JPS60181168A - Resin covering composition of heat curing type - Google Patents

Abstract

PURPOSE:The titled composition useful as a cathode electrodeposition coating compound, having improved low-temperature curing properties, self-curing properties, self-curing properties, corrosion resistance, etc., comprising a specific film- forming resin containing a tertiary nitrogen atom directly bonded to a functional group, as a resin binder material. CONSTITUTION:The desired composition comprising a film-forming resin containing two or more tertiary nitrogen atoms (these tertiary nitrogen atoms may be linked to R1, R2, and a nitrogen atom bonded to them to constitute a member of a nitrogen-containing heterocyclic ring formed by them) directly linked to a functional group shown by the formula [R1 is 1-18C bifunctional saturated hydrocarbon group which may be replaced with hydroxyl group and/or linked to ether bond; R2 is H, (substituted) 1-6C alkyl, or part of main chain of the resin; R3 is H, or 1-12C hydrocarbon which may be replaced with hydroxyl group and/or linked to ether bond] in one molecule, as a resin binder material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermosetting resin coating composition, and more specifically, it is particularly suitable for cathodic electrodeposition coating and has improved properties such as low temperature curability, self-curing property, and corrosion resistance. The present invention relates to a heat-curable resin composition.

Conventionally, the most commonly used resin binder in resin compositions for cathodic electrodeposition coatings is a type in which a capolyamine resin, such as an amine-added epoxy resin, is cured with an aromatic polyisocyanate compound blocked with an alcohol. The coating has received excellent reviews for its anti-corrosion properties. However, this type of resin composition for coatings has an essential problem of a high curing initiation temperature (180° C. or higher). Furthermore, this type of paint resin composition requires an organotin compound as a curing catalyst, which poisons the exhaust combustion catalyst of the baking furnace, and when heated to high temperatures, the thermally decomposed polyisocyanate generates tar and soot. However, it also has serious drawbacks such as yellowing, bleeding, and curing inhibition in the top coat, extremely poor weather resistance, and easy whitening, and there is a strong need for improvement.

Therefore, the inventor of the present invention has discovered that, without using a polyisocyanate compound as a curing agent, it has coating film properties and electrodeposition properties that are equivalent to or better than those obtained when a polyisocyanate compound is used as a curing agent, and that also have the above-mentioned properties. As a result of extensive research aimed at providing a heat-curable resin coating composition that eliminates these drawbacks, in particular a resin composition for cathodic electrodeposition coating, we have found that a tertiary amino group has been added to a base resin such as an epoxy resin. via β
- It has been discovered that by introducing a hydroxyalkyl carbamate group, a resin composition for cathodic electrodeposition coating can be obtained which can achieve the above objectives and does not impair coating film performance and electrodeposition characteristics in any way, and has completed the present invention. I ended up doing it.

Thus, according to the invention, R1 is substituted with a hydroxyl group and/or an ether bond (-□
-) represents a divalent saturated aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be interposed; R2 is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms;
Represents 6 alkyl groups or a part of the main chain of the resin; R8 represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group and/or may have a Needel bond therebetween; , A tertiary nitrogen atom to which a functional group represented by, i.e., a β-hydroxyalkyl carbamate group, is directly bonded; Film-forming properties that may contain at least two in one molecule, which may together constitute a member of the completed nitrogen-containing heterocycle, and may contain a primary or secondary amine group as appropriate. A thermosetting resin coating composition is provided that contains a resin as a resin binder.

When the heat-curable resin coating composition of the present invention is heated to about 150° C. or higher, β -Hydroxyalkyl carbamate group thermally decomposes, and the following reaction formula (
As shown in 1), a urethane bond is formed between β-hydroxycarbamate groups, or as shown in the following reaction formula (2), a urethane bond is formed with a β-hydroxycarbamate group in the resin.

OROR.

R, OR30R2 + HO-0M2-CH-R.

H R207?4 0H In the above formulas (1) and (2), R,, R, and R3
has the above meaning, and R4 represents a hydrogen atom or an organic residue.

Therefore, the thermosetting resin coating composition of the present invention can be cured at a relatively low temperature of 170° C. or lower without the need for a tin catalyst. Moreover, as is clear from the above reaction formula (1) or (2), the coating composition does not dissociate the incyanate compound or its derivative during thermal decomposition, and does not cause any adverse effects on the top coat. It can have excellent advantages such as being durable, not introducing aromatic urethane bonds or aromatic urea bonds during cross-linking, and hardly impairing weather resistance.

Of course, the coating composition of the present invention, in addition to being cured using the heat curing reaction described above, can also be cured using a conventionally used polyisocyanate compound as a curing agent. .

In the above formula (1), "a divalent saturated aliphatic hydrocarbon group having 1 to 18 carbon atoms which is substituted with a hydroxyl group and/or may have an ether bond (-□-)" represented by R1 can preferably be a hydrocarbon group moiety or a part thereof constituting an aliphatic polyamine molecule, and the saturated aliphatic hydrocarbon group in the group is a linear or branched alkylene group. It is preferably an alkylene group having 1 to 18 carbon atoms, more preferably 1 to 9 carbon atoms. In addition, when the alkylene group is substituted with a hydroxyl group, the number of substitutions is 1 to 6, preferably 1.
The number of ether bonds that can be present is 6 or less, preferably 3 or less. Thus, specific examples of the above divalent saturated aliphatic hydrocarbon groups represented by R1 include: -CH2
CH2-.

