JP2007091997A - One pot type aqueous coating agent, method for producing the same and coated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one pot type (non-crosslinked type) aqueous coating agent having a good balance of close adhesion toward a polyolefin substrate material, etc., (warm) water proof property and oil resistance, and satisfying both of the (warm)water proof property and oil resistance in higher levels, a method for producing the same and a coated article obtained by applying the coating agent. <P>SOLUTION: This one pot type aqueous coating agent is provided by dispersing mixed polymer particles of (A) a chlorinated polyolefin polymer and (B) a vinyl copolymer consisting of (b1) a hydrophobic vinyl monomer having 60-200°C Tg as its homopolymer, (b2) a hydroxy group-containing vinyl monomer, (b3) an alkoxysilyl group-containing vinyl monomer and (b4) another vinyl-based monomer under the presence of (C) an emulsifying agent. The method for producing the one pot type aqueous coating agent is provided by dispersing an organic solvent solution of the (A) chlorinated polyolefin polymer and the (b1)-(b4) vinyl monomers in water and then polymerizing, and the coated article are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a one-pack type aqueous coating agent, a method for producing the same, and a coated product. More specifically, the present invention is excellent in adhesion to a polyolefin substrate having a low polarity surface, (warm) water resistance, and oil resistance. Since a film can be formed, the present invention relates to a one-part aqueous coating agent useful for automobile part materials, polyolefin films, and polyolefin moldings.

  In order to remedy the disadvantages of chlorinated polyolefins used in the past in the fields of paints, inks, etc., such as the use of large amounts of solvents and high prices, modification and compounding of chlorinated polyolefins with vinyl monomers Study on water-based treatment is being conducted. For example, a mixture of a chlorinated polyolefin organic solvent solution and a monomer is emulsified in water with an emulsifier, and then finely emulsified with a homogenizer or the like, thereby causing radical polymerization, thereby providing adhesion to a polyolefin substrate or the like, (warm) water resistance, It is known that an aqueous resin composition capable of forming a film excellent in oil resistance can be obtained (see, for example, Patent Document 1).

  However, in the aqueous resin composition described in Patent Document 1, although adhesion to a polyolefin base material, (warm) water resistance, and oil resistance are improved, the (warm) water resistance and oil resistance are at a high level. One-pack type (non-crosslinked) that has a good balance between adhesion to polyolefin substrates, etc., (warm) water resistance and oil resistance, and higher levels of (warm) water resistance and oil resistance. The appearance of water-based coating agents of the type) is desired.

Japanese Patent Laid-Open No. 11-263802

  The object of the present invention is a one-pack type (non-crosslinked type) which has a good balance of adhesion to polyolefin base materials, (warm) water resistance and oil resistance, and is compatible with higher levels of (warm) water resistance and oil resistance. ) Water-based coating agent, a method for producing the same, and a coated product obtained by applying the coating agent.

As a result of intensive studies in order to solve the above problems, the present inventors have obtained the following findings (1) to (3) and have completed the present invention.
(1) Chlorinated polyolefin polymer (A) having a chlorination degree of 5 to 50% by weight and a weight average molecular weight of 30,000 to 70,000, and a hydrophobic vinyl monomer having a homopolymer glass transition point of 60 to 200 ° C. (B1), a vinyl copolymer obtained by polymerizing a hydroxyl group-containing vinyl monomer (b2), an alkoxysilyl group-containing vinyl monomer (b3), and another copolymerizable vinyl monomer (b4) ( The one-part aqueous coating agent in which the polymer particles mixed with B) are dispersed in water in the presence of the emulsifier (C) is a balance between adhesion to polyolefin substrates and the like (warm) water resistance and oil resistance. Are both good and have both (warm) water resistance and oil resistance at a higher level,
(2) This one-pack type aqueous coating agent comprises a chlorinated polyolefin polymer solution (I) obtained by dissolving the chlorinated polyolefin polymer (A) in an organic solvent (F), the vinyl monomer (b1), ( The vinyl monomers (II) consisting of b2), (b3) and (b4) are mechanically dispersed in water in the presence of the emulsifier (C), and then the vinyl monomers (II) are polymerized. Can be manufactured by
(3) The coated product obtained by coating this one-part aqueous coating agent on a plastic substrate has a good balance of adhesion, (warm) water resistance and oil resistance, and has (warm) water resistance and oil resistance. It must be a paint with a compatible film at a higher level.

