JP2007254715A - Resin composition for use in anion-type flatting electrodeposition paint, and paint film formed by electrodeposition-coating the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for use in flatting electrodeposition paints which is excellent in the paint stability, gloss stability, external appearance, weatherability, acid resistance, sealing material adhering property, and non-oily marker repellency. <P>SOLUTION: The resin composition for use in the anion-type flatting electrodeposition paint contains as follows: 40-80 parts by weight of (A) a water-soluble or water-dispersed vinyl copolymer, which is formed by the copolymerization of 0.5-10 parts by weight of (a) a 1-5C fluoroalkyl group-containing vinyl monomer, 3-15 parts by weight of (b) a carboxy group-containing vinyl monomer, 5-30 parts by weight of (c) a hydroxy group-containing vinyl monomer, 0.5-10 parts by weight of a substituent alkoxysilyl group-containing vinyl monomer (d), and 35-91 parts by weight of (e) a vinyl monomer exclusive of the above (a) through (d); 60-20 parts by weight of (B) an amino resin; and 0.1-5 parts by weight, relative to 100 parts by weight of the sum total of (A) and (B), of (C) an alkoxy amine as a light stabilizer of an amino etherified compound from a hindered amine. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

Conventionally, a paint in which an amino resin or a blocked isocyanate is blended with a (meth) acrylic-styrene aqueous resin as a curing agent has been used for coating an aluminum base material.
In general, this paint has been put to practical use by applying an anionic electrodeposition coating to an aluminum base material as a building material such as an aluminum sash for a house or a high-rise building or a curtain wall. However, in recent years, long-term durability is required for aluminum building materials, and weather resistance is also required for electrodeposition coatings.

Up to now, as a means for improving the weather resistance of an electrodeposited coating film, a method using a silicone-based resin or the like has been disclosed in, for example, Patent Document 1 and the like, but the coating film is white blurred or adhesive with a sealing material. Have the disadvantage of lowering.
On the other hand, a copolymerizable vinyl monomer having radical scavenging ability to an acrylic resin, a copolymerizable vinyl monomer having ultraviolet absorbing ability, and a method of copolymerizing a fluorine-containing copolymerizable vinyl monomer However, it is disclosed in, for example, Patent Document 2. However, in these resin compositions, since the stability of the coating is impaired, the amount of the copolymerizable vinyl monomer having a radical scavenging ability and the copolymerizable vinyl monomer having an ultraviolet absorbing ability is limited. Further improvement of weather resistance is difficult. Further, in order to obtain a matte electrodeposition coating film using this technique, copolymerizing a copolymerizable vinyl monomer having a radical scavenging ability and an alkoxysilane-containing copolymerizable vinyl monomer, Since the copolymerizable vinyl monomer having radical scavenging ability exhibits strong basicity, the hydrolysis and condensation of alkoxysilane proceeds during the polymerization of acrylic monomer, and the stability of the paint obtained by copolymerization is improved. There was also a problem of decline.

Further, regarding acrylic melamine resin-based coating films, deterioration of the coating films due to acid rain or combustion exhaust gas has become a problem in recent years, and improvement in acid resistance and corrosion resistance has been demanded. As a method for overcoming this problem, for example, Patent Document 3 discloses a method using a fluorine-based resin. The resulting coating film shows good weather resistance and acid resistance, but is expensive and not versatile, resulting in poor adhesion to the sealing material and paint stability problems.
From a combination of a hindered amino ether light stabilizer and an acrylic resin, a matte electrodeposition coating film excellent in paint stability, weather resistance, and adhesion to a sealing material is also disclosed, for example, in Patent Document 4 and the like. However, acid resistance and corrosion resistance were still insufficient.

In this way, resin compositions for matte electrodeposition coatings that satisfy paint stability, weather resistance, acid resistance, corrosion resistance, crack resistance, adhesion to sealing materials, etc., and are well balanced to date Did not exist.
Further, copolymerization using a copolymerizable monomer having an alkoxysilyl group that can be used to form a matte electrodeposition coating film is disclosed in, for example, Patent Document 5 and the like. The use of a silicon alkoxide oligomer to obtain a coating film is disclosed in, for example, Patent Document 6 but has insufficient acid resistance. In addition, these compositions were not sufficient in crack resistance assuming deterioration under an outdoor acidic atmosphere.

Japanese Patent Laid-Open No. 06-033654 JP 2001-123107 A Japanese Patent Laid-Open No. 04-202382 Japanese Patent No. 3721406 Japanese Patent Laid-Open No. 06-041476 JP 2004-204215 A

  The present invention solves the problems in the prior art as described above, and is an electrodeposition paint excellent in paint stability, gloss stability, appearance, weather resistance, acid resistance, corrosion resistance, crack resistance, and adhesion to a sealing material. An object of the present invention is to provide a matte electrodeposition coating film excellent in oil resistance marker repellency and the like, and a resin composition for matte electrodeposition paint for constituting the same.