-CH2CB2C1i, -, -CH,CH-, -CH2
CH2CE, CH, -.

C.E.

-cn,cn, -o -cH,ch, -, -cn,c
n2cH, -o -cH2cH.

CHCH.

-CH,CH, -0-CH2CHCN, -0-CH3C
N, -R Among these, those particularly suitable as R1 are -CH, C
H2-, -CB, CH, CB, -, -CH, CB, CB
, CB, -.

In addition, the alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, represented by R2 in the above formula
It may have a hydroxyl group, an amine group, an amide group or an ether group, and specific examples thereof include methyl, ethyl, propyl, isopropyl, hydroxyethyl, hydroxypropyl, aminoethyl, aminopropyl, amidoethyl, methoxyethyl. , methoxypropyl, ethoxyethyl and the like.

Furthermore, R2 in the above formula (1) can represent a part of the main chain of the resin as long as it does not substantially adversely affect the crosslinking and curing reaction of the film-forming resin. Examples of resins include epoxy resin, polyamide resin, and poly(α, β).
-unsaturated carbonyl) resins, etc.
These resins have hydroxyl groups, carbortylate groups,
It may contain a substituent such as an amino group, an imino group, a nitrile group, an amide group, and/or has an ether bond, an imide bond, a urea bond, a urethane bond, an amide bond, an ester bond, etc. Good too.

Among these groups, particularly suitable as R2 include hydrogen atom, methyl, ethyl, hydroxyethyl, aminoethyl and the like.

Furthermore, the group R3 in the formula (ri) has 1 to 12 carbon atoms, which may contain a hydrogen atom, a hydroxyl group, or an ether group,
It preferably represents 1 to 6 hydrocarbon groups, more preferably 1 to 3 hydrocarbon groups, and the hydrocarbon groups include, for example, methyl, ethyl, propyl, inglovir, butyl, 8eC
-CrV6 such as butyl, isobutyl, tert-butyl, etc.
, preferably 'd, C1 le. Included are alkyl groups; aryl groups such as phenyl, tolyl, and xylyl; and aralkyl groups such as benzyl. Among these, a hydrogen atom and a methyl group are preferred as the group R8.

As mentioned above, 3 to which the functional group of formula (1) is bonded
The class nitrogen atom can constitute a member of a complete nitrogen-containing heterocycle together with R1 and R2 in the formula and the nitrogen atom to which they are bonded, but as such a nitrogen-containing heterocycle, , 5~, which may further contain an oxygen or sulfur atom as a heteroatom.

Representative examples of the β-hydroxyalkyl carbamate group represented by the formula (1) are as follows.

H00H C,H,00B C112CM20H0OH CM2C1120H00B o on 0 0H The tertiary nitrogen atom to which the functional group of formula (1) described above is directly bonded is part of the main chain of the base resin constituting the film-forming resin. Alternatively, it may be a part of a pendant side chain of the base resin.

The film-forming resin used as the resin binder in the coating composition of the present invention has a functional group (β
-hydroxyalkyl carbamate group) in one molecule,
If the resin contains two or more r'c primary and/or secondary amine groups as required and has the ability to form a film of the desired thickness after being applied to the object to be coated. Any resin may be used, and they have an active group capable of reacting with a primary or secondary amino group such as an epoxy group, an α, β-unsaturated carbonyl group, or a carboxyl group (or an active ester group thereof). Substitution (with Rs) of a base resin having a group and an aliphatic polyamine containing at least two or more primary or secondary amine groups and optionally containing a tertiary amine group.
Alternatively, it can be easily produced industrially by a three-way reaction with unsubstituted ethylene carbonate.

That is, the synthesis of the resin having a functional group (β-hydroxyalkyl carbamate group) represented by the formula (ri) used in the present invention involves the following reaction (, f) and reaction (B) and/or (C). This can be done in appropriate combinations.

(,4) Production of β-hydroxyalkyl carbamate group by reaction of primary or secondary amine group of aliphatic polyamine with alkylene carbonate: R201, O 20 (B) Primary or secondary amino group of aliphatic polyamine and Reaction with an epoxy group, ■ reaction with an α,β-unsaturated carbonyl group, and ■ formation of a tertiary amino group by reaction with a carboxylic acid, respectively: ■ OR OHR OHR.

0 R211 0R2 0E The above reaction CB> is a reaction aimed at producing a tertiary amino group, but it is also a reaction for introducing an amino group into the resin skeleton. For the latter reaction whose sole purpose is to introduce an amine group into the resin skeleton, the following reaction (C) can also be used in addition to the reaction (B).

(C) A primary or secondary amino group or hydroxyl group of the aliphatic polyamine is reacted with (1) a carboxyl group (or its active ester group or (2) an isocyanate group).

R20R2 R2E, OR2 or O (Here, R2 in the reactions (,4) to (C) above has the same meaning as above) Below, among the above film-forming resins used in the coated composition of the present invention The manufacturing method for typical resins will be explained in more detail, but these explanations are for ease of understanding and are not intended to limit the scope of the film-forming resin used in the present invention. should be understood.

