JP2002294167A - Cationic electrodeposition coating material composition and method for forming coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cationic electrodeposition coating material composition which contains resin compositions and has good stability and impact resistance. SOLUTION: The cationic electrodeposition coating material composition contains a resin composition (A) and a resin composition (B), wherein the resin composition (A) contains (A1) a polyester polyol, a polyether polyol, a polycarbonate polyol, a polyurethane polyol, a polyolefin polyol and an acrylic polyol, and (A2) at least one polymer selected from the group consisting of polymers obtained by reacting (A1) with a compound having in the molecule a functional group selected from the group consisting of isocyanato group, carboxyl group and epoxy group, a dialkyl carbonate, a cyclic carbonate, an alcohol, or a mixture thereof, and wherein the resin composition (B) contains sulfonium group, propargyl group and an unsaturated double bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationic electrodeposition coating composition and a coating composition having improved storage stability during storage or electrodeposition without heating while maintaining chipping resistance and impact resistance. The present invention relates to a film forming method.

[0002]

2. Description of the Related Art The coating process of automobile bodies and parts is performed by
In general, an object to be coated that has been subjected to a chemical conversion treatment with a phosphate or the like is subjected to electrodeposition coating with an electrodeposition coating material, and then an intermediate coating material and a top coating material are sequentially applied as necessary, to obtain a coating. It consists of heating and curing the coating film sequentially,
A multi-layer coating is formed on an object to be coated. Here, the electrodeposition coating film is applied in order to enhance the anticorrosion of the object to be coated.

[0003] Particularly, in the electrodeposition coating of an automobile body, since an object to be coated has various shapes, so-called throwing power, which can form a uniform coating film over details, becomes important.

Japanese Patent Application Laid-Open No. 2000-38525 aims to provide a resin composition for a cationic electrodeposition coating composition which realizes high throwing power, has excellent curability, and can achieve a sufficient curing level even under mild baking conditions. In the official gazette,
A resin composition for a cationic electrodeposition coating composition comprising a sulfonium group, a propargyl group and an unsaturated double bond is disclosed.

Unsaturated double bonds in the composition cause a decrease in reactivity or a problem due to polymerization during storage or during use in an electrodeposition tank as an electrodeposition coating, and the electrodeposition coating has a disadvantage. There was also a risk of causing gelation and deterioration of the skin and performance of the obtained coating film.

On the other hand, a coating film formed on an object to be coated such as an automobile needs to be sufficiently protected from damage caused by collision with sand particles, pebbles and the like generated during traveling. It is essential to improve the impact resistance and the like. In order to improve the impact resistance, it is common practice to improve the physical properties of the top coat and the intermediate coat. However, such a method alone cannot always sufficiently improve the impact resistance. In order to further improve the physical properties of the electrodeposition coating film and improve the impact resistance of the entire coating film, if it can be combined with conventional impact resistance technology, it will be dramatically improved There is a possibility that the impact resistance of the coating film can be improved.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention has been made to reduce the stability of a coating material without heating during storage or electrodeposition due to unsaturated double bonds introduced into a resin. The present invention provides a cationic electrodeposition coating composition containing a resin composition having a sulfonium group, a propargyl group and an unsaturated double bond, and a method for forming a coating film, in which the problems caused by the above are suppressed and the impact resistance is good. It is the purpose.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a resin composition for a cationic electrodeposition paint containing a resin composition (A) and a resin composition (B), a cation containing a phenolic polymerization inhibitor and a phospholipid. An electrodeposition coating composition, wherein the resin composition (A) has a number average molecular weight of 1,000 to 35,000, and has the following (A1) and (A2): (A1) polyester polyol, polyether polyol, polycarbonate polyol, polyurethane Polyol, Polyolefin Polyol and Acrylic Polyol (A2) Compound having at least one functional group selected from the group consisting of (A1) and an isocyanate group, a carboxyl group and an epoxy group in the molecule, dialkyl carbonate, and cyclic carbonate ,alcohol,
And at least one selected from the group consisting of polymers obtained by reaction with these mixtures, wherein the resin composition (B) has a number average molecular weight of 500 to 2
000, and the solid content of the resin composition (B) is 100
per g, 5-400 mmol of sulfonium groups, 10-485 mmol of propargyl groups and 1 unsaturated double bond
0 to 485 mmol, and the total content of the sulfonium group, the propargyl group, and the unsaturated double bond is 500 mmol or less per 100 g of the solid content of the resin composition (B), and the phenolic polymerization The content of the inhibitor is 100 to 1000 ppm by weight based on the solid content of the resin composition for cationic electrodeposition coating, and the content of the phospholipid is the same as the solid content of the resin composition for cationic electrodeposition coating. 30-1000pp by weight
m, and the content of the phenolic polymerization inhibitor / the content of the phospholipid is 100 / 100-100 / 100 by weight.
5 is a cationic electrodeposition coating composition.

Here, the phenolic polymerization inhibitor preferably contains one to three aromatic rings in the molecule in which at least one hydrogen atom is substituted by a hydroxyl group. More preferably, it contains 1 to 3 hydroxyl groups, for example, having a molecular weight of 10
0 to 500.

The phospholipid preferably has an iodine value of 120 or less, for example, lecithin or kephalin.

Further, the present invention is characterized in that the above-mentioned cationic electrodeposition coating composition is electrodeposited on an object to be coated to obtain an electrodeposition coating, and then heated to form an electrodeposition coating. This is a method for forming a coating film.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for a cationic electrodeposition paint contained in the cationic electrodeposition paint composition of the present invention contains a resin composition (A) and a resin composition (B). Since the resin composition (A) has a flexible and hydrophobic structure, it is possible to improve the impact resistance and chipping resistance of the obtained coating film and, since it is hydrophobic, obtain the obtained electrodeposition. It is considered that the corrosion resistance of the coating film can be improved. In addition, it is considered that a stable resin composition for a cationic electrodeposition paint can be formed by being integrated with a resin composition (B) described later.

The resin (A) contains at least one selected from the group consisting of (A1) and (A2). (A1) is a polyester polyol,
Polyether polyol, polycarbonate polyol, polyurethane polyol, polyolefin polyol and acrylic polyol.