  That is, the present invention relates to a chlorinated polyolefin polymer (A) having a chlorination degree of 5 to 50% by weight and a weight average molecular weight of 30,000 to 70,000, and a hydrophobic vinyl having a glass transition point of 60 to 200 ° C. A vinyl copolymer obtained by polymerizing the monomer (b1), the hydroxyl group-containing vinyl monomer (b2), the alkoxysilyl group-containing vinyl monomer (b3), and other copolymerizable vinyl monomers (b4). The present invention provides a one-part aqueous coating agent characterized in that polymer particles mixed with a polymer (B) are dispersed in water in the presence of an emulsifier (C).

  The present invention also provides a chlorinated polyolefin polymer solution (I) in which a chlorinated polyolefin polymer (A) having a chlorination degree of 5 to 50% by weight and a weight average molecular weight of 30,000 to 70,000 is dissolved in an organic solvent (F). ), A hydrophobic vinyl monomer (b1) having a glass transition point of 60 to 200 ° C., a hydroxyl group-containing vinyl monomer (b2), an alkoxysilyl group-containing vinyl monomer (b3), and other copolymers. A vinyl monomer (II) composed of a new vinyl monomer (b4) is mechanically dispersed in water in the presence of an emulsifier (C), and then the vinyl monomer (II) is polymerized. The present invention provides a method for producing a one-part aqueous coating agent.

  Furthermore, the present invention provides a coated product obtained by coating the above-described one-component aqueous coating agent of the present invention on a plastic substrate.

  The one-part aqueous coating agent of the present invention and the one-part aqueous coating agent obtained by the production method of the present invention are applied to a polyolefin substrate or the like. It is possible to provide a coated product having a coating having a good balance between adhesion, (warm) water resistance and oil resistance, and at a higher level of both (warm) water resistance and oil resistance.

  The chlorinated polyolefin polymer (A) used in the present invention must be a chlorinated polyolefin polymer having a chlorination degree of 5 to 50% by weight and a weight average molecular weight of 30,000 to 70,000. For example, polyethylene, Weight average molecular weight 30, obtained by chlorinating polyolefin polymer such as polypropylene, polybutadiene, ethylene-propylene copolymer, natural rubber, synthetic isopropylene rubber, ethylene-vinyl acetate copolymer in the range of 5 to 50% by weight, The chlorinated polyolefin of 000-70,0000 is mentioned, Preferably the chlorinated polypropylene of 10-30 weight% of chlorination degree is mentioned. As for chlorinated polypropylene, it is also possible to use those obtained by further modifying these with maleic anhydride. Normally, these chlorinated polyolefin polymers are mainly toluene, xylene, and cyclohexane solutions that have high solubility in organic solvents, especially chlorinated polyolefin polymers, and that have low boiling points and are easy to remove. These are preferably used. The amount of the organic solvent used is usually 100 to 900 parts by weight, preferably 100 to 400 parts by weight with respect to 100 parts by weight of the chlorinated polyolefin polymer.

  When the chlorination degree of these chlorinated polyolefin polymers (A) exceeds 50% by weight, the adhesion to the polyolefin substrate is lowered, and when the chlorination degree is less than 5% by weight, the solubility in an organic solvent is lowered. As a result, the stability of the aqueous resin composition is lowered, and it is likely that the aqueous resin composition will aggregate during storage at a low temperature and generate fuzz. Further, if the weight average molecular weight is less than 30,000, adhesion failure due to a decrease in the cohesive strength of the coating film is caused, and if it exceeds 70,000, wettability to a polyolefin substrate such as a polypropylene substrate is lowered. This is not preferable because the adhesiveness decreases.

  Next, the vinyl copolymer (B) used in the present invention and the one-component aqueous coating agent of the present invention will be described.

  The vinyl copolymer (B) is a homopolymer having a glass transition point of 60 to 200 ° C., a hydrophobic vinyl monomer (b1), a hydroxyl group-containing vinyl monomer (b2), and an alkoxysilyl group-containing vinyl monomer. Any vinyl copolymer may be used as long as it is a vinyl copolymer obtained by polymerizing (b3) and other copolymerizable vinyl monomers (b4). The agent is an aqueous dispersion of polymer particles in which the chlorinated polyolefin polymer (A) and the vinyl copolymer (B) are mixed, and such an aqueous dispersion is easy to synthesize the vinyl copolymer (B). A chlorinated polyolefin polymer solution (I) obtained by dissolving the chlorinated polyolefin polymer (A) in an organic solvent (D), the vinyl monomers (b1) and (b2). After the vinyl monomers (II) consisting of (b3) and (b4) are mechanically dispersed in water in the presence of the emulsifier (C), the vinyl monomers (II) are preferably radicals. A method of polymerizing in the presence of the polymerization initiator (E) is preferred. By this production method, the chlorinated polyolefin polymer (A) and the vinyl copolymer (B) are simultaneously formed with the synthesis of the vinyl copolymer (B). A one-part aqueous coating agent of the present invention in which the mixed polymer particles are dispersed in water in the presence of an emulsifier (C) can be produced.