  As a result of intensive studies on the above problems, the inventors of the present invention have a copolymerizable vinyl monomer (a) having a fluoroalkyl group having 1 to 5 carbon atoms as a substituent and a carboxyl group as a substituent. A copolymerizable vinyl monomer (b), a copolymerizable vinyl monomer (c) having a hydroxyl group as a substituent, a copolymerizable vinyl monomer (d) having an alkoxysilyl group as a substituent, and A water-soluble or water-dispersible vinyl copolymer obtained by copolymerization with a copolymerizable vinyl monomer (e) other than the above (a) to (d), an amino resin as a crosslinking agent, and a light stabilizer A resin composition for an anionic matte electrodeposition paint containing an alkoxyamine which is an aminoetherified product of a hindered amine, an anionic electrodeposition paint comprising the composition, and a coating film obtained by electrodeposition coating of the paint The above problem And knowledge to be able to clothes has led to the present invention.

That is, the present invention provides a copolymerizable monomer having 0.5 to 10 parts by weight of a copolymerizable vinyl monomer (a) having a C1-C5 fluoroalkyl group as a substituent and a carboxyl as a substituent. 3 to 15 parts by weight of a copolymerizable vinyl monomer (b) having a group, 5 to 30 parts by weight of a copolymerizable vinyl monomer (c) having a hydroxyl group as a substituent, and an alkoxysilyl group as a substituent Using 0.5 to 10 parts by weight of the copolymerizable vinyl monomer (d) and 35 to 91 parts by weight of the copolymerizable vinyl monomer (e) other than the above (a) to (d), The water-soluble or water-dispersible vinyl copolymer (A) obtained by copolymerizing these monomers (40) to 80 parts by weight, amino resin (B) 60 to 20 parts by weight, and (A) And (B) in total 100 parts by weight of hindered amine as a light stabilizer Anionic matte electrodeposition resin composition characterized by the inclusion of alkoxyamine (C) 0.1 to 5 parts by weight of ether compound, it is.
2. The anionic matte electrodeposition coating material according to claim 1, wherein the anionic matting electrodeposition resin composition further contains 0.5 to 20 parts by weight of a silicon alkoxide oligomer (D). Resin composition.

  The resin composition for matte electrodeposition coating of the present invention is excellent in paint stability, and the electrodeposition paint formed using the same and the matte electrodeposition coating film formed thereby have good weather resistance and acid resistance. It has corrosion resistance, crack resistance, sealant adhesiveness, oil resistance marker repellent properties, is effective in improving these properties, and is extremely useful industrially.

The present invention will be described in more detail.
In the present invention, each component of (A) water-soluble or water-dispersible vinyl copolymer, (B) amino resin, and (C) alkoxyamine comprises a matte electrodeposition coating film and a matte electrodeposition coating resin. It is an essential component for obtaining a liquid.
The copolymerizable vinyl monomer having a fluoroalkyl group having 1 to 5 carbon atoms as a substituent (a) constituting the water-soluble or water-dispersible vinyl copolymer of the component (A) includes 2, 2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2- (par Fluoroethyl) ethyl acrylate, 2- (perfluoroethyl) ethyl methacrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate and the like. Tosoh F-Tech: product name), Biscote 3F, Biscote 3FM (Osaka Organic) Company Ltd. trade name), Light Ester M-3F (manufactured by Kyoeisha Chemical Co.: trade name) is used one or two or more, and the like. Of these, it is desirable to use 2,2,2-trifluoroethyl methacrylate or 2,2,3,3-tetrafluoropropyl methacrylate.

These copolymerizable vinyl monomers having a fluoroalkyl group having 1 to 5 carbon atoms are effective in improving weather resistance, as seen in conventional fluororesins because the fluorine component is uniformly present in the coating film. There is no problem of poor adhesion of the sealing material, and it is excellent in acid resistance and corrosion resistance, and is particularly effective in improving crack resistance assuming an outdoor acidic atmosphere.
When a vinyl copolymer containing a long-chain fluoroalkyl group having 6 or more carbon atoms as a substituent such as 2- (perfluorooctyl) ethyl methacrylate is used for a matte electrodeposition coating film with irregularities on the coating film surface In this case, since the fluoroalkyl group is oriented on the outermost surface of the coating film, the sealant adhesiveness and the oil resistance marker repelling property are lowered, and the effect in the present invention cannot be expected.
The copolymerizable vinyl monomer containing a carboxyl group as a substituent (b) constituting the water-soluble or water-dispersible vinyl copolymer of the component (A) includes acrylic acid, α-chloroacrylic acid, Examples include methacrylic acid, itaconic acid, maleic anhydride, maleic acid, fumaric acid, crotonic acid, citraconic acid, and mesaconic acid.

  (A) Component (c) constituting the water-soluble or water-dispersible vinyl copolymer of component (c) As a copolymerizable monomer containing a hydroxyl group as a substituent, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, cyclohexane dimethanol monoacrylate And cyclohexanedimethanol monomethacrylate.

  As the copolymerizable vinyl monomer having an alkoxysilyl group as a substituent (d) constituting the water-soluble or water-dispersible vinyl copolymer of the component (A), γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxy Examples include propyltriethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, and vinyltrimethoxysilane.

