JPS6159355B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel resin composition for cationic electrodeposition coating, and more specifically, a compound component having a primary amino group blocked with a carbonyl compound is formed into a compound having an isocyanate-reactive functional group via a diisocyanate compound component. The present invention relates to a blocked isocyanate group-curable resin composition for cationic electrodeposition coating, which contains as a main component a resinous product introduced into the above. Various resin compositions for cationic electrodeposition coating have been proposed. For example,
Publication No. 25488 describes coating material particles made of amino group-containing addition polymers or condensation polymers (including amino group-containing polyamide resins) and blocked polyisocyanate (substantially all of the isocyanate groups are blocked). A composition for electrodeposition coating is disclosed in which a so-called completely blocked isocyanate is dispersed in an aqueous medium. The electrodeposited coating film obtained from this composition was not satisfactory in terms of corrosion resistance, and to compensate for this, the above publication states that polyepoxide may be contained in an amount of up to 50% by weight of the composition. However, it can be said that the coating film performance is practically unsatisfactory. As a composition similar to the above-mentioned electrodeposition coating composition, JP-A-47-759 discloses a soluble polyamine resin (substantially an amino group-containing polyamide resin).
An electroplating method using a water-soluble bath of a composition comprising a block polyisocyanate and a block polyisocyanate is disclosed, but this is also a composition for electrodeposition coating showing properties similar to those described in the above-mentioned Japanese Patent Publication No. 50-25488. It can be called a thing. Furthermore, it is widely known that cured products of polyepoxides such as bisphenol A-epichlorohydrin type epoxy resins have excellent corrosion resistance and adhesion. Methods of making substances water-soluble by neutralizing them with acids are also already known. As an electrodeposition coating composition that takes advantage of such properties of polyepoxides and acid adducts, JP-A-51-103135 discloses an aqueous electrodeposition composition that is a mixture of the above-mentioned epoxy resin amine adduct and blocked polyisocyanate. Compositions are disclosed. However, the electrodeposited coating film obtained using this composition has excellent corrosion resistance but is poor in plasticity components, and has poor surface smoothness and bath stability [during continuous coating, coating surface condition, deposited film thickness, (meaning properties that can be maintained within the expected range without any change or particularly decrease in membrane performance, etc.) are unsatisfactory.
In addition, the coating has insufficient throwing power when coating objects with complicated shapes, and is therefore unsatisfactory for practical use. On the other hand, Japanese Patent Publication No. 52-6306 describes a self-curing aqueous coating composition for electrodeposition comprising an epoxy resin, a primary and/or secondary amine, and a partially blocked polyisocyanate. Although the product can be positioned as an improved version of the product described in JP-A-51-103135, it cannot be said that it has been sufficiently improved in terms of surface smoothness, flexibility, bath stability, throwing power, etc. It is difficult to achieve, and is not fully satisfactory industrially, and its performance is also inferior to that of
This is not much different from Publication No. 51-103135. Further, as similar to the one described in the above-mentioned Japanese Patent Publication No. 52-6306, Japanese Patent Application Laid-open No. 11228/1986 discloses that an epoxy group-containing resin and at least one primary amino acid blocked by a ketimine group are used. An aqueous composition for electrodeposition is disclosed in which a partially blocked polyisocyanate is further added to an acid-neutralized amino group-containing resin obtained by reacting a polyamine derivative having a secondary amino group and a polyamine derivative having a secondary amino group. According to the composition, in principle, the resin can be dispersed in water with a low degree of neutralization, and the PH and throwing power of the bath can be improved to some extent, and the activity against blocking isocyanate groups is increased. It has been shown that considerable improvements can be made in terms of improving the curability of the coating film. However, it is very difficult to quantitatively react the epoxy group-containing resin with the secondary amino groups in the ketiminated polyamine derivative, and in reality, unreacted polyamine derivatives are present in the aqueous composition. However, problems such as residual residual or significant increase in viscosity due to forced completion of the reaction occur, and it is almost impossible to fully achieve the above-mentioned improvements. In order to improve the defects of the compositions described in the above-mentioned publications, the present applicant previously disclosed in Japanese Patent Publication No. 53-8568 that an amine-added epoxy resin was mixed or reacted with an amino group-containing polyamide resin, and further a partial block was added. We have proposed a resin composition for cationic electrodeposition coatings to which polyisocyanate has been added, and have also proposed a composition for electrodeposition coatings having similar constituents to the composition described in the above-mentioned Japanese Patent Publication No. 53-8568. Akira
52-77144 and JP-A-52-101238, at least two of a reaction product of an epoxy resin and a basic amino compound, a basic amino group-containing polyamide resin, and a partially blocked isocyanate are disclosed.
discloses a resin composition for cationic electrodeposition coating containing as a main component a mixture of the reaction product of the inventor and the remaining components;
A polyether having specific properties is blended into the amine-added epoxy resin - fatty acid or amino group-containing polyamide resin - partially blocked polyisocyanate resin composition system, thereby making the painted surface smooth without impairing the corrosion resistance of the paint film. We proposed a technology that significantly improves sexual performance. However, the recent demands on the performance of resin compositions for electrodeposition coatings in the market are becoming increasingly strict, and the present inventors have further improved the performance of resin compositions for cationic electrodeposition coatings to meet the current market requirements. As a result of extensive research in order to provide products that fully satisfy the requirements, we have developed a primary amino group blocked with a carbonyl compound and an isocyanate-reactive functional group (primary or secondary amino group or hydroxyl group).
By bonding a compound having at least two isocyanate-reactive functional groups (primary or secondary amino groups or hydroxyl groups) via a diisocyanate compound, a sufficient amount of primary It is possible to produce a resinous product having a class amino group in an extremely simple manner, and furthermore,
The resin-like product thus formed not only has excellent properties such as bath pH, throwing power, and curing properties, but also produces coating films with excellent properties such as adhesion, flexibility, and impact resistance. The present invention has been completed based on the discovery that it is possible to form the same structure. Thus, according to the present invention, (A) a compound having at least two isocyanate-reactive functional groups selected from active hydrogen-containing amino groups and hydroxyl groups in one molecule [hereinafter referred to as "compound A"]
(B) At least one primary amino group blocked with a carbonyl compound in one molecule and at least one isocyanate-reactive functional group selected from active hydrogen-containing amino groups and hydroxyl groups in one molecule. (hereinafter referred to as "Compound B"), and (C) a diisocyanate compound having two free isocyanate groups in one molecule (hereinafter referred to as "Compound C").
], and (D) has at least two isocyanate groups in one molecule, one or more of which is blocked, and one free isocyanate group is
Component (B) is a diisocyanate compound, which is obtained by reacting or mixing a partially or completely blocked polyisocyanate compound (hereinafter referred to as "compound D") containing no more than 10% of blocked primary amino groups. There is provided a blocked isocyanate group-curable resin composition for cationic electrodeposition coating, which contains as a main component a resinous product introduced into the compound (A) component via the component (C). According to the present invention, a primary amino group is introduced into the base resin forming component through a urea bond or urethane bond forming reaction between compound C, that is, a diisocyanate compound and an active hydrogen-containing amino group or hydroxyl group. This makes it possible to introduce a sufficient amount of primary amino groups even into the base resin forming component that does not contain any epoxy groups, and overcomes the various limitations when using epoxy group-containing resins in the prior art described above. A resin composition for cationic electrodeposition coatings that not only can completely overcome the disadvantages but also has far superior performance to resin compositions for cationic electrodeposition coatings using such conventional epoxy group-containing resins as base resins. can provide things. Hereinafter, the resin composition of the present invention will be explained in more detail. Compound A: Compound A is a main base resin forming component of the resinous product of the present invention, and is a compound having at least two isocyanate-reactive functional groups selected from active hydrogen-containing amino groups and hydroxyl groups in one molecule. be. The active hydrogen-containing amino group has 2 active hydrogen atoms.
