NL8101245A - CATIONIC, ELECTROLYTICALLY DETACHABLE RESIN COMPOSITIONS. - Google Patents

Description

VO 1T12 * "Λ

Cationic, electrolytically deposable resin compositions.

The invention relates to new cationic, electrolytically deposable resin compositions. More particularly, the invention relates to blocked isocyanate group-cured cationic electrolytically deposable resin compositions, the main component of which contains a resinous product in which a component with a primary amino group (or groups) blocked by a carbonyl compound via an diisocyanate component in an isocyanate reactive functional group-containing compound is introduced.

Various cationic electrolytically deposable resin compositions are known. British patent specification 1,303-80 discloses, inter alia, an electrolytically deposable composition containing film-forming resin particles dispersed in an aqueous medium and containing an amino group-containing addition polymer or polycondensation product (including of an amino group-containing polyamide resin) and a blocked isocyanate (a so-called completely blocked isocyanate, of which almost all isocyanate groups are blocked). The electrolytic coating film obtained from this composition cannot be considered satisfactory from the viewpoint of corrosion resistance. In order to improve the corrosion resistance, said publication proposes adding a polyepoxide resin up to an amount of up to 50% by weight, based on the total weight of the composition, but even then, in practical use, the composition is somewhat the quality of the films concerned is not satisfactory.

An analogous composition is described in U.S. Pat. No. 3,799,855, which uses an aqueous bath method of an electrolytic coating method of a composition comprising a soluble polyamine resin (essentially an amino group-containing polyamide resin) and a blocked polyisocyanate includes. This electrolytically deposable coating composition exhibits substantially the same properties as those described in said British Patent Specification 1,303-180.

It is further well known that cured polyepoxides, such as the bisphenol-A-epichlorohydrin epoxy resin type, exhibit excellent corrosion resistance and adhesion, while it is also known to adduct an epoxy resin and a primary or secondary amino by neutra-8101245%. ... 'V.. __ 2 water solubilisation with acids. Such an electrolytically deposable coating composition using such epoxides and adducts is described in U.S. Pat. No. 3,998,999, namely an aqueous electrolytically deposable composition comprising a mixture of said resin. amine adduct and the blocked polyisocyanate. Although the coating obtained by electrolytically depositing this composition has excellent corrosion resistance, but due to a lack of plasticizer component, its surface smoothness and bath stability are not satisfactory (this includes in continuous electrolytic coating properties such as the ability of the state of maintain the coated surface, the thickness of the deposited film and the coating quality within a certain range, without any change, in particular a deterioration, occurring, while the coating further, when applied to objects of complicated shapes, does not have sufficient covering power so that its practical application is ultimately unsatisfactory.

U.S. Pat. No. 3,922,263 discloses a self-curing electrolytically deposable aqueous coating composition consisting of an epoxy resin, a primary and / or secondary amine, and a partially blocked polyisocyanate, which composition as an improved type of that described in the U.S. Patent 3,998k,299 can be considered; yet the surface smoothness, the bendability, the bath stability, the covering capacity, etc. are not yet. sufficiently improved and this composition for industrial use is therefore not fully acceptable; furthermore, the film quality thereof is not particularly different from that of U.S. Pat. No. 3,998,299. US patent 3, 9, 339 describes an electrolytically deposable aqueous composition consisting of an acid neutralized amino group-containing resin obtained by reacting an epoxy group-containing resin with a polyamine derivative containing at least one primary amino or secondary amino group blocked by ketimine groups, with further addition of a partially blocked polyisocyanate. It is indicated that in principle in this aqueous composition the resin with a low neutralization degree can be dispersed in water and some improvement in the pH value of the bath composition as well as in the covering power 8101245 3 * ί is obtained and that a considerable improvement can be achieved in coating curability due to the increased activity of the blocked isocyanate groups. However, it is very difficult to perform quantitatively the reaction between the epoxy group-containing resin and the secondary amino group in said diminished polyamine derivative. It has been found in practice that the said polyamine derivative in the aqueous composition is not converted or that the viscosity increases markedly when one tries to force the reaction. It is therefore almost impossible to obtain the said improvements.

To improve the drawbacks of the compositions described in the above publications, it has been proposed in U.S. Pat. No. 1,036-795 to prepare an electrolytically deposable cationic resin composition by mixing or reacting an epoxy resin anrin adduct with an amino group-containing polyamide resin and further reacting the obtained product with a partially blocked polyisocyanate. US Pat. Nos. 4,183,666 and 13,18865 also disclose electrolytically deposable cationic resin compositions, the main component of which is a mixture of a reaction product of at least two components 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, the residual component of which is the electrolytically deposable coating composition, which contains similar components to those of the composition described in U.S. Pat. No. 036,795. U.S. Patent No. 190,564 proposed to make a composition by mixing the epoxy resin fatty acid amino adduct or the system of amino group-containing polyamide resin partially blocked polyisoyanate resin composition with a polyether having specific properties; hereby, the surface smoothness of the film could be markedly improved without the erosion resistance deteriorating.

However, the demands placed on the quality of an electrolytically deposable resin composition are increasing.

Thus, there is a need for an electrolytically deposable cationic resin composition of improved quality.

It has now been found that resinous products with a sufficient amount of primary amino groups can be produced much more easily by leaving a compound containing carbonyl compound-blocked primary amino groups and isocyanate-reactive functional groups (primary or secondary amino groups or hydroxyl groups). reacting with a compound containing at least two isocyanate-reactive functional groups (primary or secondary amino groups or hydroxyl groups) via a diisocyanate compound and that not only an excellent resinous product is obtained, both in terms of the pH of the bath composition, the hiding power, curability, etc., but that also a coating can be formed with excellent adhesion, bendability, impact resistance and the like, upon which results the invention is based.

Thus, in accordance with the invention, there is provided a blocked isocyanate group-cured type cationic electrolytically deposable resin composition, which is obtained by 15 I) (A) a compound containing in one molecule at least 2 isocyanate-reactive functional groups selected from active hydrogen containing amino groups and hydroxyl groups (hereinafter referred to as compound "A"), - (B) a compound comprising in one molecule at least one primary carbonyl-blocked amino group and at least one isocyanate-reactive functional group selected from active hydrogen-containing amino groups and hydroxyl groups (hereinafter referred to as compound "B") and (C) a diisocyanate compound containing in one molecule 2 free isocyanate groups (hereinafter referred to as compound "C") and II) reacting said reaction mixture or to be mixed with (D) a partially or completely blocked poly-30 isocyanate compound, which contains at least 2 isocyanate groups in one molecule n, one or more of which are blocked, and which contains no more than one free isocyanate group (hereinafter referred to as compound "D"), the main component of which contains a resinous product in which the "Β" component having said blocked primary amino group or groups is present in the (A) component via the dixsocyanate (C) component.

8101 245 ^ 4 5 '1 ----

According to the invention, primary amino groups are introduced into a base resin component via a urea bonding or urethane bonding reaction between the compound C, i.e., the dixsocyanate compound, and the active hydrogen-containing amino group or hydroxyl group.

Thus, it is possible to introduce a sufficient amount of primary amino groups even into a base resin component which does not contain an epoxy group, and not only does this prevent the various limitations and drawbacks of using an epoxy group-containing resin, but also also obtains a cationic electrolytically deposable resin composition of much higher quality than conventional cationic resin compositions using an epoxy group-containing resin as the base resin.

The resin composition of the invention will now be explained in more detail.

15 Connection A

Compound A is the main base resin component of the resinous product of the invention and is a compound containing in one molecule at least two isoeyanate-reactive functional groups selected from active hydrogen-containing amino and hydroxyl groups.

Either a primary amino group containing two active hydrogen atoms or a secondary amino group containing one active hydrogen atom will suffice for said active hydrogen-containing amino group, but it is generally preferred that a secondary amino group be used since it has a has mild reactivity with the isocyanate-25 group. The reactivity of the hydroxyl group to the isocyanate group, on the other hand, is greatest for the group attached to the primary carbon atom, while the group attached to the secondary carbon or tertiary carbon atom has lower reactivity in this order. Thus, the hydroxyl group is preferably bonded to the primary carbon atom, although, of course, the presence of a hydroxyl group bonded to a secondary or tertiary carbon atom does not interfere.

Compound A may contain at least two such isoeyanate-reactive functional groups in one molecule and although the preferred numbers of said functional groups differ according to the type of the functional group, the molecular weight of 8101 245 6 * v compound A, etc., Compound A generally should contain on average 2-10 isocyanate-reactive functional groups per molecule. Furthermore, preferably isocyanate-reactive functional groups 100-200 and in particular 200-1000 should be present, expressed as the isocyanate-reactive functional group equivalent number. A plurality of the isocyanate-reactive functional groups present in compound A may be the same or different from each other.

