μm, and then the clear paint was spray-coated to a dry film thickness of 30 μm. And it dried at 80 degreeC for 30 minutes, and produced the test piece. The obtained test piece was subjected to an adhesion test, a water resistance test, a moisture resistance test, a gasohol resistance test, and a moist heat resistance test by the following methods. The results are shown in Table 5.

[Examples 2 to 25, Comparative Examples 1 to 4]
A test piece was prepared in the same manner as in Example 1 except that the aqueous coating compositions A2-A27, A29, and A30 were used instead of the aqueous coating composition A1. The obtained test pieces were subjected to an adhesion test, a water resistance test, a moisture resistance test, a gasohol resistance test, and a moist heat resistance test by the following methods. The results are shown in Tables 5 and 6. In addition, the aqueous coating composition A28 was poor in stability of the aqueous coating composition and could not be applied.

[Adhesion test]
In accordance with JIS K-5400, a cellophane tape peel adhesion test was performed on the grid of the test piece. A cut was made on the surface of the test piece using a cutter to form 100 squares of 2 mm square. After the cellophane tape was affixed to the surface, the cellophane tape was peeled off from the surface of the test piece vigorously, and the number of grids that were not removed was counted. Of the 100 grids, the larger the number of grids that were not peeled, the better.
5: 100/100 (no peeling)
4: 90/100 to 99/100
3: 70/100 to 89/100
2: 50/100 to 69/100
1: 0/100 to 49/100

[Water resistance test]
The test piece was immersed in 40 ° C. water for 10 days. After the immersion, it was allowed to stand for 30 minutes in an atmosphere of 23 ° C. and 60% humidity. About this test piece, the adhesiveness test was done like the above. It was judged that the larger the number of grids that did not peel off, the better.
5: 100/100 (no peeling)
4: 90/100 to 99/100
3: 70/100 to 89/100
2: 50/100 to 69/100
1: 0/100 to 49/100

[Moisture resistance test]
The test piece was allowed to stand for 10 days in an atmosphere of 50 ° C. and 98% humidity, and then an adhesion test was performed in the same manner as described above. It was judged that the larger the number of grids that did not peel off, the better.
5: 100/100 (no peeling)
4: 90/100 to 99/100
3: 70/100 to 89/100
2: 50/100 to 69/100
1: 0/100 to 49/100

[Gasohol resistance test]
After the test piece was immersed in gasohol (regular gasoline containing 10% by volume of ethanol), the time until peeling from the edge of the coating to 2 mm was measured. The case where the time until peeling was 30 minutes or more was evaluated as “◯”, and the case where it was less than 30 minutes was evaluated as “x”.

[Moisture and heat resistance test]
The test piece was allowed to stand for 10 days in an atmosphere of 80 ° C. and 80% humidity, and then an adhesion test was performed in the same manner as described above. It was judged that the larger the number of grids that did not peel off, the better. Usually, if the score of the heat and humidity resistance test is 2 or more, the coating film will not be peeled off even when an impact is applied to the molded body when a vehicle or the like using the molded body is shipped.
5: 100/100 (no peeling)
4: 90/100 to 99/100
3: 70/100 to 89/100
2: 50/100 to 69/100
1: 0/100 to 49/100

[Chlorine concentration]
The obtained aqueous coating composition was spray-coated (dry film thickness: 10 μm) on a polypropylene resin test piece washed with a neutral detergent, and dried at 80 ° C. for 30 minutes. After cooling, the coating film was scraped off and the chlorine concentration was measured with an ion chromatograph. The case where the chlorine concentration was 300 ppm or less was evaluated as “◯”, and the case where the chlorine concentration exceeded 300 ppm was evaluated as “x”.

[Amount of alicyclic monomer unit]
The primer layer was scraped from the obtained molded body, and the primer layer was dissolved in tetrahydrofuran (THF). A fixed amount of styrene dissolved in known THF and methyl methacrylate dissolved in THF were added to the THF dissolved content of the primer layer. This THF mixed solution was quantified with a pyrolysis gas chromatograph mass spectrometer (manufactured by Shimadzu Corporation, “GCMS-QP2010”). Based on the measurement results, the monomer units constituting the copolymer in the primer layer were analyzed. The unit of isobornyl acrylate was “isobornyl monomer unit”, and the unit of cyclohexyl acrylate and cyclohexyl methacrylate was “cyclohexyl monomer unit”. The amount of the alicyclic monomer unit in the THF-soluble component is the sum of the amount of isobornyl monomer unit and the amount of cyclohexyl monomer unit.

Each example and each comparative example are shown in the following table. The abbreviations in each table are as follows.
Non-reactive emulsifier: sodium dodecyl diphenyl ether disulfonate Reactive emulsifier: Aqualon KH-10
IA: Itaconic acid (component (a-2))
IBXA: isobornyl acrylate (component (a-1))
CHMA: cyclohexyl methacrylate (component (a-1))
CHA: cyclohexyl acrylate (component (a-1))
IBA: Isobutyl acrylate (component (a-3))
IDA: Isodecyl acrylate (component (a-3))
MMA: methyl methacrylate (component (a-3))
2EHA: 2-ethylhexyl acrylate (component (a-3))
MAA: methacrylic acid (component (a-2))
AA: acrylic acid (component (a-2))
DDM: t-dodecyl mercaptan (mercaptan chain transfer agent)
APS: ammonium peroxodisulfate (initiator)

  From the said table | surface, it was confirmed that the molded object obtained from each Example is favorable for all the performances including moisture heat resistance. On the other hand, in the molded body obtained from each comparative example, what satisfy | filled all the performance was not obtained.

  Since the molded article of the present invention is excellent in adhesion, moisture and heat resistance, etc., it has high applicability in various fields such as the automobile industry.

Claims (5)

A substrate;
A primer layer (A) formed on the substrate;
One or more layers (T) formed on the primer layer (A);
A molded body containing
The tetrahydrofuran-soluble component in the primer layer (A) contains 14 to 50% by mass of a component derived from an alicyclic monomer unit,
The primer layer (A) has a chlorine concentration of 300 ppm or less,
The molded body has a cross-cut adhesion test score of 2 to 5 after the wet heat test,
Molded body. The primer layer (A) is formed by applying an aqueous coating composition on the substrate,
The aqueous coating composition comprises (a-1) an alicyclic monomer, (a-2) an ethylenically unsaturated carboxylic acid monomer, and (a-3) the component (a-1) and (a -2) The molded article according to claim 1, comprising a copolymer latex (a) obtainable by copolymerization with another monomer copolymerizable with the component.   The molding according to claim 1 or 2, wherein the base material contains a polyolefin resin.   The molded body according to any one of claims 1 to 3, wherein the layer (T) includes a base coating layer and a clear coating layer.   The number average molecular weight of the component derived from the alicyclic monomer unit contained in the tetrahydrofuran soluble part in the said primer layer (A) is 5000-100000, It is any one of Claims 1-4. Molded body.