Primary amino group or active hydrogen atom containing 1
Although it may be any of the secondary amino groups contained therein, secondary amino groups are generally preferred because they have milder reactivity with isocyanate groups. Conversely, the reactivity of hydroxyl groups to isocyanate groups is highest for those bonded to primary carbon atoms, followed by those bonded to secondary carbon atoms, and then to tertiary carbon atoms. As reactivity decreases,
The above hydroxyl group is preferably bonded to a primary carbon atom, but it is of course possible that a hydroxyl group bonded to a secondary carbon atom or a tertiary carbon atom exists. Compound A can have at least two such isocyanate-reactive functional groups in one molecule,
The preferred number of functional groups varies depending on the type of functional group, the molecular weight of Compound A, etc., but it is generally preferable to have an average of 2 to 10 isocyanate-reactive functional groups per molecule, and further, It is desirable to have an isocyanate-reactive functional group in the range of 100 to 2000, more preferably 200 to 1000, expressed in terms of the equivalent number of isocyanate-reactive functional groups. Compound A
The plurality of isocyanate-reactive functional groups present therein may be the same or different. Here, "isocyanate-reactive functional group equivalent"
represents the number of grams of isocyanate-reactive functional group-containing compound per gram equivalent of isocyanate-reactive functional group. Compound A may also contain a functional group with low isocyanate reactivity, such as an acid amide bond, an ester bond, an ether bond, a urethane bond, a urea bond, an allophanate bond, a biuret bond, etc., but generally active hydrogen It is preferable that there is substantially no functional group such as an epoxy group that can react with an amino group or a hydroxyl group. That is, it is desirable that Compound A is an epoxy-free compound. Compound A that can be used in the present invention includes low molecular weight compounds and high molecular weight compounds (that is, polymeric compounds) as long as they have at least two isocyanate-reactive functional groups in one molecule. It may be either aliphatic type or aromatic type (including aromatic-fat type), but from the viewpoint of corrosion resistance of the coating film, aromatic type is generally used. (in the case of polymers, the main chain is mainly formed from aromatic rings), and Compound A generally has a molecular weight within the range of about 100 to about 10,000, preferably about 200 to about 5,000. It is desirable to have a number average molecular weight of . Examples of typical compounds that can be used as compound A in the present invention are as follows. () One active hydrogen atom, such as an epoxy resin and a diamine containing two amino groups (primary or secondary amino groups) having at least one active hydrogen atom, or a primary or secondary amine containing a hydroxyl group. Adducts with amine compounds containing two or more in the molecule: Epoxy resins useful for forming this adduct include aromatic epoxy resins, such as bisphenol A' and bisphenol F, formed by reaction with epihalohydrin. The bisphenol type epoxy resins produced are included. Such epoxy resins usually have a molecular weight of about 300 to about 4000, preferably about 400
Number average molecular weight within the range of ~3000 and generally about
It can have an epoxy equivalent weight ranging from 150 to about 4000, preferably from about 200 to about 2000. Specific examples of such bisphenol type epoxy resins include the following. Epoxy resin manufactured by Ciel Chemical Co., Ltd.: Epikote828 (bisphenol A type, average molecular weight approx.
380, epoxy equivalent approximately 190), Epikote 1001 (bisphenol A type, average molecular weight approximately
900, epoxy equivalent approximately 475), Epikote 1004 (bisphenol A type, average molecular weight approximately
1400, epoxy equivalent approximately 950), Epikote 1007 (bisphenol A type, average molecular weight approximately
2900, epoxy equivalent approximately 1900), Dainippon Ink Chemical Co., Ltd. Epoxy resin: Epiclon 830 (Bisphenol F type, average molecular weight approximately
360, epoxy equivalent approximately 180). On the other hand, amines that can be added to these epoxy resins are selected from those having the following structural formula. R′−NH ₂ , H ₂ N−R ₁ −NH ₂ , H ₂ N−R ₁ −
NHR′, H ₂ N−R ₁ −NR′R″, R′HN−R ₁ −
NHR″, HO−R ₁ −NH ₂ , HO−R ₁ −NHR′ In the formula, R ₁ represents an alkylene group, a cycloalkylene group, an arylene group, or an aralkylene group, and R′ and R″ are an alkyl group and a cycloalkylene group, respectively. representing an alkyl, aryl or aralkyl group, such as ethylamine, propylamine, butylamine, cyclohexylamine, aniline,
Examples include primary monoamines such as benzylamine, diamines such as ethylenediamine, N,N-dimethylethylenediamine, piperazine, and metaphenylenediamine. Further, examples of the hydroxyl group-containing primary or secondary amine include lower alkanol primary or secondary amines such as monoethanolamine, diethanolamine, N-methylethanolamine, and N-hydroxyethylpiperazine. It is desirable that the addition reaction between the amine and the epoxy resin is carried out until the epoxy groups in the epoxy resin are substantially completely consumed. () Adduct of epoxy resin and water or polyhydric alcohol: The epoxy resins that can be used to form this adduct are preferably those mentioned in () above, and the polyhydric alcohol added to this is preferable. For example, ethylene glycol,
Lower alkylene glycols such as propylene glycol; glycerin, trimethylolpropane; poly(lower alkylene glycols) such as diethylene glycol and triethylene glycol
etc. The addition reaction between the epoxy resin and water or polyhydric alcohol is also desirably carried out until the epoxy groups are substantially completely consumed. () Diphenol compounds or bisphenol compounds, such as bisphenol A, bisphenol F (4,4'-dihydroxyphenylmethane), dihydroxydiphenylethane, 4,
4'-Hydroxyphenylisobutane, 4,4'-
Dihydroxybenzophenone, 1,5-dihydroxynaphthylene, etc. () A phenol-terminated prepolymer formed by the addition polymerization reaction of a bisphenol compound and a diepoxy compound or a diisocyanate compound: Diepoxy compounds that can be used to form such a prepolymer include, for example, diglycidyl of the above-mentioned bisphenol compound. Ethers (e.g. Epikote 827 manufactured by Ciel Chemical Company; Araldite GY-250 manufactured by Ciba Geigy; DER-330 manufactured by Dawa Chemical Company, etc.), diglycidyl ethers of polyalkylene glycols (e.g. Epikote 812 manufactured by Ciel Chemical Company, K-425 manufactured by Asahi Ciba Company) ), vinylcyclohexene dioxide (e.g.
