JP2006016598A - Electrodeposition coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pollution-free electrodeposition coating which is excellent in corrosion resistance, finishing property, etc. without containing harmful substances such as a lead compound or a chromium compound. <P>SOLUTION: The electrodeposition coating contains at least one silica-modified phosphorus compound chosen from the group consisting of formula (1): (xMHPO<SB>4</SB>3H<SB>2</SB>O)-(ySiO<SB>2</SB>)-(mCaSiO<SB>3</SB>)-(nCaCO<SB>3</SB>) and formula (2)(Ca<SB>3</SB>(PO<SB>4</SB>)<SB>2</SB>3H<SB>2</SB>O)-(ySiO<SB>2</SB>)-(mCaSiO<SB>3</SB>)-(nCaCO<SB>3</SB>) (wherein M is Mg or Ca; x, y and m are each an integer of 1-3; and n is an integer of 0-3) as a rust preventive agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a pollution-free electrodeposition coating material that forms a coating film that does not contain a lead compound or a chromium compound and has excellent anticorrosion properties, coating finish, and coating stability.

  Electrodeposition paints are used in a wide range of application fields including automobile bodies and automobile parts, and those having various characteristics have been developed.

  For example, in addition to baking-type electrodeposition paints such as automobile body coatings, coatings that have a large heat capacity and do not sufficiently transfer the heat of the drying furnace, or that cannot be heated because they contain plastic or rubber. For objects (for example, industrial machines such as tractors), a room temperature curing type electrodeposition paint is used.

  Conventionally, lead compounds and chromium compounds have been blended into electrodeposition paints for the purpose of improving the anticorrosion properties of the coating film, but in recent years, lead compounds and chromium compounds have been used in electrodeposition paints for environmental protection. It is regulated.

  Patent Document 1 discloses that aluminum dihydrogen phosphate is used as a non-toxic or low-toxic rust preventive agent in place of a lead compound or a chromium compound. Although this compound has few problems from the viewpoint of toxicity, it has insufficient corrosion resistance, so it must be added in a large amount to the electrodeposition paint. There is a problem that is damaged.

In addition, as a room temperature curing type electrodeposition paint that does not use harmful metals, Patent Document 2 discloses rust prevention for zinc phosphate, zinc calcium phosphite, zinc strontium phosphite, calcium molybdate, aluminum phosphomolybdate, etc. An electrodeposition paint formulated as an agent is disclosed. However, these compounds are relatively inexpensive but have insufficient anticorrosion properties, and if they are contained in a large amount in an electrodeposition paint to ensure the anticorrosion properties of the paint film, the finish properties and paint stability of the paint film are poor. There is a problem of being damaged.
JP 7-331129 A JP 2003-277679 A

  The object of the present invention is a pollution-free and anti-corrosion agent containing an anticorrosion agent, excellent in anticorrosion, paint finish, paint stability, etc. It is to provide a type of electrodeposition paint.

  As a result of intensive studies to solve the above-mentioned object, the present inventors have found that certain silica-modified phosphate compounds of this type are not toxic and have a very strong anticorrosive property. It has been found that it is extremely useful as a rust inhibitor for electrodeposition coatings, and has led to the completion of the present invention.

Thus, the present invention provides the following formulas (1) and (2)

(xMHPO ₄ 3H ₂ O) · (ySiO ₂ ) · (mCaSiO ₃ ) · (nCaCO ₃ ) (1)

(Ca ₃ (PO ₄ ) ₂ 3H ₂ O) · (ySiO ₂ ) · (mCaSiO ₃ ) · (nCaCO ₃ )
(2)
Where
M is Mg or Ca, x, y and m are each an integer of 1 to 3, and n is an integer of 0 to 3,
An electrodeposition coating material comprising at least one silica-modified phosphoric acid compound selected from the group consisting of rust preventive agents is provided.

  The electrodeposition paint of the present invention does not contain lead compounds or chromium compounds, is non-toxic, does not cause environmental pollution, and gives a coated article excellent in corrosion resistance and finish of the coating film.

  In the compounds of the formulas (1) and (2), since the amount of ions eluted into the paint or coating film is moderately suppressed, the electric current of the present invention containing the compound of the formula (1) or (2) is used. Even if the paint is subjected to mechanical share or long-term agitation, the paint stability and the finish of the paint film are not impaired, and the paint film formed has excellent anti-corrosion properties. It exhibits a wide range of anticorrosive properties.

  Hereinafter, the electrodeposition paint of the present invention will be described in more detail.

  Substances that are blended into paints as rust inhibitors generally suppress metal corrosion by eluting ions necessary for rust prevention to form a protective film on the metal surface or exhibiting a pH buffering action on the metal surface. Although the effect is exhibited, those having a small amount of ion elution necessary for rust prevention have low anticorrosion properties of the coating film, and on the contrary, those having a large amount of ion elution have a poor coating stability.

  The silica-modified phosphoric acid compounds of the above formulas (1) and (2) blended in the electrodeposition paint according to the present invention are non-toxic and elute ions necessary for the corrosion protection of metals over a long period of time. It has outstanding features such as little change in quantity over time, and also has excellent dispersibility in electrodeposition paints, making it ideal as a pollution-free rust inhibitor for blending into electrodeposition paints. It is.

The compound of said Formula (1) can be manufactured as follows, for example.
(A) An appropriate amount of calcium carbonate or magnesium oxide is charged into a reaction kettle, water is added, and the mixture is heated to about 50 to about 80 ° C. and stirred for about 1 to about 3 hours to prepare “Dispersion A”.
(B) Phosphoric acid is put into another container, and water is added to dilute to 1 to 30% to prepare an aqueous phosphoric acid solution. Next, the above phosphoric acid aqueous solution is uniformly dropped over about 10 to about 60 minutes while stirring in a state where the temperature is maintained at about 50 to about 80 ° C. to the reaction vessel containing the dispersion A. Thereafter, the reaction is carried out at about 60 ° C. for about 30 minutes to about 3 hours.
(C) An appropriate amount of calcium carbonate is taken into a container equipped with another stirring blade, water is added and stirred, and nitric acid and water are further added to prepare “dispersion B”.
(D) To the reaction kettle after the reaction described in (b) above, while maintaining the temperature at about 50 to about 80 ° C., the dispersion B is added dropwise over about 30 to about 120 minutes, and the mixture is sufficiently stirred. “Dispersion C” is prepared.
(E) An appropriate amount of sodium silicate is taken in a container equipped with another stirring blade, heated to about 50 to about 80 ° C. while adding water and stirring, and then stirred for about 1 to about 3 hours. D "is prepared.
(F) In the reaction kettle to which the dispersion C described in (d) above was added, while maintaining the temperature at about 50 to about 80 ° C., the dispersion D was stirred for about 30 to about 120 minutes. Add dropwise, then stir well.
(G) The product is removed from the reaction kettle, washed thoroughly with water and filtered, and the resulting cake is dried at about 100 to about 120 ° C. for about 10 to about 120 minutes and then ground.

Thus, the compound of formula (1) can be obtained in high yield. Specific examples of the compound of formula (1) include, for example,
_{2MgHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{3MgHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
MgHPO ₄ · 3H ₂ O · 2SiO ₂ · CaSiO ₃ · 2CaCO _{3
2MgHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · CaCO 3
_{2CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{3CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{2CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
Etc.

  The compound of the formula (2) is, for example, a compound of the formula (1) using calcium carbonate in the step (a) in the production of the compound of the formula (1) and the amount of phosphoric acid added in the step (b). The compound can be produced in the same manner as in the production of the compound of the formula (1) except that it is changed as compared with the case of.