  (A) The water-soluble or water-dispersible vinyl copolymer of the component (e) Other copolymerizable vinyl monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl Acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal butyl methacrylate, normal hexyl acrylate, normal hexyl methacrylate, normal heptyl acrylate, normal heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, normal lauryl acrylate Up to about 20 carbon atoms such as lauryl methacrylate, stearyl acrylate, stearyl methacrylate Similar copolymerizable vinyl ester having an alkyl group, copolymerizable vinyl ester monomer containing alicyclic hydrocarbon group as a substituent such as cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate And vinyl monomers containing aromatic groups such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene and the like can be used. Further, acrylamide, N-methylol acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-isobutoxymethyl acrylamide, N-butoxymethyl acrylamide, methacrylamide, N-methylol methacrylamide, N-methoxymethyl methacrylamide, N (Meth) acrylamides such as ethoxymethyl methacrylamide, N-isobutoxymethyl methacrylamide, N-butoxymethyl methacrylamide, acrylonitrile, vinyl acetate and the like can also be used.

  Furthermore, as the amino resin of the component (B), melamine resin, benzoguanamine resin, urea resin and the like can be used. Particularly, in the melamine resin, alkoxylated melamine in which at least a part of the methylol group is alkoxylated with a lower alcohol is preferable, As the lower alcohol, one or more of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and the like can be used.

  Examples of the organic amine that can be used to neutralize the carboxyl group of the water-soluble or water-dispersible vinyl copolymer (A) in the present invention include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine. , Monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, alkylamines such as tributylamine, monoethanolamine, diethanolamine, triethanolamine, mono (2-hydroxypropyl) amine, di (2-hydroxy) Propyl) amine, tri (2-hydroxypropyl) amine, dimethylaminoethanol, diethylaminoethanol, and other alkanolamines, ethylenediamine, propylenediamine, Triamine, an alkylene polyamine such as triethylene tetramine, ethylene imine, alkylene imine such as propylene imine, piperazine, morpholine, pyrazine, pyridine, and the like. What is necessary is just to add an organic amine so that molar ratio may be set to 0.3-0.9 with respect to the carboxyl group in (A) component.

As the alkoxyamine of the component (C), an amino etherified product of a hindered amine is desirable. In general, hindered amines and hindered alkylamines used as light stabilizers contain N—H bonds or N-alkyl bonds. However, since these compounds have strong basicity, the stability of the emulsion is reduced. In addition to elution from the emulsion, it inhibits the curing reaction when cured with an amino resin. In addition, when obtaining a matte electrodeposition coating film, coexistence of an alkoxysilane-containing vinyl copolymer and a hindered amine or hindered alkylamine promotes condensation of alkoxysilane during storage and decreases paint stability. There is a bug.
However, when the hindered amine aminoetherified product is used as the light stabilizer, the basicity is low, and thus weather resistance can be improved without inhibiting the curing with the amino resin or reducing the coating stability. In addition, as a light stabilizer having a low basicity as in the case of hindered amine amino ethers, acylated products of hindered amines can also be mentioned, but since these are highly water-soluble, they are not easily present in the electrodeposition coating film, and active species are selected. Since the generation rate of the nitroxide radical to be captured is also slow, the effect in the present invention cannot be expected.

The light stabilizer of component (C) may be added to the resin, or a hydroxyl group may be introduced and incorporated into a crosslinking system with an amino resin or isocyanate. In terms of elution from the coating film and polymerization stability of the acrylic resin, it is desirable to use an alkoxyamine having a hydroxyl group introduced.
The alkyl ether group of the alkoxyamine as the component (C) contains a group represented by the general formula, N—O—R, and as a hydrocarbon group (R) that can be used as the group represented by the group, Chain hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, hexyl and octyl, alicyclic hydrocarbon groups such as cyclohexyl and isobornyl, and aromatics such as benzyl, 1-phenylethyl and 1,2-diphenylethyl A hydrocarbon group is mentioned.

  As the component (C) used as the alkoxyamine, alicyclic amino ethers such as dialkyl amino ethers, chain amino ethers of diaryl amino ethers, tetraalkyl pyrrolidinyl ethers, tetraalkyl piperidinyl ethers, and the like Can be used. These alkoxyamines are considered to generate stable nitroxide radicals by irradiation with light or heat, and the nitroxide radicals capture active species that promote the deterioration of the coating film and suppress the deterioration of the coating film. Among these, it is preferable to use a tetraalkylpiperidinyl ether derivative from the viewpoint of production cost.

  Specific examples of the alkoxyamine that can be used in the present invention include bis- (1-hexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate and bis- (1 sebacate) (1 -Octyloxy-2,2,6,6-tetramethyl-4-piperidinyl), bis- (1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate and the like can be used, As commercially available products, Tinuvin 123, Tinuvin 5100 (manufactured by Ciba Specialty Chemicals Co., Ltd .: trade name) and the like can be used, but are not limited thereto.

