JP6461618B2 - Cationic electrodeposition coating composition - Google Patents

Description

  The present invention relates to a cationic electrodeposition coating composition that is excellent in coating stability, coating finish, and corrosion resistance.

  Conventionally, cationic electrodeposition paints are widely used in automobile parts, electrical equipment parts, and other industrial equipments that require these performances because of the excellent coating workability and good corrosion resistance of the formed coating film. ing. Such electrodeposition coating equipment for cationic electrodeposition paints includes collection water washing equipment, UF filtration equipment, precision filtration equipment, etc. in addition to the electrodeposition paint tank, and filtration equipment if the cationic electrodeposition paint has poor paint stability. May cause clogging or deterioration of finish. For this reason, various cationic electrodeposition coatings that have excellent coating stability and satisfy performances such as anticorrosion, finishing, and throwing power have been proposed.

  For example, a cationic coating composition containing, as a vehicle component, a xylene formaldehyde resin-modified amino group-containing epoxy resin produced by reacting an xylene formaldehyde resin and an amino group-containing compound with an epoxy resin having an epoxy equivalent of 180 to 2500 It is disclosed that it is excellent in corrosion resistance, adhesion, electrodeposition coating suitability of rust-proof steel sheet and paint stability. (Patent Document 1) However, there are cases where the balance of electrodeposition coating suitability, throwing power, finish, and corrosion resistance is insufficient.

  Moreover, the cationic electrodeposition coating material containing the water-soluble polyester resin whose number average molecular weight is 1,000-10,000, an acid value is 20-80, and a hydroxyl value is 50-200 is disclosed (patent document 2). . However, when a polyester resin having an acid value of 20 to 80 is used for a cationic electrodeposition paint containing an amino group-containing epoxy resin as a base resin, the paint stability may be impaired due to acid-base interaction.

  And a cationic electrodeposition coating composition comprising a polyester resin having an acid value of 10 mgKOH / g or less and a number average molecular weight of 1,000 or more and 7,000 or less, an amino group-containing epoxy resin and a blocked polyisocyanate curing agent. In addition, it is disclosed that the paint stability is good, and the throwing power and corrosion resistance are excellent. (Patent Document 3) However, an electrodeposition paint in which aqueous dispersions having different resin compositions are mixed may impair the paint stability when a load is applied on the painting line.

  Also disclosed is a cationic electrodeposition coating composition excellent in water dispersibility (paint stability) containing a polyether-modified amino group-containing epoxy resin, a xylene-formaldehyde resin-modified amino group-containing epoxy resin and a blocked polyisocyanate curing agent. Has been. (Patent Document 4) However, the balance between paint stability and anticorrosion properties is insufficient, and paint stability may be inferior in a long-term stability test.

JP 2003-221547 A JP 2003-10774 A JP2013-241582A JP 2009-84567 A

  The problem to be solved by the present invention is to provide a cationic electrodeposition coating composition excellent in coating stability, finish, and corrosion resistance, and a coated article excellent in these various coating film performances.

  As a result of intensive studies in order to solve the above-mentioned problems, the inventors contain an amino group-containing epoxy resin (A) obtained by reacting a specific amine compound and a blocked polyisocyanate curing agent (B). The present inventors have found that the above-mentioned problems can be solved by the cationic electrodeposition coating composition, and have completed the present invention.

That is, the present invention provides the following cationic electrodeposition coating composition and a coated article obtained by electrodeposition-coating the cationic electrodeposition coating composition on an object to be coated:
Item 1. An amino group-containing epoxy resin (A) obtained by reacting an amine compound (a1) containing at least one amine compound (a1-1) represented by the following formula (1) with an epoxy resin (a), and a blocked poly A cationic electrodeposition coating composition comprising an isocyanate curing agent (B).
R ₁ —NH—R ₂ —OH Formula (1)
(In the formula, R ₁ and R ₂ are linear or branched hydrocarbon groups having 1 to 8 carbon atoms, which may be different or the same.)

Item 2. R ₁ is a linear or branched hydrocarbon group having 3 to 4 carbon atoms, the cationic electrodeposition coating composition according to claim 1.

Item 3. Item 3. The item 1 or 2, wherein R ₁ is a linear or branched hydrocarbon group having 3 carbon atoms, and R ₂ is a linear or branched hydrocarbon group having 3 to 4 carbon atoms. Cationic electrodeposition coating composition.

Item 4. Item 1. The amine compound (a1) further contains an amine compound (a1-2) represented by the following formula (2) or a ketiminate thereof in addition to the amine compound (a1-1). The cationic electrodeposition coating composition of any one of -3.
_{X 1 -R 3 -NH-R 4} -X 2 ··· (2)
(In the formula, R ₃ and R ₄ are linear or branched hydrocarbon groups having 1 to 8 carbon atoms, which may be different or the same. X ₁ and X ₂ may be a hydroxyl group and / or (It is an amino group, and they may be different or the same. However, when X ₁ and X ₂ are amino groups, at least one of R ₃ and R ₄ is a hydrocarbon group having 1 to 2 carbon atoms.)

  Item 5. The amino group-containing epoxy resin (A) is composed of at least one modifier selected from xylene formaldehyde resin, polyalkylene glycol compound, fatty acid, alkylene glycol, polyamidoamine, polycarboxylic acid, polyisocyanate compound, lactone compound, and catechol compound. Item 5. The cationic electrodeposition coating composition according to any one of Items 1 to 4, which is an amino group-containing modified epoxy resin (A1) that is modified.

  Item 6. The cationic electrodeposition coating composition further contains a hydroxyl group-containing resin (C), and the component (A) is contained in an amount of 40 to 85 on the basis of the total resin solid mass of the components (A), (B) and (C). Item 6. The cationic electrodeposition coating composition according to any one of Items 1 to 5, comprising 10% by mass to 10% by mass of the component (B) and 5 to 50% by mass of the component (C).

  Item 7. The hydroxyl group-containing resin (C) is at least one selected from a hydroxyl group-containing acrylic resin (C1), a hydroxyl group-containing polyester resin (C2), and a hydroxyl group-containing epoxy resin (C3) not containing an amino group. Item 7. The cationic electrodeposition coating composition according to Item 6.

  Item 8. Item 6 or 7 is characterized in that the solubility parameter δA of the amino group-containing epoxy resin (A) and the solubility parameter δC of the hydroxyl group-containing resin (C) have a relationship of | δA−δC | <1.3. The cationic electrodeposition coating composition as described.

  Item 9. The amine value of the amino group-containing epoxy resin (A) is 50 mg KOH / g or more based on the resin solid content, and the amine value obtained by adding the components (A), (B) and (C) is based on the resin solid content. The cationic electrodeposition coating composition according to any one of Items 6 to 8, wherein the composition is in the range of 20 to 100 mg KOH / g.

  Item 10. Item 1-9, wherein the cationic electrodeposition coating composition contains 0.01 to 10.0% by mass of at least one metal compound (D) based on the total mass of the resin solids. The cationic electrodeposition coating composition according to any one of the above.

  Item 11. Item 11. The cationic electrodeposition coating composition, wherein the metal compound (D) according to Item 10 is a bismuth compound and / or a zinc compound.

  Item 12. The cationic electrodeposition coating composition according to any one of Items 1 to 11 is used as an electrodeposition coating bath, and a metal coating including an alloyed hot-dip galvanized steel sheet is immersed in the electrodeposition coating bath and obtained by electrodeposition coating. Painted article.

The cationic electrodeposition coating composition of the present invention ensures good coating stability, and the coating film obtained by electrodeposition coating of the cationic electrodeposition coating composition is excellent in finish and corrosion resistance.
Specifically, an automobile body coated with the product of the present invention has little corrosion deterioration even when traveling in an environment where snow melting salt is dispersed for a long period of time. Further, the coating composition of the present invention has good coating stability without causing the UF filter to clog over a long period even in a coating line for UF filtration.

FIG. 1 shows an outline of the paint stability in Examples of the present application.

  The present invention relates to a cationic electrodeposition coating composition containing an amino group-containing epoxy resin (A) reacted with a specific amine compound and a blocked polyisocyanate curing agent (B). The cationic electrodeposition coating composition can be rephrased as a cationic electrodeposition coating composition containing an aqueous dispersion containing the components (A) and (B). Details will be described below.

Amino group-containing epoxy resin (A)
As an amino group-containing epoxy resin (A) that can be used in the electrodeposition coating composition of the present invention, an amine compound (a1) containing at least one amine compound (a1-1) of the following formula (1) is used. An amino group-containing epoxy resin (A) reacted with the epoxy resin (a).
R ₁ —NH—R ₂ —OH Formula (1)
(In the formula, R ₁ and R ₂ are linear or branched hydrocarbon groups having 1 to 8 carbon atoms, which may be different or the same.)
The epoxy resin (a) used as a raw material for the amino group-containing epoxy resin (A) is a compound having at least one, preferably two or more epoxy groups in one molecule. The epoxy resin (a) preferably has a number average molecular weight in the range of at least 300, preferably 400 to 4,000, more preferably 800 to 2,500. Moreover, as the said epoxy resin (a), what has the epoxy equivalent in the range of at least 160, Preferably 180-2,500, More preferably 400-1,500 is suitable. As this epoxy resin, what is obtained by reaction of a polyphenol compound and epihalohydrin (for example, epichlorohydrin etc.) can be used, for example.

  Examples of the polyphenol compound used for forming the epoxy resin include bis (4-hydroxyphenyl) -2,2-propane [bisphenol A], bis (4-hydroxyphenyl) methane [bisphenol F], bis ( 4-hydroxycyclohexyl) methane [hydrogenated bisphenol F], 2,2-bis (4-hydroxycyclohexyl) propane [hydrogenated bisphenol A], 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1, 1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-3-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, tetra ( 4-hydroxyphenyl) -1,1,2,2-ethane, 4,4 - it can be exemplified dihydroxydiphenyl sulfone, phenol novolak, and cresol novolak.

  Moreover, as an epoxy resin (a) obtained by reaction of a polyphenol compound and epihalohydrin, a resin of the following formula derived from bisphenol A or a resin using this as a raw material (for example, a resin of the following formula and a polyphenol compound further) And the like are preferred.

Here, what is shown by n = 0-8 is suitable.