Specific examples of the compound of formula (2) include, for example,
_{Ca 3 (PO 4) 2 ·} 3H 2 O · 2SiO 2 · CaSiO 3 · 2CaCO 3
_{Ca 3 (PO 4) 2 ·} 3H 2 O · 2SiO 2 · CaSiO 3 · 3CaCO 3
Ca ₃ (PO ₄ ) ₂ · 3H ₂ O · 2SiO ₂ · 2CaSiO ₃ · 2CaCO ₃
Ca ₃ (PO ₄ ) ₂ · 3H ₂ O · 3SiO ₂ · CaSiO ₃ · 2CaCO ₃
Etc.

Suitable as the compounds of formulas (1) and (2)
_{3CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{2CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{Ca 3 (PO 4) 2 ·} 3H 2 O · 2SiO 2 · CaSiO 3 · 2CaCO 3
Etc.

  The content of these silica-modified phosphate compounds in the electrodeposition paint can be changed according to the type of electrodeposition paint to be blended, etc., but usually the resin components (base resin and curing agent) in the paint It can be in the range of 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight per 100 parts by weight of the total solid content.

There are no particular restrictions on the electrodeposition paint in which the compound of the above formula (1) and / or (2) can be blended according to the present invention, and any of the cationic or anionic electrodeposition paints can be dried at room temperature. It is applicable to any type or thermosetting type electrodeposition paint, and specifically, for example, room temperature drying type electrodeposition paint, thermosetting anion electrodeposition paint, thermosetting type cationic electrodeposition paint, etc. Is mentioned. Hereinafter, these electrodeposition paints will be further described.

Room temperature dry electrodeposition paint:
Examples of the room temperature drying type electrodeposition coating include those capable of curing the coating film by leaving it at room temperature (50 ° C. or lower) for 24 hours to 10 days, preferably 3 to 7 days. Those containing a fatty acid-modified acrylic resin are preferred.

  Examples of the fatty acid-modified acrylic resin used as the resin component include fatty acid-modified acrylic monomers (a), carboxyl group-containing radical polymerizable unsaturated monomers (b), and other radical polymerizable unsaturated monomers. The copolymer of (c) is mentioned.

The fatty acid-modified acrylic monomer (a) can be obtained, for example, by reacting an unsaturated fatty acid with a hydroxyl group-containing acrylic ester.

  Examples of the unsaturated fatty acid include aliphatic monocarboxylic acids containing at least two double bonds in a molecule that are not conjugated to each other, and dry oil fatty acids and semi-dry oil fatty acids are particularly preferable. Here, the dry oil fatty acid generally means an unsaturated fatty acid having an iodine value of 130 or more, and the semi-dry oil fatty acid means an unsaturated fatty acid having an iodine value of 100 to 130. Examples of such unsaturated fatty acids include safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, hemp oil fatty acid, grape kernel oil fatty acid, corn oil fatty acid, tall oil Fatty acids, sunflower oil fatty acids, cottonseed oil fatty acids, walnut oil fatty acids and the like can be mentioned, and these fatty acids can be used alone or in combination of two or more.

  The amount of these unsaturated fatty acids to be used can be appropriately changed depending on the performance required for the coating film, but generally 5 to 5% of the total amount of monomers constituting the fatty acid-modified acrylic resin. It is preferably in the range of 65% by weight, particularly 10 to 60% by weight. Further, if necessary, an unsaturated fatty acid having a conjugated double bond such as tung oil fatty acid, eutica oil fatty acid, dehydrated castor oil fatty acid, and high diene fatty acid is used in combination at a ratio of 30% by weight or less, preferably 20% by weight or less. May be.

  As an acrylic acid ester or methacrylic acid ester containing a hydroxyl group that can be reacted with an unsaturated fatty acid (hereinafter sometimes referred to as a hydroxyl group-containing acrylic ester), one hydroxyl group in the ester residue portion of acrylic acid or methacrylic acid And 2 to 24, preferably 2 to 8 carbon atoms in the ester residue portion. Examples of such a hydroxyl group-containing acrylic ester include hydroxyalkyl acrylates or hydroxy methacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

  The fatty acid-modified acrylic monomer (a) can be produced by reacting an unsaturated fatty acid with a hydroxyl group-containing acrylic ester in the presence of an esterification catalyst in an inert solvent. The reaction temperature is usually in the range of about 100 to about 180 ° C., preferably about 120 to about 160 ° C., and the reaction time can be about 0.5 to about 10 hours, preferably about 1 to about 6 hours. .

  The hydroxyl group-containing acrylic ester is usually used in a proportion of 0.5 to 1.9 mol, preferably 1.0 to 1.5 mol, per mol of unsaturated fatty acid.

Examples of the esterification catalyst used in the above reaction include sulfuric acid, aluminum sulfate,
Examples include potassium hydrogen sulfate, p-toluenesulfonic acid, hydrochloric acid, methyl sulfate, phosphoric acid and the like, and these are in the range of 0.05 to 2.0% by weight based on the total amount of unsaturated fatty acid and hydroxyl group-containing acrylic ester. It is preferable to use within.

  The inert solvent is preferably a water-immiscible organic solvent that can be refluxed at a temperature of about 180 ° C. or lower. For example, aromatic hydrocarbons such as benzene, toluene, xylene; heptane, hexane, octane, etc. Aliphatic hydrocarbons are mentioned. In addition, a polymerization inhibitor such as hydroquinone, methoxyphenol, tert-butylcatechol, benzoquinone or the like is added to the reaction system as necessary to suppress polymerization of the hydroxyl group-containing acrylic ester and / or the fatty acid-modified acrylic ester to be produced. be able to.

  In the above reaction, esterification occurs between the hydroxyl group of the hydroxyl group-containing acrylic ester and the carboxyl group of the unsaturated fatty acid, and an acrylic ester modified with the unsaturated fatty acid is obtained.

  Further, as another method, a fatty acid-modified acrylic monomer (a) modified with an unsaturated fatty acid can also be obtained by reacting a glycidyl group-containing acrylic ester or methacrylic ester such as glycidyl methacrylate with an unsaturated fatty acid by an acid epoxy reaction. ) Can be obtained. In this case, it is preferable to use a polymerization inhibitor as necessary as described above.

  Examples of the carboxyl group-containing radical polymerizable unsaturated monomer (b) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and the like. Two or more types can be used in combination.

  As other radical polymerizable unsaturated monomers (c), those exemplified below can be used.

Esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, C ₁ -C ₁₈ alkyl esters of methacrylic acid octyl, acrylic acid or methacrylic acid lauryl methacrylate; methoxybutyl acrylate, methoxybutyl methacrylate, acrylic Acrylic acid or methacrylic acid alkoxyalkyl ester such as methoxyethyl acid, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate; Acid hydroxyethyl, hydroxyethyl methacrylate, hydroxypropyl acrylate, C ₂ -C ₈ hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxypropyl methacrylate; allyl oxyethyl acrylate, acrylic acid or methacrylic acid such as allyloxy methacrylate Such as alkenyloxyalkyl esters.

  Vinyl aromatic compounds: For example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, vinylpyridine and the like.

  Polyolefin compounds: For example, butadiene, isoprene, chloroprene and the like.

  Amides of acrylic acid or methacrylic acid: for example, acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide and the like.

  In addition, acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, etc.

  As another radical polymerizable unsaturated monomer (c), a vinyl monomer (d) having a nitrogen-containing heterocyclic ring can also be used. The vinyl monomer (d) includes a monomer in which a monocyclic or polycyclic heterocyclic ring containing 1 to 3, preferably 1 or 2 nitrogen atoms is bonded to a vinyl group. A mer can be exemplified.