  As a case of crosslinking with amino resin or isocyanate, 2,4-bis- [N-butyl-N- (octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) amino] -6 (Hydroxyethylamine) -1,3,5-triazine, 2,4-bis- [N-butyl-N- (cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) amino] -6 (Hydroxyethylamine) -1,3,5-triazine and the like can be used, and as a commercially available product, Tinuvin 152 (manufactured by Ciba Specialty Chemicals Co., Ltd .: trade name) can be used, but is not limited thereto. .

In these compositions, an ultraviolet absorber can be used in combination for further improving the weather resistance.
In order to obtain scratch resistance and a matte coating film, silicon alkoxide oligomer (D) may be used. Silicon alkoxide oligomers that can be used for these include MKC silicate MS-51, MKC silicate MS-56, MKC silicate MS-57, MKC silicate MS-56S, MKC silicate MS-58, MKC silicate MS-58B15, MKC silicate MS- 58B30 (manufactured by Mitsubishi Chemical Corporation: trade name), methyl silicate 51 (manufactured by Fuso Chemical Co., Ltd .: trade name), M silicate 51, silicate 40, silicate 45 (manufactured by Tama Chemical Industry Co., Ltd .: trade name), ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd .: trade name) and the like are used, but are not limited thereto.

Copolymerizable vinyl having a fluoroalkyl group having 1 to 5 carbon atoms as a substituent constituting the water-dispersible vinyl copolymer of the water-soluble or water-dispersible vinyl copolymer (A) component in the present invention The electrodeposition coating film of 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight of the system monomer (a) has particularly good acid resistance, corrosion resistance, crack resistance and sealant adhesion. Moreover, the copolymerizable vinyl monomer (b) having a carboxyl group as a substituent of the component (A) is obtained in an amount of 3 to 15 parts by weight, preferably 4 to 12 parts by weight. The electrodeposition resin composition obtained with 5-30 parts by weight, preferably 8-25 parts by weight of the copolymerizable vinyl monomer (c) having a hydroxyl group has particularly good water dispersibility. The membrane is excellent in performance.
Furthermore, the copolymerizable vinyl monomer (d) having an alkoxysilyl group as a substituent constituting the water-soluble or water-dispersible vinyl copolymer of the component (A) (d) 0.5 to 10 parts by weight, preferably 1 The electrodeposition coating obtained using ~ 8 parts by weight forms a beautiful matte electrodeposition coating.

In the water-soluble or water-dispersible vinyl copolymer (A) of the present invention, the proportion of the vinyl monomer (a) having a fluoroalkyl group having 1 to 5 carbon atoms is less than 0.5 parts by weight. If there is, the acid resistance, corrosion resistance and crack resistance deteriorate, and if it exceeds 10 parts by weight, the adhesion to the sealing material and the oil resistance marker repellent property are poor, the production cost is remarkably increased, and the copolymerization having a carboxyl group as a substituent is present. If the proportion of the vinyl monomer (b) is less than 3 parts by weight, the liquid stability is poor, and if it exceeds 15 parts by weight, the water resistance is poor. Further, if the proportion of the copolymerizable vinyl monomer (c) having a hydroxyl group as a substituent is less than 5 parts by weight, sufficient coating performance (chemical resistance, coating hardness) cannot be obtained, and 30 wt. When it exceeds the part, the water resistance becomes worse.
Further, if the proportion of the copolymerizable vinyl monomer (d) having an alkoxysilyl group as a substituent is less than 0.5 parts by weight, it is sufficient to contain no matte component such as a silicon alkoxide oligomer (D). When the amount exceeds 10 parts by weight, the paint stability deteriorates.

  The water-soluble or water-dispersible vinyl copolymer (A) of the present invention is 40 to 80 parts by weight, preferably 50 to 75 parts by weight, and the amino resin (B) is 20 to 60 parts by weight, preferably 25 to 25 parts by weight. Use 50 parts by weight. If the proportion of the water-soluble or water-dispersible vinyl copolymer (A) is less than 40 parts by weight, sufficient water dispersibility cannot be obtained, resulting in liquid separation and sedimentation. The film performance cannot be obtained. When the proportion of the amino resin (B) is less than 20 parts by weight, sufficient film performance (chemical resistance, film hardness) cannot be obtained, and when it exceeds 60 parts by weight, sufficient film hardness cannot be obtained. Manufacturing costs also increase significantly.

Water-soluble or water-dispersible vinyl copolymer (A) component + amino resin (B) component = 100 parts by weight, alkoxyamine (C) component is 0.1 to 5 parts by weight, preferably 0 The electrodeposition coating film of the electrodeposition resin composition obtained in the range of 0.1 to 3 parts by weight has particularly good weather resistance and production cost balance. If the alkoxyamine (C) is less than 0.1 parts by weight, the weather resistance is poor, and if it exceeds 5 parts by weight, the production cost increases, which is not preferable.
Further, when obtaining a scratch-resistant and more beautiful matte coating film, a silicon alkoxide oligomer (water-soluble or water-dispersible vinyl copolymer (A) component + amino resin (B) component = 100 parts by weight) It is desirable to use 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight of component D). If the ratio of the silicon alkoxide oligomer (D) component is less than 0.5 parts by weight, the scratch resistance and sufficient matting effect cannot be obtained, and if it exceeds 20 parts by weight, the coating stability becomes poor.