The above resin contains at least two functional groups represented by the formula (1) in one molecule, but the preferable content of the functional groups varies depending on the molecular weight of the resin, etc.
The molecular weight per unit, that is, when expressed in equivalent weight, is preferably 250 to 5000, more preferably 500 to 25
00 is advantageous.

Furthermore, the resin used in the present invention desirably has an amine group selected from aliphatic primary and secondary amine groups in addition to the functional group of the formula (RI), and the content of the amine group is generally determined by the amine value ( When expressed in terms of KOH (in terms of KOH per gram of resin), the range is preferably from 10 to 200, preferably from 20 to 100.

Production method 1 An epoxy resin (base resin) having at least two epoxy groups is reacted with an aliphatic polyamine containing at least two active amine groups selected from primary and secondary amine groups, and the epoxy resin and the After introducing primary and/or secondary amine groups into the epoxy resin by addition reaction with active amine groups, alkylene carbonate is reacted. This reaction can be expressed by the following reaction formula, taking as an example the case where an aliphatic diamine containing two primary or secondary amino groups is used as the aliphatic polyamine.

Reaction formula! In the formula, CD represents the main body of the epoxy resin [however, in the above formula (i), only one epoxy group is shown for simplicity, but ■ has at least one other epoxy group bonded to it. R3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group; The two nitrogen atoms may be combined to form a nitrogen-containing heterocycle which may further contain an oxygen or sulfur atom as a heteroatom.

The reaction shown in the above reaction formula I converts a primary or secondary amino group into 2
Other aliphatic polyamines containing only
b) [However, when R1s'<H], it can be similarly applied to polyamines such as those shown in (d) and (g).

In addition, as an aliphatic polyamine, for example, in the following formula, R6 represents a divalent saturated aliphatic hydrocarbon group having 1 to 18 carbon atoms, which may be substituted with a hydroxyl group and/or may have an ether bond. −= p is an integer of 1 or more. When using a polyamine containing a total of 3 or more primary and secondary amino groups represented by Alternatively, the reaction may be carried out by temporarily protecting the primary amino groups at both ends, for example, by ketimination or alaldimination, and then reacting one of the secondary amine groups in the chain with the epoxy resin. In the case of this latter reaction, two primary amine groups can be simultaneously introduced into the epoxy resin.

This latter reaction can be illustrated by the following reaction formula using an aliphatic triamine as an example.

Reaction formula■ B During the ceremony, Zii represents a ketimine or aldimine protecting group; OOH eagle, I; ■; RIIR3 and R6 have the above meanings.

Alternatively, as exemplified by the following reaction formula (2), an aliphatic polyamine and an alkylene carbonate may be reacted in advance, and then the resulting product may be reacted with an epoxy resin.

Reaction formula (1) R, R, 0011 (vl) (1-1) In the formula, (1), R,, R,, R3 and R6 have the above meanings.

Reaction formula 1 described above. The unit reactions shown in II and II do not require any catalyst and can be carried out at relatively low reaction temperatures from about room temperature to about 100° C. or less, and the reactions proceed almost quantitatively.

The nitrogen atom to which the functional group R, 00H is bonded is tertiary, and therefore, in the resin produced as described above, for example, as shown in formula (■-1), the functional group represented by the above formula is When the directly bonded amine group is secondary, this secondary
The secondary amine group may be tertiaryized by reacting the secondary amine group with, for example, a monoepoxy compound or a mono-α,β-unsaturated carbonyl compound described below.

A high molecular weight substance having an average of 2 or more molecules in the base resin used as the base resin in the above reaction, and generally has a molecular weight of at least 350, preferably 500 to 10,000, more preferably 1,000 to 5,000. Those having a number average molecular weight are suitable. As such epoxy resins, those known per se can be used, and include, for example, polyglycidyl ethers of polyphenols that can be produced by reacting polyphenols with epichlorohydrin in the presence of an alkali.

Examples of polyphenols that can be used here include:
bis(4-hydroxyphenyl)-2,2-propane,
4,4/-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1゜1-ethane, bis-(4-
hydroxyphenyl)-1', 1-isobutane, bis(4-hydroxy-1ert-butyl-phenyl)-
Examples thereof include 2,2-propane, bis(2-hydroxynaphthyl)methane, and 1,5-dihydroxynaphthane. Furthermore, it is also possible to use an epoxy resin obtained by reacting diglycidyl ether with the polyphenol described above and further reacting this with epichlorohydrin.

Other usable epoxy resins include polyglycidyl ethers of phenolic novolac resins and polyglycidyl ethers of polyhydric alcohols. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-
Examples include propylene glycol, 1,4-propylene glycol, 1,5-propylene glycol, 1,2,6-hexandriol, chrycerol, bis(4-hydroxycyclohexyl)-2,2-propane, and the like.

Furthermore, polycarboxylic acids such as succinic acid, glu p-
It is also possible to use polyglycidyl esters such as phosphoric acid, monoterephthalic acid, 2,6-naphthalenedicarboxylic acid, trimerized lylunic acid, and the like.

An epoxy group-containing monomer, such as glycidyl acrylate or glycidyl methacrylate, may itself or be combined with one or more other polymerizable ethylenically unsaturated monomers, such as methyl acrylate, ethyl acrylate, methyl methacrylate. Epoxy group-containing acrylic polymers obtained by polymerization with , acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, etc. can also be used.