  Vinylpyrrolidones: For example, 1-vinyl-2-pyrrolidone, 1-vinyl-3-pyrrolidone and the like.

  Vinylpyridines: For example, 2-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine and the like.

  Vinyl imidazoles: For example, 1-vinyl imidazole, 1-vinyl-2-methylimidazole and the like.

  Vinylcarbazoles: For example, N-vinylcarbazole and the like.

  Vinylquinolines: For example, 2-vinylquinoline.

  Vinyl piperidines: For example, 3-vinyl piperidine, N-methyl-3-vinyl piperidine and the like.

  Among the above vinyl monomers, those in which the ring nitrogen atom is tertiaryized are particularly suitable. These monomers can be used alone or in combination of two or more.

  The copolymerization of the fatty acid-modified acrylic monomer (a), the carboxyl group-containing radical polymerizable unsaturated monomer (b) and the other radical polymerizable unsaturated monomer (c) is, for example, a solution polymerization method, An emulsion polymerization method, a suspension polymerization method, or the like can be used.

  The proportion of each monomer used in the copolymerization is usually based on the total weight of the monomers (a), (b) and (c), and the fatty acid-modified acrylic monomer (a) is 7 to 94% by weight, preferably 10 to 80% by weight, the carboxyl group-containing radical polymerizable unsaturated monomer (b) is 3 to 20% by weight, preferably 5 to 15% by weight, and other radical polymerizable monomers. The saturated monomer (c) can be in the range of 1 to 88% by weight, preferably 18 to 78% by weight.

  The proportion of the vinyl monomer (d) having a nitrogen-containing heterocyclic ring is usually 1 to 80% by weight, preferably based on the total weight of the monomers (a), (b) and (c), preferably It can be in the range of 25 to 65% by weight.

  The copolymerization reaction of these monomers is preferably carried out in a solvent in the presence of a polymerization catalyst at a temperature of about 30 to about 180 ° C., preferably about 40 to about 170 ° C. for about 1 to 20 hours. Can be performed for about 6 to about 10 hours.

  The resulting fatty acid-modified acrylic resin can generally have an acid value in the range of 20 to 150 mg KOH / g, preferably 25 to 120 mg KOH / g. The fatty acid-modified acrylic resin can generally have a number average molecular weight in the range of 500 to 100,000, preferably 2,000 to 20,000.

  Furthermore, in the case of an electrodeposition paint that requires high anticorrosive properties as a coating film performance, an epoxy resin having an epoxy equivalent in the range of 180 to 2,500 is further reacted with the fatty acid-modified acrylic resin as described above as a resin component. It is also possible to use an epoxy resin-modified / fatty acid-modified acrylic resin.

  The epoxy resin can be obtained, for example, by reacting a polyphenol compound with an epihalohydrin such as epichlorohydrin. Examples of the polyphenol compound that can be used for forming the epoxy resin include bis (4-hydroxyphenyl) -2,2-propane (bisphenol A), 4,4-dihydroxybenzophenone, and bis (4-hydroxyphenyl). ) Methane (bisphenol F), bis (4-hydroxyphenyl) -1,1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-tert-butyl-phenyl) -2, Examples include 2-propane, bis (2-hydroxynaphthyl) methane, tetra (4-hydroxyphenyl) -1,1,2,2-ethane, 4,4-dihydroxydiphenyl sulfone, phenol novolac, and cresol novolac. .

  Moreover, as an epoxy resin obtained by reaction of a polyphenol compound and epichlorohydrin, the following formula induced | guided | derived from bisphenol A is mentioned especially,

Those represented by are preferred.

  Examples of such commercially available epoxy resins include those sold by Japan Epoxy Resins Co., Ltd. under the trade names of Epicoat 828EL, 1002, 1004, and 1007.

  When the epoxy resin modified / fatty acid modified acrylic resin is produced, the proportion of the fatty acid modified acrylic resin and the epoxy resin having an epoxy equivalent of 180 to 2,500 is usually 100 parts by weight of the solid content of the fatty acid modified acrylic resin. The epoxy resin is preferably in the range of 0.01 to 50% by weight, particularly 0.1 to 35% by weight.

  The reaction can be performed, for example, by mixing a fatty acid-modified acrylic resin and an epoxy resin in an organic solvent at a temperature of room temperature to about 200 ° C. for about 0.2 to about 30 hours. Further, as the catalyst, a tertiary amine, a quaternary ammonium salt or the like that is usually used in an acid-epoxy reaction can be used. The progress of the reaction can be grasped by following the decrease in the acid value of the resin by titration.

  The compound of the formula (1) and / or (2) is introduced into the room temperature dry electrodeposition paint in accordance with the usual method for preparing an electrodeposition paint. Alternatively, epoxy resin-modified / fatty acid-modified acrylic resin or the like is used, and these dispersing resins include compounds of formula (1) and / or (2), and pigments, for example, colored pigments such as titanium oxide, carbon black, and bengara; clay Extender pigments such as mica, barita, calcium carbonate, silica; antirust pigments such as aluminum phosphomolybdate and aluminum tripolyphosphate; curing catalysts such as zinc octylate and zinc formate; bismuth, bismuth hydroxide, basic bismuth carbonate, Bismuth compounds such as bismuth nitrate and bismuth silicate; surface blending agents, surfactants, etc. A pigment-dispersed paste is prepared by dispersion treatment using a pigment dispersion, and mixed with an emulsion for electrodeposition paint containing the above-described fatty acid-modified alkyl resin or epoxy resin-modified / fatty acid-modified acrylic resin as a separately prepared resin component Can be done.

  The above-mentioned emulsion for electrodeposition coatings is, for example, an organic solvent, an anti-repellent agent, a surface conditioner, a film-forming agent, etc. added to a fatty acid-modified acrylic resin or an epoxy resin-modified acrylic resin as necessary. Or 0.1 to 1.1 equivalents, preferably 0.5 to 1.1 equivalents of neutralizing agent, for example, ammonia, diethylamine, ethylethanolamine, diethanolamine, monoethanolamine, based on the carboxyl group of the epoxy resin-modified acrylic resin Organic amines such as monopropanolamine, isopropanolamine, ethylaminoethylamine, hydroxyethylamine, triethylamine, tributylamine, diethylenetriamine; alkali metal hydroxides such as caustic soda and caustic potash; add deionized water and disperse It can be prepared by dispersing using. The above pigment dispersion paste is mixed with this emulsion, deionized water is added to adjust the pH to 7.0 to 10.0, and the solid content of the paint is diluted to 5 to 30% by weight, preferably 10 to 20% by weight. By this, the room temperature drying type electrodeposition coating material which contains the compound of Formula (1) and / or Formula (2) as a rust preventive agent can be manufactured.

  The content of the compound of formula (1) and / or (2) in the room temperature dry electrodeposition paint can vary over a wide range depending on the required coating film performance, etc. The amount of 0.1 to 50 parts by weight, particularly 1 to 20 parts by weight, and more particularly 2 to 8 parts by weight per 100 parts by weight of the solid content of the resin component therein is suitable.

  Electrodeposition coating is performed by using a room temperature drying type electrodeposition paint prepared as described above as an electrodeposition paint bath, and adjusting the bath temperature to 15 to 40 ° C., preferably 20 to 35 ° C., and a load voltage of 20 to 400 V. Preferably, it can be performed by energizing at 30 to 300 V for 1 to 10 minutes.