Chitso Nox 206) manufactured by Chitso Company, etc. are mentioned, and as the diisocyanate compound, those described below for Compound C are suitable. () Addition polymerization prepolymer of bisphenol compound and alkylene oxide: Examples of alkylene oxides that can be used to form such a prepolymer include ethylene oxide and propylene oxide. () Styrene-allyl alcohol copolymer prepolymer: As such a copolymer prepolymer, one having an average molecular weight of 3000 or less is suitable, and Monsanto's RJ-101 (average molecular weight approximately 1700, hydroxyl equivalent approximately
220) RJ-100 (average molecular weight approximately 2300, hydroxyl equivalent approximately 300). () Condensation polymerization prepolymer of aromatic dicarboxylic acid and cyamine, alkanolamine or polyol: As the aromatic dicarboxylic acid, those commonly used for producing polyamide or polyester can be used, for example, Phthalic acid, isophthalic acid, terephthalic acid, etc. are included, and examples of diamines that can be reacted with these include ethylenediamine, hexamethylenediamine, m-phenylenediamine, etc., and examples of alkanolamines include, for example, monoethanol. Examples of polyols include amine, diethanolamine, triethanolamine, hydroxyethylpiperazine, etc., and examples of polyols include ethylene glycol, propylene glycol,
Glycerin, 2,2-dimethylpropanediol, trimethylolpropane, etc. can be mentioned. The condensation polymerization reaction between the aromatic dicarboxylic acid and the diamine, alkanolamine or diol can be carried out in accordance with a known polyamide or polyester forming reaction. () Novolac type phenol-formaldehyde resin: It is generally desirable that this resin have a number average molecular weight of about 1000 or less. () Aromatic (primary amine): For example, m-phenylene diamine, 4,4'-methylene dianiline, benzidine, 2,4-trienediamine, diaminodiphenyl ether,
4,4'-thiodianiline, diaminodiphenylsulfone, dianisidine, etc. () A primary amine-terminated prepolymer formed by the addition polymerization reaction of an aromatic (primary amine) with a dicarboxylic acid or a diepoxy compound or a diisocyanate compound: Examples of the primary diamine) and the diepoxy compound or diisocyanate compound include those mentioned above. In addition, examples of dicarboxylic acids include aliphatic dichloric acids such as adipic acid, sebacic acid, and dimerized linoleic acid. (XI) Aliphatic (including alicyclic) hydroxyl group-containing compounds: For example, epoxy group-containing prepolymers such as hydrogenated bisphenol epoxy resins, polypropylene diglycidyl ether, and epoxidized polybutadiene, and aliphatic primary monoamines. Or adducts with alkanolamines; hydroxyl group-containing prepolymers such as polypropylene glycol, polytetraethylene glycol, polycaprolactone diol, polybutadiene glycol, and the like. Among the compounds exemplified above, those particularly suitable as compound A are the above (), (), (),
Those listed in (), especially adducts of bisphenol A type epoxy resin and alkanolamine;
A phenol-terminated prepolymer of bisphenol A and diisocyanate; and a styrene-allyl alcohol copolymer prepolymer. Each of the above compounds can be used alone, or two or more kinds can be used in combination. Compound B Compound B used in the present invention has at least one primary amino group blocked with a carbonyl compound in one molecule and one isocyanate-reactive functional group selected from an active hydrogen-containing amino group and a hydroxyl group. This compound is a necessary component for introducing a highly basic primary amino group into the resinous product of the present invention. Therefore, a "primary amino group blocked with a carbonyl compound" is a protected amino group that can be converted into a free primary amino group by a simple operation such as hydrolysis, and is typically represented by the following formula: In the formula, R ₂ represents a hydrogen atom or a monovalent hydrocarbon group such as an alkyl group or a cycloalkyl group, and R ₃
represents a monovalent hydrocarbon such as an alkyl group or a cycloalkyl group, or R ₂ and R ₃ together represent an alkylene group, and is a temporarily protected primary amino group that can be represented by . In addition, the above active hydrogen-containing amino group and hydroxyl group are isocyanate-reactive functional groups necessary for bonding Compound B to Compound A via Compound C (diisocyanate compound), which will be described later. The active hydrogen-containing amino group or hydroxyl group is preferably a secondary amino group or a primary hydroxyl group. Therefore, as compound B, (a) a polyamine compound having both a primary amino group and a secondary amino group; (b) a hydroxyl group-containing amine compound having both a primary amino group and a hydroxyl group; and (c) Each compound of a hydroxyl group-containing polyamine compound that simultaneously has three groups: a primary amino group, a secondary amino group, and a hydroxyl group [hereinafter, these compounds (a), (b), and (c) will be referred to as "(poly)amine compounds". It includes those in which at least some, preferably substantially all, of the primary amino groups present in A polyprimary amino compound having only a primary amino group partially blocked with a carbonyl compound can also be used as compound B. The above (poly)amine compound may be of low molecular weight or high molecular weight, and may be either aliphatic (including alicyclic) or aromatic. Generally, aliphatic ones are more suitable. As mentioned above, compound B is a necessary component for introducing a strongly basic primary amino group into the resinous product of the present invention to acid-neutralize and make the resin composition water-soluble. (Poly)amine compounds are generally about
It is advantageous to have a primary amino group equivalent weight in the range of 2000 or less, preferably about 1000 or less, and
The isocyanate-reactive functional group equivalent weight is generally about 2000
Desirably, it is within a range of about 1000 or less. In addition, the (poly)amine compound generally has about 5000
Hereinafter, it is advantageous to have a number average molecular weight preferably within the range of about 3000 or less. Therefore, the (poly)amine compound that can be suitably used in the present invention has the following general formula in ^cm2 . In the above formula, R ₄ , R ₆ , R ₇ , R ₈ , R ₇ ′, R ₈ ′, R ₉ ,
R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ each represent an alkylene group (preferably a lower alkylene group) or a cycloalkylene group, and R ₅ , R ₅ ′, R ₅ ″ and R ₁₂ represent an alkyl group (preferably a lower alkyl group). group) or a cycloalkyl group, and a, b, c, d and e are each an integer of 1 or more, particularly an integer of 1 to 5.Specifically, the following (poly)amine compounds can be exemplified. (a) N-alkylalkylene diamines H2N _- CH2- _CH2 -NH- _CH3 , H2N _{- CH2} - _CH2 - _{CH2 -} NH- _CH3 , (b) Polyalkylene polyamines H ₂ N−CH ₂ −CH ₂ −NH−CH ₂ −CH 2 −NH ₂ , H ₂ N−CH ₂ −CH _{2 −NH} −CH ₂ −CH ₂ −NH −CH ₂ −CH ₂ −NH ₂ , H ₂ N−CH ₂ −CH ₂ −NH−CH ₂ −CH ₂ −NH −CH ₂ −CH ₂ −NH−CH ₂ −CH ₂ −NH ₂ , H ₂ N−CH ₂ −CH ₂ −NH−CH ₂ −CH ₂ −NH CH ₂ −CH ₂ −NH−CH ₂ −CH ₂ −NH −CH ₂ −CH ₂ −NH ₂ , H ₂ N−CH ₂ −CH ₂ −CH ₂ −NH−CH ₂ −CH ₂ −CH ₂ −NH ₂ . (c) N-Hydroxyalkylalkylene diamines _H2N -CH2-CH2 _{- NH} -CH2-CH2 _- OH, H2N _{- CH2-CH2 - CH2} - _NH - _CH2 - _CH2 −
CH ₂ −OH, H ₂ N−CH ₂ −CH ₂ −NH−CH ₂ −CH ₂ −CH ₂ −
Oh. (d) Mono(hydroxyalkyl)amines _H2N - _CH2 - _CH2- OH, H2N _{- CH2} -CH2 _{- CH2-} OH, (e) N-(aminoalkyl)piperazine In addition to those listed above, (poly)amine compounds include adipic acid, sebacic acid, dimer acid (dimeric linolenic acid), maleated fatty acids [e.g. maleated oleic acid, linoleic acid, linolenic acid] dehydrated ricinoleic acid or eleostearic acid] and aliphatic polybasic acids such as polybutadiene dicarboxylic acid; A primary amino group-terminated prepolymer (polyamide polyamine) formed by a condensation reaction with an alkylene group polyamine can also be suitably used. As such, specific examples of polyamide polyamines include:
For example, Versamid 100 from Japan General Mills Co., Ltd.