  As the electrodeposition conditions using the matte electrodeposition resin composition constituted according to the present invention, the voltage applied in the energization step is 10 to 400 V, preferably 50 to 250 V, and the energization time is 0.5 minutes to 7 minutes, preferably 1 to 4 minutes. The higher the voltage, the shorter the energization time, and the lower the voltage, the longer the energization time. The applied voltage may be either a hard start in which a set voltage is applied simultaneously with energization, or a soft start in which the voltage is gradually raised to the set voltage. The electrodeposition-coated object is washed with water and then heated at 150 to 200 ° C. for 15 to 60 minutes to cure the coating film. The object to which the present invention can be applied is not particularly limited as long as it has conductivity.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the part in an Example and a comparative example is a weight part unless there is particular notice.
(Production Example 1)
12.0 parts of isopropanol and 8.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 18.0 parts of isopropanol, 9 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 5 parts of styrene, 5 parts of 2-ethylhexyl acrylate, 10 parts of cyclohexyl methacrylate, 20 parts of n-butyl acrylate , 33 parts of methyl methacrylate, 3 parts of 2,2,2-trifluoroethyl methacrylate, and 1 part of azobisisobutyronitrile were charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.4 part of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and then the reaction was continued at 90 ° C. for 90 minutes. The obtained copolymer was a water-dispersible vinyl copolymer (solid content: 72.2%) having an acid value of 68.9 mgKOH and a hydroxyl value of 68.7 mgKOH.

(Production Example 2)
12.0 parts of isopropanol and 8.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 18.0 parts of isopropanol, 10 parts of 2-hydroxyethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 5 parts of styrene, 5 parts of 2-ethylhexyl acrylate, 10 parts of cyclohexyl methacrylate, 20 parts of n-butyl acrylate, 37 parts of methyl methacrylate , 3 parts of 2,2,2-trifluoroethyl methacrylate, 5 parts of γ-methacryloyloxypropyltrimethoxysilane, and 1 part of azobisisobutyronitrile were charged into a dropping funnel and placed in the flask over 120 minutes. It was dripped. After completion of the dropwise addition, 0.4 part of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 90 minutes. The obtained copolymer was a water-dispersible vinyl copolymer (solid content: 72.2%) having an acid value of 0 mgKOH and a hydroxyl value of 68.7 mgKOH.

(Production Example 3)
12.0 parts of isopropanol and 8.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 18.0 parts of isopropanol, 7 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 8 parts of styrene, 5 parts of 2-ethylhexyl methacrylate, 15 parts of cyclohexyl acrylate, 19 parts of n-butyl acrylate , 26 parts of methyl methacrylate, 3 parts of 2,2,2-trifluoroethyl methacrylate, 2 parts of γ-methacryloyloxypropyltrimethoxysilane and 1 part of azobisisobutyronitrile were charged into a dropping funnel, Over 120 minutes. After completion of the dropwise addition, 0.4 part of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and then the reaction was continued at 90 ° C. for 90 minutes. The obtained copolymer was a water-dispersible vinyl copolymer (solid content: 72.2%) having an acid value of 53.6 mgKOH and a hydroxyl value of 68.7 mgKOH.

(Production Example 4)
12.0 parts of isopropanol and 8.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 18.0 parts of isopropanol, 7 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 8 parts of styrene, 5 parts of 2-ethylhexyl methacrylate, 15 parts of cyclohexyl acrylate, 19 parts of n-butyl acrylate , 26 parts of methyl methacrylate, 3 parts of 2,2,3,3-tetrafluoropropyl methacrylate, 2 parts of γ-methacryloyloxypropyltrimethoxysilane and 1 part of azobisisobutyronitrile were charged into the dropping funnel, The solution was dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.4 part of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and then the reaction was continued at 90 ° C. for 90 minutes. The obtained copolymer was a water-dispersible vinyl copolymer (solid content: 72.2%) having an acid value of 53.6 mgKOH and a hydroxyl value of 68.7 mgKOH.

(Production Example 5)
12.0 parts of isopropanol and 8.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 18.0 parts of isopropanol, 9 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 5 parts of styrene, 5 parts of 2-ethylhexyl acrylate, 10 parts of cyclohexyl acrylate, 20 parts of n-butyl acrylate , 36 parts of methyl methacrylate and 1 part of azobisisobutyronitrile were charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.4 part of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and then the reaction was continued at 90 ° C. for 90 minutes. The obtained copolymer was a water-dispersible vinyl copolymer (solid content: 72.2%) having an acid value of 68.9 mgKOH and a hydroxyl value of 68.7 mgKOH.