  Examples of such commercially available epoxy resins include those sold by Mitsubishi Chemical Corporation under the trade names jER828EL, jER1002, jER1004, and jER1007.

Amine compound (a1)
The amine compound (a1) which is a raw material of the amino group-containing epoxy resin (A) used in the present invention contains at least one amine compound (a1-1) represented by the following formula (1).
R ₁ —NH—R ₂ —OH Formula (1)
(In the formula, R ₁ and R ₂ are linear or branched hydrocarbon groups having 1 to 8 carbon atoms, which may be different or the same.)
Amine compound (a1-1)
Examples of the amine compound (a1-1), in the formula (1), the carbon number of _{R 1} is usually 1-8, preferably 2-6, more preferably 3-4, particularly preferably 3, It is suitable that the carbon number of R2 is usually 1 to 8, preferably 2 to 4, more preferably 3 to 4, particularly preferably 3.
Specifically, for example, monomethylethanolamine, monomethylpropanolamine, monomethylbutanolamine, monoethylethanolamine, monoethylpropanolamine, monoethylbutanolamine, monopropylethanolamine, monopropylpropanolamine, monopropylbutanolamine, mono Examples thereof include butylethanolamine, monobutylpropanolamine, and monobutylbutanolamine, and these can be used alone or in combination of two or more.
In addition, the hydrocarbon groups of R ₁ and R ₂ described above include all possible isomers. Thus, for example, propyl shall include isopropyl and butyl shall include n-butyl, isobutyl and t-butyl.

The amine compound (a1-1) can be obtained, for example, by reacting a monoalkylamine and an alkylene oxide. The monoalkylamine is not particularly limited, but monomethylamine, monoethylamine, mono n-propylamine, monoisopropylamine, mono n-butylamine, monoisobutylamine, monosec-butylamine, mono-t-butylamine, mono-n -Linear or branched monoalkylamines having 1 to 6 carbon atoms such as pentylamine, isopentylamine, mono n-hexylamine, etc. can be used, preferably monomethylamine, monoethylamine, Mono n-propylamine, monoisopropylamine, mono n-butylamine, monoisobutylamine, mono-t-butylamine can be used, and monomethylamine, monoethylamine, mono n-propylamine, monoisopropylamine, mono n-Buchi Amines can be used. Although there is no restriction | limiting in particular as said alkylene oxide, For example, alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, can be used, Ethylene oxide and propylene oxide can be used suitably.
The method for synthesizing the amine compound (a1-1) is not particularly limited, and is described in, for example, JP-A Nos. 2004-275933, 59-13751, and 8-333310. Can be synthesized by known methods.

The amine compound other than the amine compound (a1-1) The amine compound other than the amine compound (a1-1) is not particularly limited as long as it is an amine compound having reactivity with the above-described epoxy resin (a). Dialkylenetriamines such as dimethylenetriamine and diethylenetriamine; monomethylamine, dimethylamine, monoethylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, dioctylamine, monoisopropylamine, diisopropylamine, monobutylamine, monooctylamine, methyl Mono-alkylamines or di-alkylamines such as butylamine and dibutylamine; monoethanolamine, diethanolamine, mono (2-hydroxypropyl) amine, di (2-hydroxypropyl) Min, dipropanolamine, N- (2-hydroxypropyl) ethylenediamine, 3-methylamine-1,2-propanediol, 3-tert-butylamino-1,2-propanediol, N-methylglucamine, N- Alkanolamines such as octylglucamine; polymethylenediamine, polyetherdiamine, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, dimethylaminopropylamine, diethylaminopropylamine, bis (4-aminobutyl) amine Alkylene polyamines such as mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, metaxylylenediamine, metaphenylenediamine, naphthylenediamine Aromatic or alicyclic polyamines such as dimethylaminomethylbenzene; polyamines having a heterocyclic ring such as piperazine, 1-methylpiperazine, 3-pyrrolidinol, 3-piperidinol, 4-pyrrolidinol; Epoxy-added polyamine obtained by adding 1 to 30 mol of an epoxy group-containing compound; the above polyamine and aromatic acid anhydride, cyclic aliphatic acid anhydride, aliphatic acid anhydride, halogenated acid anhydride and / or dimer A polyamide polyamine containing at least one primary or secondary amine in the molecule of the polyamide resin formed by condensation with an acid; reacting one or more primary or secondary amines in the polyamine with a ketone compound; Ketiminized amines, etc., which may be used alone or in combination of two or more. Can be used.

Especially, it is more preferable from a viewpoint which balances sclerosis | hardenability and hydrophilicity to contain the amine compound (a1-2) or its ketimine compound represented by following formula (2) with the said amine compound (a1-1). .
_{X 1 -R 3 -NH-R 4} -X 2 ··· (2)
(In the formula, R ₃ and R ₄ are linear or branched hydrocarbon groups having 1 to 8 carbon atoms, which may be different or the same. X ₁ and X ₂ may be a hydroxyl group and / or (It is an amino group, and they may be different or the same. However, when X ₁ and X ₂ are amino groups, at least one of R ₃ and R ₄ is a hydrocarbon group having 1 to 2 carbon atoms.)
Examples of the amine compound (a1-2) include amine compounds represented by the following formulas (3) to (5).
_{HO-R 3 -NH-R 4} -OH ··· formula (3)
Specific examples of the amine compound of the above formula (3) include dialkanolamines such as dibutanolamine, dipropanolamine, diethanolamine, and dimethanolamine. Of these, hydrocarbon groups of R ₃ and R ₄ having 1 to 2 carbon atoms are preferred, and specifically, dimethanolamine and diethanolamine are preferred.
HO—R ₃ —NH—R ₄ —NH ₂ Formula (4)
Specific examples of the amine compound of the above formula (4) include N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, and N- (aminomethyl). ) Butanolamine, N- (aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl) methanolamine, N -(Aminopropyl) ethanolamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- (aminobutyl) Propanolamine, N- (aminobutyl) buta Alkanolamine having an alkyl group having 1 to 4 carbon atoms such as Ruamin like. Of these, hydrocarbon groups of R ₃ and R ₄ having 1 to 2 carbon atoms are preferred. Specifically, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- ( Aminoethyl) methanolamine and N- (aminoethyl) ethanolamine are preferred.
NH ₂ —R ₃ —NH—R ₄ —NH ₂ Formula (5)
As the amine compound of the above formula (5), the hydrocarbon group of at least one (preferably both) of R ₃ and R ₄ has 1 to 2 carbon atoms, specifically, dimethylenetriamine, diethylenetriamine, and the like. Can be mentioned. Of these, diethylenetriamine is preferable.
The hydrocarbon groups represented by R ₃ and R ₄ described above include all possible isomers. Thus, for example, propyl shall include isopropyl and butyl shall include n-butyl, isobutyl and t-butyl.

In addition, the amine compound (a1-2) represented by the above formulas (4) and (5) is obtained by reacting a primary amine at the terminal of the amine compound with a ketone compound in order to prevent high molecular weight during resin synthesis. A production method in which the secondary amine and the epoxy group of the epoxy resin are reacted after ketiminization and then converted back to the primary amine by hydrolysis when forming a paint (emulsion) is preferable. The amino group-containing epoxy resin (A) used in the present invention has a primary amino group that is a water-dispersing group at the end of the resin, so that good paint stability can be obtained in an aqueous paint.
The ketone used for ketiminization is not particularly limited as long as it reacts with the primary amine of the amine compound (a1-2) to be a ketimine compound and further hydrolyzes in the aqueous coating composition. For example, methyl isopropyl ketone (MIPK), diisobutyl ketone (DIBK), methyl isobutyl ketone (MIBK), diethyl ketone (DEK), ethyl butyl ketone (EBK), ethyl propyl ketone (EPK), dipropyl ketone (DPK), Examples thereof include methyl ethyl ketone (MEK). Of these, methyl isobutyl ketone (MIBK) is preferable. These ketones can be used alone or in combination of two or more.

  The reason why the cationic electrodeposition coating composition of the present invention is excellent in coating stability, finish, and corrosion resistance is not known in detail, but the amino group-containing epoxy resin used in the present invention is relatively basic strength and By using the amine compound (a1-1) having a strong hydrophilic property as a constituent component, the affinity for water is increased, the stability in the aqueous coating composition is increased, and the amine compound (a1 having a further hydrophilic property). -2) is considered to be able to balance hydrophilicity (coating stability) and curability. Here, the “basic strength is strong” of the amine compound means that when the hydrocarbon group bonded to the amine compound has a relatively large number of carbon atoms, it becomes an electron donating group, so that the basic strength of the amino group is higher. It is thought that it is raised.

Denaturant The amino group-containing epoxy resin (A) used in the present invention can be modified with a denaturant as necessary. Such modifiers include, for example, xylene formaldehyde resins, polyether polyols, polyester polyols, fatty acids, phenols, alkylene glycols, monohydric alcohols, polyamidoamines, polycarboxylic acids, polyisocyanate compounds, lactone compounds, catechol compounds, acrylics. The compound etc. which carried out the polymerization reaction of the monomer and the acrylic monomer are mentioned, These modifiers can be used individually by 1 type or in combination of 2 or more types.

  Among these, as the modifier, it is preferable to use at least one selected from fatty acids, xylene formaldehyde resins, polyether polyols, and alkylene glycols from the viewpoints of paint stability and / or anticorrosion properties.

The fatty acid is preferably a long-chain fatty acid having 8 to 22 carbon atoms. For example, caprylic acid, capric acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearin Examples include acids, oleic acid, linoleic acid, and linolenic acid. These can be used alone or in combination of two or more.
Of these, phenol and cresols are preferred. Especially, a C10-20 long chain fatty acid is more preferable, and a C13-18 long chain fatty acid is still more preferable.

  The xylene formaldehyde resin can be produced, for example, by subjecting xylene, formaldehyde and phenols to a condensation reaction in the presence of an acidic catalyst.

  As said formaldehyde, the compound which generate | occur | produces formaldehyde, such as formalin, paraformaldehyde, and trioxane which are industrially easy to obtain, can be used, for example. The phenols include monovalent or divalent phenolic compounds having two or three reaction sites. Specifically, for example, phenol, cresols, para-octylphenol, nonylphenol, bisphenol. Examples include propane, bisphenol methane, resorcinol, pyrocatechol, hydroquinone, para-tert-butylphenol, bisphenol sulfone, bisphenol ether, para-phenylphenol, etc., and these may be used alone or in combination of two or more. it can. Of these, phenol and cresols are preferred.