Isocyanate-reactive functional group equivalent is understood to mean the number of grams of the isocyanate-reactive functional group-10-containing compound per gram equivalent of the isocyanate-reactive functional group.

Compound A may also contain a functional group or functional groups of lower reactivity with isocyanate, such as an acid amide, ester, ether, urethane, urea, allophanate and biuret bond. In general, it is preferred that functional groups that can react with an active hydrogen-containing amino group or hydroxyl group, such as an epoxy group, be substantially absent. This thus means that compound A preferably does not contain epoxy groups.

As long as at least two such isocyanate-reactive functional groups are present in a molecule, both low molecular weight and high molecular weight compounds (eg polymeric compounds) for compound A useful in the invention will suffice, furthermore either aliphatic and aromatic groups (including the araliphatic groups) will suffice. However, as regards the corrosion resistance of the coating, the aromatic compounds (in the case of a polymer whose main chain is mainly formed of aromatic rings) are generally preferred.

In general, compound A should have a number average molecular weight of about 100-10,000, preferably 200-5,000. *;

Representative examples useful as compound A in the invention will now be explained.

(i) An adduct of an epoxy resin and a diamine containing two amino groups (primary or secondary amino groups) containing at least one active hydrogen atom; or an adduct of an epoxy resin and an amine compound containing in one molecule two or more active 81 01 245 * 4 τ hydrogen atoms, such as a hydroxyl group-containing primary or secondary amine.

As the epoxy resin useful for the formation of the adduct are mentioned aromatic epoxy resins such as bisphenol type 5 epoxy resins prepared by reaction of bisphenol A or bisphenol F and epi-halohydrin. Such epoxy resins usually have a number average molecular weight of about 300-1,000,000, preferably about 100-300,000, while generally having an epoxy equivalent of about 150,000,000, preferably about 200,000. - have 2,000. Specific examples of such bisphenol type epoxy resins are set forth below.

Epoxy resin from Shell Chemical Co. Ltd. Japan:

Epikote 828 (bisphenol A type, number average molecular weight about 380, epoxy equivalent about 190).

Epikote 1001 (bisphenol A type, number average molecular weight about 900, epoxy equivalent about kJ5).

Epikote 100¾ (bisphenol A type, number average molecular weight about 1 ^ 00, epoxy equivalent about 950).

Epikote 1007 (bisphenol A type, number average molecular weight about 2,900, epoxy equivalent about 1,900).

20 Epoxy resin from Dainippon Ink, and Chemicals Ine. Japan:

Epiclon 830 (bisphenol F type, number average molecular weight about 3βθ, epoxy equivalent about 180).

Amines capable of adduct formation with such epoxy resins, on the other hand, are selected from the amines having the following structural formulas: R'-NH2, Hg-B -HHg, HgN - ^ - NHR », B'HN-R ^ NHR ", HO-R ^ BHg, HO-R ^ HBR", wherein an alkylene group, a cycloalkylene group, an arylene group, or an aralkylene group, and R 'and R "represent an alkyl group, a cycloalkyl group, an aryl group, or an ar-alkyl group .

Heterocyclic compounds containing one or two H atoms are also useful. E.g. primary monoamines, e.g. alkyl-35 amines, such as ethylamine, propylamine and butylamine, cyclohexylamine, aniline and benzylamine; diamines, such as ethylenediamine, N, N-dimethyl-8101245 * -.

Furthermore, as hydroxyl group-containing primary or secondary amines, lower alkanol, primary or secondary amines, such as monoethanolamine, diethanolamine, ethylene diamine, piperazine and meta-phenylenediamine. U-methyl ethanolamine and N-hydroxyethylpiperazine, includes,.

The addition reaction of such amines and epoxy resins is preferably carried out until the epoxy groups in the epoxy resin have been completely consumed.

(il) Adducts of epoxy resins and water or polyvalent -V; alcohols: ·· '- ·.

As epoxy resins useful for forming this adduct, the resins mentioned under (1) are preferred. Polyhydric alcohols to be added to the epoxy resins have lower alkylene glycols, such as ethylene glycol, propylene glycol; glycerol, trimethylol-propane, poly (lower alkylene glycols), such as diethylene glyeol and triethylene glycol are preferred. The addition reaction of the epoxy resin and water or polyhydric alcohols should also preferably be carried out until the epoxy groups have been completely consumed.

(III) Diphenol compounds or bisphenol compounds, such as bisphenol A, bisphenol F (,, V-dihydroxydiphenylmethane), dihydroxydiphenylethane, V, V-hydroxyphenylisobutane, U, U1-dihydroxybenzophenone and 1,5-dihydroxynaphthylene.

(IV) Phenol-terminated prepolymers formed by the addition polymerization reaction of bisphenol compounds, and dipoxy compound-x '

things or diisocyanate compounds: C

As the dipoxy compounds which are useful for the formation of such prepolymers, it is possible to use e.g. mention: diglycidyl ethers of said bisphenol compounds (examples: Epikote 827, a product of Shell Chemical Co. Ltd. Japan; Avaldite Gy-250, a product of Ciba Geigy AG DER-330, a product of Dow Chemical Co, etc.), 30 diglycidyl ethers of polyalkylene glycols (examples: Epikote 812, a product of Shell Chemical Co. Ltd. Japan, K-25, a product of Asahi Ciba Co. Japan, etc.), vinyleyclohexene dioxide ( Example: Chissonox 206, a product of Chisso Co. Ltd. Japan), etc. as diisocyanate compounds are those mentioned below with respect to Compound C and are preferred.

(V) Addition-polymerized prepolymers of bisphenol compounds and alkylene oxides: 8101245 9

For example, as alkylene oxides which are smellable for the formation of such prepolymers, one can e.g. ethylene oxide, propylene oxide, and the like.

(VI) Styrene-allyl alcohol copolymerized prepolymers:

As such opolymerized prepolymers are mentioned those having an average molecular weight of 3000 or less. Examples include: EJ-101 (number average molecular weight about 1700, hydroxyl group-10 equivalent about 220) and RJ-100 (number average molecular weight about 2,300, hydroxyl group equivalent about 300), products of Monsanto Chemical Co.

(VII) Poly-condensed prepolymers of aromatic dicarboxylic acids and diamines, alkanolamines or polyols: As the aromatic dicarboxylic acids, those acids which are commonly used for the preparation of polyamides or polyesters can be used. Examples include baleic acid, isophthalic acid, terephthalic acid, etc. As diamines to be reacted with these acids, e.g. ethylenediamine, hexamethylenediamine, m-phenylenediamine, etc. are mentioned. As alkanolamines, e.g. monoethanolamine, diethanolamine, triethanolamine, hydroxyethylpiperazine, etc. are mentioned and as polyols e.g. ethylene glycol, propylene glyeol, glycerol, 2,2-dimethylpropane diol, trimethylolpropane, etc.

The polycondensation reaction of said aromatic di-25 carboxylic acids and diamines, alkanolamines or diols can be carried out according to the known polyamide or polyester-forming reactions.

(VIII) Movolak type phenol-formaldehyde resins:

Generally, this resin should have a number average molecular weight of about 1000 or less.

(IX) Aromatic di (primary amine): e.g. m-phenylenediamine, U, U'-methylenediamiline, benzidine, 2, k-tolylenediamine, diaminediphenyl ether, U'-thiodianiline, diaminodiphenylsulfone, dianisidine, and the like.

(X) Primary amino-terminated prepolymers formed by the addition polymerization reaction of aromatic di (primary amine) and dicarboxylic acids, dipoxy compounds or diisocyanate compounds: 8101 245 10

As the aforementioned compounds, further mention may be made of aromatic di (primary amine) and dipoxy compounds or diisocyanate compounds used in the formation of these prepolymers.

As dicarboxylic acids can be mentioned inter alia aliphatic dibasic acids, such as adipic acid, sebacic acid, dimerized linoleic acids, etc.

(XI) Aliphatic (including alicyclic) hydroxyl group-containing compounds:

Examples are adducts of epoxy group-containing prepolymers, such as hydrogenated bisphenol-type epoxy resins, polypropylene diglycidyl ether and epoxidized polybutadiene, and aliphatic mono (primary amines) or alkanolamines; as well as hydroxyl group-containing prepolymers such as polypropylene glycol, polytetraethylene glycol, polycaprolactone diol and polybutadiene glycol, and the like.

Of the aforementioned examples, as compound A

the compounds mentioned under (I), (II), (IV) and (VI) are particularly suitable, in particular the adducts of bisphenol A-type epoxy resins and alkanolamines; phenol-terminated prepolymers of bisphenol A and diisocyanates; and styrene-allyl alcohol copolymerized prepolymers.

The aforementioned compounds can be used individually or in combination with each other.