Examples include 115, 125, 140, etc. Among the above-mentioned (poly)amine compounds, particularly preferred are monoethanolamine, monopropanolamine, monobutanolamine, diethylenetriamine, or dimer acid-polyalkylene polyamine condensate; These can be used alone or in combination of two or more. The above (poly)amine compound can be used as compound B after blocking at least a portion, preferably substantially all, of the primary amino groups present with a carbonyl compound. As the carbonyl compound that can be used for this blocking, any ketone or aldehyde that is commonly used for the temporary protection of an amino group by ketimination or aldimination can be used, but specific examples of the ketone include acetone, etc. , methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, etc., and suitable aldehydes include, for example, acetaldehyde, propionaldehyde, benzaldehyde, pivaldehyde, etc. The reaction between a (poly)amine compound and these carbonyl compounds can be carried out by a method known per se [for example, J.Org.Chem., 19, 1054-
76 (1954)], it is desirable to use quantitative proportions and reaction conditions such that substantially all of the primary amino groups present react with the carbonyl compound, and the reaction (dehydration reaction) is facilitated. It is generally advantageous to use ketones with poor water solubility and low steric hindrance, such as methyl isobutyl ketone. Compound C In constituting the resinous product of the present invention, compound C, which primarily serves as a crosslinking agent in bonding the compound A with compound B, is:
It is a diisocyanate compound having two free isocyanate groups in one molecule. Such diisocyanate compounds include any one commonly used in the production of polyurethane, such as aliphatic (including alicyclic systems as described above) and aromatic systems (including aromatic-aliphatic systems as described above). diisocyanate compounds of the type and also triisocyanate and tetraisocyanate compounds partially blocked with lower alcohols etc. can be used, but generally about 100 to about 2000, preferably about 150
Those having molecular weights within the range of from to about 1000 are preferred. Such diisocyanate compounds are generally represented by the following formula. (1) Diisocyanate OCN−R ₁₅ −NCO (7) (2) Triisocyanate monourethane (3) Diurethane of tetraisocyanate In the above formula, R ₁₅ , R ₁₆ and R ₁₈ are each monovalent,
Represents the above group containing a divalent and trivalent aliphatic (including alicyclic) or aromatic hydrocarbon group, or an ether bond, thioether bond, carbonyl group, sulfonyl group, urethane bond or urea bond, R ₁₇ , R ₁₉ and R ₂₀ each represent an alkyl group, a cycloalkyl group or an aryl group. Specific examples of the diisocyanate compounds represented by these general formulas are as follows.

【formula】 【formula】

【formula】 【formula】

[Formula] Lysine diisocyanate, isophorone diisocyanate,

【formula】

【formula】

(However, G represents a lower alkyl group, a cycloalkyl group, or an aryl group) In addition, diisocyanates obtained by addition of these diisocyanates with diols such as ethylene glycol and diethylene glycol; and addition of the above diisocyanates with glycerin or trimethylolpropane. It is also possible to use monourethanes from triisocyanates and monoalcohols obtained by addition with triols such as These diisocyanate compounds can be used alone, or in combination of two or more. Among the above diisocyanate compounds, those which are particularly suitable as compound C include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,
4'-diphenylmethane diisocyanate, 1,4
-xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, ethylene glycol, diethylene glycol, 2,4-tolylene diisocyanate adduct of propylene glycol, 2,4 of trimethylolpropane -A reaction product of 1 mol of tolylene diisocyanate adduct and 1 mol of lower aliphatic monoalcohol, etc. can be mentioned. Compound D Compound D is a partially or completely blocked polyisocyanate compound that has at least two isocyanate groups in one molecule, at least one of which is blocked, and does not contain more than one free isocyanate group. is used. This compound D is a component that acts as a crosslinking agent for crosslinking and curing the coating film when the resin composition of the present invention is formed into an electrodeposition coating film and then baked. The polyisocyanate compound used in the preparation of compound D may be of either aliphatic type or aromatic type as long as it has two or more isocyanate groups, and generally has a polyisocyanate group of 100 to 2000,
Preferably, it can have a molecular weight within the range of 150-1000. As such a polyisocyanate compound, the diisocyanate compounds represented by the formulas (7) to (9) described above for compound C can be used. The above polyisocyanate compound can be used as compound D after being blocked with a blocking agent until it contains no more than one free isocyanate group on average per molecule. This blocking can be carried out by methods known per se [for example
[method described in Angew.Chem., 59, 257 (1947)]
This can be done by In addition, as a blocking agent for the polyisocyanate compound, 1
Active hydrogen compounds such as functional alcohols, phenols, lactams, oximes, and tertiary amino alcohols are included, but there are those that thermally dissociate at the baking temperature of the coating film and easily regenerate free isocyanate groups. Preferably, volatile low-molecular active hydrogen compounds are used, examples of which include methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, hexanol, cyclohexanol, benzyl alcohol, and ethylene glycol. Aliphatic or aromatic monoalcohols such as monoethyl ether (also known as cellosolve), ethylene glycol monobutyl ether; hydroxy tertiary amines such as dimethyl- or diethylaminoethanol; oximes such as acetoxime, methyl ethyl ketone oxime; acetylacetone, acetoacetic acid Active methyl compounds such as esters and malonic acid esters; lactams such as ε-caprolactam; phenols and phenols such as cresol; and the like. Among these, aliphatic monoalcohols are particularly preferred from the viewpoint of odor and toxicity during baking after electrodeposition. Compound D can be used in both partially blocked and fully blocked forms, but it is generally preferred that it be present in a bound form in the resinous products of the invention, and therefore in partially blocked form. type is preferable. Preparation of resinous product The resinous product of the present invention comprises the aforementioned compound A,
It can be produced by appropriately reacting the three components of Compound B and Compound C, or optionally the four components to which Compound D (limited to the case of a partially blocked polyisocyanate compound) is added. The order of the reaction at this time can be changed depending on the type or property of the compounds A to D used, and for example, the reaction can be appropriately selected from among the reaction modes described below. A person skilled in the art can easily determine which reaction mode to select, taking into consideration the properties of the compounds A to D used (for example, is one with a low molecular weight or one with a high molecular weight), the type of reactive group, etc. can do. In addition, in the description of the reaction mode below, it is assumed that Compound D is also reacted, but when a completely block type polyisocyanate compound is used as Compound D, the reaction of Compound A, Compound B, and Compound C is It can be added to the reaction mixture or reaction components at any stage of the reaction or after the reaction. Also,
A partially block type polyisocyanate compound and a completely block type polyisocyanate compound are used together, the partially block type polyisocyanate compound is reacted according to the reaction mode described below, and the completely block type polyisocyanate compound is reacted after the reaction or at any stage of the reaction. Polyisocyanate compounds may be mixed. Reaction mode: A mixture of compound C and compound D is added to a mixture of compound A and compound B, and the mixture is reacted. Reaction mode: Compound A and Compound C, and Compound B and Compound D
are reacted respectively, and the resulting two reaction products are mixed and further reacted, or
and Compound D, and Compound B and Compound C, respectively, and the resulting two reaction products are mixed and further reacted. Reaction mode: Compound A is reacted with the mixture of invention C and invention D, and then further reacted with compound B. Reaction mode: Compound A is reacted with compound C, the resulting reaction product is reacted with compound D, and then compound B is reacted, or compound A is reacted with compound D, and the resulting reaction product is reacted with compound C. is reacted, and then compound B is reacted. Reaction mode: Compound A is reacted with compound C, the resulting reaction product is reacted with compound B, and finally compound D is reacted. Reaction mode: Compound A is reacted with Compound D, and the resulting reaction product is mixed with Compound B, and then Compound C is reacted. Reaction mode: Compound B is reacted with compound C, the resulting reaction product is reacted with compound A, and then compound D
react. Reaction mode: Compound B is reacted with a mixture of compounds C and D, and then the reaction product is reacted with compound A. Reaction mode: Compound B is reacted with Compound D, and the resulting reaction product is mixed with Compound A, and then Compound C is reacted. Reaction mode: Compound B is reacted with compound C, and the resulting reaction product is mixed with compound D, and then reacted with compound A. In the reaction embodiments described above, the term "reaction product" refers not only to quantitative reaction products of the reaction components described therein, but also to unreacted reaction components and/or partial reactions of the three reaction components. Used to mean that products are included. In addition, in the above reaction mode, when compound D is reacted with compound A or compound B before reacting compound C, all of the isocyanate-reactive functional groups present in compound A or compound B are to prevent it from reacting with compound D.