  The polyether polyol can usually have a number average molecular weight in the range of 62 to 10,000, preferably 62 to 2,000, such as alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc.). ), Which are produced by a ring-opening addition reaction of), include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene propylene) glycol, bisphenol A polyethylene glycol ether, bisphenol A polypropylene glycol ether, and the like. Can be used alone or in combination of two or more. Among these, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol are preferable.

  Moreover, the said polyalkylene glycol contains what contains polyalkylene glycol in the resin frame | skeleton of an epoxy resin (a). Usually, such an epoxy resin is (α) a method of reacting an epoxy resin having at least one, preferably two or more epoxy groups, with an alkylene oxide or a polyalkylene glycol, (β) the above polyphenol compound, and an epoxy group. Can be obtained by, for example, a method of reacting a polyalkylene glycol having at least one, preferably two or more with a polyphenol compound, if necessary. Moreover, you may use the epoxy resin already containing polyalkylene glycol. (For example, see the specification of JP-A-8-337750)

  Examples of commercially available products include Glycier PP-300P (trade name, manufactured by Sanyo Chemical Industries, polypropylene glycol diglycidyl ether), Epolite 200E, Epolite 400E (both manufactured by Kyoeisha Chemical Co., Ltd., trade name, polyethylene glycol diglycidyl ether). These can be used alone or by reacting with a polyphenol compound such as bisphenol A and / or an epoxy resin, and can be used as an epoxy resin (a) which is a raw material of the amino group-containing epoxy resin (A).

  Moreover, as an alkylene group of polyalkylene glycol, a C2-C8 alkylene group is preferable, an ethylene group, a propylene group, or a butylene group is more preferable, and a propylene group is especially preferable.

  Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,3-propanesiol, 3-methyl-1,5-pentanediol, 2 -Methylpentane-2,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol, etc. Can be used alone or in combination of two or more. Among these, a linear dihydric alcohol having 2 to 8 carbon atoms is preferable, and 1,6-hexanediol is more preferable.

  In addition, the alkylene glycol includes those that already contain alkylene glycol in the resin skeleton of the epoxy resin (a). Examples of commercially available products include Denacol EX-212L (trade name, manufactured by Nagase ChemteX, 1,6-hexanediol diglycidyl ether), Denacol EX-214L (trade name, manufactured by Nagase ChemteX, 1,6- Hexanediol diglycidyl ether), SR-16H (trade name, manufactured by Sakamoto Pharmaceutical Co., Ltd., 1,6-hexanediol diglycidyl ether), SR-NPG (trade name, manufactured by Sakamoto Pharmaceutical Co., Ltd., neopentyl glycol diglycidyl ether) ), SR-PG (trade name, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., propylene glycol diglycidyl ether) and the like. These may be used alone or reacted with a polyphenol compound such as bisphenol A and / or an epoxy resin to produce an amino group. Epoxy resin (a) that is a raw material for the epoxy resin (A) It can be used in.

Production Method The above-mentioned addition reaction of the amine compound and / or the modifier to the epoxy resin (a) is usually carried out at a temperature of about 80 to about 170 ° C., preferably about 90 to about 150 ° C. in a suitable solvent. About 6 hours, preferably about 1 to 5 hours.

  Examples of the solvent include hydrocarbons such as toluene, xylene, cyclohexane, and n-hexane; esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone. Amides such as dimethylformamide and dimethylacetamide; Alcohols such as methanol, ethanol, n-propanol and iso-propanol; Ether alcohol compounds such as ethylene glycol monobutyl ether and diethylene glycol monoethyl ether; or a mixture thereof Can be mentioned.

  The number average molecular weight of the amino group-containing epoxy resin (A) is usually in the range of 1,000 to 50,000, and more preferably in the range of 1,300 to 20,000, from the viewpoints of finish and corrosion resistance. More preferably, it is preferably in the range of 1,600 to 10,000. The amine value of the amino group-containing epoxy resin (A) is usually 50 mgKOH / g or more, preferably in the range of 54 to 200 mgKOH / g, more preferably in the range of 57 to 150 mgKOH / g, based on the resin solid content. preferable.

  The amine value in this specification is measured according to JIS K 7237-1995. All are amine values (mgKOH / g) per resin solid content.

  In addition, in this specification, the number average molecular weight and the weight average molecular weight are the retention time (retention capacity) measured using a gel permeation chromatograph (GPC), and the retention time of standard polystyrene with a known molecular weight measured under the same conditions. (Retention capacity) is a value obtained by converting to the molecular weight of polystyrene. Specifically, “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” are used as columns. ”And“ TSKgel G-2000HXL ”(trade names, all manufactured by Tosoh Corporation), and can be measured under the conditions of mobile phase tetrahydrofuran, measurement temperature 40 ° C., flow rate 1 mL / min, and detector RI. it can.

Blocked polyisocyanate curing agent (B)
The blocked polyisocyanate curing agent (B) is an addition reaction product of approximately the theoretical amount of a polyisocyanate compound and an isocyanate blocking agent. As the polyisocyanate compound used in the blocked polyisocyanate curing agent (B), known compounds can be used, such as tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,2′-diisocyanate. , Diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, crude MDI [polymethylene polyphenyl isocyanate], bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate, etc. Aromatic, aliphatic or alicyclic polyisocyanate compounds; cyclized polymers or polymers of these polyisocyanate compounds It can be mentioned, or a combination thereof; Rett body.

  In particular, aromatic polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, crude MDI (preferably crude MDI, etc.) are anticorrosive. More preferred for this.

  On the other hand, the isocyanate blocking agent is blocked by adding to the isocyanate group of the polyisocyanate compound, and the blocked polyisocyanate compound produced by the addition is stable at room temperature, but the baking temperature of the coating film (usually about 100). When heated to ˜about 200 ° C., it is desirable that the blocking agent dissociates to regenerate free isocyanate groups.

  Examples of the blocking agent used in the blocked polyisocyanate curing agent (B) include oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenol compounds such as phenol, para-t-butylphenol and cresol; n-butanol, Alcohol compounds such as 2-ethylhexanol, phenyl carbinol, methyl phenyl carbinol, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol, propylene glycol; lactam compounds such as ε-caprolactam and γ-butyrolactam; malonic acid Active methylene compounds such as dimethyl, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone (preferably alcohol-based compounds) Compound).

Hydroxyl-containing resin (C)
The cationic electrodeposition coating composition of this invention can contain a hydroxyl-containing resin (C) as needed with an amino group-containing epoxy resin (A) and a blocked polyisocyanate curing agent (B). The hydroxyl group-containing resin (C) is not particularly limited as long as it reacts with the blocked polyisocyanate curing agent (B), but a hydroxyl group-containing acrylic resin (C1), a hydroxyl group-containing polyester resin (C2), and an amino group. It is preferable that it is at least 1 sort (s) chosen from the hydroxyl-containing epoxy resin (C3) which does not contain.

  As content of each resin component, when the hydroxyl group-containing resin (C) is contained, the component (A) is 40 to 40 on the basis of the total resin solid mass of the components (A), (B) and (C). It is preferable to contain 85% by mass, 10-40% by mass of component (B), and 5-50% by mass of component (C).

  The relationship between the solubility parameter δA of the amino group-containing epoxy resin (A) and the solubility parameter δC of the hydroxyl group-containing resin (C) is usually | δA−δC | <1.3, preferably | δA −δC | <1.0, more preferably | δA−δC | <0.8, and even more preferably | δA−δC | <0.5. By satisfying such a relationship, the compatibility between the resins becomes good, and a paint excellent in paint stability and a coating film excellent in finish can be obtained.

  Here, the solubility parameter δ is generally called an SP value (solubility parameter) and is a scale indicating the degree of hydrophilicity or hydrophobicity of the resin. In addition, it is an important measure for determining the compatibility between resins, and resins with close solubility parameter values (small absolute difference in solubility parameters) generally have good compatibility It becomes. The solubility parameter is quantified numerically based on a turbidity measurement method known to those skilled in the art. Specifically, the following formula (6), K.I. W. SUH, J. et al. M.M. It can be calculated according to the CORBETT equation (Journalof Applied Polymer Science, 12, 2359, 1968).

[In the formula (6), the volume fraction of the VH is n- hexane, the volume fraction of _{V D} deionized water, delta] H is the SP value of n- hexane, [delta] _D is the SP value of the deionized water. ]

In the cloud point titration, 0.5 g of resin (solid content) as a sample was dissolved in 10 ml of tetrahydrofuran, n-hexane was gradually added, and the titration amount H (ml) at the cloud point was read. read titre D (ml) at the turbidity point of the addition of ion water, calculated applying VH, V _D, delta] H, a [delta] _D of these in the following equation. In addition, SP value of each solvent is tetrahydrofuran: 9.52, n-hexane: 7.24, deionized water: 23.43.
[VH = H / (10 + H), V _D = D / (10 + D), δH = 9.52 × 10 / (10 + H) + 7.24 × H / (10 + H), δ _D = 9.52 × 10 / (10 + D ) + 23.43 × D / (10 + D)]

  In addition, since the hydroxyl group-containing resin (C) is stably present in a paint for a long period of time with a cationic amino group-containing epoxy resin, an anionic resin having a acid value of 10 mgKOH / g or less, a nonionic resin, and It is preferably a cationic resin, more preferably an anionic resin, a nonionic resin, and / or a cationic resin having an acid value of 5 mgKOH / g or less, and a nonionic resin and / or a cationic resin. More preferably it is.

Hydroxyl group-containing acrylic resin (C1)
The hydroxyl group-containing acrylic resin (C1) that can be used in the cationic electrodeposition coating composition of the present invention can be produced by radical copolymerization of a hydroxyl group-containing acrylic monomer and other monomers.

  Examples of the hydroxyl group-containing acrylic monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and addition of 2-hydroxyethyl (meth) acrylate and caprolactone. Products (for example, Plaxel FA-2 and FM-3 as trade names manufactured by Daicel Corporation) can be used, and these can be used alone or in combination of two or more.