Connection B

Compound B as used in the invention is a compound containing in one molecule at least one primary amino group blocked by a carbonyl compound and at least one isocyanate-reactive functional group selected from active substance containing amino groups and hydroxyl groups wherein this compound is a necessary component for introducing strongly basic primary amino groups into the resinous product of the invention.

The "primary amino group blocked by a carbonyl compound" is a protected amino group, which can be converted into a free primary amine group by simple treatment, such as hydrolysis. Typically it is a temporarily protected primary amino group, represented by the formula -N = C (Rg) (R ^), wherein Rg is a hydrogen atom or a monovalent hydrocarbon group with 1 to 6 carbon atoms, such as an alkyl group and represents a cycloalkyl group, R ^ a mono- 8101 245 ιι-ιιι «ι <^« ΜΜ ·· Ι I »» -> ..μ »» rr, 11 valued hydrocarbon group with 1-6 carbon atoms, such as an alkyl group and a cyeloalkyl group represents whether and R 1 together form an alkylene group having up to 9 carbon atoms.

Said active hydrogen-containing amino groups and hydroxyl groups are isocyanate-reactive functional groups necessary for binding compound B to compound A via compound C (diisocyanate compound) as described below and may have the same properties as previously described for compound A Secondary amino groups or primary hydroxyl groups are most preferred as the active hydrogen-containing amino groups or hydroxyl groups.

Compound B comprises resp. the compounds (a) a polyamine compound containing a primary amino group together with a secondary amino group; (b) a hydroxyl-containing amino compound containing a primary amino group together with a hydroxyl group and (c) a hydroxyl-containing polyamino compound containing three components, namely a primary amino group, a secondary amino group and a hydroxyl group (these compounds (a ), (b) and (c) are commonly referred to as the polyamine compound), wherein at least a portion, but preferably substantially all of the primary amino groups present are blocked by carbonyl compounds. Although not preferred, primary amino compounds with two or more primary amino groups, which are only partially blocked by carbonyl compounds, can also be used as compound B.

Both low molecular weight and high molecular weight compounds will suffice for said (poly) amine compound and both the aliphatic type (including the alicyclic type) and the aromatic type are useful. Generally, the aliphatic (poly) amine compounds have the most preferred.

As mentioned previously, compound B is a necessary water solubilizing component, followed by volume neutralization of the resin composition, by introducing strongly basic primary amine groups into the resinous product of the invention. Said (poly) amine compound should generally contain a primary amine group 35 equivalent, which falls in the range up to 2,000 or less, preferably up to about 1,000, while the isoran-reactive cyanate-reactive functional group equivalent will generally fall in the range of up to 2,000, most preferably up to 1,000.

The (poly) amine compound should generally have a number average molecular weight of about at most 5,000, preferably at most 3,000.

The (poly) amine compound, which is preferably used in the invention, is indicated by the following general formulas 1, 2, 3, 3, 5, 6 of the formula sheet, wherein R 1, Rg, R 1, Rg,

R'js R'g »Rg» R10, R ^, R ^ g and R ^ each represent an alkylene group (preferably an alkylene group with at most 6 carbon atoms) or a cycloaliylene group (preferably a cyeloalkylene group with at most 9 carbon atoms); R ^, R '^, R' <- and R ^ each an alkyl group (at,

preferably a lower alkyl group with at most 6 carbon atoms) or a cycloalkyl group, (preferably a cycloalkyl group with at most 9 carbon atoms), while a, b, c, d and e are each an integer of 1 or more, in the especially an integer from 1-5.

Specific examples of the (poly) amine compounds are the following: 20 (a) H-allylalkylenediamines h2n-ch2-ch2-m-ch3, h2i-ch2-ch2-ch2-nh-ch3,

HgT-CH-CHg-IIH-CHg.

CHg ^ (b) Polyalkylene polyamines H2N-CH2-C12-NH-CH2-CH2-NH2, H2U-CH2-CH2-M-CH2-CH2-NH-0H2-CH2-IIH2, H2W-CH2-CH2-NH-CH2- CH2-NH-CH2-CH2-M-CH2-CH2-m2, H2N-CH2-CH2-NH-CH2-CH2-M-CH2-CH2-IIH-CH2-CH2-li-CH2-CH2-m2, 30 HgN -C ^ -CHg-CHg-NH-CHg-CHg-CHg-BHg - (c) II- (hydroxyalkyl) alkyl endiamines h2n-ch2-ch2-ih-ch2-c12-oh, H2i-CH2-C12 CH2-NH-CH2-CH2-CH2-0H, H2i-CH2-CH2-M-CH2-CH2-CH2-0H.

8101245 13 (d) Monohydroxyalkylamines h2n-ch2-ch2-oh, H2N-CH2-CH2-CH2-0H, H2N-CH2-CH-0H.

®3 5 (e) N- (aminoalkyl (piperazine CH-CH \ H0H-CH0-CH "-H C M" 2 2 2 \ N ch2-ch2 ^ ^ CVCH2 \ H2i-CH2-CE2-CH2-N ^ HH.

ch2-ch ^

In addition to the aforementioned, prepolymers (polyamide polyamines) terminated with (primary) amino groups can also suitably be used as (poly) amine compounds, formed by the condensation reaction between aliphatic polybasic acids, such as adipic acid, sebacic acid, dimer acids (dimerized linolenic acid), a maleized fatty acid (such as maleized oleic, linoleic, linolenic, dehydrated ricinolenic or eleostearic acid) or polybutadiene-dicarboxylic acid, and an alkylenediamine, such as ethylenediamine, propylene diamine, butylenediamine and hexamethylenediamine, polyamine, or a polyamine 2. Specific examples of such polyamide polyamines are eg Versamid 100, 115, 125 and 1 ^ 0, etc. from Japan General Mills Co. Ltd. Japan.

Of the aforementioned (poly) amine compounds, monoethanolamine, monopropanolamine, monobutanolamine, diethylene triamine or a dimer acid polyalkylene polyamine condensate are particularly preferred; the aforementioned (poly) amine compounds can be used individually or optionally in combination of two or more thereof.

The (poly) amine compounds can be used as component B.

are used after at least a portion, and preferably substantially all, of the primary amine groups present are blocked by carbonyl groups. Carbonyl groups suitable for blocking are optionally ketones or aldehydes normally used for temporary protection of the amino group by ketimination or aldimination. In particular ~ 'Λ * O /. R

1U

ketones are used, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dixsobutyl ketone, cyclopentanone, cyclohexanone, etc. As aide bydenes are e.g. acetaldehyde, propionaldehyde, benzaldehyde, pivalde-hyde, etc. suitable.

The reaction of the (poly) amine compounds and these carbonyl compounds is carried out by following procedures known per se (see, e.g., J. Org. Chem; J9., 105 ^ - 76 (195 * 0). quantitative amount and reaction conditions such that virtually all, preferably more than $ 80, most preferably more than $ 90, of the primary amino groups react with said carbonyl groups, generally being advantageous ketones with low or poor water solubility and low steric hindrance, such as methyl isobutyl ketone, can be used to allow the said reaction to proceed smoothly (dehydration reaction).

Connection C

Compound C, which primarily plays the role of crosslinker for binding compound A to compound B in preparing the resinous product of the invention, is a dixoso-cyanate compound containing 2 free isocyanate groups in a molecule.

As such diisocyanate compounds, both types of diisocyanate compounds can be used, which are commonly used in the formation of polyurethanes, such as e.g. those of the aliphatic series (including the above alicyclic series) and the aromatic series (including the aromatic aliphatic series, as mentioned previously) or dixsocyanates, which are obtained by partially triisocyanate and tetraisocyanate compounds with lower alcohols and the like. In general, compounds with a molecular weight of about 100-2,000 are preferred, in particular the molecular weight is 150-1,000.

Such diisocyanate compounds generally include a group of compounds represented by the formulas 7 (dixsocyanate), 8 (monourethane of diisocyanate), 9 (di-urethane of tetraxsocyanate), wherein R 1, R 1 g and R ^ g each represent a monova-35 spring, divalent and trivalent aliphatic (including the alicyclic series) or aromatic hydrocarbon group or the 8101245 15 group containing an ether bond, thioether bond, carbonyl group, sulfonyl group, urethane bond or urea bond, etc., and R20 each represent an alkyl group, cycloalkyl group or aryl group.

In the formula sheet, specific examples of the diisocyanate compounds represented by the above general formulas are indicated.

See formulas 10 - 3S where G represents a lower alkyl, cycloalkyl or aryl group.

Furthermore, diisocyanates obtained by addition of these diisocyanates and diols, such as ethylene glycol and diethylene glycol, and monourethanes from trilocyanates obtained by addition of such diisocyanates and triols, such as glycerol and trimethylol propane, and mono aleols can be used.