Examples of the above-mentioned polyester polyol include those obtained by reacting a polyol with a polycarboxylic acid, an acid anhydride and / or an ester compound of the polycarboxylic acid. The polycarboxylic acid is not particularly limited as long as it has two or more carboxyl groups. Examples thereof include succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, dodecanedicarboxylic acid, and butanetricarboxylic acid. Saturated low-molecular aliphatic polycarboxylic acid; unsaturated low-molecular aliphatic polycarboxylic acid such as maleic acid, fumaric acid, and itaconic acid; saturated or unsaturated long-chain poly such as polybutadiene dicarboxylic acid and IPU22 (manufactured by Okamura Oil Co., Ltd.) Carboxylic acids; examples thereof include aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. The acid anhydride and / or ester compound of the polycarboxylic acid is not particularly limited, and examples thereof include acid anhydrides of these polycarboxylic acids and / or ester compounds such as methyl esters and ethyl esters of these polycarboxylic acids. Can be mentioned.

Of these, polybutadiene dicarboxylic acid is preferred because of its excellent curability and hydrophobicity.
NISSO-PB C1000 (Nippon Soda Co., Ltd.), HY
CAR CTB and HYCAR CTBN (all manufactured by Ube Industries, Ltd.) can be used. One or more of the above polycarboxylic acids can be used.

As the acid component other than the above polycarboxylic acid,
It may include low or high molecular weight saturated or unsaturated monocarboxylic acids such as acetic acid, acrylic acid, methacrylic acid, crotonic acid, oleic acid, linoleic acid, linseed oil fatty acid, soybean oil fatty acid and the like.

The polyol is not particularly limited as long as it has two or more hydroxyl groups. Examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 3-methyl- Saturated low-molecular polyols such as pentanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, trimethylolpropane, hydrogenated bisphenol A and hydrogenated bisphenol F; 2-butyne-1,4- Diol, 2-butene-1,
Unsaturated high molecular polyols such as 4-diol; unsaturated high molecular polyols such as polybutadiene glycol and polyisoprene glycol; Of these, polybutadiene glycol containing an unsaturated group and 2-butyne-1,4-
Diols are preferred, and 2-butyne-1,4-diol is more preferred.

The polybutadiene glycol includes:
For example, Poly bd R-45HT, Poly b
d R-45M (Idemitsu Petrochemical Co., Ltd.), NISS
O-PB G1000, NISSO-PB G2000
(Nippon Soda Co., Ltd.). One or more of the above polyols can be used.

As the above-mentioned polyester polyol, a reaction product of a polycarboxylic acid and an epoxy compound can also be used. Examples of the polycarboxylic acid include those described above. The epoxy compound is not particularly limited as long as it has one or more epoxy groups. For example, monoglycidyl compounds such as phenylglycidyl ether and glycidyl (meth) acrylate;
Epibisepoxy resins such as YDF-170, YDF-803 (all manufactured by Toto Kasei Co., Ltd.), FLEP (manufactured by Toray Thiokol Co., Ltd.), and bisphenol A diglycidyl ether;
The above-mentioned epibisepoxy resin is chain-extended with a diol, dithiol, dicarboxylic acid, diamine or the like; a hydrogenated product of the above-mentioned epibisepoxy resin or the above chain-extended product; Denarex R-45EPT (manufactured by Idemitsu Petrochemical Co., Ltd.)
Saturated or unsaturated aliphatic polyglycidyl ethers such as polybutadiene diglycidyl ether; IPU22
And higher saturated or unsaturated polyglycidyl esters such as G and SB-20G (manufactured by Okamura Oil Co., Ltd.). The carboxylic acid, the epoxy compound, and / or the reaction product thereof may be used alone or in combination of two or more.

The above reaction product preferably has an acid value of 20 or less, more preferably 10 or less. When the acid value exceeds 20, emulsification at the stage of coating may be difficult.

The above polyether polyol is, for example,
Those obtained by ring-opening polymerization of alkylene oxide or heterocyclic ether can be mentioned. The alkylene oxide is not particularly limited and includes, for example, ethylene oxide, propylene oxide, butylene oxide and the like.

The heterocyclic ether is not particularly restricted but includes, for example, cyclic acetals such as 1,3-dioxolane. The alkylene oxide and / or the heterocyclic ether can be used alone or in combination of two or more.

Examples of such polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene random glycol, and poly (tetraoxymethylene) glycol. These may be used alone or in combination of two or more. can do.

As the above-mentioned polyether polyol, a reaction product of a polyol and a polyepoxy compound can also be used. Examples of the polyol and the polyepoxy compound include those described above.

Examples of the polycarbonate polyol include those obtained by reacting a polyol with a polycarbonate such as an alkylenedicarbonate.
The above polycarbonate polyols are excellent in hydrolysis resistance and excellent in water resistance as compared with ordinary esters, so that the corrosion resistance of the obtained electrodeposition coating film can be further improved.
The polycarbonate polyol is not particularly limited, and examples thereof include polyhexamethylene carbonate diol and polyethylene carbonate diol. One or more of the above polycarbonate polyols can be used.

The above polyurethane polyol is, for example,
Those obtained by reacting a polyol with a polyisocyanate compound are exemplified. Examples of the polyol include those described above. Since the polyurethane polyol has a high cohesive force and the urethane functional group has excellent hydrolysis resistance, the processability and adhesion of the obtained electrodeposition coating film can be further improved. The polyisocyanate compound is not particularly limited. For example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate (HDI) 1,4-cyclohexanediisocyanate, 4,4'-dicyclohexylmethanediisocyanate, and urethanes thereof,
Modified products such as carbodiimide, ureotin, dimer and trimer can be mentioned. One or more of the above polyols and / or polyisocyanate compounds can be used.

The above-mentioned polyolefin polyol is, for example, a polymer of a radical polymerizable monomer having two or more unsaturated double bonds, or a mixture of these radical polymerizable monomers and other radical polymerizable monomers. Which has two or more hydroxyl groups. The radical polymerizable monomer is not particularly limited, and examples thereof include butadiene, isoprene, styrene, methylstyrene, and acrylonitrile. Examples of the polyolefin polyol include unsaturated polymer polyols such as polybutadiene glycol and polyisoprene glycol exemplified as the above polyol. The above-mentioned polyolefin polyol is excellent in reactivity, hydrophobicity, and can further improve the curability and the anticorrosion property of the electrodeposition coating film, and is low in polarity, so that the oil repelling resistance at the time of cationic electrodeposition coating is further improved. Can be improved.

As the above-mentioned polyolefin polyol,
In particular, those having a polybutadiene derivative are particularly preferred because they are excellent in reactivity and hydrophobicity, have very excellent curability, and the obtained electrodeposition coating film has high corrosion resistance. Although it does not specifically limit as what has the said polybutadiene derivative, For example, the said polybutadiene glycol can be mentioned.