  Examples of the other monomers include aromatic vinyl monomers such as styrene, vinyl toluene, and α-methyl styrene, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. , N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, polyalkylene glycol (meth) acrylate, N, N-dimethyl Aminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-di-t-butylaminoethyl (meth) acrylate, N, - dimethylaminopropyl (meth) acrylamide. These can be used alone or in combination of two or more.

  The hydroxyl group-containing acrylic resin (C1) can be obtained by subjecting the above monomer to a radical copolymerization reaction by a known method.

  The hydroxyl value of the hydroxyl group-containing acrylic resin (C1) is usually in the range of 10 to 300 mgKOH / g, preferably in the range of 50 to 200 mgKOH / g, and the number average molecular weight is usually in the range of 1,000 to 100,000. The amine value is preferably in the range of 2,000 to 30,000, and the amine value is usually in the range of 0 to 300 mgKOH / g, preferably in the range of 10 to 150 mgKOH / g.

  Moreover, the amine compound containing active hydrogen can be added to the glycidyl group of the copolymer of the radically polymerizable unsaturated monomer containing glycidyl (meth) acrylate to impart water dispersibility to the acrylic resin. Examples of the amine compound include primary mono- and polyamines, secondary mono- and polyamines, or primary and secondary mixed polyamines, secondary mono- and polyamines having a ketiminated primary amino group, and ketiminated primary. Examples thereof include hydroxy compounds having an amino group, and specific examples include diethylamine, diethanolamine, and ketiminates of diethyltriamine.

Hydroxyl-containing polyester resin (C2)
The hydroxyl group-containing polyester resin (C2) that can be used in the cationic electrodeposition coating composition of the present invention can be produced by an esterification reaction and / or a transesterification reaction of an acid component and an alcohol component.

  As the acid component, a compound usually used as an acid component can be used without particular limitation in the production of a hydroxyl group-containing polyester resin. Examples of the acid component include alicyclic polybasic acids, aliphatic polybasic acids, aromatic polybasic acids, aromatic monocarboxylic acids, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and those acids. A lower alkyl esterified product or the like can be used.

  Generally, an alicyclic polybasic acid is a compound having one or more alicyclic structures (mainly 4 to 6-membered rings) and two or more carboxyl groups in one molecule, an acid anhydride of the compound, and the compound. The esterified product.

  The aliphatic polybasic acid is generally an aliphatic compound having two or more carboxyl groups in one molecule, and an acid anhydride of the aliphatic compound.

  The aromatic polybasic acid is generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, and an esterified product of the aromatic compound.

  Moreover, aromatic monocarboxylic acid, aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, etc. can also be used as needed.

  As the alcohol component, a compound usually used as an alcohol component can be used without particular limitation in the production of the polyester resin, but dihydric alcohols such as alicyclic diol, aliphatic diol, aromatic diol, and 3 What contains the polyhydric alcohol more than valence is preferable.

  As a manufacturing method of the said hydroxyl-containing polyester resin (C2), it can manufacture by reacting the said acid component and alcohol component by a well-known method.

  Further, the hydroxyl group-containing polyester resin (C2) can be modified with a fatty acid, an oil or fat, a polyisocyanate compound, an epoxy compound or the like during the preparation of the resin, or after the esterification reaction and / or after the transesterification reaction.

  The number average molecular weight of the hydroxyl group-containing polyester resin (C2) is usually 1,000 to 20,000, preferably 1,050 to 10,000, more preferably 1,100 to 5, from the viewpoint of finish. It is preferable to be within the range of 000.

  The hydroxyl value of the hydroxyl group-containing polyester resin (C2) is usually 20 to 300 mgKOH / g, preferably 30 to 250 mgKOH / g, more preferably 40 to 180 mgKOH / g, from the viewpoint of curability of the resulting coating film. It is preferable to be within the range of g.

Hydroxyl-containing epoxy resin (C3)
The hydroxyl group-containing epoxy resin (C3) that does not contain an amino group that can be used in the cationic electrodeposition coating composition of the present invention is obtained by reacting an epoxy resin with a polyhydric alcohol and, if necessary, a modifier. Can do. Here, “not containing an amino group” means substantially not containing an amino group, and having a slight amount of amine value (less than 5.0 mgKOH / g) also means “not containing an amino group”. The amino group-containing epoxy resin (A) is clearly distinguished in the range of the amine value.

  As an epoxy resin that can be used as a raw material for the hydroxyl group-containing epoxy resin (C3), known epoxy resins that are usually used in the production of amino group-containing epoxy resins for cationic electrodeposition coatings can be used. The epoxy resin (a) described in the above-mentioned amino group-containing epoxy resin (A) can be preferably used.

  The polyhydric alcohol that can be used as a raw material for the hydroxyl group-containing epoxy resin (C3) is not particularly limited as long as it is a polyhydric alcohol component having reactivity with the epoxy resin. For example, ethylene glycol, diethylene glycol, propylene glycol , Dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7 -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol 2,2,4-trimethyl-1,3-pentanediol, triethyleneglycol 2-butyl-2-ethyl-1,3-propanediol, tricyclodecane dimethanol, triethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexane Dihydric alcohols such as dimethanol, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F; polyether diols such as polyethylene glycol, polypropylene glycol, polybutylene glycol; glycerin, trimethylolpropane, tris (2- Hydroxyethyl) isocyanurate and other trihydric alcohols; pentaerythritol and other tetrahydric alcohols; polymers such as polyester polyols and acrylic polyols. In or may be used in combination of two or more.

  Moreover, a hydroxyl-containing epoxy resin (C3) can make a modifier react with an epoxy resin further as needed. Such a modifier is not particularly limited as long as it has reactivity with the epoxy resin and is a compound other than the polyhydric alcohol. For example, acetic acid, propionic acid, butyric acid, valeric acid, acrylic acid, olein Acid, glycolic acid, lactic acid, benzoic acid, gallic acid, fatty acid, dibasic acid and other acidic compounds; methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, n-octanol, Monohydric alcohols such as 2-ethylhexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol; phenols such as phenol, cresol, ethylphenol, para-tert-butylphenol, nonylphenol, catechol, resorcinol, 4-tert-butylcatechol lactones such as γ-butyrolactone and ε-caprolactone; isocyanate compounds such as hexamethylene diisocyanate and isophorone diisocyanate, or cyclized polymers thereof (for example, isocyanurates) or biuret type adducts; xylene formaldehyde compounds, etc. Can be used singly or in combination of two or more.

  As a manufacturing method of the said hydroxyl-containing epoxy resin (C3), it can manufacture by making the said epoxy resin, a polyhydric alcohol, and a modifier as needed react by a well-known method.

  The number average molecular weight of the hydroxyl group-containing epoxy resin (C3) is usually in the range of 1,000 to 50,000, preferably 1,300 to 20 from the viewpoints of paint stability, finish, corrosion resistance, and the like. Is within the range of 1,000, more preferably within the range of 1,600 to 10,000. The hydroxyl value of the hydroxyl group-containing epoxy resin (C3) is usually 10 to 300 mgKOH / g, preferably 20 to 250 mgKOH / g, more preferably 30 to 200 mgKOH / g, from the viewpoint of curability of the resulting coating film. It is preferable to be within.

Metal compound (D)
The cationic electrodeposition coating composition of this invention can contain a metal compound (D) as needed. As the metal compound (D), known compounds can be used without particular limitation. For example, titanium, cobalt, vanadium, tungsten, molybdenum, copper, indium, zinc, aluminum, bismuth, yttrium, lanthanoid metal, alkali A metal, an alkaline earth metal, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Of these, bismuth compounds and / or zinc compounds are preferred.

  Examples of the bismuth compounds include inorganic bismuth-containing compounds such as bismuth chloride, bismuth oxychloride, bismuth bromide, bismuth silicate, bismuth hydroxide, bismuth trioxide, bismuth nitrate, bismuth nitrite, and bismuth oxycarbonate; Examples thereof include bismuth, triphenyl bismuth, bismuth gallate, bismuth benzoate, bismuth citrate, bismuth methoxyacetate, bismuth acetate, bismuth formate, and bismuth 2,2-dimethylolpropionate.

  Examples of the zinc compound include zinc acetate, zinc lactate, zinc oxide, zinc nitrate, and zinc formate.

  In addition, as a density | concentration of the metal compound (C) used for the cationic electrodeposition coating composition of this invention, it is a metal element with respect to the mass of a cationic electrodeposition coating composition from a viewpoint of the anticorrosion improvement on an untreated steel plate. It is usually in the range of 0.01 to 10% by mass, preferably in the range of 0.05 to 8% by mass, and more preferably in the range of 0.1 to 5% by mass. Is preferred.

About the cationic electrodeposition coating composition The amino group-containing epoxy resin (A), the blocked polyisocyanate curing agent (B) in the cationic electrodeposition coating composition of the present invention, and the hydroxyl group-containing resin (C) blended as necessary The blending ratio of the component (A) is 30 to 90 parts by mass, preferably 40 to 85 parts by mass, based on the total resin solid mass of the components (A), (B) and (C). The coating stability is good when (B) is in the range of 10 to 50 parts by weight, preferably 10 to 40 parts by weight, and the component (C) is in the range of 0 to 50 parts by weight, preferably 5 to 50 parts by weight. Therefore, it is also preferable for obtaining a coated article having excellent finish and corrosion resistance. The amine value of the entire resin contained in the paint is usually in the range of 20 to 100 mgKOH / g and in the range of 25 to 90 mgKOH / g based on the resin solid content. More preferred.
If the mixing ratio or the amine value of the entire resin is out of the above range, either the above-mentioned paint properties or coating film performance may be impaired, which is not preferable.

  The method for producing the cationic electrodeposition coating composition of the present invention is not particularly limited. For example, the resin (A), the curing agent (B), and, if necessary, the curing agent (C), surface activity. It can be obtained by thoroughly mixing various additives such as agents and surface conditioners into a compounded resin, then dispersing in water and mixing it with pigment dispersion paste, water, organic solvent, neutralizing agent, etc. it can. As the neutralizing agent, known organic acids can be used without particular limitation, and formic acid, lactic acid, acetic acid or a mixture thereof is particularly preferable.