These diisocyanate compounds can be used alone or in combination with each other.

Particular preference of these diisocyanate compounds as component C are 2, U-tolylene diisocyanate, 2,6-tolylene dixsocyanate, U, U'-diphenylmethane diisocyanate, 1, U-xylylene diisocyanate, U, Uf-dicyclohexylmethane diisocyanate, 1,6-hexamethylenedix 20 diisocyanate, 2,2-tolylene-dipsoeyanate adducts of ethylene glycol, diethylene-glycol or propylene-glycol, reaction products of 1 mole of 2-tolyl-en-dipsyocyanate adducts of trimethylolpropane and 1 mole of lower aliphatic monoalcohols, etc.

Connection D

As compound D, partially or completely blocked, the polyisocyanate compounds are used, which contain in one molecule at least two isocyanate groups, at least one of which is blocked and which have no more than one free isocyanate group.

Compound D is a component which functions as a crosslinking agent during cross-linking to cross-link and cure the electrolytically precipitated film of the resin composition of the invention.

Whether an aliphatic or aromatic polyisocyanate compound used for the preparation of compound D will suffice as long as two or more isocyanate groups are present in the compound, generally having a molecular weight of from 100 to 2,000, preferably from 8101245 to 150 - is 1,000. As such polyisocyanate compounds, one can use diisocyanate compounds represented by the formulas 7-9 as mentioned above with respect to compound C.

Such polyisocyanate compounds can be used as component D after they have been blocked with a blocking agent until no more than an average of free isocyanate groups per molecule is present. The blocking reaction can be effected by methods known per se (eg the method described in Angew. Chem; 59, 257 (19 ^ 7). As a blocking agent for said poly-10 isocyanate compounds, active hydrogen-containing compounds can be used, such as monofunctional alcohols, phenols, lactams, oximes, tertiary amine alcohols, etc. Preferred are those compounds which are capable of easily reproducing the free isocyanate groups by heat dissociation at the baking temperatures. molecular weight, preferably not more than 300, most preferably not more than 200. Examples include aliphatic or aromatic monoalcohols, such as methanol, ethanol, propanol, isopropanol, n-butanol, tertiary butanol, hexanol, cyclohexanol, benzyl alcohol, 20 ethylene glycol monoethyl ether (also called commercial cellosolve) and ethylene glycol mono butyl ether; hydroxy tertiary amine, such as dimethyl or diethylamine ethanol; oximes, such as accetoxime and methyl ethyl ketone oxime; active methylene compounds such as acetylacetone, acetate ester and malone ester; lactams, such as &-caprolactam; phenols, such as phenol and cresol, and the like. Of these compounds, the aliphatic monoalcohols are particularly preferred because of their low odor and toxicity during the baking of the electrolytically deposited film.

Any of the partially blocked and fully blocked type of compounds can be used as compound D, which should generally be present in a state in which it is bound to the resinous product of the invention. Therefore, the partially blocked connection type is most preferred.

Preparation of resinous product

The resinous product of the invention can be prepared by reacting the three components, compound A, compound B and compound C, optionally in this order. In some cases 81012 4 5 I w »ι ** lil» * 1 ι * ΙΙι ··· '· Ι'. *> ··· 1ΙΜ * »» - '· - - - 17 times it can also be prepared by reacting four components, namely said three components plus a component D (which is limited to the case that the reaction system contains a partially blocked polyisocyanate compound). The order of the reactions between the reactants can be varied according to the class or properties of the compounds A-D used. are reacted by an appropriate choice of the reaction forms i-x mentioned below. The desired type of reaction can easily be chosen, taking into account the specific properties of compounds A-D (e.g., a low or high molecular compound) and the type of the reactive group, and the like. In this connection, the following description of these reactions assumes that compound D is also reacted with the other compounds, but if the fully blocked polyisocyanate compound 15 is used as compound D, it can be added at any stage of the reaction. reaction mixture or reactants are added or after the reaction of compounds A, B and C. Furthermore, the partially blocked polyisocyanate compound can be used together with the fully blocked polyisocyanate compound. In such a case, the partially blocked polyisocyanate compound can be reacted according to the reaction form described below and the completely blocked polyisocyanate compound can be mixed after or at any stage of this reaction.

Reaction form A mixture of compounds C and D is added to a mixture of compounds A and B, after which the reaction takes place. Reaction form ii

Compounds A and C, as well as compounds B and C, are respectively. reacted and then two types of reaction products obtained are mixed and reacted further, or compounds A and D, as well as compounds B and C are reacted, respectively. reacted, after which the two types of reaction products obtained are mixed and reacted further.

Reaction form iii 35 Compound A is reacted with a mixture of compounds C and D and then further reacted with compound B.

8101245 18

Response form iv

Compound A is reacted with compound C. The resulting reaction product is reacted with compound D and then with compound B. Or compound A is reacted with compound D and the resulting reaction product is reacted with compound C and then with connection B.

Response form v

Compound A is reacted with compound C, after which the resulting reaction product is reacted with compound B and finally with compound D.

Reaction form vi

Compound A is reacted with compound D and the resulting reaction product is mixed with compound B and then reacted with compound C.

Reaction form vii

Compound B is reacted with compound C and the resulting reaction product is reacted with compound A and then with compound D.

Reaction form viii. Compound B is reacted with a mixture of compound C and compound D, after which the reaction product obtained is reacted with compound A.

Reaction form ix

Compound B is reacted with compound 25 D and the resulting reaction product mixed with compound A and then reacted with compound C.

Response form x

Compound B is reacted with compound G, after which the resulting reaction product is mixed with compound D and then reacted with compound A.

In the above-described reaction forms, the tena "reaction product" is used in the sense that it concerns not only the quantitative reaction product of the reactants used therein, but also the unreacted reactants and / or the partially reacted reactants of the three reactants .

In the aforementioned reaction forms, it is important in reacting compound A or compound B with compound D before reacting with compound C, the reaction rate and / or reaction conditions of compound D relative to compound A or compound B such controlling all isocyanate-reactive functional groups in compound A or compound B to not react with compound D.

In order to further achieve as much binding of compound A and compound D as possible via compound C, it is desirable that the reactivities of the isocyanate-reactive functional groups in compound 10 A and compound B be equalized or that the reaction process be so that one first is reacted with compound C and then the other, etc.

The reaction of compounds A - D according to said reaction forms can be carried out in accordance with procedures known per se for the urea bond-forming reaction between an active hydrogen atom-containing amino group and the isocyanate groups, and for the urethane bond-forming reaction between the hydroxyl group and the isocyanate group. are carried out. The reaction can generally be carried out at relatively low temperatures, preferably at temperatures in the range of from about 20 DEG to 120 DEG C. and in a substantially dry solvent which is inert to the isocyanate groups, with stirring to ensure that the reaction proceeds as smoothly as possible. Useful solvents are preferably aromatic hydrocarbons, such as toluene and xylene; ketones, such as methyl ethyl ketone and isophorone; ethers, such as dioxane and ethylene glycol dimethyl ether; tertiary alcohols, such as t-butanol and diacetone alcohol. Furthermore, secondary alcohols such as isopropanol and propylene glycol monomethyl ether which have a relatively low activity with respect to the isocyanate group may optionally be used. The hydrophobic solvents of these solvents should be used in an amount such that they do not affect or deteriorate the water dispersibility of the resin formed. Whatever solvents are used, they should preferably be used in amounts of 60 parts by weight or less, based on 100 parts by weight of the solid resin, so as not to reduce the high hiding power of the resin composition formed.

Although the amounts of the compounds A, B, C and D used depend on the type of these compounds and no general 81 01 245

a

It is generally stated that the following quantities can be given in accordance with the applicable regulations.

Connection A

In view of the corrosion resistance of the resinous product, it is desirable, of this 30-80 wt.%, Preferably kO-TO wt. % t based on the total amount of compounds A - D to be used.

Connection B

In view of the water dispersibility of the resinous product, it is desirable to use such amounts that a primary amino group equivalent of the product of 300-3000, preferably 500-2500 is achieved.

Connection C

It is desirable to use it in an amount which is nearly one mole per mole of compound B, since this is a necessary amount to achieve water dispersibility when introducing compound B into compound A. It is clear that the compound can be present separately. If compound C is a high molecular compound, it can be used in an amount not greater than one mole per mole of compound B. If, in addition to the reaction of compounds B and C, a reaction of compounds A and C is assumed, the compound C amounts to more than one mole per mole of the compound B.

Connection D

In connection with the curability of the resinous product, it is desirable to adjust the amounts thereof so that a blocked isocyanate group equivalent of the resinous product is from 0 to 2,000, preferably 600 to 3,000. (ie, # molecular weight / number of blocked isocyanate groups introduced into the molecule).

