DE2163143C3 - 22.12.70 V.St.v.Amerika 100834 29.03.71 V.St.v.Amerika 129267 29.07.71 V.St.v.Amerika 167470 Aqueous dispersion of a non-gelled water-dispersible epoxy resin - Google Patents

Description

The invention relates to aqueous dispersions of ungelled water-dispersible epoxyhar / s and their use / around electrical layers of electrically conductive substrates

Although the electrical deposition has been around for a long time is known, hai mu .ils process / .ur manufacture of Coatings only recently, technical Ikdetituhg attained. Ropes side by side with clits Use of this process has led to the development of certain preparations with which satisfactory Coatings are obtained. If there are lots of tubs turigen can be deposited electrically, see below one with most drafts / .preparations,> venn

if applied by electrodeposition, none Coatings that meet industrial requirements. Moreover, the electrical deposition is of many Coating compositions, even if they otherwise lead to good results, often with disadvantages like that Formation of non-uniform coatings or poor dispersion. They also have after this process c-Kiltenen coatings in the Most traps lack mn respect for certain properties that make for their use for purposes are essential for which the electrical deposition sons: suitable is. Above all, it is difficult to do so Properties such as good corrosion resistance and good resistance to alkalis, with resins such as those commonly found in electrodeposition used to achieve. This is especially true for you conventional preparations used in electrodeposition. those with ever Base contain solubilized polycarboxylic acid resins. These are deposited on the anode and tend because of their acidic character to the sensitivity to corrosive attacks of the usual kind. For example by Salts or alkalis. Many deposits electrically deposited on the anode suffer as a result exercise or staining. that at the anode metal ions go into solution.

F.poxy resins. which have excellent corrosion resistance and other valuable properties, pay for many uses / u the suitable sien fabrics. They are used in many coatings; however, they are not found to be dispersible in water. suitable / prepare for electrical deposition gen used because they are unler the terms These deposition methods fail to disperse man hai sufficiently in water esterified and also amino group-containing epoxy resins used, but they fade away like you do Pnlvv / carboxylic acid / e. and if they are also opposite P () l \ caihonsaurehar / en vtcic advantages.so are they also have many of their disadvantages

The object of this invention is therefore an improved one Dispersion of an E.poxyhar / es. those for the electric Deposition is suitable

According to the invention, this object is achieved by an aqueous dispersion of an ungelled in water dispergierbarcn i poxyhar / es. which may optionally contain solvents, which is characterized. that it consists of 1 to 25 percent by weight of a Fpoxvhar / es with at least one epoxy group in the molecule and a content of chemically bound nitrogen of at least 0.05% in the form of a ¹ · Sal / es of a quaternary ammonium base and an acid 1111 'of a disso / iaiion constant greater than 1 10 ·. 0.01 to 8 per cent by weight of boron in the form of boric acid and optionally other customary resinous materials, plasticizers, coupling solvents. Pigments. Oxidation preventers. Surface equipment and net / means

Aqueous dispersions of this type are excellent suitable as Übci7.tigs.mas.s.en. You can follow them traditional method, for example by Eintain chcn or painting, apply. You are suitable but especially excellent for electrodeposition application.

The electrodeposition coatings obtained with dispersions of this type are all inexpensive Properties of the groove the previously known electrical

depositable resins obtained liberal and above in addition, there are other excellent advantages and properties. These include an excellent one Resistance to salt fog, alkalis and similar corrosive substances, even on non-primed Metals or in the absence of corrosion preventive Pigments as well as the resistance to staining or discoloration, as is often the case with electrical power shows deposited coatings of anionic resins. E, η another advantage of the dispersions according to the Invention then is that they have a significantly higher spread than in the electrical deposition similar preparations, for example those like her from US Patent 33 01 804 are known.

In the dispersions according to the invention are Epoxy resins are either the sole resin component or the main ingredient among other resinous ones or film-forming materials.

In the dispersions according to the invention Resins contained are ungelled. in water dispersible epoxy resins in their molecule at least one 1,2-epoxy group. chemically bound quaternary ammonium salts and optionally oxaikylene groups contain, the ammonium salts are salts of an acid that has a Dissoziaiionskonstanie bigger than 110``. You can have an acid like this take from the series of organic and inorganic acids. Preferably used mar one Carboxylic acid and as such currently with preference Lactic acid

The concentration of the epoxy resin in the dispersion depends on the conditions of use The main rule, however, is water Dispersion and the concentration of the epoxy resin is 1 to 25 percent by weight of the ί ispeismn and the boric acid content is 0.01 to 8 percent by weight Boron in the form of boric acid The Hcgnll used here "Dispersion" also includes colloidal weighing solutions the epoxy resins.