  The hydrophobic vinyl monomer (b1) used here is not particularly limited as long as it is a hydrophobic vinyl monomer having a homopolymer glass transition point of 60 to 200 ° C. For example, cyclohexyl methacrylate (Glass transition point of homopolymer: 70 ° C.), isobornyl (meth) acrylate (homopolymer glass transition point of 155 ° C.), and the like.

  As the amount of the hydrophobic vinyl monomer (b1) used, a vinyl copolymer (from which a water-based coating agent having excellent adhesion to a polyolefin substrate such as a polypropylene substrate can be obtained can be synthesized. It is preferable that it is 30-95 weight part with respect to 100 weight part of total amount of the vinyl monomer used for the synthesis | combination of B), It is more preferable that it is 40-80 weight% especially, It is 50-80 weight% Most preferred.

  Next, the hydroxyl group-containing vinyl monomer (b2) is not particularly limited as long as it is a vinyl monomer containing a hydroxyl group. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta) ) Acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) Hydroxyl group-containing (meth) acrylates such as acrylate; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate or these and ε -Capro Adducts of Becton, "PLACCEL FM or FA Monomer" [Daicel Chemical Co., Ltd. caprolactone addition monomer] and the like. Among these, 2-hydroxyethyl (meth) acrylate is particularly preferable because the hydroxyl value of the vinyl copolymer (B) can be easily adjusted within the following range.

  In addition, the amount of the hydroxyl group-containing vinyl monomer (b2) used can synthesize a vinyl copolymer from which an aqueous coating agent excellent in oil resistance, adhesion to a polyolefin base material and water resistance (warm) can be obtained. The hydroxyl value of the vinyl copolymer after polymerization is preferably in the range of 10 to 100 (mgKOH / g), and particularly preferably in the range of 20 to 80.

  Furthermore, the alkoxysilyl group-containing vinyl monomer (b3) is not particularly limited as long as it is a vinyl monomer containing an alkoxysilyl group. For example, the following general formula (1)

で示されるメトキシシリル基又はエトキシシリル基を１〜３個含有するビニル単量体が挙げられる。

And vinyl monomers containing 1 to 3 methoxysilyl groups or ethoxysilyl groups.

  Specific examples of the vinyl monomer represented by the general formula (1) include vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (Meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropylmethoxydimethoxysilane, γ- (meth) acryloxypropylmethoxydiethoxysilane, γ- (meth) acryloxypropylmethoxydipropoxysilane, γ- (Meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxybutylphenyldiethoxysilane, γ- (meth) acryloxybutylphenyldipropoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (Meth) acryloxypropyl Dimethylethoxysilane and the like are mentioned, and among them, a vinyl copolymer can be synthesized which can provide an aqueous coating agent having high curability and excellent (warm) water resistance and oil resistance, so three methoxysilyl groups or ethoxysilyl groups The vinyl monomer contained is preferred.

  The amount of the alkoxysilyl group-containing vinyl monomer (b3) used depends on the type of the alkoxysilyl group-containing vinyl monomer, but is excellent in oil resistance and film-forming properties. Since a vinyl copolymer capable of obtaining an aqueous coating agent having excellent adhesion to a polyolefin substrate can be synthesized, the amount of vinyl monomer used in the synthesis of the vinyl copolymer (B) is 0.1 part by weight. The amount is preferably 3 to 5.0 parts by weight, and particularly preferably 0.4 to 2.0% by weight.

  Other copolymerizable vinyl monomers (b4) include copolymerizable vinyl monomers other than the vinyl monomers (b1), (b2) and (b3), and are not particularly limited. Any of these can be used, for example, styrene monomers such as styrene, vinyl toluene, p-methyl styrene, ethyl styrene, propyl styrene, isopropyl styrene, p-tert-butyl styrene, benzyl (meth) acrylate, etc. (Meth) acrylates not containing functional groups in the chain, aromatic vinyl compounds such as vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, iso (i) -propyl (meth) acrylate , N-butyl methacrylate, n-butyl acrylate, i-butyl (meth) acrylate , Tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, “Acryester SL” [manufactured by Mitsubishi Rayon Co., Ltd. C12-C13 methacrylate mixture], alkyl (meth) acrylates such as stearyl (meth) acrylate, carboxyl group or acid anhydride group-containing monofunctional group such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride Monomers,

Monofunctional (meth) acrylates having functional groups such as diethylaminoethyl (meth) acrylate, (methyl) glycidyl (meth) acrylate, acrylamide, ethylene glycol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, Multifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, vinyl acetate Vinyl esters such as vinyl benzoate, “Beoba” (a vinyl ester of a branched (branched) aliphatic monocarboxylic acid manufactured by Shell of the Netherlands), diallyl phthalate, divinylbenzene, allyl acrylate, etc. Such as a monomer having two or more unsaturated bonds in the molecule. They may be used alone or in combination of two or more vinyl monomers from these alone or in combination.