According to the aforementioned reaction forms, mainly the following reactions will take place: (i) Cross-linking reaction between compound A and compound B, wherein compound C functions as cross-linking agent; (ii) polymerization between compounds A and C; 8101245 21 (iii) polymerization reaction between compounds B and C; (iv) blocked isocyanate-introducing reaction between compounds A and D and (v) a blocked isocyanate-introducing reaction between compounds B and D, resulting in two or more of these reactions being combined to form of the resinous product of the invention.

The constituent components of the resinous product thus formed may have any of the structures indicated by the following schematic diagrams.

ACB, A- (CB) nCA (n ^ l), ACA, A- (CA) nCA (n è l), BCB, B- (CB) nCB (n £ l), 15 ACBD, DACBD, ACAD, DAGAD , BCBD, DBCBD, A-D, B-D, A, B, D.

The resinous products of the invention should preferably have the following properties:

Primary amino group equivalent: about 300-3000, especially 500-2500;

Blocked isocyanate group equivalent: about 40-4000, especially about 600-3000; Ratio of residual isocyanate-reactive functional group equivalent (including primary amino groups) to blocked isocyanate group equivalent: about 0.5-4.0.

Since the above resinous product of the invention contains in the molecule strong basic primary amino groups blocked by carbonyl groups, in an amount sufficient to render the resinous product water-soluble or water-dispersible by neutralization with an acid, also including the blocked isocyanate groups serve to cure the coating after electrolytic deposition, this product is effective when the film-forming component 35 is used in the electrolytically deposable cationic resin composition of the invention.

8101245

V

22

Preparation of electrolytically deposable cationic resin composition

In the preparation of the electrolytically deposable cationic resin composition of the invention using the resinous product of the invention, said resinous product can be easily used as a clear electrolytically deposable composition. In general, it can be used advantageously as a pigmented electrolytic deposable composition by pigments and ...

to include other conventional additives. Pigments available for conventionally formulated electrolytically deposable dyes can be added. E.g. color pigments, so-. . : as red iron oxide, titanium white and carbon black; diluent pigments or rollers, such as talc, clay and mica, and rust inhibiting pigments, such as lead chromate, strontium bromate and basic lead silicate. These pigments can be used in arbitrary amounts. Furthermore, metal salts (such as lead, tin, bismuth, iron and manganese) of organic or inorganic acids (such as acetic acid, naphthenic acid, hydrochloric acid and nitric acid); oxides and hydroxides of such metals are also added as a curing promoter or catalyst. Usually, the addition of a surfactant to the composition of the invention is not necessary, but if desired, various known surfactants (such as nonionic surfactants) commonly used in electrolytically deposable cationic paint products may be used in a reasonable amount should be added. Furthermore, if necessary, conventional leveling agents (such as the copolymer of alkyl acrylate esters and polyalkylsiloxane) can be mixed in.

The electrolytically deposable resin composition of the invention, prepared as indicated above, can form a stable aqueous bath for electrolytic coatings by neutralization with water-soluble inorganic or organic acids, such as water soluble lower aliphatic monocarboxylic acids such as formic acid, acetic acid, hydroxyacetic acid, propionic acid, butyric acid and lactic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, fumaric acid and.

maleic acid; aromatic ear 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, and in particular with said water-soluble aliphatic monocarboxylic acids.

8101245 · ι wmM - «—— W · <· ι ι —.μ ^ · μμ · ι ··« ιιι ι ι.ιι »· -. «- 23

The primary amino groups present in the resinous product blocked by carbonyl compounds are hydrolysed by this neutralization step, thereby producing strongly basic primary amino groups, which in turn are neutralized. The amount of acid required for the neutralization should be determined as the amount or more necessary for solubilizing or finely dispersing the present resinous product in the aqueous medium, as well as the amount or less necessary for it. completely neutralizing the maino groups in said resinous product. IQ This amount is preferably in the range of 0.1 - 0.6 equivalent% based on the amino value (defined below). The aqueous bath thus obtained should preferably be neutralized in such a way that its pH value is generally in the range of about 3-8, preferably about 5-7.

The concentration of the total solids content in the aqueous bath, when the composition of the invention is neutralized with an acid and dissolved or dispersed in the aqueous medium, is generally adjusted to 3 - 30% by weight, and is preferably 5-20 wt%, based on the weight of the aqueous bath.

The aqueous bath thus prepared, which serves for the electrolyte! can be used as a coating bath with the article to be coated acting as a cathode.

Methods and devices known in the field of the cathodic electrode position can be used for the method and device for electrolytically coating a substrate with the aid of this aqueous bath. It is desirable for this purpose to use a carbon plate as an anode and of course as substrate the substrate.

In the electrolytic coating of the composition of the invention, the operating conditions are not specifically critical and this electrolytic coating should generally be carried out at a bath temperature of 20 - 30 ° C, a DC voltage of 100 - -00 -00 volts, 2 ( preferably 200 - 300 Volts), a current density of 0.01 - 3 A / dm, a current lead time of 1-5 minutes, an electrode surface ratio (A / C) of 2/1 - 1/2, at a distance between the two electrodes 35 of 1G - 100 cm and with stirring.

The film deposited on the substrate (cathode) can be cured by chopping about 10-250 ° C, preferably about 170-200 ° C, after washing. During the chopping process, the blocked isocyanate group in the film-forming resin releases alcohols and a blocking agent. : "wherein a crosslinking reaction with the amino groups, amide groups and hydroxyl groups in the resin molecule is effected and finally the resin is cured.

The electrolyte-deposable resin composition provided by the invention can be used to coat or finish various metal products. It is particularly suitable for the electrolytic coating of not only conventional zinc phosphate treated steel substrates, but also other steel substrates prone to corrosion, such as iron phosphate treated steel sheet and untreated steel sheet, the composition being excellent hiding power can impart a particularly high corrosion resistance to the steel substrate. These pronounced advantages have hitherto not been achieved with conventional electrolytically deposable paint compositions. Furthermore, the composition of the invention is suitable for the electrolytic coating of galvanized steel plates, tin-plated steel plates, aluminum, copper and copper alloy substrates, and a coating with excellent covering capacity which gives excellent corrosion resistance can thus be obtained.

The invention will now be further illustrated by the following examples. These are not intended to be limiting. In the examples parts are always understood to mean parts by weight. The tests to determine the tertiary amine value, the amine value, the isocyanate value, the hiding power, the salt spray resistance, the Erichsen extrusion resistance, the impact strength and flexibility were performed in the following ways.

(1) Determination of the tertiary amine value. About 0.2 g of a sample with known solids content was carefully weighed and placed in an Erlenmeyer flask with a normal stopper; about 10 ml of acetic anhydride / acetic acid in a weight ratio of 9/1 was added. The mixture was brought to a boil for about 10 minutes so that it did not boil dry; this accomplished the acetylation. After cooling, the mixture was titrated with 0.1N perchloric acid-acetic acid solution, 81 01 245 «. 25 using crystal violet as an indicator until the solution turned from purple to blue-green.

Tertiary amine value (mg KDH / g) = 5 »61 x titrated volume (ml) x factor of N / 10 ICIO ^ solid content sample (g) 5 (2) Determination of amine value 0.2 - 0.3 g of a sample put in a 100 ml

Erlenmeyer flask, heated, dissolved and then cooled. The sample was then titrated with N / 10 HCl aqueous solution, using brocphenol blue as an indicator. The titration endpoint was determined when the indicator's color changed from blue to yellow. The amine value was calculated by the following equation: _ volume (ml) of N / 10 HCl x factor of N / 10 HCl-1 -new value of sample (g) x solid content (%) / * 100 (3) Determination of isocyanate value

About 0.5 g of a sample with an isocyanate group 15 (NCO) was carefully weighed and placed in a stoppered flask and dissolved in 10 ml of dioxane (purity: reaction quality 1). After carefully adding 10 ml of a solution of 2/10 N dibutylamine dioxane, the mixture was heated to 80 ° C with shaking for 30 minutes. Then, 100 ml of isopropyl alcohol (purity: reaction vali-text 1) was added and excess dibutylamine titrated with 1/10 N hydrochloric acid, with bromophenol blue as indicator until the indicator color changed from blue to yellow-green. Separately, a blancc test was run simultaneously without the sample being applied.

The NCO value was calculated from the following equation:

NCO- ^ arde = (A ~ B) ΛΡ, «Λ? rj.UOOO

W.

where A: amount (ml) N / 10 hydrochloric acid required to neutralize 2/10 N dibutylamine in the blank test, B: amount (ml) N / 10 hydrochloric acid used in the titration of the sample, 0 0.00l2: amount (mg) of isocyanate group corresponding to 1 ml N / 10 hydrochloric acid.