  The above-mentioned pigment dispersion paste is obtained by dispersing pigments such as color pigments, rust preventive pigments and extender pigments in advance in fine particles. For example, a pigment dispersion resin, a neutralizing agent and a pigment are blended, and a ball mill, a sand mill, or the like. The pigment dispersion paste can be prepared by dispersing in a dispersion mixer such as a pebble mill.

  As the pigment dispersing resin, known resins can be used without any particular limitation. For example, epoxy resins having a hydroxyl group and a cationic group, acrylic resins, surfactants, etc., tertiary amine type epoxy resins, quaternary ammonium salt type epoxies. Resin, tertiary sulfonium salt type epoxy resin, tertiary amine type acrylic resin, quaternary ammonium salt type acrylic resin, tertiary sulfonium salt type acrylic resin and the like can be used.

  As the above-mentioned pigments, known pigments can be used without particular limitation, for example, coloring pigments such as titanium oxide, carbon black, bengara, etc .; extender pigments such as clay, mica, barita, calcium carbonate, silica; The aforementioned metal compound (D) having the function can be added.

  In addition, for the purpose of improving coating film curability, organic tin compounds such as dibutyltin dibenzoate, dioctyltin oxide, and dibutyltin oxide can be used. By applying (increasing) and / or miniaturizing the zinc compound and / or bismuth compound of the metal compound (D), it is possible to improve the coating film curability without containing these organotin compounds. . The blending amount of these pigments is preferably in the range of 1 to 100 parts by weight, particularly 10 to 50 parts by weight per 100 parts by weight of the total solid content of the resin.

Coating film forming method The present invention is a method for forming a cationic electrodeposition coating film , comprising the steps of immersing a coating object in an electrodeposition bath comprising the above-mentioned cationic electrodeposition coating composition, and a step of energizing the coating object as a cathode. Provide a method.

  Examples of the object to be coated with the cationic electrodeposition coating composition of the present invention include automobile bodies, motorcycle parts, household equipment, other equipment, and the like.

  Examples of metal steel plates to be coated include cold-rolled steel plates, galvannealed steel plates, electrogalvanized steel plates, electrogalvanized steel double-layer plated steel plates, organic composite plated steel plates, Al materials, Mg materials, and these metals. The surface of the plate may be subjected to surface treatment such as phosphate chemical treatment, chromate treatment, complex oxide treatment, etc. after cleaning the surface such as alkali degreasing as required.

  The cationic electrodeposition coating composition can be applied to the surface of a desired substrate to be coated by cationic electrodeposition coating. The cationic electrodeposition method is generally diluted with deionized water or the like so that the solid content concentration is about 5 to 40% by mass, preferably 10 to 25% by mass, and the pH is 4.0 to 9.0. Preferably, the cationic electrodeposition coating composition adjusted in the range of 5.5 to 7.0 is used as a bath, usually adjusted to a bath temperature of 15 to 35 ° C., and a load voltage of 100 to 400V, preferably 150 to 350V. The current is applied by using the object to be coated as a cathode. After electrodeposition, usually ultrafiltrate (UF filtrate), reverse osmosis permeate (RO water), industrial water, pure water, etc. are sufficient to remove the cationic electrodeposition paint that has adhered to the object. Wash with water.

  Although the film thickness of an electrodeposition coating film is not specifically limited, Generally, it can be in the range of 5-40 micrometers based on a dry coating film, Preferably it can be in the range of 10-30 micrometers. The coating film is baked and dried by using a drying facility such as an electric hot air dryer or a gas hot air dryer, and the coating surface temperature is 110 to 200 ° C., preferably 140 to 180 ° C. The time is 10 to 180 minutes, preferably 20 to 50 minutes by heating the electrodeposition coating film. A cured coating film can be obtained by baking and drying.

  Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. In each example, “parts” indicates mass parts, and “%” indicates mass%.

Production and Production Example 1 of Amino Group-Containing Epoxy Resin (A) Production of Amino Group-Containing Epoxy Resin A1 Into a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 1000 parts of jER828EL (Note 1) were added to bisphenol A. 400 parts and 0.2 parts of dimethylbenzylamine were added and reacted at 130 ° C. until an epoxy equivalent of 700 was reached.
Next, 128 parts of monomethylethanolamine was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain an amino group-containing epoxy resin A1 solution having a solid content of 80%. The amino group-containing epoxy resin A1 had an amine value of 62 mgKOH / g.
(Note 1) jER828EL: trade name, epoxy resin manufactured by Japan Epoxy Resin, epoxy equivalent 190, number average molecular weight 350.

Production Example 2 Production of amino group-containing epoxy resin A2 To a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 500 parts of bisphenol A and 0.2 parts of dimethylbenzylamine were added to 1200 parts of jER828EL, and 130 parts. The reaction was allowed to proceed until the epoxy equivalent was 850 at ℃.
Next, 151 parts of monoethylethanolamine was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain an amino group-containing epoxy resin A2 solution having a solid content of 80%. The amino group-containing epoxy resin A2 had an amine value of 52 mgKOH / g.

Production Example 3 Production of Amino Group-Containing Epoxy Resin A3 To a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 1000 parts of jER828EL, 400 parts of bisphenol A and 0.2 parts of dimethylbenzylamine were added, and 130 The reaction was continued at 700C until an epoxy equivalent of 700 was reached.
Next, 151 parts of monomethyl-n-propanolamine was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain an amino group-containing epoxy resin A3 solution having a solid content of 80%. The amino group-containing epoxy resin A3 had an amine value of 61 mgKOH / g.

Production Example 4 Production of amino group-containing epoxy resin A4 To a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, 1000 parts of jER828EL, 400 parts of bisphenol A and 0.2 parts of dimethylbenzylamine were added, and 130 The reaction was continued at 700C until an epoxy equivalent of 700 was reached.
Next, 199 parts of mono-n-propyl-n-propanolamine was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain an amino group-containing epoxy resin A4 solution having a solid content of 80%. It was. The amino group-containing epoxy resin A4 had an amine value of 60 mgKOH / g.

Production Example 5 Production of amino group-containing epoxy resin A5 To a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 500 parts of bisphenol A and 0.2 parts of dimethylbenzylamine were added to 1200 parts of jER828EL, and 130 parts. The reaction was allowed to proceed until the epoxy equivalent was 850 at ℃.
Next, 83 parts of monomethylethanolamine and 160 parts of a ketimine product of diethylenetriamine and methyl isobutyl ketone were added and reacted at 120 ° C. for 4 hours. A resin A5 solution was obtained. The amino group-containing epoxy resin A5 had an amine value of 91 mgKOH / g.

Production Example 6 Production of amino group-containing epoxy resin A6 To a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, 500 parts of bisphenol A and 0.2 parts of dimethylbenzylamine were added to 1200 parts of jER828EL, and 130 parts. The reaction was allowed to proceed until the epoxy equivalent was 850 at ℃.
Next, 83 parts of monomethylethanolamine and 74 parts of diethanolamine were added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain an amino group-containing epoxy resin A6 solution having a solid content of 80%. The amino group-containing epoxy resin A6 had an amine value of 54 mgKOH / g.

Production Example 7 Production of amino group-containing epoxy resin A7 To a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, 500 parts of bisphenol A and 0.2 part of dimethylbenzylamine were added to 1200 parts of jER828EL. The reaction was allowed to proceed until the epoxy equivalent was 850 at ℃.
Next, 83 parts of monomethylethanolamine and 112 parts of a ketimine product of N- (aminoethyl) ethanolamine and methyl isobutyl ketone were added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain a solid content. An 80% amino group-containing epoxy resin A7 solution was obtained. The amino group-containing epoxy resin A7 had an amine value of 68 mgKOH / g.

Production Example 8 Production of amino group-containing epoxy resin A8 To a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, 1000 parts of jER828EL, 400 parts of bisphenol A and 0.2 parts of dimethylbenzylamine were added, and 130 The reaction was continued at 700C until an epoxy equivalent of 700 was reached.
Next, 83 parts of monomethylethanolamine and 44 parts of diethylamine were added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain an amino group-containing epoxy resin A8 solution having a solid content of 80%. The amino group-containing epoxy resin A8 had an amine value of 62 mgKOH / g.

Production Example 9 Production of Amino Group-Containing Epoxy Resin A9 To a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, 680 parts of jER828EL, Denacol EX-212 (trade name, manufactured by Nagase ChemteX Corporation, 1, 6 -Hexanediol diglycidyl ether, epoxy equivalent of about 151) 300 parts, 410 parts of bisphenol A and 0.2 part of dimethylbenzylamine were added and reacted at 130 ° C. until the epoxy equivalent reached 690.
Next, 128 parts of monomethylethanolamine was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain an amino group-containing epoxy resin A9 solution having a solid content of 80%. The amino group-containing epoxy resin A9 had an amine value of 63 mgKOH / g.

Production Example 10 Production of Amino Group-Containing Epoxy Resin A10 In a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, 50% formalin 480 parts, phenol 110 parts, 98% industrial sulfuric acid 202 parts and meta-xylene 424 The parts are charged and reacted at 84-88 ° C. for 4 hours. After the reaction is completed, the resin phase is separated from the sulfuric acid aqueous phase by standing, then the resin phase is washed with water three times, and unreacted metaxylene is stripped for 20 minutes under the condition of 20-30 mmHg / 120-130 ° C. 480 parts of a phenol-modified liquid xylene formaldehyde resin (hereinafter simply referred to as liquid xylene formaldehyde resin P) having a viscosity of 1050 PaS (25 ° C.) was obtained.
To another flask, 1000 parts of jER828EL, 400 parts of bisphenol A and 0.2 part of dimethylbenzylamine were added and reacted at 130 ° C. until an epoxy equivalent of 700 was reached. Next, 300 parts of liquid xylene formaldehyde resin P and 120 parts of monomethylethanolamine were added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain amino group-containing epoxy resin A10 having a solid content of 80%. It was. The amino group-containing epoxy resin A10 had an amine value of 49 mgKOH / g.

Production Example 11 Production Example of Amino Group-Containing Epoxy Resin A11 In a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 162 parts of Glicier PP-300P (Note 2), 1000 parts of jER828EL, bisphenol A 440 parts and 0.2 parts of dimethylbenzylamine were added and reacted at 160 ° C. until the epoxy equivalent was 800. Next, 128 parts of monomethylethanolamine was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain an amino group-containing epoxy resin A11 solution having a resin solid content of 80%. The amino group-containing epoxy resin A11 had an amine value of 55 mgKOH / g.
(Note 2) Glycier PP-300P: trade name, polypropylene glycol diglycidyl ether, manufactured by Sanyo Chemical Industries, epoxy equivalent of about 296.