The epoxy resin occurring in the dispersions according to the invention preferably contains 0.05 to 16 percent by weight nitrogen, of which at least 1%. / wake-up 20%, more appropriate 50% and preferred essentially all of the chemically bound groups are quaternary ammonium salts, while the remainder of the nitrogen is amino nitrogen.

Any desired epoxy resins can be used to prepare the epoxy resins contained in the dispersions according to the invention monomeric or polymeric compounds with a 1.2 F.poxy equivalent of more than 1.0, i.e. in which the Average number of 1.2 f.poxy groups in the molecule is greater than 1. or mixtures of such compounds use. A resinous epoxy compound is preferably used. d. H. a polyepoxide. the contains more than one epoxy group in the molecule Polyepox'd can be any known epoxy. In advance “The fact that it is useful is that it is F.poxy groups must contain in such an amount. that in the product after oxyalkylation some epoxy groups are available for the reaction with the ammo compound described below. Epoxides of this type are for example in the US 'Paienschriften 24 67 171, 26 15 007, 27 16 123, 30 30 336, 30 53 855 and 30 75 999 mentioned. A particularly suitable class full of polyep oxides are the polyglycidyl ethers of polyphenols, for example bisphenol A. These ethers can be used for example, by producing a polyphenol with epichlorohydrin or dichlorohydrin in counter

was etherified by an alkali. As a phenolic compound you can here

Bis (4 hydroxy phenyl) -2,2-propane,

3,4'-dihydroxybenzophenone,

Bis (4-hydroxypheny!) - l, l-ethane,

Bis (4-hydroxyphenyl) -1,1-isobutane,

Bis- (4 hydroxy-tert-butylpheny!) - 2,2-propane,

Bis (2-hydrexynaphthyl) methane and

1,5-dihydroxynaphthalene

use. Another class of very suitable polyepoxides can be found in the same way Manufacture novolak resins or similar polyphenol resins.

Other particularly suitable epoxy-containing compounds and resins are epoxy resins made from 1,1-methylene-bis (5-substituted hydantoin), see U.S. Patent 33 91097, and N.N'-diglycidyl heterocyclic compounds, see U.S. Patent 3,50J,979; also nitrogen-containing diepoxides, see US Pat. No. 3,365,471; Aminoepoxyphosphonates, see GB-PS 11 72 916 and 1,3,5-triglycidyl isocyanurate.

The corresponding polyglycidyl ethers are also suitable polyhydric alcohols. As polyhydric alcohols in this context

Ethylene glycol, diethyl glycol, triethylene glycol,

1,2-propylene glycol, 1,4-butylene glycol,

1,5-pentanediol, 1,2,6 · hexanetriol, glycerol and

Bis (4hydroxycyclohexyl) 2,2-propane
called.

Polyglycidylsyls of polycarboxylic acids can also be used use. This is sterile by reacting epichlorohydrin or a similar epoxy compound mn an aliphatic or aromatic polycarboxylic acid, for example oxalic acid, succinic acid. Glutaric acid. Terephthalic acid, 2,6-naphthyl dicarboxylic acid and dimerized linolenic acid. Examples such esters are diglycidyl adipate and 'las Diglycidyl phthalate.

But those due to epoxidation are also olefinic Polyepoxides prepared from unsaturated alicyclic compounds are suitable. These include fliepoxidc. the partly a monoepoxide or several monoepoxides contain. These polyepoxides are non-phenolic. Man obtained by using alicychic olefins for example mn oxygen in the presence of selected metal catalysts epoxidized with perbene acid, with acetaldehyde monoperacetate or with peracetic acid. To this Polyepoxides include the epoxyalicytlic ethers and Esters, which are known from the l.iteratu /.

Another and preferred in many cases The class of polyepoxides used includes those polyepoxides which have oxaikylene groups in the epoxy molecule contain. The oxaikylene groups of these compounds are usually groups of the general formula

CH, (H
R.

in which R is hydrogen or alkyl, preferably a lower alkyl having, for example, 1 to 6 carbon atoms, and in most cases m is a number from 1 to 4 and π is a number from 2 to 50. These groups can be attached to the main molecular chain of the polyepoxide or be part of this chain. The amount of oxaikylene groups in the polyepoxide depends on a number of factors, such as the

21

c rz up 143

Chain length of the oxalkylene group, of the nature of the Epoxy and of the desired degree of water solubility.