8101245 26 f: hydrochloric acid factor W: amount (g) of sample.

(k) Test method of covering power (pipe method)

Test device: as schematically shown in Figures 1, 2 and 3.

In this regard, the respective symbols in the diagrams have the following meanings. , V; Stainless steel round barrel (diameter, 0 = 100 mm, thickness t = 1 mm) free of magnetism, f 10 Z: insulator, D: bearing bar (0 = 3 mm, height H = 170 mm), .7 = P: stainless steel pipe (0 = 16 mm, h = 3 ^ 0 mm, t = 1 mm) free of magnetism, A: measuring plate film thickness (30 x 150 x 0.8 mm) (see figure 2), 15 B: covering plate measuring capacity (15 x 300 x 0.1 mm), see figure 3), T: mercury thermometer (50 ° G scale), K: rotor, C: cooling water tank (made of plastic), M: magnetic stirrer, 20 L: liquid surface level of paint sample .

Procedures 1) A paint sample is placed in the stainless steel vessel V as in Figure 1 up to L 27 cm above the bottom and set to a predetermined temperature (usually 30 ° C) with homogeneous stirring (bath temperature 30 ° C).

2) The outer plate A, pipe D and the inside B are placed in the support rod D and placed in vessel V.

3) The anode and the cathode are applied, establishing that they are not short-circuited.

H) The tension is increased from 0 to the predetermined tension in 10 seconds, with the film thickness on the outer plate reaching 20-25 micrometers. At that time the voltage rise rate is set so that it does not exceed 10 A.

5) 3 minutes after a circuit is closed, it is turned off, after which the outer plate, the inner plate and the pipe are washed with water.

8101245 —----------------—------- ------------------------ --------------------- ------- -

2T

6) The outer plate and inner plate are baked.

T) The pipe is washed twice with solvent and in particular the inner surface of the pipe is carefully washed.

5 8) The height of the film deposit on the inner plate is measured (see figure U).

(5) Salt spray resistance

This was tested according to J.I.S. Z-2371 · When the corrosion creep width on one side relative to the linear scratched part is within 2.0mm and blistering of the film other than in the scratched part is up to 8 F (ASTM), it is judged satisfactory .

(6) Erichsen Extrusion Resistance. Using the Eriehsen extrusion meter, the extruded distance is measured until film cracking was observed.

Of the test results, e.g. J mm or more, that no cracking was observed even when the coated panel was extruded 7 mm deep.

(7) Impact Resistance (DuPont Impact Resistance Measurement System) 20 A test panel was placed in a chamber for 2k hours whose temperature and humidity were set to resp. 20 + 1 ° G and 75 + 2 $, after which a carrier and impact bar with a predetermined spherical end were attached to the DuPont impact resistance meter; the test panel was placed therebetween with the coated surface facing upwards, and a weight of a prescribed weight was dropped onto the rod from a prescribed height. A film that does not tear or peel is considered satisfactory.

(8) Bending Test 30 A white coating of the alkyd melamine resin type (AMILHC white, a product of Kansai Paint Co. Ltd.) was spray-coated on the electrolytically coated panel such that the film thickness in the dry state is 20 - 30 micrometer, then the panel was baked at 20 ° C for 30 minutes to obtain the sample.

According to J.I.S.-K 5 ^ 00-1979, 6.16 (bending spring resistance), the test piece was filmed around a cylindrical rod with a diameter of 10 mm.

bows. When no film tearing or peeling is observed in the curved area of the film, it is rated as satisfactory. Example I

465 Parts of bisphenol A type epoxy resin having a number average molecular weight of about 900 and an epoxy equivalent of about 465 (Araldite No. 6071; a product of Nippon Ciba Geigy Co., Ltd. Japan) were dissolved in 200 parts of methyl ethyl ketone and at 80 ° C reacted by adding 105 din diethanolamine until the tertiary amine value rose to 98 (about 3 hours or more) to give compound A-1 (hydroxyl group equivalent 285).

200 parts of the dimer acid-type polyamide resin with a number average molecular weight of about 1,000 and an amine value of about 300 (Tobmide No. 225X, a product of Fuji Kasei Co. Ltd. Japan) and 50 parts of methyl isobutyl ketone were heated, refluxed Boils and reacted until dehydration ceases, then the unreacted materials are removed by distillation under reduced pressure to give 240 parts of compound B-1 (primary amino group equivalent about 485).

259 parts of 4,4'-diphenylmethane diisocyanate were dissolved in 162 parts of methyl ethyl ketone and reacted at 50 ° C by adding 112.5 parts of ethylene glycol monoethyl ether until the isocyanate value dropped to 116, after which hexamethylene diisocyanate was added. A mixture of compound C-1 and compound D-1 was obtained.

Compound B-1 and 124 parts of methyl ethyl ketone were added to the compound A-1 obtained above and heated to 80 ° C. Then, the mixture of compound C-1 and D-1 was slowly added dropwise at the same temperature and reacted at that temperature until the viscosity increase came to an end (about 30 minutes or more), whereby the resinous product of the invention was obtained.

14 parts of the resinous product were mixed well with the addition of 0.6 parts of acetic acid and 26 parts of deionized water. It was then ball milled and dispersed until a particle size of 15 microns or less was obtained with the addition of 15 parts of titanium white, 5 parts of clay, 0.5 parts of carbon black and 1 part of bismuth nitrate, giving 62.1 parts of pigment paste (I).

8101 245 nrrrr tr ~ ι · ν * ΐτ-ϊ ~ τττ i n ~ .mr.ii ι i inn—- 29

Separately, 126 parts of the resinous product of the invention were well mixed with the addition of 5 parts diethylene monobutyl ether and 2 parts polypropylene glycol with an average molecular weight of U. 000 (Sannix FP-U.000, product of Sanyo Kasei Co., 5 Ltd . Japan). Then 0.8 parts acetic acid and 20 parts of a 10 # lead acetate aqueous solution were added and mixed thoroughly.

The mixture was diluted to a solids content of 30% of the resin by adding 166 parts of deionized water to obtain a water-dispersed clear varnish resin varnish.

This clear composition was mixed well with the pigment paste (I) prepared as above and then diluted with deionized water to a solid resin content of 15%, after which it was further mixed at 30 ° C for 2 hours by stirring and an electro-coating bath was obtained. With this electrocoating bath, a zinc phosphate-treated steel panel and an untreated steel panel were electrolytically coated to a film thickness of 20 microns, then baked at 180 ° C for 20 minutes, and the film was examined. The test results were as follows: (1) Coverages: 22.0 cm (pipe method, 250 V x 3 minutes).

20 (2) Salt spray resistance: untreated steel panel: 360 hours or more; zinc phosphate treated steel panel: 8l0 hours or more.

(3) Eriehsen extrusion resistance: 7mm or more.

(k) Impact strength: 50 cm or more on the top side, 50 cm or more on the bottom side (1.3 cm, 1 kg).

(5) Bending test (after top coating with alkyd melamine white coating): 10 mm O-satisfactory.

Example II

575 parts of styrene / allyl alcohol copolymer with a number average molecular weight of about 1,150 and a hydroxyl group equivalent of about 220 (RJ-101, a product of Monsanto Chemical Co. U.S.A.) were dissolved in 505 parts of methyl ethyl ketone (compound A-2).

300 parts of a primary amino group-terminated polyamide resin with a number average molecular weight of about 1,500 and an amine value of about 250 (Versamide 115, a product of Hippen 35 Eenckel Co. Ltd. Japan) and 50 parts of methyl isobutyl ketone were heated, refluxed and reacted until the dehydration stopped, 8101 245 30, then the unreacted materials were distilled off under reduced pressure to give compound B-2.

13¾ Parts of diethylene glycol monoethyl ether were added dropwise at 1 + 0 ° C to 217.5 parts of 2.1 + and 2.6-tolylene diiso-5 cyanate mixture (weight ratio 2.1 + - / 2.6- = 80/20) and at the same temperature was converted until the isocyanate value had dropped to 205, whereby a mixture of 1 + 3.5 parts of unreacted diisocyanate and 308 parts of mono-blocked diisocyanate was obtained (mixture of compound C-2 and compound D-2).

Compound B-2 was added and mixed with compound A-2. To this a mixture of compound C-2 and compound D-2 was slowly added dropwise at 80 ° C and reacted at the same temperature until the viscosity increase ceased. Then 250 parts of methyl ethyl ketone were distilled off under reduced pressure with the addition of 250 parts of ethylene glycol monoethyl ether, whereby the resinous product according to the invention was obtained.