Production Example 12 Production of amino group-containing epoxy resin A12 To a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, 1000 parts of jER828EL, 400 parts of bisphenol A and 0.2 parts of dimethylbenzylamine were added, and 130 The reaction was continued at 700C until an epoxy equivalent of 700 was reached.
Next, 87 parts of soybean oil fatty acid, 90 parts of monomethylethanolamine and 53 parts of a ketimine product of diethylenetriamine and methyl isobutyl ketone were added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain a solid content of 80 % Amino group-containing epoxy resin A12 solution was obtained. The amino group-containing epoxy resin A12 had an amine value of 62 mgKOH / g.

Production Example 13 Production Example of Amino Group-Containing Epoxy Resin A13 In a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 162 parts of Glicier PP-300P, 1000 parts of jER828EL, 440 parts of bisphenol A and dimethyl 0.2 part of benzylamine was added and reacted at 160 ° C. until the epoxy equivalent was 800. Next, 117 parts of mono-n-propyl-n-propanolamine and 74 parts of diethanolamine were added and reacted at 120 ° C. for 4 hours, then adjusted with ethylene glycol monobutyl ether and an amino group-containing epoxy having a resin solid content of 80%. A resin A13 solution was obtained. The amino group-containing epoxy resin A13 had an amine value of 53 mgKOH / g.

Production Example 14 Production of amino group-containing epoxy resin A14 To a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, jER828EL (1000 parts), bisphenol A (440 parts) and dimethylbenzylamine (0.2 parts) were added, and 130 The reaction was allowed to proceed until the epoxy equivalent was 720 at 0C.
Next, 87 parts of soybean oil fatty acid, 15 parts of monomethylethanolamine, and 401 parts of a ketimine product of diethylenetriamine and methyl isobutyl ketone were added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain a solid content of 80 parts. % Amino group-containing epoxy resin A14 solution was obtained. The amino group-containing epoxy resin A14 had an amine value of 156 mgKOH / g.

Production Example 15 Production Example of Amino Group-Containing Epoxy Resin A15 In a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 162 parts of Glicier PP-300P, 1000 parts of jER828EL, 440 parts of bisphenol A and dimethyl 0.2 part of benzylamine was added and reacted at 160 ° C. until the epoxy equivalent was 800. Next, 214 parts of ketimine product of diethylenetriamine and methyl isobutyl ketone and 105 parts of diethanolamine were added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to give an amino group-containing epoxy resin having a resin solid content of 80%. An A15 solution was obtained. The amino group-containing epoxy resin A15 had an amine value of 99 mgKOH / g.

Production Example 16 Production of amino group-containing epoxy resin A16 To a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, 500 parts of bisphenol A and 0.2 parts of dimethylbenzylamine were added to 1200 parts of jER828EL, and 130 parts. The reaction was allowed to proceed until the epoxy equivalent was 850 at ℃.
Next, 200 parts of diethanolamine was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain an amino group-containing epoxy resin A16 solution having a solid content of 80%. The amino group-containing epoxy resin A16 had an amine value of 56 mgKOH / g.

Production Example 17 Production of amino group-containing epoxy resin A17 solution To a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, jER828EL 1200 parts, bisphenol A 500 parts and dimethylbenzylamine 0.2 parts were added, The reaction was carried out at 130 ° C. until the epoxy equivalent was 850.
Next, 300 parts of the liquid xylene formaldehyde resin P produced in Production Example 10 and 335 parts of a ketimine product of N- (aminoethyl) ethanolamine and methyl isobutyl ketone were added and reacted at 120 ° C. for 4 hours, and then ethylene glycol. An amino group-containing epoxy resin A17 solution having a solid content of 80% was obtained by adjusting with monobutyl ether. The amino group-containing epoxy resin A17 had an amine value of 86 mgKOH / g.

Production Example 18 Production of amino group-containing epoxy resin A18 To a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser, 500 parts of bisphenol A and 0.2 part of dimethylbenzylamine were added to 1200 parts of jER828EL, and 130 parts. The reaction was allowed to proceed until the epoxy equivalent was 850 at ℃.
Next, after adding 139 parts of diethylamine and making it react at 120 degreeC for 4 hours, it adjusted with ethylene glycol monobutyl ether and obtained the amino group containing epoxy resin A18 solution of solid content 80%. The amino group-containing epoxy resin A18 had an amine value of 58 mgKOH / g.

Production Example 19 Production Example of Amino Group-Containing Epoxy Resin A19 In a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 162 parts of Glicier PP-300P, 1000 parts of jER828EL, 440 parts of bisphenol A and dimethyl 0.2 part of benzylamine was added and reacted at 160 ° C. until the epoxy equivalent was 800. Next, 335 parts of a ketimine product of N- (aminoethyl) ethanolamine and methyl isobutyl ketone was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to prepare an amino group having a resin solid content of 80%. An epoxy resin A19 solution was obtained. The amino group-containing epoxy resin A19 had an amine value of 104 mgKOH / g.

Production Production Example 20 of Blocked Polyisocyanate Curing Agent (B) Production of Curing Agent In a reaction vessel, 270 parts of Cosmonate M-200 (trade name, manufactured by Mitsui Chemicals, Crude MDI) and 127 parts of methyl isobutyl ketone were added. The temperature was raised to 70 ° C. In this, 236 parts of ethylene glycol monobutyl ether was added dropwise over 1 hour, then heated to 100 ° C., sampled over time while maintaining this temperature, and unreacted isocyanate group was measured by infrared absorption spectrum measurement. It was confirmed that the absorption of the resin was lost, and a blocked polyisocyanate curing agent having a resin solid content of 80% was obtained.

Production and Production Example 21 of Hydroxyl-Containing Acrylic Resin (C1) Production Example of Hydroxyl-Containing Acrylic Resin C1-1 246 parts of propylene glycol monomethyl ether was charged into a 2 liter four-necked flask and maintained at 110 ° C. after nitrogen substitution. In this, the mixture shown below was dripped over 3 hours.
Styrene 160 parts n-butyl methacrylate 160 parts 2-ethylhexyl acrylate 160 parts 2-hydroxyethyl methacrylate 320 parts 2,2'-azobis (2-methylbutyronitrile) 40 parts

  One hour after the completion of the dropwise addition, a solution prepared by dissolving 5 parts of 2,2′-azobis (2-methylbutyronitrile) in 56 parts of propylene glycol monomethyl ether was added dropwise over 1 hour. After completion of dropping, this was further maintained at 110 ° C. for 1 hour, and then adjusted with methyl isobutyl ketone to obtain a hydroxyl group-containing acrylic resin C1-1 solution having a solid content of 70%. The hydroxyl group-containing acrylic resin solution C1-1 had a hydroxyl value of 172 mgKOH / g, an amine value of 0 mgKOH / g, a number average molecular weight of 10,000, and an SP value (δC) of 10.0.

Production Example 22 Production Example of Hydroxyl-Containing Acrylic Resin C1-2 A 2-liter four-necked flask was charged with 246 parts of propylene glycol monomethyl ether and maintained at 110 ° C. after nitrogen substitution. In this, the mixture shown below was dripped over 3 hours.
Styrene 240 parts n-butyl methacrylate 280 parts 2-hydroxyethyl methacrylate 200 parts N, N-dimethylaminoethyl methacrylate 80 parts 2,2'-azobis (2-methylbutyronitrile) 40 parts

  One hour after the completion of the dropwise addition, a solution prepared by dissolving 5 parts of 2,2′-azobis (2-methylbutyronitrile) in 56 parts of propylene glycol monomethyl ether was added dropwise over 1 hour. After completion of dropping, this was further maintained at 110 ° C. for 1 hour, and then adjusted with methyl isobutyl ketone to obtain a hydroxyl group-containing acrylic resin C1-2 solution having a solid content of 70%. Hydroxyl group-containing acrylic resin C1-2 had a hydroxyl value of 108 mgKOH / g, an amine value of 35 mgKOH / g, a number average molecular weight of 10,000, and an SP value (δC) of 10.2.

Production Example 23 Production Example of Hydroxyl-Containing Acrylic Resin C1-3 A 2-liter four-necked flask was charged with 246 parts of propylene glycol monomethyl ether and maintained at 110 ° C. after substitution with nitrogen. In this, the mixture shown below was dripped over 3 hours.
Styrene 80 parts n-butyl methacrylate 120 parts 2-ethylhexyl acrylate 400 parts 2-hydroxyethyl methacrylate 200 parts 2,2'-azobis (2-methylbutyronitrile) 40 parts

  One hour after the completion of the dropwise addition, a solution prepared by dissolving 5 parts of 2,2′-azobis (2-methylbutyronitrile) in 56 parts of propylene glycol monomethyl ether was added dropwise over 1 hour. After completion of dropping, this was further maintained at 110 ° C. for 1 hour, and then adjusted with methyl isobutyl ketone to obtain a hydroxyl group-containing acrylic resin C1-3 solution having a solid content of 70%. Hydroxyl group-containing acrylic resin C1-3 had a hydroxyl value of 108 mgKOH / g, an amine value of 0 mgKOH / g, a number average molecular weight of 10,000, and an SP value (δC) of 9.5.

Production Example 24 Production Example of Hydroxyl-Containing Acrylic Resin C1-4 246 parts of propylene glycol monomethyl ether was charged into a 2 liter four-necked flask and purged with nitrogen, and kept at 110 ° C. In this, the mixture shown below was dripped over 3 hours.
Styrene 80 parts n-butyl methacrylate 120 parts 2-ethylhexyl acrylate 480 parts 2-hydroxyethyl methacrylate 120 parts 2,2'-azobis (2-methylbutyronitrile) 40 parts

  One hour after the completion of the dropwise addition, a solution prepared by dissolving 5 parts of 2,2′-azobis (2-methylbutyronitrile) in 56 parts of propylene glycol monomethyl ether was added dropwise over 1 hour. After completion of dropping, this was further maintained at 110 ° C. for 1 hour, and then adjusted with methyl isobutyl ketone to obtain a hydroxyl group-containing acrylic resin C1-4 solution having a solid content of 70%. The hydroxyl group-containing acrylic resin C1-4 had a hydroxyl value of 65 mgKOH / g, an amine value of 0 mgKOH / g, a number average molecular weight of 10,000, and an SP value (δC) of 9.3.