(Production Example 6)
12.0 parts of isopropanol and 8.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 18.0 parts of isopropanol, 10 parts of 2-hydroxyethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 5 parts of styrene, 5 parts of 2-ethylhexyl acrylate, 10 parts of cyclohexyl acrylate, 20 parts of n-butyl acrylate, 40 parts of methyl methacrylate A mixed solution of 5 parts of γ-methacryloyloxypropyltrimethoxysilane and 1 part of azobisisobutyronitrile was charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.4 part of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and then the reaction was continued at 90 ° C. for 90 minutes. The obtained copolymer was a water-dispersible vinyl copolymer (solid content: 72.2%) having an acid value of 0 mgKOH and a hydroxyl value of 68.7 mgKOH.

(Production Example 7)
12.0 parts of isopropanol and 8.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 18.0 parts of isopropanol, 7 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 8 parts of styrene, 5 parts of 2-ethylhexyl acrylate, 15 parts of cyclohexyl acrylate, 19 parts of n-butyl acrylate , 39 parts of methyl methacrylate, 2 parts of γ-methacryloyloxypropyltrimethoxysilane, and 1 part of azobisisobutyronitrile were charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.4 part of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and then the reaction was continued at 90 ° C. for 90 minutes. The obtained copolymer was a water-dispersible vinyl copolymer (solid content: 72.2%) having an acid value of 53.6 mgKOH and a hydroxyl value of 68.7 mgKOH.

(Production Example 8)
12.0 parts of isopropanol and 8.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 18.0 parts of isopropanol, 7 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 5 parts of styrene, 5 parts of 2-ethylhexyl methacrylate, 10 parts of cyclohexyl acrylate, 15 parts of n-butyl acrylate , 26 parts of methyl methacrylate, 15 parts of 2,2,2-trifluoroethyl methacrylate, and 1 part of azobisisobutyronitrile were charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.4 part of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and then the reaction was continued at 90 ° C. for 90 minutes. The obtained copolymer was a water-dispersible vinyl copolymer (solid content: 72.2%) having an acid value of 53.6 mgKOH and a hydroxyl value of 68.7 mgKOH.

(Production Example 9)
12.0 parts of isopropanol and 8.0 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 18.0 parts of isopropanol, 7 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 8 parts of styrene, 5 parts of 2-ethylhexyl methacrylate, 15 parts of cyclohexyl acrylate, 19 parts of n-butyl acrylate , 26 parts of methyl methacrylate, 3 parts of 2- (perfluorooctyl) ethyl methacrylate, 2 parts of γ-methacryloyloxypropyltrimethoxysilane, and 1 part of azobisisobutyronitrile were charged into a dropping funnel, It was dripped over 120 minutes. After completion of the dropwise addition, 0.4 part of isopropanol and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and then the reaction was continued at 90 ° C. for 90 minutes. The obtained copolymer was a water-dispersible vinyl copolymer (solid content: 72.2%) having an acid value of 53.6 mgKOH and a hydroxyl value of 68.7 mgKOH.
Table 1 shows the compositions of the water-dispersible vinyl copolymers obtained in Production Examples 1 to 9.

[Example 1]
61 parts of the vinyl copolymer obtained in Production Example 1 and 29 parts of the vinyl copolymer obtained in Production Example 2 and melamine resin (manufactured by Nippon Cytec Industries, Ltd .; C-235, active ingredient 100%) 35 Next, 2 parts of alkoxyamine (manufactured by Ciba Specialty Chemicals Co., Ltd .; Tinuvin 152) was mixed, and 2.4 parts of dimethylaminoethanol was added and mixed. While continuing to stir, 146.4 parts of deionized water was added to perform phase inversion emulsification to obtain a stock solution for electrodeposition paint. In a separate container, 728.2 parts of deionized water was charged, 270.3 parts of the stock solution for electrodeposition paint was added while stirring, and then 1.5 parts of dimethylaminoethanol was added to obtain an electrodeposition paint.

[Example 2]
90 parts of the vinyl copolymer obtained in Production Example 3 and 35 parts of melamine resin (manufactured by Nippon Cytec Industries Co., Ltd .; C-235, 100% active ingredient) are mixed, and then alkoxyamine (Ciba Specialty Chemicals Co., Ltd.). Manufactured; Tinuvin 152) 2 parts were mixed, and 2.8 parts of dimethylaminoethanol was added and mixed. While continuing stirring, 146.0 parts of deionized water was added to carry out phase inversion emulsification to obtain a stock solution for electrodeposition paint. In a separate container, 728.0 parts of deionized water was charged, 270.3 parts of the stock solution for electrodeposition paint was added while stirring, and then 1.7 parts of dimethylaminoethanol was added to obtain an electrodeposition paint.