The acrylic polyol is obtained, for example, by copolymerizing (meth) acrylic acid and / or a derivative thereof with a radical polymerizable monomer having a hydroxyl group. The radical polymerizable monomer having a hydroxyl group is not particularly limited, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate,
Hydroxybutyl methacrylate, allyl alcohol,
Methacryl alcohol and the like can be mentioned. The above (meth) acrylic acid derivative and / or the above-mentioned radical polymerizable monomer having a hydroxyl group are each one kind or two kinds.
More than one species can be used.

The method (A1) can be carried out according to a conventional method, and the above-mentioned commercially available products can also be used. The above (A1)
Can be used alone or in combination of two or more.

(A2) is a compound of the above (A1) and a compound having at least one functional group selected from the group consisting of an isocyanate group, a carboxyl group and an epoxy group in the molecule, a dialkyl carbonate, a cyclic carbonate, Alcohols, as well as polymers obtained by reaction with these mixtures.

The compound having an isocyanate group is not particularly restricted but includes, for example, monoisocyanate compounds such as hexyl isocyanate and phenyl isocyanate in addition to the above-mentioned polyisocyanate compounds.

The compound having a carboxyl group is not particularly limited, and examples thereof include the saturated or unsaturated mono- or polycarboxylic acids.

The compound having an epoxy group is not particularly limited. For example, in addition to the above-mentioned polyepoxy compound,
For example, monoepoxy compounds such as phenyl glycidyl ether and glycidyl methacrylate can be used.

The dialkyl carbonate is not particularly restricted but includes, for example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate and the like.

The above-mentioned cyclic carbonate is not particularly restricted but includes, for example, ethylene carbonate, propylene carbonate and the like.

The alcohol is not particularly limited.
For example, in addition to the above-mentioned polyols, saturated or unsaturated monoalcohols such as methanol, ethanol, allyl alcohol, and propargyl alcohol can be exemplified.

The reaction of the above compound or a mixture thereof with the above (A1) is not particularly limited. For example, these compounds may be dissolved in a solvent capable of dissolving both the above compound and the above (A1) in a small amount. Depending on the conditions, a method of mixing a catalyst and other additives under heating and reacting with stirring can be employed. Regarding the above (A2), even if a part of (A1) remains without reacting all of the raw material (A1), it can be used as the resin composition (A).

It is preferable that the resin composition (A) has a functional group capable of effectively reacting with the resin composition (B). By the above functional group, reactivity with the resin composition (B) and curability can be improved, a strong electrodeposition coating film can be formed, and corrosion resistance can be improved.

As the above functional group, an unsaturated functional group is preferable. When the resin composition (A) has an unsaturated functional group, the curability and the corrosion resistance of the obtained electrodeposition coating film can be further improved.

The source for introducing the unsaturated functional group is not particularly limited. For example, a compound having an unsaturated functional group can be used among the above-mentioned compounds, and preferably, a polydiene derivative and / or an unsaturated compound is used. A compound having a saturated triple bond is used.

The polydiene derivative is not particularly limited, but a polybutadiene derivative is more preferable since the curability and the corrosion resistance of the resulting coating film can be further improved as described above.

The compound having an unsaturated triple bond is not particularly limited as long as it has a carbon-carbon triple bond. Particularly, the compound having good reactivity and compatibility with the main resin and having a cationic electrodeposition coating composition Propargyl alcohol and 2-butyne-1,4-diol are more preferable since the curability of the product can be further improved.

The compound having an unsaturated triple bond can be used in an amount of 1 to 50% by weight based on the solid content of the obtained resin composition (A). If the content of the source of the unsaturated functional group is less than 1% by weight based on the weight of the solid content of the obtained resin composition (A), the effect of introducing these may not be sufficiently obtained, 50
When the content is more than 10% by weight, the hydrophilicity of the resin composition (A) becomes too high, and the water barrier property of the obtained electrodeposition coating film is reduced, and the corrosion resistance may be reduced. Preferably, it is 5 to 50% by weight.

The above resin composition (A) has a unsaturated bond group, so that a cationic electrodeposition coating composition excellent in curability and corrosion resistance of the obtained electrodeposition coating film can be obtained. It is particularly preferable to use a polyolefin polyol, a polyester polyol obtained by using a polyolefin dicarboxylic acid, and / or a polyurethane polyol, and 2-butyne-1,4
Those using a diol as a monomer are also particularly preferred.

The resin composition (A) has a number average molecular weight of 1
000-35,000. When the number average molecular weight of the resin composition (A) is less than 1000, the coating efficiency of the cationic electrodeposition coating becomes poor, and when it exceeds 35,000, it becomes difficult to form a good film on the surface of the object to be coated. .

The resin composition (A) preferably has a glass transition temperature of -80 to 150 ° C. When the glass transition temperature is lower than -80 ° C, preparation is substantially difficult. When the glass transition temperature is higher than 150 ° C, flexibility is reduced and chipping resistance may be reduced. The temperature is more preferably -70 to 100 ° C, and still more preferably -50.
８０80 ° C.

The above resin composition (A) has a hydroxyl value of 2 to 2.
Preferably, it is 120 mgKOH / g. When the hydroxyl group is less than 2 mgKOH / g, the resin may have poor compatibility with the resin composition (B) described below and may have poor curability. If it exceeds 120 mgKOH / g, the hydrophilicity becomes too high, and the water barrier property of the electrodeposition coating film is reduced, so that the anticorrosion property may not be sufficient. More preferably 2-110 mg
KOH / g, more preferably 2-95 mg KO
H / g.

The content of the resin composition (A) is preferably 5 to 80% by weight based on the solid content of the resin composition for a cationic electrodeposition coating. When the content of the resin composition (A) is less than 5% by weight with respect to the resin solid content, impact resistance may not be sufficiently exhibited. Separation of the composition (A) and the resin composition (B) may occur, and the storage stability of the resulting cationic electrodeposition coating composition may decrease. More preferably, it is 5 to 40% by weight.

The resin composition (B) contained in the cationic electrodeposition coating composition of the present invention has a sulfonium group, a propargyl group and an unsaturated double bond group in the molecule. The sulfonium group is a hydrated functional group of the resin composition for cationic electrodeposition coating, and exhibits excellent throwing power in electrodeposition coating. The propargyl group and the unsaturated double bond group contribute to reactivity and curability.