Production and Production Example 25 of Hydroxyl-Containing Polyester Resin (C2) Production of Hydroxyl-Containing Polyester Resin C2-1 A reaction apparatus having a heating apparatus, a stirrer, a nitrogen introduction tube and a fractionation tower was added with 335 parts of phthalic anhydride and 357 hexahydrophthalic acid. Part, glycerin 42 parts, ethylene glycol 190 parts, neopentyl glycol 159 parts, heating was started under dry nitrogen, and the temperature was gradually raised to 230 ° C. to carry out the esterification reaction. After maintaining the temperature at 230 ° C. and carrying out the esterification reaction until the resin acid value becomes 5 mgKOH / g, the solution is cooled to 170 ° C., added with ethylene glycol monobutyl ether, and a hydroxyl group-containing polyester resin C2- having a resin solid content of 80% by mass. One solution was obtained.

  The obtained hydroxyl group-containing polyester resin C2-1 had an acid value of 5 mgKOH / g, a hydroxyl value of 81 mgKOH / g, a number average molecular weight of 1,840, an oil length of 0% by mass, and an SP value (δC) of 10.5.

Production Example 26 Production of Hydroxyl-Containing Polyester Resin C2-2 A reaction apparatus having a heating apparatus, a stirrer, a nitrogen introduction tube and a fractionation tower was added to 335 parts of phthalic anhydride, 357 parts of hexahydrophthalic acid, 42 parts of glycerin, ethylene glycol 190. Part, neopentyl glycol 159 parts, heating was started under dry nitrogen, and the temperature was gradually raised to 230 ° C. to carry out the esterification reaction. After maintaining the temperature at 230 ° C. and carrying out the esterification reaction until the resin acid value becomes 8 mgKOH / g, it is cooled to 170 ° C., added with ethylene glycol monobutyl ether, and a hydroxyl group-containing polyester resin C2- having a resin solid content of 80% by mass. Two solutions were obtained.

  The obtained hydroxyl group-containing polyester resin C2-2 had an acid value of 8 mgKOH / g, a hydroxyl value of 84 mgKOH / g, a number average molecular weight of 1,700, an oil length of 0% by mass, and an SP value (δC) of 10.5.

Production Example 27 Production of Hydroxyl-Containing Polyester Resin C2-3 In a reaction apparatus having a heating device, a stirrer, a nitrogen introduction tube and a fractionation tower, 538 parts of phthalic anhydride, 70 parts of soybean oil, 75 parts of glycerin, 155 parts of trimethylolpropane Then, 155 parts of ethylene glycol was charged, heating was started under dry nitrogen, and the temperature was gradually raised to 230 ° C. to conduct an esterification reaction. After maintaining the temperature at 230 ° C. and carrying out the esterification reaction until the resin acid value becomes 5 mgKOH / g, the solution is cooled to 170 ° C., added with ethylene glycol monobutyl ether, and a hydroxyl group-containing polyester resin C2- having a resin solid content of 80% by mass. Three solutions were obtained.

  The obtained hydroxyl group-containing polyester resin C2-3 had an acid value of 5 mgKOH / g, a hydroxyl value of 156 mgKOH / g, a number average molecular weight of 1,840, an oil length of 8% by mass, and an SP value (δC) of 10.5.

Production Example 28 Production of Hydroxyl-Containing Polyester Resin C2-4 In a reaction apparatus having a heating device, a stirrer, a nitrogen introduction tube and a fractionation tower, 117 parts of adipic acid, 402 parts of phthalic anhydride, 146 parts of benzoic acid, 55 parts of glycerin, 109 parts of trimethylolpropane and 270 parts of 3-methyl-1,3-butanediol were charged, heating was started under dry nitrogen, and the temperature was gradually raised to 230 ° C. to conduct an esterification reaction. After maintaining the temperature at 230 ° C. and carrying out the esterification reaction until the resin acid value becomes 5 mgKOH / g, the solution is cooled to 170 ° C., added with ethylene glycol monobutyl ether, and a hydroxyl group-containing polyester resin C2- having a resin solid content of 80% by mass. Four solutions were obtained.

  The obtained hydroxyl group-containing polyester resin C2-4 had an acid value of 5 mgKOH / g, a hydroxyl value of 70 mgKOH / g, a number average molecular weight of 1,760, an oil length of 0% by mass, and an SP value (δC) of 9.9.

Production and Production Example 29 of Hydroxyl-Containing Epoxy Resin (C3) Production of Hydroxyl-Containing Epoxy Resin C3-1 A flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 1200 parts of jER828EL, 500 parts of bisphenol A and dimethyl. 0.2 part of benzylamine was added and reacted at 130 ° C. until the epoxy equivalent was 850.
Next, after adding 410 parts of bisphenol A and making it react at 120 degreeC for 4 hours, it adjusted with ethylene glycol monobutyl ether and obtained the hydroxyl-containing epoxy resin C3-1 solution of solid content 80%. The hydroxyl group-containing epoxy resin C3-1 had an amine value of 0 mgKOH / g, a number average molecular weight of 2,900, and an SP value (δC) of 10.2.

Production Example 30 Production of Hydroxyl-Containing Epoxy Resin C3-2 To a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 500 parts of bisphenol A and 0.2 part of dimethylbenzylamine were added to 1200 parts of jER828EL, The reaction was carried out at 130 ° C. until the epoxy equivalent was 850.

  Next, 212 parts of 1,6-hexanediol was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain a hydroxyl group-containing epoxy resin C3-2 solution having a solid content of 80%. The hydroxyl group-containing epoxy resin C3-2 had an amine value of 0 mgKOH / g, a number average molecular weight of 2,600, and an SP value (δC) of 10.2.

Production Example 31 Production of Hydroxyl-Containing Epoxy Resin C3-3 To a flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser, 500 parts of bisphenol A and 0.2 parts of dimethylbenzylamine were added to 1200 parts of jER828EL, The reaction was carried out at 130 ° C. until the epoxy equivalent was 850.

  Next, 198 parts of catechol was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain a hydroxyl group-containing epoxy resin C3-3 solution having a solid content of 80%. The hydroxyl group-containing epoxy resin C3-3 had an amine value of 0 mgKOH / g, a number average molecular weight of 2,200, and an SP value (δC) of 10.2.

Production Example 32 Production of Hydroxyl-Containing Epoxy Resin C3-4 In a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 480 parts of 50% formalin, 110 parts of phenol, 202 parts of 98% industrial sulfuric acid and metaxylene 424 parts are charged and reacted at 84-88 ° C. for 4 hours. After the reaction is completed, the resin phase is separated from the sulfuric acid aqueous phase by standing, then the resin phase is washed with water three times, and unreacted metaxylene is stripped for 20 minutes under the condition of 20-30 mmHg / 120-130 ° C. 480 parts of a phenol-modified liquid xylene formaldehyde resin having a viscosity of 1050 PaS (25 ° C.) were obtained.

  To another flask, 1000 parts of jER828EL, 400 parts of bisphenol A and 0.2 part of dimethylbenzylamine were added and reacted at 130 ° C. until an epoxy equivalent of 700 was reached. Next, 300 parts of liquid xylene formaldehyde resin and 189 parts of 1,6-hexanediol were added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to prepare a hydroxyl group-containing epoxy resin C3- having a solid content of 80%. Four solutions were obtained. The hydroxyl group-containing epoxy resin C3-4 had an amine value of 0 mg KOH / g, a number average molecular weight of 2,300, and an SP value (δC) of 10.2.

Production Example 33 Production of Hydroxyl-Containing Epoxy Resin C3-5 In a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 162 parts of Glicier PP-300P, 1000 parts of jER828EL, 440 parts of bisphenol A and dimethylbenzylamine 0.2 part was added and it was made to react until it became the epoxy equivalent 800 at 160 degreeC. Next, 212 parts of 1,6-hexanediol was added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to obtain a hydroxyl group-containing epoxy resin C3-5 solution having a resin solid content of 80%. The hydroxyl group-containing epoxy resin C3-5 had an amine value of 0 mgKOH / g, a number average molecular weight of 2,500, and an SP value (δC) of 10.6.

Production Example 34 Production of Hydroxyl-Containing Epoxy Resin C3-6 To a flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 500 parts of bisphenol A and 0.2 parts of dimethylbenzylamine were added to 1200 parts of jER828EL, The reaction was carried out at 130 ° C. until the epoxy equivalent was 850.

  Next, 290 parts of soybean oil fatty acid and 144 parts of 1,6-hexanediol were added and reacted at 120 ° C. for 4 hours, and then adjusted with ethylene glycol monobutyl ether to prepare a hydroxyl group-containing epoxy resin C3- having a solid content of 80%. 6 solutions were obtained. The hydroxyl group-containing epoxy resin C3-6 had an amine value of 0 mgKOH / g, a number average molecular weight of 2,400, and an SP value (δC) of 10.2.

Production and production example 35 of pigment dispersion paste Production of 1 To a flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 1010 parts of jER828EL, 390 parts of bisphenol A, Plaxel 212 (trade name, polycaprolactone diol, Daicel Chemical Industries, Ltd., weight average molecular weight) About 1,250) 240 parts and 0.2 part of dimethylbenzylamine were added and reacted at 130 ° C. until the epoxy equivalent was about 1,090. Next, 134 parts of dimethylethanolamine and 150 parts of a 90% aqueous lactic acid solution were added and reacted at 120 ° C. for 4 hours. Subsequently, methyl isobutyl ketone was added to adjust the solid content, and a quaternary ammonium salt resin resin solution for pigment dispersion having a solid content of 60% was obtained.

  Subsequently, 8.3 parts of the pigment dispersion resin solution (5 parts of solid content), 14.5 parts of titanium oxide, 8.0 parts of purified clay, 0.3 part of carbon black, 1 part of dioctyltin oxide, and deionized water 20.3 parts was added and dispersed in a ball mill for 20 hours. 1 was obtained.