It is important to control the reaction ratio of Compound D to Compound A or Compound B and/or the reaction conditions. Furthermore, in order to increase the rate of bonding between compound A and compound B via compound C, it is necessary to equalize the reactivity of the isocyanate-reactive functional groups in compound A and compound B, or to It is desirable to perform an operation such as reacting the other compound after reacting the compound C. The reactions of Compounds A to D according to the above reaction mode are related to the urea bond forming reaction between an active hydrogen-containing amino group and an isocyanate group and the urethane bond forming reaction between a hydroxyl group and an isocyanate group, and are performed using conventionally known reactions. This can be carried out according to a method known per se. For example, the reaction is generally carried out at relatively low temperatures, preferably in the range of about 0 to about 120°C, and in a substantially anhydrous solvent that is inert to the isocyanate, so that the reaction proceeds as uniformly as possible. This can be done while stirring.
Examples of solvents that can be used include aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and isophorone; ethers such as dioxane and ethylene glycol dimethyl ether; t-butanol and diacetone alcohol. Mention may be made of tertiary alcohols, and also secondary alcohols, such as isopropanol, propylene glycol monomethyl ether, which have a relatively low activity towards isocyanates, may optionally also be used. Among these solvents, non-hydrophilic solvents should be used within a range that does not impede the water dispersibility of the resulting resin. In addition, regardless of which solvent is used, in order not to interfere with the high throwing power of the resin composition to be produced, it is usually
It is desirable to use it in an amount of no more than parts by weight. The usage ratios of Compound A, Compound B, Compound C, and Compound D vary depending on the type of these compounds and are difficult to define unconditionally, but the following usage ratios can be considered as a tentative guide. Compound A: 30 to 80% by weight based on the total of Compounds A to D from the viewpoint of corrosion resistance of the resinous product.
It is desirable to Compound B: From the viewpoint of water dispersibility of the product, it is desirable to use a proportion such that the equivalent of primary amino groups in the product is 300 to 3,000. Compound C: The amount necessary for introducing Compound B into Compound A to exhibit water dispersibility is preferably used in an amount that is approximately equimolar to Compound B or more. Compound D: From the viewpoint of curability of the resinous product, it is desirable to use a proportion such that the equivalent weight of blocked isocyanate groups in the resinous product is 400 to 4,000. According to the above reaction mode, the reactions are mainly as follows: (a) A crosslinking reaction between compound A component and compound B component using compound C as a crosslinking member; (b) Between compound A and compound C. (c) polymerization reaction between compound B and compound C, (d) blocking isocyanate introduction reaction between compound A component and compound D, and (e) blocking between compound B component and compound D. Isocyanate introduction reactions occur and two or more of these reactions are combined to form the resinous products of the present invention. The components in the resinous product thus formed can have any of the structures shown in the schematic diagrams below. A-C-B, A-(C-B) _o -C-A(n≧
1), A-C-A, A-(C-A) _o -C-A(n≧
1), B-C-B, B-(C-B) _o -C-B(n≧
1), A-C-B-D, D-A-C-B, D-A-C
-B-D, A-C-A-D, D-A-C-A-D, B-C-B-D, D-B-C-B-D, A-D, BD, A , B, D _p It is also desirable that the resinous product of the present invention has the following properties. Primary amino group equivalent: about 300 to about 3000, blocked isocyanate group equivalent: about 400 to about
4000, ratio of residual isocyanate-reactive functional group equivalents (including primary amino groups) to blocked isocyanate group equivalents: about 0.5 to about 4.0. The resinous product of the present invention described above is blocked with a sufficient amount of carbonyl compound to make the resinous product water-soluble or water-dispersible by neutralizing it with an acid in the molecule. Since it has both a strongly basic primary amino group and a blocked isocyanate group that is useful for curing the coating after coating, it can be used as a coating forming component in a resin composition for cationic electrodeposition coating. . Preparation of a resin composition for cationic electrodeposition coating When the resin composition of the present invention is used to prepare a resin composition for cationic electrodeposition coating according to the present invention, the resinous product can be directly used for clear electrodeposition coating. Although it can be used as a composition, it can generally be used as an electrodeposition coating composition by adding pigments and other commonly used additives. Pigments that can be added include those commonly used in electrodeposition paints, such as colored pigments such as red iron, titanium white, and carbon black; extender pigments such as talc, clay, and mica; and chromic acid. Lead, strontium chromate,
Antirust pigments such as basic lead silicate are used, and these can be used in any amount.
Furthermore, salts of metals such as lead, tin, bismuth, iron, and manganese with organic or inorganic acids (e.g., acetic acid, naphthenic acid, hydrochloric acid, nitric acid, etc.); oxides of the metals;
A hydroxide of the metal may also be added as a curing accelerator. Further, although the present composition does not normally require the addition of a surfactant, if desired, a small amount of a known surfactant (for example, a nonionic active agent) commonly used in cationic electrodeposition paints may be added. Furthermore, a coating film extender (for example, an acrylic acid alkyl ester copolymer, a polyalkylsiloxane) may be added as necessary. The resin composition for electrodeposition coating of the present invention prepared as described above can be prepared using acids such as water-soluble lower aliphatic monocarboxylic acids such as formic acid, acetic acid, hydroxyacetic acid, propionic acid, butyric acid, and lactic acid; oxalic acid, and succinic acid. , aliphatic dicarboxylic acids such as fumaric acid and maleic acid; aromatic carboxylic acids such as benzoic acid and phthalic acid; organic sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid; inorganic acids such as phosphoric acid, sulfuric acid, and hydrochloric acid. In particular, by neutralizing with the above-mentioned water-soluble aliphatic monocarboxylic acid, a stable aqueous bath for electrodeposition coating can be formed. This neutralization treatment hydrolyzes the carbonyl compound-blocked primary amino groups present in the resinous product to form strongly basic primary amino groups, which in turn are neutralized. be harmonized. Therefore, the amount of the acid required for neutralization is at least the amount necessary to solubilize or stably finely disperse the present composition, that is, the resinous product as a coating film-forming component, in the aqueous medium. In addition, it is preferable that the amount is less than or equal to the amount necessary to completely neutralize the amino groups present in the resinous product. Specifically, the amine value (defined below) of the resinous product is preferably A range of about 0.1 to 0.6 equivalent percent, based on the amount, is preferred. Regarding the pH of the aqueous bath obtained, it is advantageous to neutralize the aqueous bath so that the pH of the aqueous bath generally ranges from about 3 to about 8, preferably from about 5 to about 7. When the composition of the present invention is neutralized with an acid and dissolved or dispersed in an aqueous medium, the concentration of total resin solids in the aqueous bath is generally 3 to 30% by weight, preferably 5 to 20% by weight. can do. The aqueous bath for electrodeposition coating prepared in this way can be used as an electrodeposition coating bath capable of cathodic electrodeposition using the object to be coated as the cathode. As the method and apparatus for applying electrodeposition coating to the object to be coated using this aqueous bath, known methods and apparatuses conventionally used in cathodic electrodeposition coating 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 in general, bath temperature: 20
~30℃, voltage: 100~400V (preferably 200~
300V), current density: 0.01 to 3A/ ^dm2 , energizing time:
It is preferable to electrodeposit for 1 to 5 minutes, electrode area ratio (A/C): 2/1 to 1/2, distance between electrodes: 10 to 100 cm, and stirring. After cleaning, the coating film deposited on the cathode is maintained at a temperature of about 140 to about 250°C, preferably about 170 to about 200°C.