Furthermore, epoxidized polybutadiene, epoxidized polycycloalkene, etc. can also be used.

Among the above-mentioned epoxy resins, those particularly suitable for cathodic electrodeposition coating resin compositions have a number average molecular weight of at least about 3.
50, preferably about 350 to 3,000, and an epoxy coverage of 150 to 4,000, preferably 190 to 000, especially the following general formula %) The epoxy resin shown is most suitable. As a commercially available product, for example, epoxy resin manufactured by Shell Chemical Co., Ltd.: Epilcot
e 828 (bisphenol A type, average molecular weight approximately 380, epoxy equivalent approximately 190), Epikote 1
001 (Bis7: r-/-le A type, average molecular weight about 900, epoxy equivalent weight about 475), tt 1002 (bisphenol A type, average molecular weight about 1300, epoxy equivalent weight about 650), #1004 (bisphenol A type, Average molecular weight approximately 1400, epoxy equivalent approximately 950), #1'007 (
Bisphenol A type, average molecular weight of about 2900, epoxy equivalent of about 1900), etc.

Further, as the aliphatic polyamine used as a starting material in the above reaction, the following can be exemplified.

((L) HN -R,o-NH I Rtt R12 (Here, Rlo has 1 to 18 carbon atoms, preferably 2
~9 alkylene groups; RI8 and R1□ are each an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, which may be substituted with a hydrogen atom or a hydroxyl group and/or may have an intervening ether bond. for example ethylenediamine, 1,2- and 1,3-diaminopropane,
1,4-diaminobutane, hexamethylenediamine, 1
, 3-bisaminomethylcyclohexane, bis-(3-
aminopropyl, ether, N-methylethylenediamine, hydroxyethylaminoethylamine, hydroxyethylaminopropylamine, N,Nl-dimethylethylenediamine, N,Nl-dihydroxyethylethylenediamine, etc.

R.I.

(Here, R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may be substituted with a hydroxyl group;
m represents an integer of 1 to 9, preferably 1 to 6; R1° has the above meaning) For example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis(hexamethylene)triamine, Methyliminobisethylamine, methyliminobispropylamine, etc.

(Here, R14 and RI each have 1 to 1 carbon atoms.
(representing three alkylene groups), etc.

(Here, R, o, R, and R1 have the above-mentioned meanings.) For example, N-aminoethylpiperazine, N-aminopropylbeverazine, and the like.

(e) (wherein RlG + R14 and R1 have the meanings given above), for example, N,N'-bisaminopropylpiperazine.

Among the above aliphatic polyamines, those that are commercially and industrially easily available and suitable for the present invention include ethylenediamine, hexamethylenediamine, diethylenetriamine, piperazine) hydroxyethylethylenediamine, N-aminoethylpiperazine, and the like. It will be done.

Furthermore, alkylene carbonates that can be used include:
For example, ethylene carbonate, propylene carbonate, glycerin carbonate, styrene carbonate,
butylene carbonate, glycerin carbonate), preferred and commercially available are ethylene carbonate and propylene carbonate.

Examples of monoepoxide compounds that can be used to tertiaryize the aforementioned secondary amine groups include ethylene oxide, propylene oxide, styrene oxide, phenyl glycidyl ether, and mono-α, β-
- Examples of unsaturated carbonyl compounds include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylate.
Examples include phthyl acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylamide, and (meth)acrylonitrile.

Production method 1 This method uses a resin containing at least two α, β-, β-carbonyl groups [hereinafter referred to as poly(α, β)
- uses unsaturated unsaturated carcinyl],
Poly(α,
A resin having the functional group of formula (1) according to the present invention can be obtained in the same manner as Production Method 1 except that a β-, β-carbonyl) resin is used.

An example of this production method is shown in the following reaction formula by taking as an example the case where an aliphatic diamine of formula (11) is used corresponding to the reaction formula (1) above.

Reaction formula■ OR, (vii) R5Rz (ii) OR, R, R.

(viii) Ono? , R, R, 00M -(na) In the formula, (2) represents the main body of poly(α,β-unsaturated unsaturated carcinyl [However, in (v ii) above, α,β- Only one unsaturated carponyl group is displayed,
It should be understood that at least one other α, β-, β-carbonyl group is bonded to (2); R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
In particular it represents a methyl group; R1, R2, R and R3 have the meanings given above.

Poly(unsaturated carbonyl) resins that can be used as the base resin include (1) esterified products of polyepoxide and α, β-, β-monocarboxylic acids, (2) polycarboxylic acids (or their acid anhydrides). ) and α.

Glycidyl esters of β-unsaturated monocarboxylic acids [e.g. glycidyl (meth)acrylate] or hydroxyalkyl esters thereof [e.g. hydroxyethyl (meth)acrylate]
acrylate, etc.], (3) urethane products with polyolt α,β-unsaturated monocarboxylic acid hydroxyalkyl ester-diisocyanate adducts, (41, l-” polyolt α,β-unsaturated monocarboxylic acid or its lower Examples include (Cyu6) esterified products or transesterified products with alcohol esters.

In the above (1) to (4), those preferably used in the present invention include, for example, the epoxy resin described in Production Method I as the polyepoxide; the styrene-maleic anhydride copolymer as the polycarboxylic acid; and the polyol Examples include styrene-allyl alcohol copolymer; examples of α,β-unsaturated monocarboxylic acids include acrylic acid.