  Among the other vinyl monomers (b4) that can be polymerized, a vinyl copolymer that can provide a coating agent with excellent water dispersion stability can be synthesized, so acrylic acid, methacrylic acid, itaconic acid, maleic anhydride Monofunctional monomers containing carboxyl groups or acid anhydrides such as are preferred.

  The amount of the carboxyl group- or acid anhydride-group-containing monofunctional monomer used is an aqueous coating agent having further excellent water dispersion stability by neutralizing with a basic compound after the synthesis of the vinyl copolymer (B). Therefore, the acid value of the vinyl copolymer (B) is preferably in the range of 3 to 60 (mgKOH / g), and particularly preferably in the range of 5 to 30.

  The amount of the basic compound used for neutralizing the carboxyl group or the acid anhydride group is preferably in a range where the pH of the aqueous coating agent is 7.5 to 9.5. Examples of the basic compound used for neutralization include ammonia (water); primary to tertiary amines such as ethylamine, diethylamine, and triethylamine. Among them, aqueous ammonia is preferable.

  The amount of the vinyl monomers (II) used is not particularly limited, but since an aqueous coating agent having excellent oil resistance, dispersion stability and adhesion to a polyolefin substrate such as a polypropylene substrate can be obtained, The amount is preferably 100 to 1,000 parts by weight, particularly preferably 100 to 500 parts by weight, based on 100 parts by weight of the chlorinated polyolefin polymer (A).

  The emulsifier (C) used in the present invention is an anionic emulsifier and / or a nonionic emulsifier, and any of them can be used. For example, alkylbenzene sulfonates, alkylene disulfonates, alkyl diphenyl ether disulfonates, alkyl sulfate esters, polysulfate Oxyethylene alkylphenyl sulfonates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene polycyclic phenyl ether sulfates, dialkyl succinate sulfonates, monoalkyl succinate sulfones Anionic emulsifiers such as acid salts, salts of naphthalenesulfonic acid formalin condensate,

Polyoxyethylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene glycol, polyoxyethylene alkate, sorbitan alkate, polyoxyethylene sorbitan alkate, polyoxyethylene polycyclic phenyl ether, poly Nonionic emulsifiers such as oxyalkylene alkylphenyl ether and polyoxyethylene-polyoxypropylene block copolymer can be exemplified.

  Furthermore, as the emulsifier (C), vinyl sulfonates, (meth) acryloyloxy polyoxyethylene sulfate esters, (meth) acryloyloxy polyoxyethylene sulfonates, polyoxyethylene alkenyl phenyl sulfonates, Reactive anionic emulsifiers such as polyoxyethylene alkenyl phenyl ether sulfates, sodium allyl alkyl sulfosuccinate, (meth) acryloyloxy polyoxypropylene sulfonates, polyoxyethylene alkenyl phenyl ether, polyoxyethylene methacryloyl ether, etc. Reactive emulsifiers such as reactive nonionic emulsifiers can also be used. Of course, a plurality of these emulsifiers can be used.

  Examples of commercially available reactive emulsifiers include, for example, Aqualon KH-1025, HS-1025, Aqualon KH-10, HS-10, New Frontier A-229E [above, Daiichi Kogyo Seiyaku Co., Ltd. )], Adeka Soap SE-3N, SE-5N, SE-10N, SE-20N, SE-30N [above, manufactured by Asahi Denka Kogyo Co., Ltd.], AntoxMS-60, MS-2N, RA-1120, RA-2614 [above, manufactured by Nippon Emulsifier Co., Ltd.], Eleminol JS-2, RS-30 [above, manufactured by Sanyo Chemical Industry Co., Ltd.], LATEMUL S-120A, S-180A, S-180 [above, Reactive anionic emulsifiers such as kao manufactured by Kao Corporation, Aqualon RN-20, RN-30, RN-50 New Frontier N-177E (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Asope NE-10, NE-20, NE-30, NE-40 [above, manufactured by Asahi Denka Kogyo Co., Ltd.], RMA-568, RMA-1114 [above, manufactured by Nippon Emulsifier Co., Ltd.], NK Ester M- Reactive nonionic emulsifiers such as 20G, M-40G, M-230G [manufactured by Shin-Nakamura Chemical Co., Ltd.] can be used without any problem as long as they are generally used in emulsion polymerization reactions. Of course, other commercially available reactive emulsifiers may be used.