  The film thickness of the electrodeposition coating film is not particularly limited, but generally it is preferably within the range of 10 to 40 μm based on the cured coating film. The object to be coated is lifted from the electrodeposition bath, and the coated surface is washed with water as necessary. In some cases, forced drying is performed at about 100 ° C. or less for about 5 to about 40 minutes in order to improve the curability of the coating film. Then, the coating film can be cured by leaving it at about 50 ° C. or lower for 24 hours to about 10 days, preferably 3 to 7 days.

  The object to be coated is not particularly limited in size and shape as long as the surface is made of a conductive metal, and any material may be used. Iron, aluminum, steel, and those whose surfaces have been subjected to chemical conversion treatment are included. Specifically, articles that have a large heat capacity and cannot sufficiently heat the coating film, articles that incorporate plastic or rubber, construction machines, etc. Is mentioned.

Thermosetting anion electrodeposition paint :
The thermosetting anionic electrodeposition coating composition in which the compound of formula (1) and / or formula (2) can be blended according to the present invention includes an anionic resin having an anion-forming functional group such as a carboxyl group and a curing agent. Is included as a resin component.

  As said anionic resin, the thing known per se mix | blended with a normal anion electrodeposition coating material can be used, Specifically, for example, an acrylic resin, a polyester resin which has a carboxyl group and a hydroxyl group, Resins such as polyurethane resins can be used.

  The anionic resin has an organic amine such as ammonia, diethylamine, ethylethanolamine, diethanolamine, monoethanolamine, monopropanolamine, isopropanolamine, ethylaminoethylamine, hydroxyethylamine, diethylenetriamine; Water neutralization or water dispersion can be achieved by neutralization with a neutralizing agent such as an alkali metal hydroxide.

  Examples of the acrylic resin having a carboxyl group and a hydroxyl group include radical polymerization of a carboxyl group-containing unsaturated monomer, a hydroxyl group-containing acrylic monomer, and, if necessary, other polymerizable monomers. A copolymer is mentioned.

  Specific examples of the monomer include the following.

  Carboxyl group-containing unsaturated monomer: a compound having one or more carboxyl groups and polymerizable unsaturated bonds in each molecule, for example, (meth) acrylic acid, maleic acid, caprolactone-modified carboxyl group-containing (meth) Examples thereof include acrylic monomers (manufactured by Daicel Chemical Industries, trade names, Plaxel FM1A, Plaxel FM4A, Plaxel FM10A) and the like.

  Hydroxyl group-containing acrylic monomer: a compound having at least one hydroxyl group and one polymerizable unsaturated bond in the molecule, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) Acrylate, (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate; these hydroxyl group-containing acrylic monomers, β-propiolactone, dimethylpropiolactone, butyrolactone, γ- Commercially available products such as valerolactone, γ-caprolactone, γ-caprolactone, γ-laurolactone, ε-caprolactone, δ-caprolactone, and other lactone compounds such as Plaxel FM1, Plaxel FM2, Plaxel FM3, Plaxel A1, PLACCEL FA2, PLACCEL FA3 (or both manufactured by Daicel Chemical Industries, trade name, caprolactone-modified (meth) acrylic acid hydroxy esters) and the like.

Other polymerizable monomers: polymerizable monomers other than the carboxyl group-containing unsaturated monomers and hydroxyl group-containing acrylic monomers described above, wherein at least a polymerizable unsaturated bond is present in one molecule 1 compound, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate C ₁ -C ₁₈ alkyl or cycloalkyl esters of (meth) acrylic acid such as lauryl (meth) acrylate and cyclohexyl (meth) acrylate; vinyl aromatic compounds such as styrene and vinyltoluene; (meth) acrylic acid (Meth) acrylics such as amide, N-butoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide Amides and derivatives thereof; (meth) acrylonitrile compounds; γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxy Examples include alkoxysilyl group-containing polymerizable monomers such as silane.

  The radical copolymerization of these monomers can be performed by, for example, a solution polymerization method known per se. The resulting acrylic resin generally has a number average molecular weight in the range of 10,000 or less, preferably in the range of 4,000 to 8,000, 20 to 200 mgKOH / g, preferably in the range of 25 to 150 mgKOH / g, And an acid number in the range of 20 to 150 mg KOH / g, preferably 25 to 120 mg KOH / g.

  Examples of the curing agent used in combination with the anionic resin include melamine resin, block polyisocyanate compound, polyoxazoline compound, etc. Among them, melamine resin is preferable.

As the melamine resin, an etherified melamine resin obtained by modifying part or all of the methylol group of a methylolated melamine resin obtained by reacting melamine with formaldehyde or the like with at least one C ₁ -C ₁₀ monoalcohol is used. It can be preferably used. As such a melamine resin, those containing from 1 to 5 (about 2 to 5) nuclei of 50% by weight or more are preferable. The melamine resin may contain an imino group, a methylol group, or other functional groups.

  The block polyisocyanate compound is obtained by blocking the isocyanate group of the polyisocyanate compound with a blocking agent. Specifically, the block polyisocyanate compound exemplified in the cationic electrodeposition coating described later is preferably used. be able to. When the blocked polyisocyanate compound is heated, the blocking agent is dissociated to regenerate free isocyanate groups, which cross-link with hydroxyl groups in the anionic resin.

The anionic resin and curing agent described above are generally based on the total solid content of both,
Anionic resins can be used in the range of 50 to 95% by weight, in particular 65 to 85% by weight, and curing agents in the range of 5 to 50% by weight, in particular 15 to 35% by weight.

Thermosetting cationic electrodeposition paint:
The thermosetting cationic electrodeposition coating composition in which the compound of the formula (1) and / or (2) can be blended according to the present invention comprises a cationic resin as a base resin and a blocked polyisocyanate compound as a curing agent. Things are included. Examples of the cationic resin used as the base resin include a resin having a cationizable group such as an amino group, an ammonium base, a sulfonium base, and a phosphonium base in the molecule. The base resin may be any type of resin that is usually used, for example, epoxy, acrylic, polybutadiene, alkyd, polyester, etc., and in particular, an amine is added to a polyepoxide compound. An amine-added epoxy resin can be preferably used.

  Examples of the amine-added epoxy resin include (1) an adduct of a polyepoxide compound and primary mono- and polyamine, secondary mono- and polyamine, or 1,2 mixed polyamine (see, for example, US Pat. No. 3,984,299). (2) Adducts of polyepoxide compounds with secondary mono- and polyamines having ketiminated primary amino groups (see, for example, U.S. Pat. No. 4,017,438); (3) ketiminated with polyepoxide compounds In addition, a reaction product obtained by etherification with a hydroxy compound having a primary amino group (see, for example, JP-A-59-43013) can be exemplified.

  The polyepoxide compound used in the production of the amine-added epoxy resin is a compound having one or more, preferably two or more epoxy groups in one molecule, and is generally at least 200, preferably 400 to 4,000, Suitable are those having a number average molecular weight (Note 1) preferably in the range of 800 to 2,500 and an epoxy equivalent weight of at least 160, preferably 180 to 2,500, more preferably 400 to 1,500. In particular, those obtained by a reaction between a polyphenol compound and epichlorohydrin are preferred.

  (Note 1) Number average molecular weight: Measured according to JIS K0124-83, using TSK GEL4000HXL + G3000HXL + G2500HXL + G2000HXL (manufactured by Tosoh Corporation) as a separation column at a flow rate of 1.0 ml / min at 40 ° C., and using GPC tetrahydrofuran as an eluent. , Calculated from a chromatogram obtained with an RI refractometer and a calibration curve of polystyrene.