The resin composition (B) is preferably composed of a resin having an epoxy resin as a skeleton. The epoxy resin is not particularly limited, and may be, for example, an epibis epoxy resin, which has been chain-extended with a diol, dicarboxylic acid, diamine, or the like; an epoxidized polybutadiene; a novolak phenol type polyepoxy resin; a novolac cresol type polyepoxy resin; Polyglycidyl acrylate; polyglycidyl ether of aliphatic polyol or polyether polyol; polyglycidyl ester of polybasic carboxylic acid, and the like. Of these, novolak phenol type polyepoxy resin, novolak cresol type polyepoxy resin, and polyglycidyl acrylate are preferable because polyfunctionalization for enhancing curability is easy. Note that a part of the epoxy resin may be a monoepoxy resin.

The number average molecular weight of the resin composition (B) is
500 to 20,000. If the number average molecular weight is less than 500, the coating efficiency of the cationic electrodeposition coating becomes poor,
If it exceeds 20,000, a good film cannot be formed on the surface of the object to be coated. The number average molecular weight can be more preferably set according to the resin skeleton. For example, in the case of a novolak phenol type epoxy resin or a novolak cresol type epoxy resin, 700 to 50
00 is more preferable.

In the resin composition (B), a sulfonium group, a propargyl group and an unsaturated double bond are introduced via an epoxy group of the epoxy resin forming the skeleton. The resin having the epoxy resin as a skeleton may contain all three of a sulfonium group, a propargyl group, and an unsaturated double bond in one molecule, but it is not always necessary. For example, in one molecule, It may contain one or two of a sulfonium group, a propargyl group and an unsaturated double bond. In the latter case, all of these three types of curable functional groups are contained in the entire resin molecule constituting the resin composition. That is,
The resin composition (B) is generally composed of a plurality of resin molecules having an epoxy resin as a skeleton and having one, two or three or more of a sulfonium group, a propargyl group, and an unsaturated double bond. It may be. In this specification, the resin composition (B) contains a sulfonium group, a propargyl group and an unsaturated double bond in such a meaning.

Therefore, the epoxy resin forming the skeleton may have a part having at least one epoxy group in one molecule, but from the viewpoint of curability, at least two epoxy groups in one molecule. It is preferably a polyepoxy resin having an epoxy group. As such a material, the polyepoxy resin or the like exemplified above can be suitably used.

The above-mentioned sulfonium group is a hydrated functional group of the above resin composition for cationic electrodeposition coating. When a voltage or current exceeding a certain level is applied during the electrodeposition coating process, the sulfonium group undergoes an electrolytic reduction reaction on the electrode to lose the ionic group and irreversibly become nonconductive. It is thought that this is why the cationic electrodeposition coating composition of the present invention can exhibit a high throwing power.

In this electrodeposition coating process, it is considered that an electrode reaction is caused and the generated hydroxide ion is retained by the sulfonium group, so that an electrogenerated base is generated in the electrodeposited film. This electrogenerated base can convert a propargyl group having low reactivity due to heating existing in the electrodeposited film into an allene bond having high reactivity due to heating.

The content of the sulfonium group is from 5 to 400 mmol per 100 g of the solid content of the resin composition (B), after satisfying the conditions for the content of the sulfonium group, propargyl group and unsaturated double bond described later. . 5mmo
When the amount is less than 1/100 g, sufficient throwing power and curability cannot be exhibited, and hydration properties and bath stability deteriorate. If it exceeds 400 mmol / 100 g,
Precipitation of the coating on the surface of the object to be coated becomes poor. This content can be set more preferably according to the resin skeleton. For example, in the case of a novolak phenol type epoxy resin or a novolak cresol type epoxy resin, the content is 5 to 250 mmol per 100 g of the solid content of the resin composition (B). And more preferably 10 to 150 mmol.

The propargyl group is converted into an allene bond as described above, thereby improving the reactivity and constituting a curing system. For unknown reasons, the coexistence with the sulfonium group can further improve the throwing power of the cationic electrodeposition coating composition of the present invention.

The content of the propargyl group is from 10 to 485 mmol per 100 g of the solid content of the resin composition (B), after satisfying the conditions for the content of the sulfonium group, the propargyl group and the unsaturated double bond described later. . 10m
If it is less than 100 mol / 100 g, sufficient throwing power and curability cannot be exhibited, and 485 mmol / 1
If it exceeds 00 g, hydration stability when used as a cationic electrodeposition paint may be adversely affected. This content can be set more preferably according to the resin skeleton. For example, in the case of novolak phenol type epoxy resin and novolak cresol type epoxy resin, 20 to 375 mm per 100 g of the resin composition solid content
ol is preferred.

The term “unsaturated double bond” used herein means a carbon-carbon double bond. Since unsaturated double bonds have high reactivity, curability can be further improved.

The content of the unsaturated double bond is 10 to 10 g per 100 g of the solid content of the resin composition (B) after satisfying the conditions for the content of the sulfonium group, propargyl group and unsaturated double bond described later. 485 mmol. 10m
If it is less than mol / 100 g, sufficient curability cannot be exhibited, and if it exceeds 485 mmol / 100 g, the hydration stability when used as a cationic electrodeposition paint may be adversely affected. This content can be more preferably set according to the resin skeleton. For example, in the case of a novolak phenol type epoxy resin or a novolak cresol type epoxy resin, the content is preferably 20 to 375 mmol per 100 g of the solid content of the resin composition.
It is.

In the present specification, the content of the unsaturated double bond is represented by an amount corresponding to the content of the epoxy group into which the unsaturated double bond has been introduced. That is, for example, even when a molecule having a plurality of unsaturated double bonds in a molecule such as a long-chain unsaturated fatty acid is introduced into an epoxy group, the content of unsaturated double bonds is A molecule having one unsaturated double bond is represented by the content of the introduced epoxy group. This is because even if a molecule having a plurality of unsaturated double bonds in one molecule is introduced into one epoxy group, only one of the unsaturated double bonds is involved in the curing reaction. It is considered that there is.

The total content of the above sulfonium group, propargyl group and unsaturated double bond is not more than 500 mmol per 100 g of the solid content of the resin composition (B). If the amount exceeds 500 mmol, the resin composition may not be actually obtained or the desired performance may not be obtained. This content can be set more preferably according to the resin skeleton. For example, in the case of a novolak phenol type epoxy resin or a novolac cresol type epoxy resin, the content is preferably 400 mmol or less.

Further, the total content of the propargyl group and the unsaturated double bond was 100 g of the solid content of the resin composition (B).
It is preferably in the range of from 80 to 450 mmol. If the amount is less than 80 mmol, the curability may be insufficient. If the amount exceeds 450 mmol, the content of the sulfonium group may decrease, and the throwing power may become insufficient. The content can be more preferably set according to the resin skeleton. For example, in the case of a novolak phenol type epoxy resin or a novolak cresol type epoxy resin, the content is more preferably 100 to 395 mmol.