Production method m This method is a method consisting of using a resin containing at least two carboxyl groups or active ester derivative groups thereof in place of the epoxy resin in the production method summer as the base resin, 1) , an example of the present production method is shown in (b) above [however, Rs s 'i H
The reaction formula is as follows, taking as an example the case in which an aliphatic polyamine shown in [Case] is used.

Reaction formula V R13 (ix) OR'R+5 (II-4) In the formula, (i) represents the main body portion of the resin having a carboxyl group or an active ester derivative group thereof [However, the above (ix)
Although only one carboxyl group is shown here for the sake of simplicity, it should be understood that at least one other carboxyl group or its active ester derivative group is bonded to ■; R3° and R13 have the above meanings.

Examples of resins that can be used as the base resin include styrene-maleic anhydride copolymers, dimer fatty acids, carboxy-terminated butadiene-acrylonitrile copolymers, and the like.

The thermosetting resin coating composition of the present invention uses a film-forming resin as a main resin binder containing two or more functional groups represented by the formula (1) in one molecule, which is produced as described above. However, if necessary, a resin having two or more aliphatic primary and/or secondary amino groups in one molecule as described below may also be included as a curing agent component.

As the curing agent resin containing two or more aliphatic primary and/or secondary amino groups in one molecule, epoxy resin and ammonia or amines having aliphatic primary and/or secondary amine groups are used. For example, (1) a reaction product of polyepoxide and ammonia (for example, see JP-A-55-149318); and (2) a reaction product of polyepoxide with primary mono- and polyamines, secondary polyamines, or 1,2 adducts with grade polyamines (e.g., U.S. Pat.
984299) (3) Adducts of polyepoxides with secondary mono- and polyamines having ketiminated primary amine groups (see, for example, US Pat. No. 4,017,438) (4) Polyepoxides and a hydroxy compound having a ketiminated primary amine group.
(See the specification of the No. 756 application).

The epoxy resin used in the above reaction product is a polyglycidyl ether of a polyphenol, prepared by reacting bisphenol A or bisphenol I'' with epichlorohydrin, and has a number average molecular weight of at least about 350, preferably about 350. 3,000 and an epoxy equivalent of 190 to 2,000.

In addition, examples of amines to be reacted with the epoxy resin include monoalkyl and monoalkanolamines such as ethylamine, propylamine, butylamine, ethanolamine, and propatoolamine, and aliphatic polyamines shown in (α) to (e) above. Among them, preferred amines include methylamine, ethylamine, monoethanolamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, and the like.

Furthermore, poly(ester)-amide-polyamine resins, polyurethane-(
Urea)-polyamine resins, polycarboxylic acid and alkylene imine adducts, etc. can also be used, and specific examples include (5) polycarboxylic acid and polyamines having primary and/or secondary amine groups (and optionally (6) a poly(ester)-amide-polyamine obtained by condensation with a polyol (and optionally a cibolyamine) (see e.g. U.S. Pat. No. 3,799,854). A polyurethane-(urea)-polyamine obtained by a three-way reaction between a hydroxy compound having a primary amine group and a diisocyanate (for example, JP-A-56-1
(Refer to Publication No. 29271) (Adduct of polycarboxylic acid and alkylene imine (
For example, see US Pat. No. 3,719,629).

Among the resins used as the curing agent component 7 mentioned above,
Particularly preferred is the condensation of an aliphatic polybasic acid such as 7-talic acid, adipic acid, sepatic acid, dimer acid with an aliphatic polyamine such as ethylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, etc. It is a polyamide polyamine resin formed by reaction. In particular, when used in a resin composition for cathodic electrodeposition coating, water dispersibility, coating surface smoothness, coating film flexibility, etc. are improved.

Specific examples of polyamide polyamine resins include Verεαmid 100, 115.
125.140 etc. can be mentioned.

In addition, as a curing agent component, the above-mentioned aliphatic primary and/or secondary
A type of resin in which less than two of the amine groups of a resin containing two or more amino groups in one molecule are substituted with β-hydroxyalkyl carbamate groups can also be used alone or in combination with the above resins.

The resin used as the curing agent component described above can be manufactured separately and added to the composition of the present invention, but
Of course, it can also be produced and used simultaneously when producing the film-forming resin containing at least two β-hydroxyalkyl carbamate groups per molecule of the present invention.

The usage ratio of the resin used as the curing agent component mentioned above is:
It is preferable that the number of aliphatic primary and/or secondary amine 7 groups in the resin is equal to or less than the equivalent amount to the β-hydroxyalkyl carbamate group.

Although the resin component of the thermosetting resin coating composition of the present invention does not necessarily have to have 7 primary and/or secondary amide groups, the composition to be oxidized of the present invention is neutralized with an acid and prepared as an aqueous dispersion. When used as a resin composition for cathodic electrodeposition coating,
It is often preferred that the resin component has an aliphatic primary and/or secondary amino group in addition to the tertiary amine group to which the β-hydroxyalkylcarbamer group of the formula (R) is bonded. In this case, these primary The amount of secondary amino groups and/or secondary amino groups may be freely adjusted depending on the water dispersibility of the resin composition, but is preferably such that the average amine value of the resin coating composition falls within the range of 10 to 100. These primary or secondary amine groups can be introduced by known methods.