  Examples of the polyphenol compound that can be used for forming the epoxide resin include bis (4-hydroxyphenyl) -2,2-propane, 4,4′-dihydroxybenzophenone, and bis (4-hydroxyphenyl) -1,1. -Ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, tetra (4-hydroxy) Phenyl) -1,1,2,2-ethane, 4,4′-dihydroxydiphenylsulfone, phenol novolak, cresol novolak and the like.

  The epoxide resin may be partly reacted with polyol, polyether polyol, polyester polyol, polyamidoamine, polycarboxylic acid, polyisocyanate compound, etc., and also caprolactone such as ε-caprolactone, acrylic monomer Or the like obtained by graft polymerization.

  Examples of the polyphenol compound that can be used for forming the epoxy resin include bis (4-hydroxyphenyl) -2,2-propane, 4,4′-dihydroxybenzophenone, and bis (4-hydroxyphenyl) -1,1. -Ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-2 or 3-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, tetra (4-Hydroxyphenyl) -1,1,2,2-ethane, 4,4′-dihydroxydiphenylsulfone, phenol novolak, cresol novolak and the like can be mentioned.

  Examples of primary mono- and polyamines, secondary mono- and polyamines, and primary and secondary mixed polyamines used in the production of the amine-added epoxy resin of (1) above include monomethylamine, dimethylamine, and monoamine. Mono- or di-alkylamines such as ethylamine, diethylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine; alkanolamines such as monoethanolamine, diethanolamine, mono (2-hydroxypropyl) amine, monomethylaminoethanol; ethylenediamine And alkylene polyamines such as propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

  Examples of the secondary mono- and polyamines having a ketimized primary amino group used in the production of the amine-added epoxy resin (2) include, for example, the production of the amine-added epoxy resin (1). Among primary mono- and polyamines, secondary mono- and polyamines, and primary and secondary mixed polyamines used, compounds having a primary amino group (for example, monomethylamine, monoethanolamine, ethylenediamine, diethylenetriamine) And the like, and ketimine compounds obtained by reacting a ketone compound.

  Examples of the hydroxy compound having a ketiminated primary amino group used in the production of the amine-added epoxy resin (3) include, for example, a first compound used in the production of the amine-added epoxy resin (1). Of primary mono- and polyamines, secondary mono- and polyamines or primary and secondary mixed polyamines, compounds having a primary amino group and a hydroxyl group (for example, monoethanolamine, mono (2-hydroxypropyl) amine And the like, and a hydroxyl group-containing ketimine compound obtained by reacting a ketone compound.

  The amine-added epoxy resin further includes a polyol compound obtained by reacting a polyol compound obtained by adding caprolactone to a compound having two or more active hydrogen-containing groups in one molecule and an amino group-containing compound. Modified amine-added epoxy resins are also included and can be suitably used.

  The compound having two or more active hydrogen-containing groups in one molecule generally has a molecular weight in the range of 62 to 5,000, and contains 2 to 30 active hydrogen-containing groups per molecule. Examples of the active hydrogen-containing group include a hydroxyl group, a primary amino group, and a secondary amino group.

  Specific examples of the compound having two or more active hydrogen-containing groups in one molecule include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol. Low molecular weight polyols such as dipropylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol; linear or branched polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A polyethylene glycol ether; Organic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid or the like Polyester polyol obtained by polycondensation reaction of water and an organic diol such as the above-mentioned low molecular weight polyol under an excess of organic diol; butylene diamine, hexamethylene diamine, tetraethylene pentamine, pentaethylene hexamine, monoethanol amine, Diethanolamine, triethanolamine, mono (2-hydroxypropyl) amine, di (2-hydroxypropyl) amine, 1,3-bisaminomethylcyclohexanone, isophoronediamine, xylylenediamine, metaxylylenediamine, diaminodiphenylmethane, phenylenediamine , Ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, and other amine compounds; piperazine and polyamides derived from these amine compounds Polyamidoamines, amine adduct of an epoxy compound, ketimine, and the like aldimine.

  Examples of caprolactone that can be subjected to addition reaction with a compound having two or more active hydrogen-containing groups in one molecule include γ-caprolactone, ε-caprolactone, δ-caprolactone, and ε-caprolactone is particularly preferable. is there.

  The addition reaction of the compound having two or more active hydrogen-containing groups in one molecule and caprolactone can be carried out by a method known per se, and a polyol compound is obtained by this addition reaction.

  The amino group-containing compound used in the production of the polyol-modified amine-added epoxy resin is a cationic component that introduces an amino group into the resin to cationize the resin, and reacts with the epoxy group. Those having at least one hydrogen can be used.

  Specific examples thereof include, for example, primary mono- and polyamines, secondary mono- and polyamines or primary and secondary mixed polyamines used in the production of the amine-added epoxy resin of (1); ) Secondary mono- and polyamines having primary amino groups ketiminized for use in the preparation of amine-added epoxy resins; and ketiminized used in the preparation of amine-added epoxy resins in (3) above. The thing etc. which can be used as a hydroxy compound which has a primary amino group can be mentioned.

  When the cationic resin has an amino group as a cationizable group, it should be neutralized with an organic carboxylic acid such as formic acid, acetic acid, propionic acid or lactic acid; an acid such as inorganic acid such as hydrochloric acid or sulfuric acid. In the case of having an onium base such as an ammonium base, a sulfonium base, or a phosphonium base as a cationizable group, the water-soluble or water-dispersed as it is without neutralization. Can be

  The block polyisocyanate compound used as a curing agent in combination with the cationic resin described above includes an addition reaction product in an approximately stoichiometric amount of the polyisocyanate compound and the blocking agent. Examples of the polyisocyanate compound used here include aromatics and fats such as tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, and isophorone diisocyanate. Terminal isocyanates obtained by reacting aliphatic or alicyclic polyisocyanate compounds, and low-molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, trimethylolpropane, hexanetriol, castor oil and the like in excess of these isocyanate compounds Examples thereof include compounds.

  On the other hand, the blocking agent is added and blocked to the isocyanate group of the polyisocyanate compound. The blocked polyisocyanate compound produced by the addition is stable at room temperature, but the baking temperature of the coating film (usually about 100 to When heated to about 200 ° C., it is desirable that the blocking agent dissociates and free isocyanate groups can be regenerated. Examples of the blocking agent that satisfies such requirements include lactam compounds such as ε-caprolactam and γ-butyrolactam; oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenols such as phenol, para-t-butylphenol, and cresol. Compounds; aliphatic alcohols such as n-butanol and 2-ethylhexanol; aromatic alkyl alcohols such as phenyl carbinol and methyl phenyl carbinol; ether alcohol compounds such as ethylene glycol monobutyl ether.

  Further, a blocked polyisocyanate using a diol having a molecular weight of 76 to 150 or a carboxyl group-containing diol having a molecular weight of 106 to 500 as a blocking agent can also be used as a curing agent.

  The diol includes two hydroxyl groups having different reactivities, for example, a combination of a primary hydroxyl group and a secondary hydroxyl group, a primary hydroxyl group and a tertiary hydroxyl group, and a combination of a secondary hydroxyl group and a tertiary hydroxyl group. For example, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,2-butanediol, 3-methyl-1,2, and the like. -Butanediol, 1,2-pentanediol, 1,4-pentanediol, 3-methyl-4,3-pentanediol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1, Examples thereof include diols having two hydroxyl groups with different reactivity, such as 3-pentanediol, 1,5-hexanediol, and 1,4-hexanediol.

  Of these, propylene glycol is preferred from the viewpoints of the reactivity of the blocked polyisocyanate, the reduction of heat loss, the storage stability of the paint, and the like. These diols usually react with an isocyanate group from the more reactive hydroxyl group to block the isocyanate group.