The resin composition (B) is described in
No. 38525, and the like. For example, an epoxy resin having at least two epoxy groups in one molecule can be obtained by adding a compound (a) having a functional group reactive with an epoxy group and a propargyl group to the epoxy resin. A step (1) of reacting a compound (b) having a functional group and an unsaturated double bond that reacts with a group to obtain an epoxy resin composition containing a propargyl group and an unsaturated double bond; )) Can be suitably produced by the step (2) of introducing a sulfonium group into the remaining epoxy group in the epoxy resin composition containing a propargyl group and an unsaturated double bond.

As the epoxy resin having at least two epoxy groups in one molecule, the above-mentioned polyepoxy resin and the like can be suitably used. Among these, a novolak phenol type polyepoxy resin, a novolak cresol type epoxy resin, and a polyglycidyl acrylate, which can be polyfunctionalized to enhance curability, are preferable. The number average molecular weight of such an epoxy resin is
400 to 15000, preferably 650 to 1
More preferably, it is 2000.

Examples of the compound (a) having a functional group that reacts with the epoxy group and a propargyl group include, for example,
It may be a compound containing both a functional group that reacts with an epoxy group such as a hydroxyl group and a carboxyl group and a propargyl group, and specific examples thereof include propargyl alcohol and propargyl acid. Of these, propargyl alcohol is preferred in terms of availability and ease of reaction.

The compound (b) having a functional group which reacts with the epoxy group and an unsaturated double bond includes, for example,
It may be a compound containing both a functional group that reacts with an epoxy group such as a hydroxyl group and a carboxyl group and an unsaturated double bond. Specifically, when the group that reacts with the epoxy group is a hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, methacryl alcohol And the like. When the group which reacts with the epoxy group is a carboxyl group, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, phthalic acid, itaconic acid; maleic acid ethyl ester, fumaric acid ethyl ester, itaconic acid ethyl ester, succinic acid Half esters such as mono (meth) acryloyloxyethyl ethyl ester and mono (meth) acryloyloxyethyl phthalate; synthetic unsaturated fatty acids such as oleic acid, linoleic acid and ricinoleic acid; natural unsaturated acids such as linseed oil and soybean oil Saturated fatty acids and the like can be mentioned.

The cationic electrodeposition coating composition of the present invention contains a phenolic polymerization inhibitor. The phenolic polymerization inhibitor preferably contains one to three aromatic rings in the molecule in which at least one hydrogen atom is substituted with a hydroxyl group. The aromatic ring is not particularly limited, but is preferably a benzene ring or a chroman ring.

The phenolic polymerization inhibitor preferably has one to three phenolic hydroxyl groups in the molecule. In the present specification, the phenolic hydroxyl group is a hydroxyl group directly bonded to a benzene ring which may be condensed with a saturated or unsaturated homo- or heterocyclic ring.

Examples of such a phenolic polymerization inhibitor include those containing two to three aromatic hydrocarbon groups having one phenolic hydroxyl group in the molecule or those having one to three phenolic hydroxyl groups in the molecule. More preferably, one ring is contained in the molecule. The phenolic polymerization inhibitor may further contain an aromatic hydrocarbon group having no phenolic hydroxyl group in the molecule.

The above-mentioned phenolic polymerization inhibitor is used when one molecule contains one aromatic ring in which at least one hydrogen atom is substituted by a hydroxyl group, such as one molecule containing one phenolic benzene ring. Is, from the viewpoint of the effect of the present invention,
The molecular weight is preferably from 100 to 500, and among those having one hydroxyl group in the molecule, for example, 4-methoxyphenol, 4-phenoxyphenol, 2,6-di-t-butyl- p-cresol (or dibutylhydroxytoluene), t-butylhydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, tocopherol, t-butylphenol, butyl parahydroxybenzoate, propyl paraoxybenzoate and the like. . Examples of the compound having two hydroxyl groups in the molecule include hydroquinone, 2-t-butylhydroquinone, and 4-t-butylcatechol, with hydroquinone being preferred. Furthermore, examples of those having three hydroxyl groups in the molecule include propyl gallate and the like.

The above-mentioned phenolic polymerization inhibitor has two to three aromatic rings in which at least one hydrogen atom is substituted by a hydroxyl group, such as one having two to three phenolic benzene rings in the molecule. When it contains, from a viewpoint of the effect of this invention, it is preferable that molecular weight is 200-450, for example, 2,2'- methylenebis (4-methyl-6
-T-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,2-
Bis (hydroxyphenyl) ethane, 1,1′-bis (hydroxyphenyl) ethane, 1,1′-bis (hydroxyphenyl) -2-phenylethane, bis (hydroxyphenyl) furfone, 2,2′-bis (hydroxy Phenyl) -propane, bis (hydroxyphenyl)
Methane, tris (hydroxyphenyl) methane and the like can be mentioned.

As the above-mentioned phenolic polymerization inhibitor, preferably, the above-mentioned phenolic polymerization inhibitor may be, for example, a commercially available product, or may be produced by a conventionally known method. , 4-methoxyphenol and tocopherol are used. In addition, one or more of these phenolic polymerization inhibitors can be used.

The content of the phenolic polymerization inhibitor is as follows:
It is preferably 0.01 to 0.5% by weight based on the resin solid content of the cationic electrodeposition coating composition of the present invention.
When the content is less than 0.01%, the generated radical cannot be sufficiently suppressed, so that the action as a polymerization inhibitor becomes insufficient,
If it exceeds 0.5%, the curing reaction of the film after electrodeposition coating is suppressed. More preferably, it is 0.01 to 0.2%.

In preparing the cationic electrodeposition coating composition of the present invention, the prepared cationic electrodeposition coating composition
The phenolic polymerization inhibitor may be added later, but when the solubility in water is not high, it is preferable to add and mix after synthesizing the above-mentioned resin composition for cationic electrodeposition coating.

The cationic electrodeposition coating composition of the present invention may contain another polymerization inhibitor in combination with the phenolic polymerization inhibitor. The other polymerization inhibitors are not particularly limited and include, for example, citric acid compounds such as isopropyl citrate; phosphorus compounds such as triphenyl phosphite and diphenyl isodecyl phosphite; dilauryl 3,3′-thiodipropionate; Radical scavengers capable of scavenging carbon radicals and oxygen radicals such as sulfur compounds.