In particular, as a method for preferentially introducing a primary amine group and making it remain until dispersion in neutralized water, as is known, the primary amino group is reacted with a carbonyl compound (ketone or aldehyde) in advance to form a ketimine or aldimine group. A method of protection is effective.

The thermosetting resin coating composition of the present invention does not necessarily require a curing medium, but of course a compound known as a urethane dissociation catalyst, such as a metal salt such as lead, tin, zinc, iron, or manganese, may be added. It can accelerate the curing reaction. Particularly effective are lead salts such as lead octoate, lead naphthenate, and lead silicate.

In the present invention, when the thermosetting resin coating composition described above is used as a cathodic electrodeposition coating composition, primary and/or secondary amine groups in the resin are Alternatively, it can be partially neutralized with an inorganic acid to form an aqueous dispersion. Neutralization is 0.1 to 0.7 (preferably 0.
It is preferable to carry out the reaction within the range of 2-0.5) equivalent. The pH of the resulting aqueous dispersion is generally between 3 and 9, preferably between 5 and 7.
The resin concentration is generally 3 to 30% by weight, preferably 5 to 15% by weight.

A pigment is optionally added to the aqueous dispersion. Pigments that can be added include those commonly used in electrodeposition paints, such as coloring pigments such as red iron, titanium white, and carbon black; extender pigments such as talc, clay, and squid; Rust-inhibiting pigments such as halogenate, strontium chromate, and basic lead silicate are used, and these can be used in any amount.

Furthermore, a small amount of a known surfactant (for example, a nonionic surfactant) commonly used in cathodic electrodeposition coatings may be added to the composition of the present invention, if desired.

As a method and apparatus for electrocoating the object to be coated using this aqueous dispersion, known methods and apparatuses conventionally used in cathodic electrodeposition coatings can be used. In this case, it is desirable to use the object to be coated as a cathode and to use a carbon plate as an anode. The electrodeposition coating conditions that can be used are not particularly limited, but generally,
Bath temperature: 20-30°C, voltage: 100-400V (preferably 200-aooF), current density: 0.01-3A/
dye, energization time = 1 to 5 minutes, pole area ratio (A/C) = 2
/1 to 1/2, distance between electrodes: 10 to 100 a1 It is desirable to electrodeposit in a stirred state.

After washing, the coating film deposited on the cathode coating material was approximately 15
It can be hardened by baking at 0 to about 180°C.

The composition of the present invention can be used as a solvent-type baking coating composition by dissolving and diluting it in a common organic solvent as it is, instead of as the resin composition for cathodic electrodeposition coating described above.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 First, an L-class amine group is introduced into an epoxy resin via a tertiary amine group using the following recipe.

(Raw materials) (Parts by weight) Epos1002 (*1) '1300 ethylene glycol monoethyl agel 390 (*1) Epoxy resin manufactured by Shell Chemical Co., Ltd., epoxy equivalent: approximately 650 (*2) Diethylenetriamine is heated with excess methyl isobutyl ketone and refluxed. After dehydration, excess methyl in butyl ketone is removed.

Epon 1002 was heated and dissolved in ethylene glycol monoethyl ether, diethylenetriamine/methylimptylketone diketimine was added, and the mixture was reacted at 90°C for about 90 minutes. At this time, the tertiary amine (*3) is. It was 0.

Value (*3) Amine value obtained by dissolving the sample in acetic anhydride/acetic acid = 9/1 (weight ratio), boiling it to acetylate it, and titrating it with a perchloric acid/acetic acid solution using crystal violet as an indicator. (ITfKOE7' sample solid content W).

Same below.

Next, half of the primary amino groups in the reaction product are converted to β-hydroxyalkyl carbamate groups using the following recipe.

(Raw materials) (Parts by weight) The above reaction product 2224 Deionized water 72 Ethylene carbonate 176 Deionized water was added to the above reaction product and the reaction was carried out at 90°C for 30 minutes to hydrolyze the ketimine group. In addition, the mixture was reacted at 90°C for 60 minutes. The resulting resin composition had a solid content of 68%, an amine value of 67, and an estimated weight of the functional group represented by the formula (2) of about 840 (theoretical value).

The resin composition was diluted with ethylene glycol monoethyl ether to a solid content of 50%, and lead octenoate (PB content 38%) was diluted with ethylene glycol monoethyl ether.
%) was added to a tin plate and an untreated cold rolled steel plate and baked at 160°C for 30 minutes to obtain a smooth and hard coating film with a thickness of 20μ. The hardenability was investigated by drying, and the corrosion resistance was investigated by a turt spray test using the coating film on an untreated steel plate.

Gel fraction (* 4 i: s3 chloride spray resistance (according to JIS K-5400-7°8): more than 5 hours (* 4) in a mixed solvent of acetone/methanol: = 1/l (volume ratio) for 5 hours Extract under reflux and claim the coating film residual rate.

Example 2 First, a primary amino group is introduced into an epoxy resin via a tertiary amino group using the following recipe.

(Raw materials) (Parts by weight) Epon 1004 (*5) 2.000 (*5) Epoxy resin manufactured by Shell Chemical Co., Ltd., epoxy equivalent 950 Epon 1004 was heated and dissolved in ethylene glycol mbutyl ether, and diethylene triamine methyl in butyl ketone was added. Diketimine was added and reacted at 100°C for 60 minutes. At this time, the tertiary amine value was 44.