About the kind of emulsifier (C), it is not restrict | limited to an above-described thing, It can select suitably and can use and can use what is generally marketed.
From the viewpoint of environmental protection and occupational health, it is preferable to use an emulsifier having no alkylphenol skeleton.

  The amount of the emulsifier (C) used is an aqueous coating having high dispersion stability of polymer particles in which the chlorinated polyolefin polymer (A) and the vinyl copolymer (B) are mixed, and having excellent (warm) water adhesion resistance. Since the agent is obtained, a range of 0.2 to 10 parts by weight is preferable with respect to 100 parts by weight of the vinyl monomers (II), and a range of 0.5 to 5 parts by weight is particularly preferable.

  The organic solvent (D) is required to be an organic solvent capable of dissolving the chlorinated polyolefin polymer (A), and among them, toluene, xylene and cyclohexane are preferable because of low boiling point and easy solvent removal. .

  The amount of the organic solvent (D) used is preferably 100 to 900 parts by weight, particularly 100 to 400 parts by weight, with respect to 100 parts by weight of the chlorinated polyolefin polymer (A). preferable.

  Examples of the radical initiator (E) include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, azobisisobutyronitrile and its hydrochloride, 2,2′-azobis (2-amidinopropane). ) Dihydrochloride, azo initiators such as 4,4'-azobis (4-cyanovaleric acid), peroxide initiators such as hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, etc. Can be mentioned. These radical initiators (E) can be used in combination with a reducing agent, and examples of the reducing agent that can be used in combination include sodium sulfooxylate formaldehyde, sodium pyrosulfite, and L-ascorbic acid. Further, when a reducing agent is used in combination, a compound that generates a so-called polyvalent metal salt ion represented by iron ions, copper ions, or the like can be used in combination as an accelerator. The amount of these radical polymerization initiator (E) and reducing agent used is preferably in the range of 0.1 to 10 parts by weight, independently of 100 parts by weight of the vinyl monomers (II). .

  In addition, a chain transfer agent can be used to control the degree of polymerization in the emulsion polymerization of the vinyl copolymer (B). Examples of the chain transfer agent include alkyl mercaptans such as n-butyl mercaptan, n-octyl mercaptan and n-lauryl mercaptan, thioglycolic acid esters such as butyl thioglycolate and octyl thioglycolate, thiomalic acid, 3- Examples thereof include water-soluble mercaptans such as mercaptopropionic acid and thioglycolic acid, and alcohols such as isopropyl alcohol.

  In the method for producing a one-component aqueous coating agent of the present invention, first, a vinyl monomer comprising the chlorinated polyolefin polymer (A) and vinyl monomers (b1), (b2), (b3), and (b4). Class (II), emulsifier (C) and organic solvent (D) are mechanically emulsified and dispersed in the presence of water. As this emulsification dispersion process, the method of emulsifying dispersion using mechanical emulsification dispersion apparatuses, such as a homomixer, is mentioned, for example. In addition, since such an emulsified dispersion is a uniform fine particle, the generation of aggregated particles and the sedimentation of polymer particles can be prevented. Therefore, the average particle size is preferably 0.05 to 0.3 μm. It is particularly preferable that the thickness is 0.08 to 0.2 μm.

  In the method for producing a one-component aqueous coating agent of the present invention, the vinyl monomers (II) in the emulsion dispersion are emulsified with stirring in a nitrogen atmosphere in the presence of the radical polymerization initiator (E). Polymerization is preferred. The reaction temperature is preferably in the range of 40 to 100 ° C. The radical polymerization initiator (E) may be added in advance in the reaction kettle, or may be added sequentially as the polymerization reaction proceeds.

  In the method for producing a one-component aqueous coating agent of the present invention, the vinyl copolymer (B) in the one-component aqueous coating agent of the present invention obtained by emulsion polymerization is a part of the vinyl monomer (b4). Alternatively, in the case of an acid group-containing vinyl copolymer obtained by using the above-mentioned carboxyl group or acid anhydride group-containing monofunctional monomers as a whole, neutralization with the basic compound further improves water dispersion stability. And a good aqueous coating agent. In addition, it is preferable to prepare neutralization by a basic compound so that the pH of the aqueous coating agent after neutralization may be in the range of 7.5 to 9.5.

  Moreover, in the manufacturing method of the one-component aqueous coating agent of the present invention, the organic solvent (D) in the one-component aqueous coating agent obtained by polymerization can be removed by distillation under reduced pressure. The conditions for vacuum distillation are preferably a temperature of 30 to 80 ° C. and a degree of vacuum of 0.0008 to 0.04 MPa.