The cationic electrodeposition coating composition of the present invention further contains a phospholipid. The phospholipid is a nitrogen-containing glycerophospholipid, which is a derivative of phosphatidic acid having a glycerin skeleton. The phospholipid preferably has an iodine value of 120 or less. If it exceeds 120, the storage stability may not be improved.
Preferably, it is 100 or less.

Examples of such a phospholipid include phosphatidylcholine (lecithin), phosphatidylethanolamine, phosphatidyltreonine, kephalin and the like.

As the phospholipid, those derived from natural animals and plants can be used in addition to those synthesized by a conventionally known method. In this case, the phospholipid may be a purified product or one containing impurities. These natural phospholipids may be hydrogenated. The natural product is not particularly limited, and includes, for example, soybean lecithin, hydrogenated soybean lecithin, egg yolk lecithin, and the like.

The above-mentioned phospholipid is preferably lecithin or kephalin from an industrial viewpoint.

The above phospholipid is used in an amount of 30 to 1000 by weight based on the solid content of the above resin composition for cationic electrodeposition coating.
ppm. When the amount is less than 30 ppm, the storage stability of the paint cannot be maintained. When the amount exceeds 1000 ppm, the polymerization inhibition reaction of the system is inhibited, and a side reaction with radicals or the like occurs particularly with the lapse of time. Corrosion resistance and appearance of the coating film are deteriorated. Preferably, 30 to 800 pp
m.

The above-mentioned phospholipids have a phenolic polymerization inhibitor / phospholipid content of 100/10 by weight.
It is contained so as to be 0 to 100/5. 5 parts by weight of the phospholipid per 100 parts by weight of the phenolic polymerization inhibitor
If the amount is less than parts by weight, the storage stability of the paint cannot be maintained. The weight ratio is preferably 100/25
１００100/80.

The content of the phospholipid in the cationic electrodeposition coating composition of the present invention and the content of the phenolic polymerization inhibitor / the phospholipid are determined based on the fact that the phospholipid is an impurity such as a natural product-derived product. When it is accompanied by the above, it is the amount of the phospholipid in the impurities. In preparing the cationic electrodeposition coating composition of the present invention, the phospholipid is preferably added and mixed after synthesizing the above-described resin composition for a cationic electrodeposition coating composition. It may be added to the coating composition later.

The cationic electrodeposition coating composition of the present invention does not necessarily require a curing agent because the above-mentioned resin composition for the cationic electrodeposition coating itself has curability. However, it may be used to further improve the curability. As such a curing agent, for example, a compound having a plurality of at least one kind of a propargyl group and an unsaturated double bond, for example, polyepoxides such as novolak phenol and pentaerythritol tetraglycidyl ether, and the like, propargyl alcohol and the like Examples thereof include compounds obtained by subjecting a compound having a propargyl group or a compound having an unsaturated double bond such as acrylic acid to an addition reaction.

The cationic electrodeposition coating composition of the present invention may contain a metal catalyst in order to promote a curing reaction between unsaturated bonds. As such a metal catalyst, for example, nickel, cobalt, copper, manganese, palladium,
Examples thereof include those in which a transition metal such as rhodium or a typical metal such as aluminum or zinc is bonded to a ligand such as cyclopentadiene or acetylacetone or a carboxylic acid such as acetic acid. Among these, those containing aluminum, copper, and cerium are preferable, and for example, acetylacetone complex, acetylacetonate complex, and acetate are preferable. These are preferably used in combination. The compounding amount of the curing catalyst is preferably 0.1 to 20 mmol per 100 g of the resin composition (B) solid content of the above-mentioned cationic electrodeposition coating composition resin composition.

When the metal catalyst contains, for example, copper, it may form acetylide with a propargyl group in the resin composition (B).

The cationic electrodeposition coating composition of the present invention may further contain an amine. The addition of the amine is expected to increase the conversion ratio of sulfonium groups to sulfides by electrolytic reduction in the electrodeposition process. The amine is not particularly limited, and examples thereof include primary to tertiary monofunctional and polyfunctional aliphatic amines, alicyclic amines, and aromatic amines. Among these, water-soluble or water-dispersible ones are preferable, for example, monomethylamine, dimethylamine,
C2-8 alkylamines such as trimethylamine, triethylamine, propylamine, diisopropylamine and tributylamine; monoethanolamine, dimethanolamine, methylethanolamine, dimethylethanolamine, cyclohexylamine, morpholine, N-methylmorpholine, pyridine , Pyrazine, piperidine, imidazoline, imidazole and the like. These may be used alone or in combination of two or more. Of these, hydroxyamines such as monoethanolamine, diethanolamine, and dimethylethanolamine are preferred because of their excellent water dispersion stability.

The amount of the amine to be added is 0.3 to 2 per 100 g of the solid content of the resin composition for a cationic electrodeposition coating.
5 meq is preferred. When the amount is less than 0.3 meq / 100 g, a sufficient effect on throwing power cannot be obtained. When the amount exceeds 25 meq / 100 g, the effect corresponding to the added amount cannot be obtained, which is uneconomical. More preferably, it is 1 to 15 meq / 100 g.

The cationic electrodeposition coating composition of the present invention may contain, if necessary, other components used in ordinary cationic electrodeposition coating compositions. The other components are not particularly limited, for example, a pigment, a pigment dispersion resin,
Additives for paints such as surfactants and ultraviolet absorbers can be mentioned.

The above-mentioned pigments are not particularly restricted but include, for example, coloring pigments such as titanium dioxide, carbon black and red iron oxide; rust-preventive pigments such as basic lead silicate and aluminum phosphomolybdate; constitutions such as kaolin, clay and talc; Examples thereof include pigments and the like generally used in cationic electrodeposition coating compositions. The compounding amount of the pigment is preferably 0 to 50% by weight as a solid content in the cationic electrodeposition coating composition.

The pigment-dispersing resin is not particularly limited, and a commonly used pigment-dispersing resin can be used. Further, a pigment dispersion resin containing a sulfonium group and an unsaturated bond in the resin may be used. Pigment dispersion resin containing such a sulfonium group and an unsaturated bond, for example, a bisphenol type epoxy resin and a hydrophobic epoxy resin obtained by reacting a half-blocked isocyanate, or reacting a sulfide compound,
Alternatively, it can be obtained by a method in which a sulfide compound is reacted with the above resin in the presence of a monobasic acid and a hydroxyl group-containing dibasic acid.