  The carboxyl group-containing diol includes a carboxyl group-containing diol having a molecular weight of 106 to 500, and by having a carboxyl group in the molecule, low-temperature dissociation properties can be improved and curability at low temperatures can be improved. In particular, when an organic tin compound is used as the curing catalyst, the curability at low temperatures can be greatly improved.

  Examples of the carboxyl group-containing diol include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, dimethylolvaleric acid, glyceric acid and the like.

  The cationic resin and curing agent described above are generally in the range of 50 to 95% by weight, particularly 65 to 85% by weight of the cationic resin and 5 to 85% by weight of the curing agent, based on the total solid content of both. It can be used in the range of 50% by weight, in particular 15 to 35% by weight. In addition, the cationic electrodeposition coating composition can contain a cationic resin and a curing agent at a concentration in the range of 10 to 40% by weight, particularly 15 to 25% by weight as a total solid content.

  The introduction of the compound of the formula (1) and / or (2) into the thermosetting anion or cationic electrodeposition coating composition containing the resin component described above is carried out in accordance with the usual preparation method of the electrodeposition coating composition. For resins for use, compounds of formula (1) and / or (2) and pigments, for example, colored pigments such as titanium oxide, carbon black, bengara; extender pigments such as clay, mica, barita, calcium carbonate, silica; phosphorus Antirust pigments such as aluminum molybdate and aluminum tripolyphosphate; bismuth compounds such as bismuth, bismuth hydroxide, basic bismuth carbonate, bismuth nitrate and bismuth silicate; dioctyltin oxide, dibutyltin oxide, tin octoate, dibutyltin Curing catalysts such as dilaurate, dibutyltin dibenzoateoxy, zinc octylate, zinc formate; surface conditioner, field By appropriately blending an activator, etc., preparing a pigment dispersion paste by dispersing using ball mill dispersion or sand mill dispersion, and mixing with an emulsion for electrodeposition paint comprising the above-mentioned resin component separately prepared It can be carried out.

  Emulsion for electrodeposition coating is prepared by adding a curing agent to the above-mentioned anionic resin or cationic resin for thermosetting anion or cationic electrodeposition coating, and making it water-soluble or water-dispersed as described above. Can be prepared.

  Mixing the pigment dispersion paste prepared as described above and the emulsion for electrodeposition paints, and further adding deionized water to dilute the paint solids to 5-30% by weight, preferably 10-25% by weight. Can produce a thermosetting anionic or cationic electrodeposition coating composition containing the compound of formula (1) and / or (2).

  The content of the compound of formula (1) and / or formula (2) in the thermosetting anion electrodeposition paint or thermosetting cationic electrodeposition paint is usually about 100 parts by weight of the solid content of the resin component in the electrodeposition paint. 0.1 to 50 parts by weight, particularly 1 to 20 parts by weight, more particularly 2 to 8 parts by weight is preferred.

  In the electrodeposition coating, for example, the pH of the electrodeposition paint bath is usually set to 5.0 to 7.0 for the cationic electrodeposition paint and 7.0 to 10.0 for the anionic electrodeposition paint, and the bath temperature is set to 15. It can be carried out by adjusting the temperature to ˜40 ° C., preferably 20 ° C. to 35 ° C., and applying current for 1 to 10 minutes at a load voltage of 20 to 400 V, preferably 30 to 200 V.

  Although the film thickness of an electrodeposition coating film is not specifically limited, In general, it can be in the range of 10 to 40 μm, preferably 15 to 30 μm. Further, the baking curing temperature and time of the coating film are generally about 110 to about 220 ° C., preferably about 120 to about 170 ° C., and 5 to 120 minutes, preferably 10 to 50 minutes.

  Examples of the object to be coated include, for example, cold-rolled steel sheets such as automobile bodies and automobile parts, hot-dip galvanized steel sheets, electrogalvanized steel sheets, electrogalvanized steel double-layer plated steel sheets, and organic composite plated steel sheets; aluminum; A mixture etc. are mentioned.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited only to this. “Parts” and “%” are “parts by weight” and “% by weight” unless otherwise specified.

Production Example 1 Anticorrosive No. 1
(1) 60 parts of magnesium oxide was placed in a reaction kettle equipped with stirring blades, 1940 parts of water was added to 2000 parts, and the temperature was raised to 60 ° C. to prepare dispersion A.
(2) 178.7 parts of 75% phosphoric acid was placed in a flask equipped with a stirring blade, and 1021.3 parts of water was added to obtain 1200 parts of an aqueous phosphoric acid solution.
While stirring the reaction kettle containing the dispersion A, the temperature was kept at 60 ° C., and an aqueous phosphoric acid solution was added dropwise uniformly over 30 minutes, followed by reaction at 60 ° C. for 1 hour 30 minutes.
(3) Put 217.4 parts of calcium carbonate into a flask equipped with another stirring blade, add 282.6 parts of water, stir, add 152.6 parts of 67.5% nitric acid, and add water 347 4 parts was added to make 1000 parts, and dispersion B was obtained.
(4) Dispersion B was added dropwise to the reaction kettle after the reaction in step (2) while stirring at 60 ° C. over 1 hour, and further stirred for 1 hour to prepare dispersion C.
(5) 458 parts of sodium silicate was put into a flask equipped with another stirring blade, and 1542 parts of water was added to make 2000 parts, whereby a dispersion D was obtained.
(6) While maintaining the temperature at 60 ° C. in the reaction kettle after step (4), the dispersion D2000 part was added dropwise over 1 hour with stirring and further stirred for 1 hour.
(7) The product was taken out from the reaction kettle and washed well with water. The cake obtained after washing was dried at 120 ° C. and pulverized. 1 was obtained.

Antirust agent No. The composition of 1 is
_{2MgHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
Met.

Production Example 2 Anticorrosive No. 2
(1) 340 parts of calcium carbonate was added to a reaction kettle equipped with stirring blades, 4160 parts of water was added to make 4500 parts, and the temperature was raised to 60 ° C. to prepare dispersion A.
(2) 490.4 parts of 75% phosphoric acid was placed in a flask equipped with a stirring blade, and 1309.6 parts of water was added to obtain 1800 parts of an aqueous phosphoric acid solution.
While stirring the reaction kettle containing the dispersion A, the temperature was kept at 60 ° C., and an aqueous phosphoric acid solution was added dropwise uniformly over 30 minutes, followed by reaction at 60 ° C. for 1 hour 30 minutes.
(3) Put 560 parts of calcium carbonate in a flask equipped with another stirring blade, add 660 parts of water and stir, add 366 parts of 67.5% nitric acid, add 414 parts of water, and add 2000 parts. And dispersion B was obtained.
(4) Dispersion B was added dropwise to the reaction kettle after the reaction in step (2) while stirring at 60 ° C. over 1 hour, and further stirred for 1 hour to prepare dispersion C.
(5) Into a flask equipped with another stirring blade, 1080 parts of sodium silicate was added, and 7520 parts of water was added to make 8600 parts.
(6) To the reaction kettle after step (4), while maintaining the temperature at 60 ° C., 8600 parts of dispersion D was added dropwise over 1 hour with stirring, and further stirred for 1 hour.
(7) The product was taken out from the reaction kettle and washed well with water. The cake obtained after washing was dried at 120 ° C. and pulverized. 2 was obtained.

Antirust agent No. The composition of 2 is
_{2CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
Met.