Next, all the primary amine groups in the above reaction product are converted to β-hydroxyalkyl carbamate groups using the following recipe: (Raw materials) (Parts by weight) Above reaction product 3334 Deionized water 72 Propylene carbonate 408 Above reaction product Deionized water was added to the product and the mixture was reacted at 90°C for 60 minutes to hydrolyze the ketimine group, and then propylene carbonate was added and reacted at 90°C for 2 hours. The solid content of the obtained resin composition was 68.5 inches, and the amine value was 27.
Met.

This material was diluted with ethylene glycol monobutyl ether to a solid content of 40%, and lead naphthenate (PB content 30%) was added to 3PER 1. A coating film was prepared in the same manner as in Example 1 to improve gel fraction and salt spray resistance. I looked into it.

Gel fraction = 96 cm Tort spray resistance: 600 hours or more Example 3 A resinous material having a β-hydroxyalkyl carbamate group via a tertiary amino group is obtained using the following formulation.

(Raw materials) (Parts by weight) Epon 828 (*6) 380 Piperazine 172 Ethylene glycol monoethyl ether 150 Ethylene carbonate 176 (*6) Epoxy resin manufactured by Shell Chemical Co., Ltd. Epoxy f1:
190 Hyherazine was dissolved in ethylene glycol monoethyl ether, and Epon 828 was gradually added at 70°C, followed by further reaction at 80°C for 120 minutes.

The 3Mt amine value at this time was 200. Furthermore, ethylene carbonate is added and the mixture is reacted at 80° C. for 60 minutes to obtain a resinous material having a solid content of 83% and an amine value of 120.

60 parts of this material were mixed with 50 parts of a polyamide resin (Persamide 100) manufactured by Nihon General Co., Ltd. having an amine value of 90 and 40 parts of xylene, and zinc naphthenate (Zn content 10
h) Add 10 parts, apply to zinc phosphate steel plate, and heat at 180℃.
Bake for 20 minutes to create a highly flexible, 25μ thick paint film with solvent resistance (methyl in butyl ketone,
(*7) = Resistance to over 20 sprays = Impact resistance over 800 hours (pont type): Inch 50crIL or over (load: 1kg) (*7) Clean the surface of the paint film with gauze moistened with methyl isobutyl ketone. It shows the number of reciprocations until scratches and reduction in gloss occur on the coating film when the coating is strongly rubbed by reciprocating over a distance of 10 CIIL.

Example 4 A resin composition of the present invention is obtained with the following formulation: (Raw materials) (Parts by weight) EponLOOL (*8) 3800 imidacillin
2.5 Ethylene glycol motsubutyl ether 1032 Diethylene triamine methyl isobutyl ketone ketimine 1602 Deionized water 216 Ethylene carbonate 792 (*8) Epoxy resin manufactured by Shell Chemical Co., Ltd., epoxy equivalent approximately 475 (*9) Nippon Polyurethane Co., Ltd. Polytetramethylene glycol, hydroxy equivalent 550 (*10) PTG
Esterified product obtained by reacting -20o/adipic acid = I (molar ratio), acid value 82° Epon 1001 and pTG-200-adipic acid acid ester using imidacillin as a catalyst, acid value becomes 1 or less at 140°C After the reaction was carried out, ethylene glycol motubutyl ether was added and cooled, and diethylenetriamine/methylinbutylketoneketimine was added to give 9.
The reaction was carried out at 0°C for 90 minutes. The tertiary amine value at this time is 50
That's two.

Deionized water was added to the tongue and the mixture was reacted at 90°C for 30 minutes, and then ethylene carbonate was added and the mixture was reacted at 90°C for 60 minutes to obtain a resin composition with a solid content of 75% and an amine value of .20. 131 parts of this stuff plus lead octenoate (7) b=3
8%) was added, neutralized with 1.3 parts of acetic acid, and dispersed in water to obtain a clear bath with a solid content of 15%. After stirring this at 30°C overnight, it was electrodeposited on a tin plate, an untreated steel plate, and a zinc phosphate steel plate at 25°C and baked at 170°C for 20 minutes to form a coating film with a thickness of about 20 μm on each.

Gel fraction: 94 cm Impact resistance (zinc phosphate treatment): 50 cIn or more (load: 1 kg) Example 5 First, a resinous material having a β-hydroxyalkyl carbamate group via a tertiary amino group was prepared using the following formulation. Obtain the product: (Raw materials) (Parts by weight) Ethylene diamine 180 Ethylene carbonate 264 Ethylene glycol monoethyl ether 320 Epon 828 760 2-ethylhexyl acrylate 368 Dissolve ethylene diamine in ethylene glycol monoethyl ether,
Ethylene carbonate was added little by little at 60°C, and the reaction was allowed to proceed until the amine value dropped to 380. Then Epo at 60℃
Add n 828 and further react at 80°C for 60 minutes.

Finally, 2-ethylhexyl acrylate was added and the mixture was heated to 80 DEG C. to obtain a 3% resin.

Next, a resinous material having primary and/or secondary amine groups is prepared according to the following recipe.