The cationic electrodeposition coating composition of the present invention is obtained by mixing the above-mentioned components with the above-mentioned resin composition for cationic electrodeposition coating, the above-mentioned phenolic polymerization inhibitor and the above-mentioned phospholipid, if necessary. , Or by dissolving or dispersing in water. When it is used for cationic electrodeposition coating, it is preferably prepared so as to have a bath solution having a nonvolatile content of 10 to 30%.

In the method of forming a coating film of the present invention, the above-mentioned cationic electrodeposition coating composition is electrodeposited on an object to be coated to obtain an electrodeposition film, and then heated to form an electrodeposition coating film. It is characterized by the following. The object to be coated is not particularly limited as long as it is conductive, and examples thereof include iron plates, steel plates, aluminum plates, surface-treated ones thereof, and molded products thereof.

The electrodeposition coating is usually carried out by applying a voltage of 50 to 450 V between the object to be coated as a cathode and the anode.
When the applied voltage is less than 50 V, the deposition of the electrodeposition film becomes insufficient, and when the applied voltage exceeds 450 V, the power consumption increases,
It is uneconomical. When a voltage is applied within the above-mentioned range using the composition of the present invention, a uniform coating can be formed on the whole object without causing a sharp increase in the film thickness during the electrodeposition process. The bath temperature of the cationic electrodeposition coating composition when the above voltage is applied is usually preferably from 10 to 45 ° C.

The electrodeposition step comprises (i) a step of immersing the object to be coated in the cationic electrodeposition coating composition, and (ii) a voltage is applied between the above-mentioned object to be treated as a cathode and an anode to deposit a film. Preferably, the method further comprises the step of: (iii) increasing the electrical resistance per unit volume of the coating by further applying a voltage to the deposited coating. The time for applying the voltage varies depending on the electrodeposition conditions, but can be generally 2 to 4 minutes.

The electrodeposited film obtained as described above may be used as it is or after washing with water after the completion of the electrodeposition process.
260 ° C, preferably 160-220 ° C, 10-30
The coating is completed by curing by baking for a minute.

When the above cationic electrodeposition coating composition is used, the thickness of the cured electrodeposition coating film is preferably 10 to 25 μm. If it is less than 10 μm, the anticorrosion property is insufficient, and if it is more than 25 μm, the paint is wasted. In the above-mentioned cationic electrodeposition coating composition, it is thought that the film deposited on the surface of the object to be coated by electrodeposition becomes nonconductive by the above-mentioned electrolytic reduction reaction, and as a result, throwing power is dramatically improved. Can be Therefore, it is presumed that even if the film thickness of the coating film is in the above range, a uniform coating film can be formed on the entire object to be coated, and sufficient corrosion protection can be exhibited.

The object to be coated, on which the electrodeposition coating film thus obtained is formed, may be further coated with a necessary intermediate coat and / or top coat according to the purpose. For example, in the case of a car outer panel, in general, after applying and baking a solvent-based, water-based or powdered intermediate coating for imparting chipping resistance, a base coating is further applied and cured. A two-coat, one-bake method in which a clear paint is applied without being applied, that is, a so-called wet-on-wet painting method, and then these films are simultaneously baked is applied.
At this time, it is preferable to use an aqueous paint as the base paint and to use a powder paint as the clear paint in consideration of environmental problems. In addition, it is obvious that the present invention can be used for a solid paint to which the one-coat coating method is applied.

[0100]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to these examples.

Production Example 1 Production of Resin Composition B Propargyl alcohol 6 was added to 3082.5 g of a cresol novolak type epoxy resin having an epoxy equivalent of 201.8 (trade name: Epototo YDCN-703, manufactured by Toto Kasei Co., Ltd.).
21.3 g, 535.4 g of linseed oil fatty acid, 9.2 g of dimethylbenzylamine as a catalyst, a stirrer, a thermometer,
The mixture was added to a separable flask equipped with a nitrogen inlet tube and a cooling device, heated to 110 ° C. and reacted for 2 hours. When the epoxy equivalent reached 1850, 1- (2-hydroxyethylthio) -2-propanol was added. 311.6 g,
Add 110 g of glacial acetic acid and 329.9 g of deionized water, and add
After the reaction at 6 ° C. for 6 hours, it was confirmed that the residual acid value was 5 or less, and 1501.2 g of deionized water was added to obtain a desired resin composition B solution.

Production Example 2 Production of Resin Composition A Polybutadiene dicarboxylic acid (trade name: NISSO P
660 g of BC1000 (manufactured by Nippon Soda Co.) and 60 g of 2-butyne-1,4-diol (manufactured by BASF) are dissolved in 145 g of xylene, and 0.7 g of p-toluenesulfonic acid is dissolved.
Was added. The mixture was refluxed for 7 hours while being dehydrated at 150 ° C. for condensation. When the theoretical amount of water was generated, the solvent was removed under reduced pressure, and the number average molecular weight was 6070 and the glass transition temperature was −21.1.
A resin composition A solution having a hydroxyl value of 18.5 ° C. was obtained.

Example 1 Cationic electrodeposition coating composition 1 The above resin was adjusted so that the solid content of the resin composition A obtained in Production Example 2 was 17% by weight in the solid content of the resin composition for cationic electrodeposition coating composition. After mixing the composition A solution and the resin composition B solution, 0.3% by weight of an aluminum-acetylacetonate complex, 150 ppm of tocopherol, soybean lecithin (phospholipid 65 75%, iodine value 85, manufactured by Nisshin Oil Co., Ltd.) 75
ppm was added, deionized water was added to adjust the solid content to 70% by weight, and the mixture was stirred with a high-speed rotary mixer for 1 hour. Further, deionized water was added to a solid content concentration of 23.5% by weight, and cerium acetate was added to 0.3% by weight and copper acetate was added to 0.2% by weight, and then N-methylethanolamine was added. The composition for a cationic electrodeposition coating composition was added and stirred at 8 meq per 100 g of resin solid content. Further, deionized water was added to obtain a cationic electrodeposition coating composition 1 having a solid content concentration of 20% by weight.

Examples 2 to 4 and Comparative Examples 1 to 4
Electrodeposition paint composition 2-8 Cationic electrodeposition paint composition 2 having a solid content of 20% by weight in the same manner as in Example 1 except that it was blended based on Table 1.
~ 8.

Evaluation Tests The following tests were performed on the cationic electrodeposition coating compositions 1 to 8 obtained in Examples 1 to 4 and Comparative Examples 1 to 4. The results obtained are shown in Table 1.