It can be baked and hardened. During this baking process, the blocked isocyanate groups present in the resin of the coating release alcohol, which is a blocking agent, and the amino groups, amide groups, etc. present in the resin,
Cures by crosslinking with hydroxyl groups, etc. The resin composition for electrodeposition coating provided by the present invention can be used for coating various metal products,
For example, it is particularly suitable for electrodeposition coating not only on normal zinc phosphate treated steel sheets, but also on other easily corroded steel sheets such as iron phosphate treated steel sheets and untreated steel sheets. It is possible to provide a coating film that has outstanding corrosion resistance as well as thickening properties. This is a significant advantage not achieved with conventional electrodeposition coating compositions. Furthermore, the composition of the present invention can be applied to galvanized steel sheets, tin-plated steel sheets,
It is also suitable for electrodeposition coating on substrates such as aluminum, copper, and copper alloys, and can form coatings with excellent throwing power, corrosion resistance, etc. The present invention will be described in more detail below with reference to Examples, but it should be understood that the scope of the present invention is not limited thereby. In addition, "parts" in the examples refer to "parts by weight."
represents. In addition, measurements or tests of tertiary amine value, amine value, isocyanate value, throwing power, salt spray resistance, Erichsen extrusion resistance, impact resistance, and bending were performed by the following methods. (1) Method for measuring tertiary amine value Accurately weigh approximately 0.2 g of sample solid content into an Erlenmeyer flask with a stopper, add approximately 10 ml of acetic anhydride/acetic acid at a weight ratio of 9/1, and add approximately 10 ml of acetic anhydride/acetic acid at a weight ratio of 9/1. Boil for 10 minutes to complete acetylation. After cooling, titrate using 0.1N perchloric acid-acetic acid solution and crystal violet as an indicator until the color changes from purple to blue-green. Tertiary amine value (mgKOH/g) = 5.61 x titration number (ml) x N/10 HClO ₄ factor/sample solid content (g
) (2) Method for measuring amine value Take 0.2 to 0.3 g of the sample in a 100 ml Erlenmeyer flask, heat, dissolve, cool, and titrate with an aqueous N/10 HCl solution using bromophenol blue as an indicator. When the color changes from blue to yellow. is the end point. The amine value is determined by the following formula. Amine value = N/10HCl amount (ml) x N/10HCl titer/sample amount (g) x solids content (%)/100 x 5.61 (3) Method for measuring isocyanate value Samples with isocyanate groups (NCO) approx.
Weigh out 0.5g accurately, put it in a flask with a ground stopper, and dissolve it in 10ml of dioxane (grade 1 reagent). Add exactly 10 ml of a 2/10N dibutylamine solution in dioxane to this, and heat the mixture to 80°C for 30 minutes while shaking. Add 100 ml of isopropyl alcohol (1st grade reagent) and titrate excess dibutylamine with 1/10N hydrochloric acid using bromophenol blue as an indicator until the blue color changes to yellow-green. In this case, conduct a blank test without adding any sample at the same time. The NCO value is determined by the following formula. NCO value = (A-B) x 0.0042f x 1000/
W In the formula, A: Amount (ml) of N/10 hydrochloric acid required to neutralize 2/10N dibutylamine in a blank test. B: Amount (ml) of N/10 hydrochloric acid used for titration of the sample. 0.0042: N/10 Amount (mg) of isocyanate groups equivalent to 1 ml of hydrochloric acid. f: Factor of hydrochloric acid. W: Sample collection amount (g). (4) Throwing test method (pipe method) Throwing test device: Schematically shown in attached Figures 1 to 3. In addition, each symbol in the figure has the following meaning. V: Stainless steel round container (φ=100mm, t=1
mm) Non-magnetic. Z: Insulator D: Support rod (φ=3mm, h=170mm) P: Stainless steel pipe (φ=16mm, h340mm,
t=1mm) Non-magnetic. A: Outer film thickness measurement plate (30 x 150 x 0.8 mm) (second
(See figure) B: Inner plate circumference measurement plate (15 x 300 x 0.4 mm)
(See Figure 3) T: Mercury thermometer (50℃ scale) K: Rotor C: Cooling water tank (made of plastic) M: Magnetic stirrer L: Paint level Operating procedure: 1 As shown in Figure 1. Pour paint into a stainless steel round container V up to 27 cm from the bottom L, adjust the temperature to the specified temperature (usually 30°C), and stir evenly. (Bath temperature: 30°C) 2. Insert outer plate A, pipe D, and inner plate B into support rod D and place into container V. 3 Set the anode and cathode and check that there are no short circuits. 4 Change the voltage from 0 to outer skin thickness of 20 to 25μ in 10 seconds.
Increase the voltage to the specified voltage. At that time, adjust the rising speed so that it does not exceed 10A. 5 After 3 minutes of energization, cut the silicone resin, remove the outer panel,
Wash the inner plate and pipes with water. 6. Baking and drying the outer and inner panels. 7. Perform two-step solvent cleaning on pipes, especially cleaning the inner surface of the pipes thoroughly. 8. Measure the painted height of the inner panel. (4th
(see figure). (5) Salt spray resistance Tested in accordance with JIS Z2371, the creep width from the cut (linear cut) part is within 20mm on one side and the blistering of the paint film other than the cut part is 8F.
(ASTM) Pass the test if the following conditions apply. (6) Erichsen extrusion resistance Using an Erichsen extrusion tester, the extrusion distance until cracks were observed in the coating film was examined. In addition, 7mm
The above indicates that no cracking was observed even after extrusion of 7 mm. (7) Impact resistance (DuPont method) After placing the test plate in a constant temperature and humidity room at a temperature of 20 ± 1°C and humidity of 75 ± 2% for 24 hours, place it in a Dupont impact tester with a pedestal of the specified size. Attach the impact center, place the test plate with the painted surface facing upward, and then drop a weight of the specified weight onto the impact center from the specified height to ensure that the coating film does not crack or peel due to impact. Pass if there is no. (8) Bending Alkyd melamen resin paint white (Kansai Paint Company product Amirak
White) was spray-coated to a dry film thickness of 20 to 30 microns, and the specimen was baked at approximately 140°C for 30 minutes. Test specimen JIS K5400−1979, 6.16 (bending resistance)
It was bent using a rod with a diameter of 10 mm. It was judged as passing when no cracks or peeling were observed in the bent part. Example 1 465 parts of bisphenol A type epoxy resin (Nippon Ciba Geigy Co., Ltd.; Araldite #6071) having a number average molecular weight of about 900 and an epoxy equivalent of about 465 was dissolved in 200 parts of methyl ethyl ketone, 105 parts of diethanolamine was added, and the mixture was heated at 80°C. and react until the tertiary amine value reaches 98 (about 3 hours or more) to form "Compound A".