126 parts of the resinous product were thoroughly mixed with the addition of. 1.0 part of acetic acid, 2.0 parts of lead acetate and 96 parts of deionized water, whereby a water-dispersed resin varnish 20 having a solid resin content of 1 + 0% was obtained. Pigment paste (I) as prepared in Example I was added to this varnish and mixed well. Thereafter, it was diluted with deionized water to obtain a solid resin content of 18%, after which an electrolytic coating was carried out. Test panels were used for the film quality tests as in Example I. The test results were as follows: (1) Coverage (pipe method): 23.0 cm (in 300 V x 3 minutes).

(2) Salt spray resistance: untreated steel panel: 21 + 0 hours or more. Zinc phosphate treated steel panel: 720 hours or more.

(3) Erichsen extrusion: at least 7 mm.

30 (1+) Impact resistance: at least 50 cm on the side. at least 50 cm on the bottom side (1.3 cm, 500 g).

(5) Bending test (after top coat coating with a white alkyd melamine coating): 10 mm O-satisfactory.

Example III

35 228 parts bisphenol A and 200 parts diglyoidyl ether of bisphenol A with an epoxy equivalent of approximately 200 Epikote 1 + 28, product 8101245 31 from Shell Chemical Co. Ltd. Japan) were heated to 160 ° C and reacted until an epoxy value of 0 was reached, whereupon compound A-3 was obtained.

51.5 Din diethylenetriamine and 120 Din methylene isobutyl ketone were heated, refluxed, reacted until dehydration ceased, and unreacted materials were distilled off under reduced pressure to obtain 130 parts of compound B-3. Compound B-3 was slowly added dropwise at 0 ° C to a mixture of 8 parts of hexamethylenedixsocyanate (compound C-3) and 86 parts of methyl ethyl ketone and reacted at the same temperature until heat development ceased, and a reaction product of compound B- 3 and compound C-3.

A mixed solution of 56.5 parts of S-caprolactam and half parts of methyl ethyl ketone was added dropwise at 60 ° C to 15 parts of hexamethylene dipsocyanate and reacted until the isocyanate value reached about 150 to give compound D-3.

170 Parts of diethylene glycol dimethyl ether were added and dissolved in compound A-3 and the reaction product of compound B-3 and compound C-3 was slowly added dropwise at 60 ° C; the reaction was continued at the same temperature until the viscosity increase ceased by further slow addition of compound B-3 to obtain the resinous product of the invention.

3.5 parts of 70% hydroxyacetic acid and 10β, 5 parts of deionized water were added to 100 parts of the resinous product, after which a water-dispersed resin varnish having a solid resin content of 50% was obtained. With the addition of 3 parts of carbon black, 3 parts of clay and 2 parts of basic lead sulfate, the pigment resin varnish was mixed and dispersed through a paint mixer to a particle size of 20 micrometers or less, after which 0.5 parts of perfluoroalkyl acrylate copolymer (Fluorad FC-30; a product of Sumitomo Three M Co. Ltd. Japan) was added. The mixture was diluted with deionized water to a resin solids content of 18 ¾ after which it was subjected to the film quality test according to Example I.

(1) Jaw power (pipe method): 20 cm (220 V x 3 minutes).

35 (2) Salt sheet spring position: untreated steel panel: 360 hours or more, 8101 245 32 zinc phosphate treated steel panel: 720 hours or more.

(3) Eriehsen extrusion: at least 6.5mm.

(10 Impact resistance: at least 50 cm at the top side; at least 50 cm at the bottom side (1.3 cm, 500 g).

(5) Bending test (after top coating with white alkyl melamine coating): 10 mm O-satisfactory.

Example IV

228 Din bisphenol A (compound AV) was dissolved in 120 parts of methyl ethyl ketone and then slowly added to 210 parts of hexa-10 methylene diisocyanate (compound Ck) at 60 ° C and reacted at the same temperature until the isocyanate value dropped to 2 ht, after which the reaction product of compound A-11 and compound C-1f were obtained.

26 parts of hydroxyethyl ethylene diamine and 30 parts of methyl isobutyl ketone were heated, refluxed and reacted until dehydration ceased, then the unreacted materials were distilled off under reduced pressure to obtain 695 parts of compound B-4.

60 parts of methyl ethyl ketone were added to compound B-1 * and the reaction product of compound A-k and C-11 was slowly added at 20 ° C until a reaction product of compound A-h, C-k and D-k was obtained.

. . 130 parts of 2-ethylhexanol were added at 60 ° C to 87 parts of the 2.1 + and 2.6-tolylene diisocyanate mixture (weight ratio 2.1 + / 2.6- = 80/20) and converted at the same temperature until the isocyanate value was 0, after which the digblocked dixsocyanate (compound D1) was obtained. Compound Ό-k was added to the reaction product composed of compound A-k, compound C-U and compound B-11 to prepare the resinous product of the invention.

130 parts of the resinous product were converted into a water-dispersed varnish with a solids content of 50% with the addition of 1.5 parts acetic acid and 118.5 parts deionized water.

With the addition of 3 parts of carbon black, 6 parts of talc and 3 parts of basic lead sulphate, the pigmented varnish was mixed by a paint mixer dispersed until the particle size was 20 microns or less, after which 0.5 parts of perfluoroalkyl acrylate copolymer (Fluorad FC-1 + 30 a product of Sumitomo Three M Co. Ltd. Japan) was added. The mixture was diluted 8101 245 33 with deionized water to achieve a solids content of 20 /, and the film quality test as described in Example 1 was performed. The following results were achieved: (0 Coverage: 18.5 cm (250 V x 3 minutes).

5 (2) Salt spray resistance: untreated steel panel: 306 hours or more, zinc phosphate-treated steel panel: 8U0 hours or more.

(3) Erichsen extrusion: 6.5mm.

(k) Impact resistance: at least 50 cm at the top side; at least 50 cm 10 on the bottom side (1.3 cm, 500 g).

(5) Bending test (after top coating with white alkyd melamine coating): 10 mm 0 satisfactory.

Example V

V75 Parts of the bisphenol A type epoxy resin with a number average molecular weight of about 1,000 and an epoxy equivalent of about h3 (Epikote 1001, product of Shell Chemical Co.,

Ltd. Japan) were dissolved in 53 parts of toluene and reacted at 60 ° C for 3 hours with the addition of 59 parts of n-propylamine. The converted amine was then distilled off under reduced pressure to obtain compound A-5.

300 parts of the dimer acid-type polyamide resin with a number average molecular weight of about 1,500 and an amine value of about 250 (Versamid 115, a product of Hippon Henkel, Go. Ltd. Japan), 50 parts of tolylene and 50 parts of methyl ethyl ketone were heated, under Boiled and dehydrated to reflux to give compound B-5.

67.5 parts of ethylene glycol monoethyl ether were added to 130.5 parts of 2,6-tolylene diisocyanate and reacted at 14-0 ° C until the isocyanate value dropped to 159, thus obtaining compound D-5.

Compound D-5 was slowly added to compound B-5 at 60 ° C and reacted at the same temperature for 1 hour, after which compound A-5 and 300 parts of propylene glycol monoethyl ether were added; then 2 parts of hexamethylene diisocyanate (compound C-5) were slowly added at 60 ° C and reacted at the same temperature for 1 hour; thus the resinous product of the invention was obtained.

8101245 -. 100 Din of the resinous product was converted into a water-dispersed resin varnish with a solid or content of 33% with the addition of 20 Din of acetic acid and 158 Din of deionized water.

After pigmentation of the resin varnish and preparation of the electrolytic coating bath, as in Example IV, the film quality test was performed. The following results were obtained.

(1) Coverage: 20 cm (250 V x 3 minutes).

(2) Salt spray resistance: untreated steel panel: 3Ê0 hours or more, 10 zinc phosphate steel panel: 8 ^ 0 hours or more.

(3) Erichsen extrusion: at least 7 mm.

(k) Impact resistance: at least 50 cm at the top side; at least 50 cm on the bottom side (1.3 cm, 500 g).

(5) Bending test (after top coating with white alkyd melamine coating): 10 mm 15 0 satisfactory.

Example VI

800 Din of styrene-allyl alcohol copolymer with a number average molecular weight of about 1,600 and a hydroxyl equivalent of about 300 (RJ-100, a product of Monsanto Chemical Co. ™ S.A.) 20 (compound A-6) were dissolved in 320 parts of methyl ethyl ketone.

61 parts of monoethanolamine, 1U parts of toluene and 100 parts of methyl isobutyl ketone were heated, refluxed and dehydrated to give 1-3 parts of compound B-6. Further, 336 parts of hexamethylene dipsocyanate (compound C-6) were dissolved in 237 parts of methyl ethyl ketone and converted at 80 ° C by adding 113 parts of cap-caprolactam until the isocyanate value fell to 280, then cooled at 60 ° C and slowly converted "under addition of said B-6 compound until the exothermic reaction ceased, a mixture of compound D-β and the reaction product of compounds B-6 and C-6 was obtained The mixture was slowly added to the solution at 80 ° C of compound A-6 and reacted at the same temperature until the viscosity increase had almost ended, after which the resinous product of the invention was obtained.