A steel sheet (JIS G 314) treated with Surfdyne SD-5000 (trade name, manufactured by Nippon Paint Co., Ltd.)
Electrodeposition coating was performed using 1 SPCC-SD) as a cathode and a stainless steel container as an anode. The object to be coated was lifted from the electrodeposition bath, washed with water, and baked at 170 ° C. for 20 minutes to obtain an electrodeposition coating film.

30 cm, 40 cm above the electrodeposition coating film,
A 500 g weight was dropped from a height of 50 cm, and the impact resistance was evaluated. The maximum height at which the peeling of the coating film surface did not occur was shown. 40 cm or more was regarded as a pass.

The initial appearance (Ra value) of the coated plate surface of the electrodeposited coating film was measured with a surface roughness meter. The measurement condition was a cutoff of 2.5 mm. 3% N with a wound of about 10cm in length reaching the substrate at 3cm intervals
After immersing in an aCl aqueous solution and leaving it at 55 ° C. for 10 days after sealing, the tape was adhered and peeled off, the peeling width of the electrodeposition coating film was measured, and the initial anticorrosion property was evaluated. The appearance and anticorrosion properties were in accordance with the following evaluation criteria. <Appearance> ：: 0.3 μm or less, acceptable level. ：: More than 0.3 μm and 0.4 μm or less, which is a pass level. Δ: Over 0.4 μm and 0.55 μm or less, rejection level. ×: Over 0.55 μm, reject level. <Corrosion prevention> ○: The peeling width is 3 mm or less on one side. Δ: The peel width is more than 3 mm on one side and less than 5 mm. X: The peeling width is 5 mm or more on one side to the entire surface.

Further, each of the cationic electrodeposition coating compositions obtained as described above was stored with stirring at 40 ° C. for 4 weeks, and then an electrodeposition coating film was prepared in the same manner. And anticorrosion properties were evaluated.

[0110]

[Table 1]

As is clear from Table 1, the examples using the phenolic polymerization inhibitor and the phospholipid within the scope of the present invention respectively showed good impact resistance, corrosion resistance and appearance both in the initial stage and in the aging stage. In particular, those using tocopherol as a phenolic polymerization inhibitor were excellent, while those using no phenolic polymerization inhibitor and / or phospholipid or using an addition amount outside the above range were used. In each of the examples, impact resistance, corrosion resistance, and deterioration with time in appearance were observed.

[0112]

Since the cationic electrodeposition coating composition of the present invention has the above-mentioned constitution, the cationic electrodeposition coating composition of the present invention has high throwing power and the anticorrosion property of the obtained electrodeposition coating film. In a state where the resin composition has excellent impact resistance and is not heated during storage or electrodeposition, it is possible to suppress a side reaction between active oxygen, radicals, and the like and an unsaturated double bond introduced into the resin. This is considered to be because the ability of the phenolic polymerization inhibitor deteriorated by the reaction of the phospholipid with a radical or the like can be restored again.
As a result, problems of the paint due to the polymerization reaction of the unsaturated double bond are suppressed for a long time, and the temporal stability of the paint can be maintained.

Therefore, in particular, excellent impact resistance equivalent to that of the initial stage, without causing a decrease in these properties after storage,
An electrodeposition coating film having corrosion resistance, impact resistance and appearance can be obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C25D 13/06 C25D 13/06 C (72) Inventor Ichiro Kawakami 19-17 Ikedanakamachi, Neyagawa-shi, Osaka Japan Int. In-house (72) Inventor Hiroyuki Sakamoto 19-17 Ikedanakamachi, Neyagawa-shi, Osaka F-term (reference) 4J038 CB001 CB002 CG141 CG142 CH121 CH122 DB061 DB062 DB071 DB072 DB091 DB092 DB201 DB202 DB221 DB222 DB301 DB302 DB401 DB402 DD041 DD042 DE001 DE002 DF001 DF002 DG001 DG002 DG111 DG112 DG121 DG122 DG131 DG132 DG141 DG142 DG191 DG192 DG231 DG232 GA01 GA13 JA64 JC43 KA02 MA14 NA11 NA26 PA04 PA19 PB07 PC02

Claims (7)

[Claims] 1. A cationic electrodeposition coating composition comprising a resin composition (A) and a resin composition (B), and a cationic electrodeposition coating composition comprising a phenolic polymerization inhibitor and a phospholipid. The resin composition (A) has a number average molecular weight of 1
(A1) and (A)
2): (A1) Polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol, polyolefin polyol and acrylic polyol (A2) From the group consisting of (A1) and an isocyanate group, a carboxyl group and an epoxy group in the molecule A compound having at least one functional group selected, a dialkyl carbonate, a cyclic carbonate, an alcohol,
And at least one selected from the group consisting of polymers obtained by reaction with these mixtures, wherein the resin composition (B) has a number average molecular weight of 500 to 2
000, and the solid content of the resin composition (B) is 100
per g, 5-400 mmol of sulfonium groups, 10-485 mmol of propargyl groups and 1 unsaturated double bond
0 to 485 mmol, and the total content of the sulfonium group, the propargyl group and the unsaturated double bond is 500 mmol or less per 100 g of solid content of the resin composition (B), and the phenolic polymerization The content of the inhibitor is 100 to 1000 ppm by weight based on the solid content of the resin composition for cationic electrodeposition coating, and the content of the phospholipid is the same as the solid content of the resin composition for cationic electrodeposition coating. 30-1000pp by weight
m, and the content of the phenolic polymerization inhibitor / the content of the phospholipid is 100/100 to 100 /
5. A cationic electrodeposition coating composition, wherein the composition is 5. 2. The cationic electrodeposition coating composition according to claim 1, wherein the phenolic polymerization inhibitor contains one to three aromatic rings in the molecule in which at least one hydrogen atom is substituted by a hydroxyl group. Composition. 3. The cationic electrodeposition coating composition according to claim 1, wherein the phenolic polymerization inhibitor contains 1 to 3 phenolic hydroxyl groups in the molecule. 4. The cationic electrodeposition coating composition according to claim 1, wherein the phenolic polymerization inhibitor has a molecular weight of 100 to 500. 5. The cationic electrodeposition coating composition according to claim 1, wherein the phospholipid has an iodine value of 120 or less. 6. The cationic electrodeposition coating composition according to claim 1, wherein the phospholipid is lecithin or kephalin. 7. An electrodeposition coating is obtained by electrodepositing the cationic electrodeposition coating composition according to any one of claims 1 to 6 on an object to be coated, followed by heating to obtain an electrodeposition coating. A method for forming a coating film, comprising forming a coating film.