  Preferred examples of the one-part aqueous coating agent of the present invention include those obtained by the above-described method for producing the one-part aqueous coating agent of the present invention. A chlorinated polyolefin polymer (A) and a vinyl copolymer are preferable. As long as the polymer particle mixed with (B) is a one-component aqueous coating agent dispersed in water in the presence of the emulsifier (C), it may be obtained by another production method.

  In this case, the amount of the vinyl copolymer (B) used is not particularly limited, but an aqueous coating agent having excellent oil resistance, dispersion stability and adhesion to a polyolefin substrate such as a polypropylene substrate can be obtained. Therefore, the amount is preferably 100 to 1,000 parts by weight, and particularly preferably 100 to 500 parts by weight with respect to 100 parts by weight of the chlorinated polyolefin polymer (A). The average particle diameter of the polymer particles in which the chlorinated polyolefin polymer (A) and the vinyl copolymer (B) are mixed in the one-part aqueous coating agent of the present invention is the generation of aggregated particles and the precipitation of the polymer particles. Therefore, the thickness is preferably 0.05 to 0.3 μm, and particularly preferably 0.08 to 0.2 μm. Furthermore, the vinyl copolymer (B) preferably has a carboxyl group or an acid anhydride group neutralized with a basic compound because of excellent dispersion stability of the polymer particles.

  The one-component water-based coating agent of the present invention can form a film excellent in adhesion to a polyolefin substrate having a non-polar surface, (warm) water resistance, and oil resistance. As a coating agent for objects, it can be used in a wide range of fields such as automobile parts materials, electrical and electronic parts materials, civil engineering and building materials.

  When the one-pack type aqueous coating agent of the present invention is used, for example, it may be clear, or it may be in any form with a colored coating amount including a pigment. In addition to various organic pigments, the pigment includes various inorganic pigments such as titanium oxide, iron oxide, aluminum flakes, titanium coat mica, and the like.

  As a method for forming a dry film, various coating methods such as an air spray method, an airless spray method, a brush coating method or a roll coating method can be used on a polyolefin substrate or the like.

  As a drying method, depending on the drying property of the one-component aqueous coating agent of the present invention or the heat resistance of the base material, and further, depending on each application, etc. Alternatively, it is possible to set a wide range of drying conditions such as drying in a temperature range of about 40 to 120 ° C.

  EXAMPLES Next, although an Example and a comparative example are shown and this invention is demonstrated still in detail, this invention is not limited to this. In the examples, parts and% are based on weight unless otherwise specified.

Example 1
400.0 parts of a 30% toluene solution of chlorinated polypropylene having a degree of chlorination of 25.5% and a weight average molecular weight of 50,000 (Supercron 803LT: manufactured by Nippon Paper Industries Co., Ltd.) and cyclohexyl methacrylate (hereinafter abbreviated as CHMA). ) 360.0 parts, methyl methacrylate (hereinafter abbreviated as MMA) 27.6 parts, 2-hydroxyethyl methacrylate (hereinafter abbreviated as βHEMA) 83.4 parts, A-174 [γ-methacryloxypropyl Trimethoxysilane: Nippon Unicar Co., Ltd.] 3.0 parts, lauryl mercaptan (hereinafter abbreviated as L-SH) 3.0 parts, and methacrylic acid (hereinafter abbreviated as MAA) 6.0 parts. Vinyl monomers are dissolved in 261.0 parts of water with 36.0 parts of reactive emulsifier Hytenol KH-1025 and 12.0 parts of Aqualon ER-20. The obtained solution and a glass rod are mixed and coarsely emulsified, and the coarse emulsion is further finely divided over 30 minutes using a homogenizer [TK auto homomixer: manufactured by Tokushu Kika Kogyo Co., Ltd.] at 9000 rpm. To obtain an emulsified dispersion of a mixture of chlorinated polypropylene and vinyl monomers.

  Further, 3.0 parts of perbutyl H (tertiary butyl hydroperoxide) is dissolved in an emulsifier aqueous solution of 3.0 parts of New Coal 707SF [manufactured by Nippon Emulsifier Co., Ltd.] and 60.0 parts of ion-exchanged water, and radical polymerization is performed. An aqueous initiator solution was obtained. Further, 3.0 parts of redol CP [sodium sulfooxylate formaldehyde: Mitsubishi Chemical Corporation] was dissolved in 60 g of ion-exchanged water to obtain an aqueous reducing agent solution.