Production Examples 3 to 6 3-No. 6
A rust inhibitor No. 1 was prepared in the same manner as in Production Example 2 except that the types of raw materials used in the steps (1) to (7) and the amounts used were changed as shown in Table 1. 3-No. 6 was obtained.

  Rust preventive agent No. obtained. 3-No. The composition of 6 was as follows.

Antirust agent No. _{3: 3CaHPO 4 · 3H 2 O} · 2SiO 2 · CaSiO 3 ·
2CaCO ₃
Antirust agent No. _{4: CaHPO 4 · 3H 2 O} · 2SiO 2 · CaSiO 3 · 2CaCO 3
Antirust agent No. _{5: 2CaHPO 4 · 3H 2 O} · 2SiO 2 · CaSiO 3 · CaCO 3
Antirust agent No. 6: Ca ₃ (PO ₄ ) ₂ 3H ₂ O 2SiO ₂ CaSiO ₃
2CaCO ₃

Production Example 7 Fatty Acid Modified Acrylic Resin
Linseed oil fatty acid 236 parts
119 parts glycidyl methacrylate
Hydroquinone 0.4 part
0.2 parts of tetraethylammonium bromide Each of the above components was placed in a reaction vessel and reacted at a temperature of 140 to 150 ° C. with stirring. The addition reaction of the epoxy group and the carboxyl group was followed while measuring the amount of the remaining carboxyl group, and the reaction was stopped after 4 hours to obtain a reaction product (1).

  Next, 54 parts of ethylene glycol monobutyl ether was placed in a reaction vessel and heated to 120 ° C. While maintaining the temperature at 120 ° C., the following monomer mixture was added dropwise over about 2 hours.

Reaction product (1) 30 parts
40 parts of styrene
15 parts of n-butyl methacrylate
2-ethylhexyl methacrylate 8 parts
Acrylic acid 7 parts
Azobisisobutyronitrile 3 parts
After completion of the dropwise addition, 1 part of azobisisobutyronitrile was added to the reaction vessel, and then the reaction was carried out for 3 hours while maintaining at 120 ° C. to obtain a fatty acid-modified acrylic resin having an acid value of 55 mg KOH / g and a solid content of 65%.

Production Example 8 Epoxy Resin Modified / Fatty Acid Modified Acrylic Resin 50 parts of Epicoat 1001 (trade name, epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd.) were added to 1500 parts of the fatty acid modified acrylic resin obtained in the same manner as in Production Example 7 above. The reaction was continued until the acid value reached 48 mgKOH / g to obtain an epoxy resin-modified / fatty acid-modified acrylic resin having a solid content of 66%.

Production Example 9 Pigment Dispersion Paste No. 1
12.3 parts of fatty acid-modified acrylic resin obtained in Production Example 7 (8 parts solids), 3 parts of hydride PXN (Note 2), 2 parts of carbon MA-7 (Note 3), rust preventive No. 16 parts, 1 part of triethylamine as a neutralizing agent and 13.7 parts of deionized water were mixed, and the mixture was charged in a ball mill and stirred for 20 hours to obtain a pigment dispersion paste No. 1 having a solid content of 50%. 1 was obtained.

Production Examples 10 to 18 Pigment dispersion paste No. 2-No. 10
Pigment paste No. 1 was operated in the same manner as in Production Example 9 except that the blending components shown in Table 2 were used in the proportions shown in Table 2. 2-No. 10 was obtained.

(Note 2) Hydride PXN: Georgia Kaolin, trade name, aluminum silicate (Note 3) Carbon MA-7: Mitsubishi Chemical, trade name, carbon black (Note 4) P-W-2: Kikuchi Color , Trade name, zinc phosphate (Note 5) NP-1020C: manufactured by Toho Pigment, trade name, calcium zinc phosphite (Note 6) KW-840E: trade name, manufactured by Teika, trade name, aluminum dihydrogen tripolyphosphate

Production Example 19 Emulsion No. 1
154 parts of fatty acid-modified acrylic resin obtained in Production Example 7 (solid content: 100 parts), 20 parts of ethylene glycol monobutyl ether, 15 parts of benzyl alcohol, 10 parts of triethylamine as a neutralizing agent and 140 parts of deionized water were stirred with a disper. And mixed with an emulsion No. 30% solid content. 1 was obtained.

Production Example 20 Emulsion No. 2
151 parts of epoxy resin-modified / fatty acid-modified acrylic resin obtained in Production Example 8 (100 parts of solid content), 20 parts of ethylene glycol monobutyl ether, 15 parts of benzyl alcohol, 10 parts of triethylamine as a neutralizing agent and 137 parts of deionized water Mixing while stirring with a disper, emulsion No. 30% solid content. 2 was obtained.

Example 1
Emulsion No. 1 333 parts (solid content 100 parts) with pigment dispersion paste No. 1 38 parts (solid content 19 parts) was added, and 422 parts deionized water was further added and stirred. 1 was obtained.

Examples 2-7, Comparative Examples 1-4
The emulsions shown in Tables 3 and 4 were combined with the pigment dispersion paste, and in the same manner as in Example 1, the electrodeposition paint No. 2-No. 7 (Examples 2 to 7) and electrodeposition paint No. 8-No. 10 (Comparative Examples 1 to 4) was obtained.

Coating test The electrodeposition paint No. obtained by the said Example and comparative example. 1-No. 11 was immersed in a cold-rolled dull steel plate whose surface was degreased using an organic solvent, and this was used as an anode for 3 minutes at a bath temperature of 25 ° C. and a load voltage of 150 V to perform electrodeposition coating.

  The film thickness of the electrodeposition coating film was 20 μm, and after washing with water, forced drying was performed at 80 ° C. for 30 minutes using an electric hot air dryer, followed by drying at room temperature for 7 days. Electrodeposition paint No. The coating film performance of Nos. 1-7 (Examples) is shown in Table 3, and Table 4 shows the coating performance of 8 to 11 (comparative examples).

  The performance test was conducted according to the method described later.

(Note 7) Salt spray resistance:
A cross-cut wound was put on the electrodeposition coating film with a knife so as to reach the substrate on each obtained electrodeposition coating plate, and this was subjected to a salt spray resistance test for 120 hours in accordance with JIS Z-2371. Evaluation was made according to the following criteria based on the blister width.
A: The maximum width of rust and blisters is less than 2 mm from the cut part (one side),
○: The maximum width of rust and blisters is 2 mm or more from the cut part and less than 3 mm (one side),
Δ: The maximum width of rust and blisters is 3 mm or more and less than 4 mm (one side) from the cut part,
X: The maximum width of rust and blisters is 4 mm or more from the cut part (one side).
(Note 8) Paint stability:
The electrodeposition paint was put in a container, sealed, stirred at 30 ° C. for 4 weeks, and 3 L of bath paint was filtered through a 400 mesh filter net.
A: Filtration residue is less than 5 mg / L,
○: Filtration residue is less than 10 mg / L,
Δ: Filtration residue is 10 mg / L or more and less than 20 mg / L,
X: Filtration residue is 20 mg / L or more.
(Note 9) Finishability:
The appearance of the painted surface was visually evaluated.
○: Smoothness is good and there is no problem. △: Finishing properties such as swell, gloss, and chili skin are slightly lowered.
X: Deterioration of finish such as swell, gloss, and chile skin is large.

Production Example 21 Acrylic Resin Solution 210 parts of mixed solvent A (Note 10) was charged into a reaction vessel, the following monomer mixture was added dropwise over 3 hours while maintaining the temperature at 85 ° C., and then azobisdimethylvaleronitrile 3 Part was added and reacted at 85 ° C. for 4 hours to produce an acrylic resin solution having a solid content of 70% by weight.