(Raw materials) (Parts by weight) Epon 1002 1300 Ethylene glycol monobutyl ether 520 Monoethanolamine/methyl isobutyl ketone ketimine 215 Versamido 100 600 Deionized water 27 Epon 1002 Dissolved in ethylene glycol monobutyl ether to produce monoethanolamine/methylisobutyl ketone ketimine. Methyl inbutyl ketone ketimine was added and reacted at 150°C until the water-soluble amine value (*ll) became 1 or less, and then 9
Cool to 0°C, add Persamide 100, react until the viscosity increase is saturated, and then add water to give a solid content of 75%.
A resin with an amine value of 55 was obtained.

(*11) The amine value of the aqueous phase obtained by dissolving the sample in xylene/butanol/ethanol = 1/1/1 (volume ratio) and extracting with the same amount of saturated saline (■KOE//i sample solid content ) 42 parts of the above β-hydroxyalkyl carbamate group-containing resin and 8 parts of the primary and/or secondary amine group-containing resin
Mix 7 parts of lead octylate <pb content 20%) 2.5
15 parts, neutralized with 27 parts of acetic acid, and dispersed in water to reduce the solid content to 15 parts.
It was used as a clear bath of Llb. Electrodeposition was performed in the same manner as in Example 4 to create a coating film.

Gel fraction = 92 cm Sult spray resistance (untreated): 50 parts or more Time impact resistance (zinc phosphate treatment): 1 inch, 50 parts or more (load 5
00p) Example 6 First, a resinous material having a β-hydroxyalkyl carbamate group is obtained using the following recipe.

(Raw materials) (Parts by weight) Dimeric fatty acid 560 Triethylenetetramine 292 Xylene 42 Propylene carbonate 306 Dimeric fatty acid and triethylenetetramine were reacted under xylene reflux (200-220°C) until the amount of dehydration was saturated. react until reaching the target. After cooling, ethylene glycol monoethyl ether is added, propylene carbonate is gradually added at 60° C., and the reaction is continued at the same temperature until the amine value falls to 150.

Next, a resin compound containing monoepoxide is prepared according to the following formulation.

(Raw materials) (Parts by weight) Epon 1001 1800 Ethylene glycol mottyl ether 384 Monoethanolamine methyl inbutyl ketone ketimine 286 Epon 1001 was dissolved in ethylene glycol mhoptyl ether, and monoethanolamine methyl isobutyl ketone ketimine was added. The reaction is carried out at 140°C until the water-soluble amine value becomes 1 or less.

The resinous compound was added to this reaction product, and the mixture was heated to 80°C for 3 hours.
The reaction was continued until the amine value reached 37 to obtain a resin composition of the present invention having a solid content of 79 and an amine value of 56.

127 parts of this stuff plus lead naphthenate (PB content 30%) 3
1 part, neutralized with 2.1 parts of acetic acid, and using a water strainer, 2 parts of
Electrodeposited on a tin plate, an untreated steel plate, and a zinc phosphate treated steel plate at 5℃ and baked at 160℃ for 30 minutes, each having a thickness of about 2.
A coating film of 0μ was created.

Gel fraction: 98% Silt spray resistance (untreated): 7.00 hours Impact resistance (zinc phosphate treatment): V6 inch, 50 cIrL or more (load: 1 kg) Example 7 Resin composition of the present invention with the following formulation Prepared: (raw material)
(Parts by weight) Epon 1001 1900 Ethylene glycol monoethyl ether 500 Dimeric fatty acid 420 Acrylic acid 180 Imidacillin 2.5 Diethylenetriamine methyl impgel diketimine 667.5 Deionized water 45 Ethylene carbonate 264 Epon 10'01 Ethylene glycol mono Dissolve in ethyl ether, add dimer fatty acid and acrylic acid, and use imidacillin as a catalyst until the acid value reaches 1 at 140°C.
React until the following. Next, diethylenetriamine/methylimptylketone diketimine is added, and the mixture is reacted at 90°C until the tertiary amine value reaches 50. After adding deionized water and hydrolyzing at 190°C for 30 minutes, ethylene carbonate was added and the reaction was continued at the same temperature until the amine value dropped to 40.

Resin composition of the present invention thus obtained (solid content 7696)
132 parts of the solution were taken, 3 parts of lead naphthenate (PB content 30%) were added, neutralized with 2.1 parts of acetic acid, and dispersed in water to obtain a clear bath with a solid content of 15%.

Using this material, electrodeposition was performed in the same manner as in Example 6 to create a coating film.

Gel fraction = 96 inches Salt spray resistance (untreated): 500 hours or more Impact resistance (zinc phosphate treatment): 1 inch, 50 degrees or more (load 500.9)

Claims (1)

[Claims] The following formula % formula % In the formula, R1 is substituted with a hydroxyl group and/or an ether bond (-□
-) represents a divalent saturated aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be interposed; R2 is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms;
Represents 6 alkyl groups or represents a part of the main chain of the resin; R8 is a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group and/or may have an ether bond interposed therebetween; A tertiary nitrogen atom to which a functional group represented by is directly bonded, but this tertiary nitrogen atom is completed together with R1 and R2 in the above formula and the nitrogen atom to which they are bonded. 1. A thermosetting resin coating composition comprising, as a resin binder, a film-forming resin containing at least two in one molecule, which may constitute a member of a nitrogen-containing heterocycle.