A number of oxalkylene groups are created containing polyepoxides produced by some of the epoxy groups of a polyepoxide, for example one of the epoxy resins mentioned is reacted with a monohydric alcohol containing oxyalkylene groups. Monohydric alcohols of this type are conveniently prepared by using an alcohol, for example Methanol or ethanol, oxalkylated with an alkylene oxide. The alkylene oxides are ethylene oxide, 1,2-propylene oxide and 1,2-butylene oxide are particularly suitable. Also suitable as monohydric alcohols are, for example, the commercially available monoalkyl ethers of Alkylene and polyalkylene glycols. The monohydric alcohol is reacted with the polyepoxide generally in the presence of a catalyst. Formic acid is used as a catalyst, Dimethylmethanolamine, diethylethanolamine. N.N-dimethylbenzyl amine and in some cases tin (!!} chloride.

Oxalkylene group-containing polyepoxides of a similar type can be prepared by the Epoxy resin in another way, for example by a direct reaction with an alkylene oxide. oxalkylated.

The one used for the preparation of the above-mentioned oxalkylene group-containing epoxy compounds Polyepoxide should contain epoxide groups in such an amount that the number of these groups after the Umalkylation are still present in the product, im Average is greater than 1.0 per molecule. If the epoxy resin contains oxalkylene groups, theirs does Proportion from 1.0 to 90 percent by weight or more.

The epoxy resins contained in the dispersions according to the invention can be prepared in that fnan the epoxy compound with an aminosal / / u a resin containing quaternary ammonium groups.

Examples of salts are salts of ammonia, primary, secondary and tertiary amines, preferably tertiary amines and an acid with a Girier dissociation constant of greater than 1 · 10 ^s . The preferred tertiary amines react with the epoxy compounds directly to form a quaternary Ammonium compound. whereas itself dung first tertiae ^r e of the other amino compounds and the Epoxyvcrbin form amines, which are then further reacted with an excess of epoxy compound as of example of acids with a disso / ia · tion constant of greater than 1 10 ^"1 SeJCnMiIChSaUrC. acetic acid. propionic acid, Butyric acid, hydrochloric acid, phosphoric acid and sulfuric acid. Of these acids, lactic acid is currently preferred. The amines can be unsubstituted amines or amines substituted with non-reactive substituents, such as halogen or hydroxylamines. Examples of such amines are dimethylethanolimine, salts of boric acid. Lactic acid, propionic acid, butyric acid, hydrochloric acid, phosphoric acid and sulfuric acid or similar salts of the ethyiamine, diethylethanolamine, trimethyiamine, diethylamine, dipropylamine and l, -amino-2-propanol.

Within the broad class of amino compounds, the salts that may be mentioned as a special class are those of Amines with one secondary or tertiary amino group or several such groups and with one Hydroxyl group are derived.

In most cases the hydroxylamine used corresponds to the general formula

NR ₁ OH

R,

ίο In this formula are Ri and R? preferred for methyl, Ethyl or other lower alkyl groups. In principle, except for the groups mentioned, you can do any mean organic group which does not adversely affect the desired reaction. As examples are

is called benzyl and alkoxyalkyl. Ri can about it also be hydrogen. The type of group is less important than the presence of one secondary or tertiary amino nitrogen atom. Therefore, higher alkyl, aryl, alkaryl or Aralkyl groups or also subs '' fourth groups of these Kind of be present. Rj denotes a in the formula divalent organic group, for example an alkylene or substituted alkylene group such as oxalkylene or poly (oxalkylene) or, however, less expedient

2s moderate, an arylene, alkarylene or substituted arylene group. Rj can also be an unsaturated group, for example an alkenylene group. As examples

(II CH

inul

CII C

called. Ri also denotes cyclic and aromatic Groups. Suitable amines in the latter are -all those with the formula

OH

R,

(H, N

in the Ri and R; have the abovementioned meaning and η is an integer from 1 to 3. Dialkanolamines of the general formula RiN (RiOH) 2 and trialkanolamines of the general formula N (RiOH)) are also suitable. As an example of the above definitions corresponding and particularly suitable amines may be
si dimethylethanolamine, dimethylpropanolaniin,

Dimethylisopropanolamine, dimethylbutanolamine,
Diethylethanolamine, ethylethanolamine,
Methylethanolamine, N-benzylethanolamine,
Diethano'jmin, triethanolamine,
Dimethylaminoethylphenol,

Tris (dimethylaminomethyl) phenol,
2- [2- (dimethylamino) ethoxy] ethariol,
! '[!' (Dimethylaminoj ^ -propoxyJ ^ -propanol,
2 '(2-2- (dimethylamino) ethoxy] ethoxy) -alhanol,
fi ₅ I - [2- (dimel / t «- 'lamino) ethoxy] -2-propanol and

I - (I - [dimethylamino) -2-propoxy] -2-propoxy) -2-propanol
called.