-1" (hydroxyl equivalent: 285). Next, a dimer acid diameter polyamide resin having a number average molecular weight of about 1000 and an amine value of about 300 [Fuji Kasei Co., Ltd.,
200 parts of Tomide #225X] and 50 parts of methyl isobutyl ketone were heated to reflux, allowed to react until dehydration stopped, and unreacted substances were removed under reduced pressure to form "Compound B-1" (primary amino group). Equivalent weight of approximately 485) 240 parts was obtained. 4,4'-diphenylmethane diisocyanate
250 parts was dissolved in 162 parts of methyl ethyl ketone, 112.5 parts of ethylene glycol monoethyl ether was added, and the mixture was reacted at 50°C until the isocyanate value decreased to 116. Then, hexamethylene diisocyanate was added to form "Compound C-1" and Compound D. -1'' was obtained. To the compound A-1 obtained above, compound B-1 and 124 parts of methyl ethyl ketone were added and heated to 80°C.
At the same temperature, a mixture of Compound C-1 and Compound D-1 was slowly added dropwise, and the mixture was further reacted at the same temperature until the viscosity increase stopped (about 30 minutes or more) to obtain a resinous product according to the present invention. Take 14 parts of this material, add 0.6 parts of acetic acid and 26 parts of deionized water, mix well, and add 15 parts of titanium white.
1 part, 5 parts of clay, 0.5 parts of carbon black, and 1 part of bismuth nitrate were added and milled in a ball mill until the particle size became 15 μm or less to obtain 62.1 parts of pigment paste (1). Separately take 126 parts of the resinous product according to the invention,
5 parts diethylene monobutyl ether, average molecular weight
4000 polypropylene glycol [Sanyo Kasei Co., Ltd.;
Add 2 parts of Sannix PP-4000 and mix well. Next, 0.8 parts of acetic acid and 20 parts of a 10% aqueous lead acetate solution are added and mixed well, and then 166 parts of deionized water is added to dilute the resin to a solid content of 30% to obtain a water-dispersed varnish. Add the pigment paste (1) prepared above to this clear composition, mix well, dilute with deionized water to a resin solid content of 15%, and add 30% of the pigment paste.
The mixture was stirred open for 24 hours at ℃ to prepare an electrodeposition bath. Using this electrodeposition bath, electrodeposition was performed on zinc phosphate treated steel sheets and untreated steel sheets to a film thickness of 20 μm.
It was baked at ℃ for 20 minutes and subjected to a coating film performance test. The results are shown below. (1) Throwing performance: 22.0cm (pipe method, 250V x
(3 minutes) (2) Salt spray resistance: Untreated steel sheet 360 hours or more, zinc phosphate treated steel sheet 840 hours or more (3) Erichsen extrusion resistance: 7 mm or more (4) Impact resistance: Front side 50 cm or more; Back side 50 cm or more ( 1/2 inch, 1Kg) (5) Bending (after alkyd/melamine topcoating): 10mmφ Passing example 2 Styrene/allyl alcohol copolymer with number average molecular weight of approximately 1150 and hydroxyl equivalent of approximately 220 (Monsanto Co., USA; 575 parts of RJ-101) are dissolved in 505 parts of methyl ethyl ketone (compound A-2). Primary amino group-terminated polyamide resin with number average molecular weight of approximately 1500 and amine value of approximately 250 [Henkel Japan
Co., Ltd.; 300 parts of Versamide 115 and 50 parts of methyl isobutyl ketone were heated to reflux and allowed to react until dehydration stopped. Unreacted substances were distilled off under reduced pressure to form "Compound B-
2" was obtained. 134 parts of diethylene glycol monoethyl ether was added dropwise to 217.5 parts of a mixture of 2,4- and 2,6-tolylene diisocyanate (weight ratio 80/20) at 40°C, and the reaction was continued at the same temperature until the isocyanate value fell to 205. A mixture of 43.5 parts of unreacted diisocyanate and 308 parts of monoblock diisocyanate (mixture of compound C-2 and compound D-2) is obtained. Compound B-2 is added to compound A-2 and mixed.
A mixture of Compound C-2 and Compound D-2 was slowly added dropwise at 80°C, and the mixture was allowed to react at the same temperature until the viscosity increase stopped. Then, 250 parts of ethylene glycol monoethyl ether was added and the pressure was reduced, and 250 parts of methyl ketone was added. part is distilled off to obtain a resinous product according to the invention. To 126 parts of this material, 1.0 part of acetic acid, 2.0 parts of lead acetate, and 96 parts of deionized water are added and mixed well to obtain a water-dispersed varnish with a resin solid content of 40%. The pigment paste (1) prepared in Example 1 was added thereto, mixed well, diluted with deionized water to a resin solid content of 18%, and subjected to the coating film performance test in the same manner as in Example 1. did. The results were as follows. (1) Throwing performance (pipe method): 23.0cm (300V
x 3 minutes) (2) Salt spray resistance: Untreated steel sheet 240 hours or more, Zinc phosphate treated steel sheet 720 hours or more (3) Erichsen extrusion: 7 mm or more (4) Impact resistance: Front side 50 cm or more; Back side 50 cm or more (1 /2 inch, 500g) (5) Bending: 10mmφ passed (after alkyd/melamine topcoat) Example 3 228 parts of bisphenol A and epoxy equivalent of approximately 200
200 parts of bisphenol A-diglycidyl ether (Ciel Chemical Co., Ltd.; Epon428) was heated to 160°C,
React until the epoxy value becomes 0 to form "Compound A"
-3" is obtained. 51.5 parts of diethylene triamine and 120 parts of methyl isobutyl ketone are heated to reflux and reacted until dehydration stops, and unreacted substances are distilled off under reduced pressure to obtain 130 parts of "Compound B-3". This was slowly added dropwise into a mixture of 84 parts of hexamethylene diisocyanate (compound C-3) and 86 parts of methyl ethyl ketone at 40°C, and the mixture was reacted at the same temperature until the exotherm stopped, resulting in the formation of compound B-3 and compound C-3. Obtain a reaction product. A mixed solution of 56.5 parts of ε-caprolactam and 49 parts of methyl ethyl ketone is added dropwise to 74 parts of hexamethylene diisocyanate at 60°C, and the reaction is allowed to occur until the isocyanate value reaches approximately 150 to obtain "Compound D-3."
get. Add 170 parts of diethylene glycol dimethyl ether to Compound A-3, dissolve it, and dissolve the compound at 60°C.
After the reaction product of B63 and compound C-3 was slowly added dropwise, compound D-3 was further slowly added and the reaction was allowed to proceed at the same temperature until the viscosity increase stopped, thereby obtaining a resinous product according to the present invention. . 3.5 parts of 70% hydroxyacetic acid and 106.5 parts of deionized water are added to 140 parts of this to obtain a water-dispersed varnish with a resin solid content of 40%. Add 3 parts of carbon black, 3 parts of clay, and 2 parts of basic lead sulfate to this, and use a paint shaker to
The mixture was crushed until the particle size was less than μ, 0.5 part of perfluoroalkyl acrylate group copolymer [Sumitomo 3M Ltd.; Fluorad FC-430] was added, and the mixture was diluted with deionized water to a resin solid content of 18%. Thereafter, it was subjected to a coating film performance test in the same manner as in Example 1. The results were as follows. (1) Throwing performance (pipe method): 20cm (220V x
(3 minutes) (2) Salt spray resistance: Untreated steel sheet: 360 hours or more Zinc phosphate treated steel sheet: 720 hours or more (3) Erichsen extrusion: 6.5 mm or more (4) Impact resistance: Front side 50 cm or more; back 50 cm or more (1 /2 inch, 500 g) (5) Bending: 10 mmφ passed (after alkyd-melamine topcoat) Example 4 228 parts of bisphenol A (compound A-4) was dissolved in 120 parts of methyl ethyl ketone, and hexamethylene diisocyanate (compound C- 4) 210 copies to 60
Add slowly at ℃, and the isocyanate value increases at the same temperature.