  In a 2 liter reaction vessel equipped with a stirrer, a thermometer, and a cooler, 330 parts of ion exchange water was charged, and the temperature was raised to 70 ° C. while stirring while inserting nitrogen gas. After sufficiently purging the inside of the reaction vessel with nitrogen, an emulsion dispersion of a mixture of chlorinated polypropylene and vinyl monomers, an aqueous radical polymerization initiator solution, and an aqueous reducing agent solution were respectively added dropwise to the reaction vessel. The dropping time is 3 hours for the emulsion dispersion of a mixture of chlorinated polypropylene and vinyl monomers, 3 hours and 30 minutes for the radical polymerization initiator aqueous solution and the reducing agent aqueous solution, and the reaction vessel is kept at 70 ° C. during the dropping reaction. While stirring, the stirring was continued. After completion of the dropwise addition of the radical polymerization initiator aqueous solution and the reducing agent aqueous solution, the mixture was kept at 70 ° C. with stirring for 30 minutes, cooled, and adjusted to pH 8-9 with 12.5% ammonia water. Furthermore, the obtained aqueous resin composition was distilled under reduced pressure at 0.007 MPa and 42 ° C. for 1 hour with a water flow decompressor (A-3S: manufactured by Tokyo Riken). Thereafter, the pH and nonvolatile content were adjusted with 12.5% aqueous ammonia and ion-exchanged water to obtain a one-component aqueous coating agent having a nonvolatile content of 43.0%, a viscosity of 120 mPa · s, and a pH of 9.3. Further, the particle size of the polymer particles at this time was 0.17 μm when measured by a particle size measuring instrument [Microtrac particle size analyzer 9340UPA: manufactured by Nikkiso Co., Ltd.].

Examples 2-3 and Comparative Examples 1-4
Except having used the raw material of the following Table 1 and Table 2, it carried out similarly to Example 1, and obtained the one-pack type aqueous coating agent for this invention and the comparison.

Test Examples 1-3 and Comparative Test Examples 1-4
(Addition of film-forming aid)
100 g of the one-component aqueous coating agents obtained in Examples 1 to 3 and Comparative Examples 1 to 4 are each stirred with a disper. In this state, 90 parts of DBDG (diethylene glycol dibutyl ether) was added to 100 parts of the solid content of the one-part aqueous coating agent, stirred for 10 minutes with a disper and taken out, and a film-forming aid was added. A one-part aqueous coating agent was obtained.

(Coating test plate creation method)
A one-component water-based coating agent with film-forming aid added to an automotive interior grade polypropylene base material is sprayed to a dry film thickness of 15 μm, set for 5 minutes, and then heated with hot air. Drying is performed at 80 ° C. for 30 minutes using a dryer, and further drying is performed at room temperature for 3 days to obtain a test plate having a dry film. Using the obtained test plate, a primary adhesion test is performed as follows. A secondary adhesion test and an oil resistance test were conducted to evaluate the coating on the test plate.

(Primary adhesion test)
A 10 × 10 cut with 2 mm squares was made on the surface of the coating with a cutter, a peel test with a cellophane tape was performed, and the number of remaining eyes was evaluated according to the following evaluation criteria.
Evaluation criteria A: 100
○: 85-99
Δ: 65-84
X: 35-64
XX: 34 or less

(Secondary adhesion test)
The test plate was immersed in warm water at 40 ° C. for 24 hours, then taken out and dried at room temperature for 2 hours. Thereafter, a peel test using cellophane tape was performed in the same manner as the primary adhesion test, and the number of remaining eyes was evaluated according to the following evaluation criteria.
Evaluation criteria A: 100
○: 85-99
Δ: 65-84
X: 35-64
XX: 34 or less

(Oil resistance test)
After applying beef tallow grade 1 to the test plate at a rate of ² g / 100 cm ² , a flannel cloth was covered and heated at 80 ° C. for 7 days with a hot air dryer. Then, after taking out and cooling, the flannel cloth was peeled off, and the surface state of the film after peeling (nel adhesion, film dissolution) was evaluated according to the following evaluation criteria.
Evaluation criteria A: No change.
○: There is glossiness.
Δ: Slight dissolution and slight adhesion.
X: Dissolution and fouling are present.
XX: Full surface dissolution.

Claims (18)