[Example 3]
90 parts of the vinyl copolymer obtained in Production Example 1 and 35 parts of a melamine resin (manufactured by Nippon Cytec Industries, Inc .; C-235, 100% active ingredient) are mixed, and then a silicon alkoxide oligomer (Mitsubishi Chemical Corporation). MS-56) (10 parts) was mixed, then alkoxyamine (Ciba Specialty Chemicals Co., Ltd .; Tinuvin 152) (2 parts) was mixed, and further dimethylaminoethanol (3.6 parts) was added and mixed. While continuing stirring, 146.0 parts of deionized water was added to carry out phase inversion emulsification to obtain a stock solution for electrodeposition paint. In a separate container, 728.0 parts of deionized water was charged, and 270.3 parts of the stock solution for electrodeposition paint was added while stirring, and then 1.9 parts of dimethylaminoethanol was added to obtain an electrodeposition paint.

[Example 4]
An electrodeposition paint was prepared in the same manner as in Example 3 except that the vinyl copolymer obtained in Production Example 4 was used instead of using the vinyl copolymer obtained in Production Example 1.
[Example 5]
90 parts of the vinyl copolymer obtained in Production Example 1 and 35 parts of a melamine resin (manufactured by Nippon Cytec Industries, Inc .; C-235, 100% active ingredient) are mixed, and then a silicon alkoxide oligomer (Mitsubishi Chemical Corporation). MS-56) 10 parts were mixed, then alkoxyamine (Ciba Specialty Chemicals Co., Ltd .; Tinuvin 123) 2 parts were mixed, and 3.6 parts of dimethylaminoethanol was added and mixed. While continuing stirring, 146.0 parts of deionized water was added to carry out phase inversion emulsification to obtain a stock solution for electrodeposition paint. In a separate container, 728.0 parts of deionized water was charged, and 270.3 parts of the stock solution for electrodeposition paint was added while stirring, and then 1.9 parts of dimethylaminoethanol was added to obtain an electrodeposition paint.

[Comparative Example 1]
Instead of using the vinyl copolymer obtained in Production Example 1 and the vinyl copolymer obtained in Production Example 2, the vinyl copolymer obtained in Production Example 5 and the vinyl obtained in Production Example 6 were used. An electrodeposition paint was prepared in the same manner as in Example 1 except that the copolymer was used.
[Comparative Example 2]
An electrodeposition paint was prepared in the same manner as in Example 2 except that the vinyl copolymer obtained in Production Example 7 was used instead of using the vinyl copolymer obtained in Production Example 3.
[Comparative Example 3]
An electrodeposition paint was prepared in the same manner as in Example 3 except that the vinyl copolymer obtained in Production Example 5 was used instead of the vinyl copolymer obtained in Production Example 1.

[Comparative Example 4]
90 parts of the vinyl copolymer obtained in Production Example 1 and 35 parts of a melamine resin (manufactured by Nippon Cytec Industries, Inc .; C-235, 100% active ingredient) are mixed, and then a silicon alkoxide oligomer (Mitsubishi Chemical Corporation). MS-56) 10 parts were mixed, and 3.6 parts of dimethylaminoethanol was added and mixed. While continuing stirring, 158.7 parts of deionized water was added to carry out phase inversion emulsification to obtain a stock solution for electrodeposition paint. In a separate container, 727.7 parts of deionized water was charged, 270.3 parts of the stock solution for electrodeposition paint was added while stirring, and then 1.9 parts of dimethylaminoethanol was added to obtain an electrodeposition paint.

[Comparative Example 5]
An electrodeposition paint was obtained in the same manner as in Example 3 except that the vinyl copolymer obtained in Production Example 8 was used instead of the vinyl copolymer obtained in Production Example 5.
[Comparative Example 6]
An electrodeposition paint was obtained in the same manner as in Example 3 except that the vinyl copolymer obtained in Production Example 9 was used instead of the vinyl copolymer obtained in Production Example 5.
The composition of the matte electrodeposition resin solution for obtaining the matte electrodeposition coating films in Examples 1 to 5 and Comparative Examples 1 to 6 is shown in Table 2 below.

<Evaluation of resin composition>
Using the electrodeposition coating liquids prepared in Examples 1 to 5 and Comparative Examples 1 to 6, an anodized aluminum plate was used for the anode according to a conventional method, an 18-8 stainless steel plate was used for the cathode, a bath temperature of 20 ° C., A DC voltage of 180 V was applied between the two electrodes for 2 minutes. Next, the electrodeposited aluminum plate was taken out and washed thoroughly with water, and then baked and dried at a temperature of 180 ° C. for 30 minutes. The characteristics of the electrodeposition coating film formed on each aluminum plate were as shown in Table 2 below.