Monomer mixture Styrene 10.5 parts Methyl methacrylate 36.8 parts N-butyl acrylate 3.7 parts Ethyl acrylate 20.0 parts 2-Ethylhexyl methacrylate 4.0 parts Acrylic acid 5.5 parts 2-hydroxyethyl acrylate 12.0 parts 2-hydroxyethyl methacrylate 7.5 parts azobisdimethylvaleronitrile 2.1 parts

(Note 10) Mixed solvent A: propylene glycol monomethyl ether (boiling point 121 ° C.) / Isopropyl alcohol (boiling point 82 ° C.) / N-butyl alcohol (boiling point 118 ° C.) / Ethylene glycol monobutyl ether (boiling point 171 ° C.) = 42 parts / 42 Part / 42 parts / 84 parts.

Production Example 22 Pigment Dispersion Paste No. 11
A 70% solid content acrylic resin solution obtained in Production Example 21 (5 parts solids), 3 parts hydride PXN (Note 2), 2 parts carbon MA-7 (Note 3), rust inhibitor No. 1 16 parts, 0.24 part of triethylamine and 13.7 parts of deionized water were added, mixed and dispersed by a ball mill, and a pigment dispersion paste No. for 50% thermosetting anion electrodeposition coating was added. 11 was obtained.

Production Examples 23 to 28 Pigment dispersion paste No. 12-No. 17
In the same manner as in Production Example 22, except that the blending components shown in Table 5 were used in the proportions shown in Table 5, the same procedure as in Production Example 22 was carried out to obtain a pigment dispersion paste No. 12-No. 17 was obtained.

Production Example 29 Emulsion No. 3
Add 75.7 parts of the 70% acrylic resin solution obtained in Production Example 21 (solid content 60 parts), 40 parts of Cymel 232 (Note 11) (solid content 40 parts) and 1.9 parts of triethylamine, and add 184 parts of deionized water 184. 9 parts are dispersed to give an emulsion No. 32 for 32% thermosetting anionic electrodeposition coating. 3 was obtained.
(Note 11) Cymel 232: manufactured by Mitsui Cytec Co., Ltd., trade name, methyl / butyl mixed etherified melamine resin).

Example 8 Electrodeposition paint no. 12
The 32% emulsion No. obtained in Production Example 29 was obtained. 3 In 312.5 parts (solid content 100 parts), pigment dispersion paste No. 11 After blending 32 parts (solid content 16 parts), 428.5 parts of deionized water was added, and the electrodeposition paint no. 12 was obtained.

Examples 9 and 10 Electrodeposition paint no. 13 and no. 14
A combination of the emulsion shown in Table 6 and the pigment dispersion paste was used, and in the same manner as in Example 8, the electrodeposition paint No. 13 and no. 14 was obtained.

Comparative Examples 5 to 8 15-No. 18
A combination of the emulsion shown in Table 6 and the pigment dispersion paste was used, and in the same manner as in Example 8, the electrodeposition paint No. 15-No. 18 was obtained.

Coating test The electrodeposition paint No. obtained by the said Example and comparative example. 12-No. 18 was immersed in a cold-rolled steel sheet treated with zinc phosphate, and this was used as an anode for 3 minutes at a bath temperature of 25 ° C. and a load voltage of 150 V to perform electrodeposition coating. The film thickness of the electrodeposition coating film was 20 μm. After washing with water, the film was baked and dried at 170 ° C. for 20 minutes using an electric hot air dryer.

  Electrodeposition paint No. 12-No. The coating film performance of 18 is shown in Table 6.

  The performance test was conducted according to the method described later.

(Note 11) Salt spray resistance:
Each electrodeposition coating plate obtained was cut with a knife in the electrodeposition coating so as to reach the substrate, and this was subjected to a salt water spray test for 480 hours according to JIS Z-2371. ○: Rust, maximum width of bulge is less than 3 mm from cut (one side),
Δ: The maximum width of rust and blisters is 3 mm or more and less than 4 mm (one side) from the cut part,
X: The maximum width of rust and blisters is 4 mm or more from the cut part (one side).
(Note 12) Paint stability:
The electrodeposition paint was put in a container, sealed, stirred at 30 ° C. for 4 weeks, and 3 L of bath paint was filtered through a 400 mesh filter net.
A: Filtration residue is less than 5 mg / L,
○: Filtration residue is less than 10 mg / L,
Δ: Filtration residue is 10 mg / L or more and less than 20 mg / L,
X: Filtration residue is 20 mg / L or more.
(Note 13) Finishability:
The appearance of the painted surface was visually evaluated.
○: Smoothness is good and no problem
△: Slight deterioration in finish such as swell, gloss, and chile skin is seen.
X: Deterioration of finish such as swell, gloss, and chile skin is large.

  As is clear from the above examples, the electrodeposition paint of the present invention is a pollution-free electrodeposition paint that does not contain harmful metals such as lead and chromium, and has anticorrosion properties, paint finish, etc. An excellent coated article can be provided.

Claims (8)

The following formulas (1) and (2)

(xMHPO ₄ 3H ₂ O) · (ySiO ₂ ) · (mCaSiO ₃ ) · (nCaCO ₃ )
(1)
(Ca ₃ (PO ₄ ) ₂ 3H ₂ O) · (ySiO ₂ ) · (mCaSiO ₃ ) · (nCaCO ₃ )
(2)
Where
M is Mg or Ca, x, y and m are each an integer of 1 to 3, and n is an integer of 0 to 3,
An electrodeposition paint comprising at least one silica-modified phosphoric acid compound selected from the group consisting of as a rust inhibitor. Silica-modified phosphoric acid compound of the formula (1) is _{2MgHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{3MgHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
MgHPO ₄ · 3H ₂ O · 2SiO ₂ · CaSiO ₃ · 2CaCO _{3
2MgHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · CaCO 3
_{2CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{3CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{2CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
The electrodeposition paint according to claim 1, which is selected from: Silica-modified phosphoric acid compound is Ca ₃ of formula _{(2) (PO 4) 2} · 3H 2 O · 2SiO 2 · CaSiO 3 · 2CaCO 3
_{Ca 3 (PO 4) 2 ·} 3H 2 O · 2SiO 2 · CaSiO 3 · 3CaCO 3
Ca ₃ (PO ₄ ) ₂ · 3H ₂ O · 2SiO ₂ · 2CaSiO ₃ · 2CaCO ₃
Ca ₃ (PO ₄ ) ₂ · 3H ₂ O · 3SiO ₂ · CaSiO ₃ · 2CaCO ₃
The electrodeposition paint according to claim 1, which is selected from: Silica-modified phosphoric acid compound _{3CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{2CaHPO 4 · 3H 2 O · 2SiO} 2 · CaSiO 3 · 2CaCO 3
_{Ca 3 (PO 4) 2 ·} 3H 2 O · 2SiO 2 · CaSiO 3 · 2CaCO 3
The electrodeposition paint according to claim 1, which is selected from:   The electrodeposition paint according to claim 1, wherein the silica-modified phosphoric acid compound is contained in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the total solid content of the resin components in the paint.   The electrodeposition paint according to claim 1, wherein the silica-modified phosphate compound is contained in an amount of 1 to 20 parts by weight per 100 parts by weight of the total solid content of the resin components in the paint.   The electrodeposition paint according to claim 1, wherein the electrodeposition paint is a room temperature drying type electrodeposition paint, a thermosetting anion electrodeposition paint, or a thermosetting cationic electrodeposition paint.   An article electrodeposited using the electrodeposition paint according to any one of claims 1 to 7.