One part of the resinous product was converted into a water-dispersed resin varnish with a solids content of 33% with the addition of 3 parts of acetic acid and 157 parts of deionized water.

8101245 ____ 35

After pigmentation of the resin varnish and preparation of the electro-coating bath, film quality tests as in Example IV were carried out. The test results are as follows: (1) Coverage: 18.0 cm (220 V x 3 minutes).

5 (2) Salt spray resistance: untreated steel panel: 2k0 hours or more, zinc phosphate steel panel: 720 hours or more.

(3) Erichsen extrusion: 7 mm · (¾) Impact strength: 50 cm on the side t; 50 cm on the bottom side (1.3 cm, 10 500 g).

(5) Bending test (after top coating with white alkyd melamine coating): 10 mm O-satisfactory.

8101 245

Claims (25)

A composition according to claim 1, characterized in that the active hydrogen-containing amino group is a secondary amino group and the hydroxyl group is bonded to the primary carbon atom. Composition according to claim 1, characterized in that compound A contains on average 2-10 isocyanate-reactive functional groups per molecule. k. Composition according to claim 1, characterized in that compound A contains isocyanate-reactive functional groups in the range of 100-2,000, preferably 200-1,000, expressed by the isocyanate-reactive functional group equivalent number. The composition according to claim 1, characterized in that the compound A has a get as the average molecular weight of about 100-81012 4 10,000, preferably about 200-5,000. 6. A composition according to claim 1, characterized in that compound A is an aromatic type of compound, in the case of a polymer the main chain of the aromatic type of compound is mainly formed by aromatic rings. A composition according to claim 1, characterized in that / compound A is a compound selected from the group consisting of (i) an adduct of an epoxy resin and an amino compound with at least two active hydrogen atoms in a molecule; (Ii) an adduct of an epoxy resin and water or a polyhydric alcohol, (iii) a phenol-terminated prepolymer formed by the addition polymerization reaction of a bisphenol compound with a di-epoxy compound or a diisocyanate compound and 15 (iv) a styrene compound. allyl alcohol copolymerized for polymer. A composition according to claim 1, characterized in that the compound A is a compound selected from the group consisting of an adduct of a bisphenol-type epoxy resin and an alkanolamine; a phenol-20 terminated prepolymer of bisphenol A and diisocyanate and a styrene-allyl alcohol-copolymerized prepolymer. Composition according to claim 1, characterized in that the primary amino group blocked by a carbonyl compound in compound A is a primary amino group represented by the formula -n = c (r 2) (r 3), wherein R 1 is a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms, R 1 represents a monovalent hydrocarbon group of 1 to 6 carbon atoms or R 1 and R 1 together represent an alkylene group of not more than 12 carbon atoms. Composition according to claim 1, characterized in that at least part of the primary amino group present in the (poly) amine compound in compound B is blocked by a carbonyl group, which (poly) amine compound is selected from the group consist of (a) a polyamine compound, which simultaneously contains a primary amino group 8101245 * and a secondary amino group, (b) a hydroxyl-containing amino compound, which simultaneously contains a primary amino group and a hydrokyl group, and (c) a hydroxyl group-containing polyamine compound, which simultaneously contains a primary amino group, a secondary amino group and a hydroxy 1 group. Composition according to claim 10, characterized in that the (poly) amine compound has a primary amino group equivalent of about 2,000 or less. Composition according to claim 1, characterized in that compound B has an isocyanate-reactive functional group equivalent of at most 2,000. Composition according to claim 10, characterized in that the (poly) amine compound has a number average molecular weight of at most 5,000. 1 h. Composition according to claim 10, characterized in that the (poly) amine compound is a compound selected from the group consisting of II-alkylalkylenediamine, polyalkylene polyamines, N-hydroxyalkylalkylenediamines, mono (hydroxyalkyl) amines, II- (aminoalkyl) pipera-20 zines and polyamide polyamines. Composition according to claim 10, characterized in that the (poly) amine compound is selected from monoethanolamine, monopropanolamine, monobutanolamine, diethylene triamine and a dimer acid polyalkylene polyamine condensate. 16. A composition according to claim 1, characterized in that the diisocyanate compound C has a molecular weight of about 100-2000. 171 A composition according to claim 1, characterized in that the diisocyanate compound is a compound selected from 2, W-colylene-30 diisocyanate, 2,6-tolylene diisocyanate, U, H-diphenylmethane diisocyanate, 1, Λ-xylylene diisocyanate, U, ^-dicyclohexylmethane diisocyanate 1,6-hexamethylene diisocyanate, isophorene diisocyanate, ethylene glycol, diethylene glycol, 2 U-tolylene diisocyanate adducts of propylene glycol and reaction products of 1 mole of 2, U-tolylene diisocyanate adduct and of tri-methylolpropane with 1 mole of lower aliphatic monoalcohols. 18. Composition according to claim 1, characterized in that Λ 1 n / C νΤΤΪΓ -i **** '* I: ι ΐ r ^. The partially or completely blocked polyisoeyanate compound is obtained by partially or completely blocking the isocyanate groups present in the polyisoeyanate compound, and the molecular weight is in the range of 100-2,000. A composition according to claim 18, characterized in that the blocking is carried out with a volatile active hydrogen-containing compound with a low molecular weight of at most 300. 20. A composition according to claim 19, characterized in that the low molecular weight active hydrogen-containing compounds are aliphatic monoalcohols. A composition according to claim 1, characterized in that compound D is a partially blocked polyisoyanate compound. 22. A composition according to claim 1, characterized in that compound A is used in an amount of 30-80 wt.%, Based on the total amount of the compounds A, B, C and D. Composition according to claim 1, characterized in that the compound D is used in such amounts that 300-3000 primary amine green quivalent in the resinous product is obtained. 20 2k. Composition according to claim 1, characterized in that compound C is used in an amount of almost 1 mol / mol of compound D. Composition according to claim 1, characterized in that compound D is used in amounts such that 1 - 25-25,000 blocked isocyanate group equivalent of the resinous product is obtained. 26. Aqueous bath for cationic electrolytic coating, which bath comprises: (I) a blocked isocyanate group-cured type cationic electrolytically deposable resin composition, obtained by I) reacting (A) a compound containing in a molecule at least two isocyanate-reactive functional groups selected from active hydrogen-containing amine groups and hydroxyl groups, 35 (B) a compound containing in a molecule at least one primary amino group, blocked by a carbonyl compound and at least 81 01 245 | 1K3 st contains an isocyanate-reactive functional group selected from active hydrogen-containing amino groups and hydroxyl groups; and (ü) a diisocyanate compound, which contains two free isocyanate groups in one molecule; and II) reacting or mixing said reaction mixture with (D) a partially or completely blocked polyisocyanate compound containing in one molecule at least two isocyanate groups, one or more of which are blocked and no more than one free isocyanate group, the main component of which contains a resinous product into which the compound B with the blocked primary amino group is introduced via the diisocyanate compound C into the compound A component; (lil) a more soluble inorganic or organic acid 15 as a neutralizing agent for said resin composition and (IV) an aqueous medium. Bath according to claim 26, characterized in that it contains 3-30 wt.% 9 as a solid, of reaction product I, based on the weight of the bath. Bath according to claim 26, characterized in that it has a pill of about 3-8. Method for electrolytically coating an electrically conductive surface, which functions as a cathode, wherein an electric current is passed through the cathode and anode in contact with an aqueous electrolytic coating composition, characterized in that the electrolytic coating composition comprises: (i) a blocked isocyanate group-cured type cationic electrolytically deposable resin composition, obtained by i) a compound (A) containing in one molecule at least two isocyanate-reactive functional groups selected from active hydrogen-containing amine groups and a hydroxyl group, (B) a compound containing in one molecule at least one primary amino group blocked by a carbonyl compound and at least one isocyanate-reactive functional group selected from active hydrogen-containing amino groups and hydroxyl groups, and ( C) a diisocyanate compound containing in one molecule two 8101 245 in free isocyanate groups and II) reacting or mixing the aforementioned reaction mixture with (D) a partially or completely blocked polyisocyanate compound containing in one molecule at least two isocyanate groups, one or more of which are blocked, and no more then contains one free isocyanate group, the main component of which contains a resinous product in which the compound D with the blocked primary amino group is introduced into the A compound via the diisocyanate compound Cj (II) a water-soluble inorganic or organic acid as a neutralizing agent for said resin composition (i) and (III) an aqueous medium. ' 30. Coated article obtained according to the method of claim 26. if 01 245