Production Example 36 Pigment Dispersion Paste No. Production of 2 8.3 parts of pigment dispersion resin solution obtained in Production Example 35 (5 parts solids), 14.5 parts of titanium oxide, 7.0 parts of purified clay, 0.3 parts of carbon black, dioctyltin oxide 1 Part, 1 part of bismuth hydroxide and 20.3 parts of deionized water were added and dispersed in a ball mill for 20 hours. 2 was obtained.

Production Example 37 Pigment Dispersion Paste No. Production of 3 8.3 parts of pigment dispersion resin solution obtained in Production Example 35 (5 parts of solid content), 14.5 parts of titanium oxide, 7.0 parts of purified clay, 0.3 part of carbon black, dioctyltin oxide 1 Part, 1 part zinc acetate and 20.3 parts deionized water were added and dispersed in a ball mill for 20 hours. 3 was obtained.

Production Example 1 of Cationic Electrodeposition Paint Cationic Electrodeposition X1
87.5 parts (solid content 70 parts) of the amino group-containing epoxy resin A1 solution obtained in Production Example 1 and 37.5 parts (solid content 30 parts) of the blocked polyisocyanate curing agent solution obtained in Production Example 20 ) After mixing and mixing 13 parts of 10% acetic acid and stirring uniformly, deionized water was gradually added dropwise with vigorous stirring to obtain an emulsion having a solid content of 34%. Subsequently, 294 parts of the emulsion (solid content 100 parts), 55% pigment dispersion paste No. obtained in Production Example 35. 1 to 52.4 parts (solid content 28.8 parts) and deionized water 297.6 parts were added to produce a cationic electrodeposition paint X1 having a solid content of 20%.

Examples 2-32 and Comparative Examples 1-5 Cationic electrodeposition paints X2-X37
Cationic electrodeposition paints X2 to X37 having a solid content of 20% were produced in the same manner as in Example 1 except for those shown in Table 1 below. (When a hydroxyl group-containing resin is used, it is emulsified by mixing with an amino group-containing epoxy resin and a blocked polyisocyanate curing agent.)
Moreover, the coating stability, finishing property, and anticorrosion evaluation test were done by the method mentioned later. The evaluation results are shown in the table. If any one of the three evaluation tests yields a reject (D) evaluation result, the paint fails.

All compounding amounts in the table are values of resin solids.

Creating chemical conversion treatment of the test plate (trade name, PALBOND # 3020, Nippon Parkerizing Co., Ltd., zinc phosphate treatment agent) cold-rolled steel sheet which has been subjected to (150mm (vertical) × 70mm (horizontal) × 0.8mm (thickness)) The applied cold-rolled steel sheet (0.8 mm × 150 mm × 70 mm) was subjected to electrodeposition coating so as to have a dry film thickness of 17 μm using each cationic electrodeposition paint obtained in Examples and Comparative Examples, A test plate was obtained by baking and drying at 170 ° C. for 20 minutes.

Evaluation test <Paint stability>
1500 g of each cationic electrodeposition coating material is placed in a cylindrical sealed container (diameter 20 cm × height 15 cm) shown in FIG. 1 and stirred at a temperature of 30 ° C. for 14 days (rotating speed 700 rpm with a stirring blade having a width 8 cm × height 3 cm). )did. After 14 days, the paint was filtered through a 400 mesh wire mesh weighed in advance, and the wire mesh was dried by heating at 120 ° C. for 10 minutes. The wire mesh was weighed again and the mass of the wire mesh was subtracted to determine the amount of filtration residue. The amount of filtration residue was expressed in mg per mass (kg) of the original paint. The paint stability was evaluated according to the following criteria. The smaller the amount of filtration residue, the better. A to C are acceptable and D is unacceptable.
A, the amount of filtration residue is less than 10 mg / kg,
B is a filtration residue amount of 10 mg / kg or more and less than 25 mg / kg,
C is a filtration residue amount of 25 mg / kg or more and less than 50 mg / kg,
D shows that the amount of filtration residue is 50 mg / kg or more.

<Finish>
Using a surf test 301 (trade name, manufactured by Mitutoyo Corporation, surface roughness meter), the surface roughness value (Ra) was measured at a cutoff of 0.8 mm on the coated surface of the test plate and evaluated according to the following criteria: did. As for evaluation, AC is a pass and D is a failure.
A: Surface roughness value (Ra) is less than 0.2,
B: Surface roughness value (Ra) is 0.2 or more and less than 0.25,
C: Surface roughness value (Ra) is 0.25 or more and less than 0.3,
D: The surface roughness value (Ra) is 0.3 or more.

<Anti-corrosion>
Cross-cut flaws are made in the coating film with a cutter knife so as to reach the base of the test plate, and this is subjected to a 35 ° C. salt spray test for 840 hours in accordance with JISZ-2371. Rust and blister width on one side from the cut part Based on the following criteria.
In the evaluation, S to C are acceptable and D is unacceptable.
S, the maximum width of rust and blisters is 2.0 mm or less on one side from the cut part,
A, the maximum width of rust and blisters exceeds 2.0 mm on one side from the cut part, and 2.5 mm or less,
B, the maximum width of rust and blisters exceeds 2.5 mm on one side from the cut part, and 3.0 mm or less,
C, the maximum width of rust and swelling exceeds 3.0 mm on one side from the cut part, and 3.5 mm or less,
In D, the maximum width of rust and swelling exceeds 3.5 mm on one side from the cut part.

Claims (12)

An amino group-containing epoxy resin (A) obtained by reacting an amine compound (a1) containing at least one amine compound (a1-1) represented by the following formula (1) with an epoxy resin (a), and a blocked poly A cationic electrodeposition coating composition comprising an isocyanate curing agent (B).
R ₁ —NH—R ₂ —OH Formula (1)
(In the formula (1), R ₁ is a linear or branched hydrocarbon group having 3 to 4 carbon atoms, and R ₂ is a linear or branched hydrocarbon group having 3 to 8 carbon atoms. (However, when R ₁ is a linear or branched hydrocarbon group having 3 carbon atoms, R ₂ must not be a linear or branched hydrocarbon group having 3 carbon atoms.)
However, the following cationic electrodeposition coating composition X is excluded:
Cationic electrodeposition coating composition X. An amino group-containing epoxy resin obtained by reacting at least one amine compound (a1-1) represented by the following formula (1 ″) or an amine compound (a1) containing a ketimine compound thereof with an epoxy resin (a) ( A cationic electrodeposition coating composition comprising A) and a blocked polyisocyanate curing agent (B),
(In the formula (1 ″), R ₁ and R ₂ are hydrocarbon groups having 3 to 8 carbon atoms, which may be different or the same. N is 1.)
A cationic electrodeposition coating composition, wherein the amine compound (a1) contains an amine compound (a1-1) or a ketimine product thereof and an alkanolamine of the following formula (2 ″).
(In Formula (2 ″), R ₃ and R ₄ are each a hydrocarbon group having 1 to 8 carbon atoms, and may be different or the same.) R ₂ is a linear or branched hydrocarbon group having 3 to 4 carbon atoms (provided that when R ₁ is a linear or branched hydrocarbon group having 3 carbon atoms, R ₂ is carbon The cationic electrodeposition coating composition according to claim 1, which must not be a linear or branched hydrocarbon group of formula (3). The cation according to claim 1 or 2, wherein R ₁ is a linear or branched hydrocarbon group having 3 carbon atoms, and R ₂ is a linear or branched hydrocarbon group having 4 carbon atoms. Electrodeposition paint composition. The amine compound (a1) further contains an amine compound (a1-2) represented by the following formula (2) or a ketiminate thereof in addition to the amine compound (a1-1). The cationic electrodeposition coating composition according to any one of 1 to 3.
_{X 1 -R 3 -NH-R 4} -X 2 ··· (2)
(In the formula, R ₃ and R ₄ are linear or branched hydrocarbon groups having 1 to 8 carbon atoms, which may be different or the same. X ₁ and X ₂ may be a hydroxyl group and / or (It is an amino group, and they may be different or the same. However, when X ₁ and X ₂ are amino groups, at least one of R ₃ and R ₄ is a hydrocarbon group having 1 to 2 carbon atoms.) The amino group-containing epoxy resin (A) is composed of at least one modifier selected from xylene formaldehyde resin, polyalkylene glycol compound, fatty acid, alkylene glycol, polyamidoamine, polycarboxylic acid, polyisocyanate compound, lactone compound, and catechol compound. The cationic electrodeposition coating composition according to any one of claims 1 to 4, wherein the cationic electrodeposition coating composition is an amino group-containing modified epoxy resin (A1) modified. The cationic electrodeposition coating composition further contains a hydroxyl group-containing resin (C), and the component (A) is contained in an amount of 40 to 85 on the basis of the total resin solid mass of the components (A), (B) and (C). The cationic electrodeposition coating composition according to any one of claims 1 to 5, comprising 10% by mass to 10% by mass of component (B) and 5 to 50% by mass of component (C). . The hydroxyl group-containing resin (C) is at least one selected from a hydroxyl group-containing acrylic resin (C1), a hydroxyl group-containing polyester resin (C2), and a hydroxyl group-containing epoxy resin (C3) not containing an amino group. The cationic electrodeposition coating composition according to claim 6. The solubility parameter δA of the amino group-containing epoxy resin (A) and the solubility parameter δC of the hydroxyl group-containing resin (C) have a relationship of | δA−δC | <1.3. The cationic electrodeposition coating composition described in 1. The amine value of the amino group-containing epoxy resin (A) is 50 mg KOH / g or more based on the resin solid content, and the amine value obtained by adding the components (A), (B) and (C) is based on the resin solid content. The cationic electrodeposition coating composition according to any one of claims 6 to 8, wherein the composition is in the range of 20 to 100 mgKOH / g. The cationic electrodeposition coating composition contains 0.01 to 10.0% by mass of at least one metal compound (D) based on the total mass of resin solids. 10. The cationic electrodeposition coating composition according to any one of 9 above. The cationic electrodeposition coating composition, wherein the metal compound (D) according to claim 10 is a bismuth compound and / or a zinc compound. The cationic electrodeposition coating composition according to any one of claims 1 to 11 is used as an electrodeposition coating bath, and a metal coating including an alloyed hot-dip galvanized steel sheet is immersed in the electrodeposition coating bath, and obtained by electrodeposition coating. Painted article.