24 to form compound A-4 and compound C.
-4 reaction product is obtained. 26 parts of hydroxyethylethylenediamine and 30 parts of methyl isobutyl ketone are heated to reflux and reacted until dehydration stops, and unreacted substances are distilled off under reduced pressure to obtain 46.5 parts of "Compound B-4". 60 parts of methyl ethyl ketone was added to this, and the above compound A-4 was prepared at 40°C.
and the reaction product of compound C-4 are slowly added,
Compound A-4, Compound C-4 and Compound B-4 3
The reaction product of the reaction product is obtained. 130 parts of 2-ethylhexanol was added to 87 parts of a mixture of 2,4- and 2,6-tridiisocyanate (weight ratio 80/20) at 60°C, and the mixture was reacted at the same temperature until the isocyanate value became 0 to diblock. A diisocyanate (compound D-4) is obtained. This is added to the reaction product of Compound A-4, Compound C-4 and Compound B-4 to form a resinous product according to the present invention. Take 130 parts of this material and add 1.5 parts of acetic acid and 118.5 parts of deionized water to make a water-dispersed varnish with a resin solid content of 40%. To this, 3 parts of carbon black, 6 parts of talc, and 3 parts of basic lead silicate were added, and the mixture was crushed in a paint shaker until the particle size became 20μ or less.
After adding 0.5 part of Fluorado FC-430 (Co., Ltd.) and diluting the resin with deionized water to a resin solid content of 20%, a coating film performance test was conducted in the same manner as in Example 1. The results were as follows. (1) Throwing performance: 18.5cm (250V x 3 minutes) (2) Salt spray resistance: Untreated steel plate: 360 hours or more Zinc phosphate treated steel plate: 840 hours or more (3) Erichsen extrusion: 6.5mm (4) Impact resistance Properties: 50cm or more on the front; 50cm or more on the back (1/2 inch, 500g) (5) Bending: 10mmφ passed (after alkyd-melamine topcoat) Example 5 Bisphenol A with a number average molecular weight of about 1000 and an epoxy equivalent of about 475 Type epoxy resin [Ciel Chemical Co., Ltd.;
Dissolve 475 parts of Epon1001 in 53 parts of toluene and
After adding 59 parts of propylamine and reacting at 60°C for about 3 hours, unreacted amine was distilled off under reduced pressure to obtain "Compound A-5". Next, 300 parts of a dimer acid type polyamide resin with a number average molecular weight of about 1500 and an amine value of about 250 (Japan Henkel Co., Ltd.; Versamide 115), 50 parts of toluene and 50 parts of methyl ethyl ketone were heated and dehydrated under reflux.
"Compound B-5" was obtained. 67.5 parts of ethylene glycol monoethyl ether was added to 130.5 parts of 2,6-tolylene diisocyanate, and the mixture was reacted at 40° C. until the isocyanate value decreased to 159 to obtain “Compound D-5”. Compound D-5 was slowly added to compound B-5 at 60°C, and after reacting at the same temperature for 1 hour, compound A-5 was added to compound B-5.
5 and 300 parts of propylene glycol monomethyl ether were added thereto, and 42 parts of hexamethylene diisocyanate ("Compound C-5") was slowly added again at 60°C, and the reaction was carried out for 1 hour at the same temperature to obtain the resinous product of the present invention. Ta. Take 140 parts of this and add 20 parts of acetic acid and 158 parts of deionized water to make a water-dispersed varnish with a resin solids content of 33%. Pigment dispersion and electrodeposition bath were prepared in the same manner as in Example 4, and a coating film performance test was conducted. The test results were as follows. (1) Throwing power: 20cm (250V x 3 minutes) (2) Salt spray resistance: Untreated steel sheet: 360 hours or more Zinc phosphate treated steel sheet: 840 hours or more (3) Erichsen extrusion: 7mm or more (4) Impact resistance : Front side 50cm or more; back side 50cm or more (1/2 inch, 500g) (5) Bending: 10mmφ passed (after alkyd-melamine topcoating) Example 6 Styrene-allyl alcohol with number average molecular weight 1600 and hydroxyl equivalent approximately 300 800 parts of copolymer [Monsanto, USA; RJ-100] ("Compound A-6") are dissolved in 320 parts of methyl ethyl ketone. 61 parts of monoethanolamine, 14 parts of toluene and 100 parts of methyl isobutyl ketone are heated and dehydrated under reflux to obtain 143 parts of "Compound B-6". Meanwhile, 336 parts of hexamethylene diisocyanate ("Compound C-6") was dissolved in 237 parts of methyl ethyl ketone, and 113 parts of ε-caprolactam was added thereto.
After reacting at 80°C until the isocyanate value falls to 280, it was cooled to 60°C and the above "Compound B-6"
is slowly added and allowed to react until the exothermic reaction subsides to obtain a mixture of the reaction product of compounds B-6 and C-6 and compound D-6. This was slowly added to the solution of Compound A-6 at 80° C., and the reaction was allowed to proceed at the same temperature until the viscosity increase substantially stopped, to obtain a resinous product of the present invention. 140 parts of this was taken, and 3.4 parts of acetic acid and 157 parts of deionized water were added to obtain a water-dispersed varnish with a resin solid content of 33%. Pigment dispersion and electrodeposition bath preparation were carried out in the same manner as in Example 4, and a coating film performance test was conducted. The test results were as follows. (1) Throwing property: 18.0cm (220V x 3 minutes) (2) Salt spray resistance: Untreated steel plate 240 hours or more Zinc phosphate steel plate 720 hours or more (3) Erichsen extrusion: 7mm (4) Impact resistance: Front 50cm; back 50cm (1/2 inch, 500
g) (5) Bending: 10mmφ passed (after alkyd-melamine topcoat).

[Brief explanation of the drawing]

Figure 1 is a schematic diagram of the equipment used to test the throwing power of electrodeposition paints, Figure 2 is a schematic diagram of the outer film measurement plate used in the test, and Figure 3 is a diagram of the inner film measurement plate used in the test. This is a schematic diagram of a throwing power measurement plate, and FIG. 4 is a diagram for explaining the painted height of the inner plate.

Claims (1)

[Scope of Claims] 1 (A) A compound having at least two isocyanate-reactive functional groups selected from active hydrogen-containing amino groups and hydroxyl groups in one molecule, (B) A primary amino compound blocked with a carbonyl compound (C) a compound having at least one free isocyanate group in one molecule and at least one isocyanate-reactive functional group selected from active hydrogen-containing amino groups and hydroxyl groups in one molecule; and (C) one molecule of free isocyanate groups. (D) has at least two isocyanate groups in one molecule, one or more of which is blocked and has no free isocyanate groups; 1
A compound (B) component having blocked primary amino groups, which is obtained by reacting or mixing partially or completely blocked polyisocyanate compounds containing no more than 100% diisocyanate, is added to the compound via the diisocyanate compound (C) component. A blocked isocyanate group-curable resin composition for cationic electrodeposition coating, which contains as a main component a resinous product introduced into component (A).