〔Evaluation methods〕
(1) Coating thickness: Measured using an eddy current film thickness meter (Fisher; ISOSCOPE).
(2) Gloss: Based on 60 ° specular reflectance.
(3) Skin feeling: Evaluated according to the following criteria by visual judgment.
◎ Good ○ Slightly insufficient × Insufficient

(4) Weather resistance: Performed using a metal weather. A black panel temperature of 80 ° C., irradiation intensity of 75 mW / cm ² , and irradiation alone were tested for 800 hours.
Gloss retention: Expressed as a ratio of 60 ° specular reflectance before and after the weather resistance test, 60 ° gloss after the weather resistance test / 60 ° gloss before the weather resistance test × 100 (%).
-Remaining film thickness ratio: Expressed by the ratio of the remaining coating thickness before and after the weather resistance test, the coating thickness after the weather resistance test / the coating thickness before the weather resistance test x 100 (%).
-Weather resistance evaluation: evaluated by the above-mentioned "Gloss retention".
A: Gloss retention rate of 80% or more and coating film thickness residual rate of 80% or more B: Gloss retention rate of 80% or more X: Less than (5) Liquid separation stability: Judgment was made based on the following criteria by visual judgment.
◎: No sedimentation separation for 1 week after liquid adjustment ○: Slight precipitation separation for 1 week after liquid adjustment ×: Large amount of sedimentation separation for 1 week after liquid adjustment

(6) Acid resistance: A ring with an inner diameter of 32 mm and a height of 30 mm was brought into contact with the surface of the coating film with petrolatum, and a 2% nitric acid aqueous solution was added up to a height of the ring of 1/2. N. (Rating number) and evaluated according to the following criteria.
A: R.I. N. Is 9.5 or more. N. Is less than 9 to 9.5 x: R.I. N. Is less than 9 (7) Corrosion resistance: in the appearance after the CASS corrosion resistance test (JIS-H-8681-2) was conducted, N. Was evaluated based on the following criteria.
◎: 600 hours or more ○: 300 hours or more, less than 600 hours ×: less than 300 hours

(8) Crack resistance: The coating was immersed in a 2% nitric acid aqueous solution, washed with water after 2 hours, air-dried, and subjected to visual observation after 3 cycles of irradiation with an SUV tester for 50 hours. The result of observation with a microscope was evaluated according to the following criteria.
◎: Visual; no change, microscope; no crack ○: Visual; slight surface roughness, microscope; no crack ×: visual; surface roughness or whitening, microscope; crack (9) Sealing material adhesion: sealing Evaluation was based on the peeled area of the material, and the following criteria were used.
◎: Peeling area is 10% or less ○: Peeling area is less than 10-30% ×: Peeling area is 30% or more

(10) Oil resistance marker repellency: Black oil marker (Zebra Co., Ltd., trade name: McKee Extra Fine) was used to evaluate the state of oil repellency when the electrodeposition coating surface was traced lightly. evaluated.
◎: No oily marker repelling ○: Oily marker is slightly repelled ×: Oily marker is completely repelled Summary of the matte electrodeposition coating films and the electrodeposition coating liquids of Examples 1 to 5 and Comparative Examples 1 to 6 The results obtained are shown in Table 3.

  The anionic matte electrodeposition resin composition of the present invention, the electrodeposition paint formed using the same, and the electrodeposition coating film formed thereby are suitably used in the field of electrodeposition coating.

Claims (4)

  0.5 to 10 parts by weight of a copolymerizable vinyl monomer (a) having a fluoroalkyl group having 1 to 5 carbon atoms as a substituent, and a copolymerizable vinyl monomer (b) 3 having a carboxyl group as a substituent 15 to 15 parts by weight, 5 to 30 parts by weight of a copolymerizable vinyl monomer (c) having a hydroxyl group as a substituent, 0.5 to 10 parts of a copolymerizable vinyl monomer (d) having an alkoxysilyl group as a substituent Water-soluble or water-dispersible vinyl copolymer (A) 40 to copolymerized by copolymerizing 35 parts by weight of a copolymerizable vinyl monomer (e) other than the above (a) to (d). Alkoxyamine (C), which is an amino etherified product of a hindered amine as a light stabilizer, with respect to 80 parts by weight, 20 to 60 parts by weight of amino resin (B) and 100 parts by weight of (A) and (B) in total. ) 0.1 to 5 parts by weight Anionic matte electrodeposition coating resin composition according to symptoms.   The resin composition for an anionic matte electrodeposition paint further contains 0.5 to 20 parts by weight of a silicon alkoxide oligomer (D). Composition.   0.5 to 10 parts by weight of a copolymerizable vinyl monomer (a) having a fluoroalkyl group having 1 to 5 carbon atoms as a substituent, and a copolymerizable vinyl monomer (b) 3 having a carboxyl group as a substituent 15 to 15 parts by weight, 5 to 30 parts by weight of a copolymerizable vinyl monomer (c) having a hydroxyl group as a substituent, and 35 to 15 parts of copolymerizable vinyl monomers (e) other than the above (a) to (c) The water-soluble or water-dispersible vinyl copolymer (A) obtained by copolymerizing 91 parts by weight with respect to 40 to 80 parts by weight, amino resin (B) 20 to 60 parts by weight, In addition, 0.1 to 5 parts by weight of an alkoxyamine (C) which is an amino etherified product of a hindered amine as a light stabilizer, and 0.5 to 20 parts by weight of a silicon alkoxide oligomer (D) are added as a light stabilizer. Anionic type matte characterized by Chakutoryo resin composition.   The coating film formed by electrodeposition-coating the resin composition for anion type matte electrodeposition coating materials of any one of Claims 1-3 on a base material.