A chlorinated polyolefin polymer (A) having a chlorination degree of 5 to 50% by weight and a weight average molecular weight of 30,000 to 70,000, and a hydrophobic vinyl monomer (b1) having a glass transition point of 60 to 200 ° C. of the homopolymer Copolymer (B) obtained by polymerizing vinyl monomer (b2), hydroxyl group-containing vinyl monomer (b2), alkoxysilyl group-containing vinyl monomer (b3), and other copolymerizable vinyl monomers (b4) A one-part aqueous coating agent, wherein polymer particles mixed with are dispersed in water in the presence of an emulsifier (C). The one-pack type aqueous coating agent according to claim 1, wherein the hydrophobic vinyl monomer (b1) is cyclohexyl methacrylate and / or isobornyl (meth) acrylate. The one-pack type aqueous coating agent according to claim 1 or 2, wherein the weight of the vinyl copolymer (B) is 100 to 1000 parts by weight with respect to 100 parts by weight of the chlorinated polyolefin polymer (A). The vinyl copolymer (B) is composed of a hydrophobic vinyl monomer (b1), a hydroxyl group-containing vinyl monomer (b2), an alkoxysilyl group-containing vinyl monomer (b3), and other copolymerizable vinyl monomers. It is obtained using 30 to 95 parts by weight of the hydrophobic vinyl monomer (b1) and 0.3 to 5 parts by weight of the alkoxysilyl group-containing vinyl monomer (b3) with respect to 100 parts by weight of the total of (b4). The one-pack type aqueous coating agent according to claim 1 or 2, which is a vinyl copolymer having a hydroxyl value of 10 to 100 mgKOH / g. The one-component aqueous coating agent according to claim 1 or 2, wherein the alkoxysilyl group-containing vinyl monomer (b3) is a (meth) acrylic monomer having three methoxysilyl groups or ethoxysilyl groups. The one-pack type aqueous coating agent according to claim 1 or 2, wherein an average particle diameter of the polymer particles in which the chlorinated polyolefin polymer (A) and the vinyl copolymer (B) are mixed is 0.05 to 0.3 µm. The one-pack type aqueous coating agent according to claim 1 or 2, wherein the vinyl copolymer (B) has a carboxyl group or an acid anhydride group neutralized with a basic compound. A chlorinated polyolefin polymer solution (I) in which a chlorinated polyolefin polymer (A) having a chlorination degree of 5 to 50% by weight and a weight average molecular weight of 30,000 to 70,000 is dissolved in an organic solvent (D); Hydrophobic vinyl monomer (b1) having a glass transition point of 60 to 200 ° C., hydroxyl group-containing vinyl monomer (b2), alkoxysilyl group-containing vinyl monomer (b3), and other copolymerizable vinyl monomers The vinyl monomer (II) comprising the body (b4) is mechanically dispersed in water in the presence of the emulsifier (C), and then the vinyl monomer (II) is polymerized. A method for producing a one-part aqueous coating agent. After mechanically dispersing the chlorinated polyolefin polymer solution (I) and the vinyl monomers (II), the vinyl monomers (II) are polymerized to have an average particle size of 0.05 to 0.3 μm. The method for producing a one-component aqueous coating agent according to claim 8, wherein the dispersion is an aqueous dispersion of polymer particles. A chlorinated polyolefin polymer solution (I) and vinyl monomers (II) are mechanically dispersed in water in the presence of an emulsifier (C) and then vinyl in the presence of a radical polymerization initiator (E). The method for producing a one-component aqueous coating agent according to claim 8, wherein the monomers (II) are polymerized. The method for producing a one-part aqueous coating agent according to claim 8, 9 or 10, wherein the vinyl monomers (II) are emulsion-polymerized and then the solvent is removed by distillation under reduced pressure. The method for producing a one-component aqueous coating agent according to claim 8, 9 or 10, wherein the hydrophobic vinyl monomer (b1) is cyclohexyl methacrylate and / or isobornyl (meth) acrylate. The method for producing a one-part aqueous coating agent according to claim 8, 9 or 10, wherein the weight of the vinyl monomer (II) is 100 to 1,000 parts by weight with respect to 100 parts by weight of the chlorinated polyolefin polymer (A). . The vinyl monomer (II) is 30 to 95 parts by weight of the hydrophobic vinyl monomer (b1) and 100% by weight of the vinyl monomer (II), and the alkoxysilyl group-containing vinyl monomer (b3). ) In an amount of 0.3 to 5 parts by weight, and the hydroxyl value of the vinyl copolymer obtained by polymerizing the vinyl monomer (b2) with the hydroxyl group-containing vinyl monomer (b2) is 10 to 100 mgKOH / The method for producing a one-component aqueous coating agent according to claim 8, 9 or 10, wherein the composition is contained in a ratio of g. The one-component aqueous coating agent according to claim 8, 9 or 10, wherein the alkoxysilyl group-containing vinyl monomer (b3) is a (meth) acrylic monomer having three methoxysilyl groups or three ethoxysilyl groups. Method. The polymerized by using a vinyl monomer containing a vinyl monomer having a carboxyl group or an acid anhydride group as the vinyl monomer (II), and then neutralized with a basic compound. The manufacturing method of the one-pack type aqueous coating agent as described in 1 above. A coated article obtained by coating the one-component aqueous coating agent according to any one of claims 1 to 7 on a polyolefin substrate. The coated article according to claim 17, wherein the polyolefin substrate is a polypropylene substrate.