Within the broad class of amino compounds amines may also be mentioned in particular, the one secondary or icrtiärc amino group or several such groups and at least one terminal group Contain carboxyl group and as such, d. left without in addition to being converted into a salt form, can be used. Usually equals one such a carboxylamine of the general formula

NK ₁ (OOII

R.

In this formula are Ri and R; preferred for Methyl. Ethyl or other lower alkyl group. They küiuiL'ii grunusiii / hiM mean every urgarii & ci'ic group, which does not adversely affect the desired reaction. Examples are benzyl and alkoxyalkyl called. In addition, Ri can also be hydrogen. The type of group is less important than the presence of a secondary or tertiary amino nitrogen atom. Therefore can also be higher Alkyl-. Aryl. Alkaryl and aralkyl groups or substituted groups of this type may be present. R. denotes a divalent organic in the formula Group, for example an alkylene or a substituted one Alkylene group c. such as oxalkylene or poly (oxalkylene) or, but less expediently, an aryl. Alkarylene or substituted arylene group. Ri can also be an unsaturated group, for example an alkenylene group.

One can use amines of this Ar; produce by known methods, for example in such a way that an acid anhydride such as succinic anhydride. Phthalic anhydride or maleic anhydride, with an alkanolamine. such as dimethylethanolamine or methyldiethanolamine. In the here received Amines contains the group labeled Ri, ester groups. Other types of amines are made for example by the fact that one alkylamines by the method of US Pat. No. 3,419,525 with Alkyl acrylates or alkyl methacrylates, for example with methyl or ethyl acrylate or methyl or Ethyl methacrylate converts. In this case, the ester group is subsequently suitably converted into a by hydrolysis free carboxyl group converted. One can also use other types of amines to produce amines Procedure work.

As you can see, those marked with Ri can Groups of very different kinds. As examples, be groups of the formulas

RfKOR

(RO) ₁₁ COR '

called, in which R 'is an alkylene group, for example -CH2CH2- or

(II.

cii.cn

or an alkenylene group, for example —CH = Ci-I- and η stands for a number from 2 to or more. R 'can also denote cyclic or aromatic groups.

As examples of those given above Particularly suitable amines are corresponding to definitions

N ₁ N ^ Dimethylaminoä thy Ihydrogehmaleai,

N.N-diethylaminoä thy! Hydrogen ma (eat.

N.N-Dimethylaminoälhylhydrogensuccinat,

N.N dimethylammoethyl hydrogen phthalate.

N.N Dimethylaminoälhylhydrogenhexahydro-

phihalat.

2 (2Dimethylaminodihoxy) ethyl hydrogen corneate.

l-methyl-2- (2Dimelhylaminoethoxy) ethyl

hydrogenmalcat.

2- (2Dimethylaminoethoxy) ethyl hydrogen

succinate.

l.I-Dimethyl ^ -pdimethylaminoälhoxyJäthyl

hydrogen succinate.

2- [2- (2-dimethylaminoethoxy) ethoxy] ethyl

hydrogcnmaleate.

beta (dimethylamine) propionic acid.

beta (dimethylamino) isobutyric acid,

beta (dimethylamino) ethyl hydrogen maleate.

beta (diethylaniino) propionic acid.

2- (Methvlamino) ethyl hydrogen succinate.

3- (Ethyfamino) propyl hydrogen malcatate,

2 [2- (dimethylamino) ethoxy] ethyl hydrogen

adipate.

N.NDimethylammoethyl hydrogen azelate.

Di- (N. N- dimethylaminoethyl) hydrogen

tricaballylat.

N.NDimethylaminoethylhydrogenitaconai.

l- (l- [l (dimethylamino) -2-propoxy] -2-propoxy) -

2-propyIhydrogen maleate and

2- [2- (2- [2- (dimethylamino) ethoxy] ethoxy) -

ethoxy] ethyl hydrogen succinate

called.

It should be noted that one is a carboxylamine as such, i.e. without it in an additional .salzform can use because the amino acid is a zwitterion. that forms an inner salt.

The boric acid contained in the dispersions according to the invention can be added to the dispersions as such or in the form of compounds which hydrolyze to boric acid. The presence of boric acid in the dispersions is beneficial in that it catalyzes the curing of a film made therefrom, enables lower curing temperatures, and / or leads to harder films. The boric acid can also be introduced into the dispersion through a special embodiment for the preparation of the nitrogen-containing epoxy compounds by first reacting epoxy compounds with a boric acid ester containing amino groups and / or a tertiary amine salt of boric acid and then reacting an acid with a dissociation constant of greater than 1 ■ 10 ⁵ adds.

As a boron compound can be used to produce the Use reaction products, for example, any triorganoborate in which at least one of the organic groups replaced by an amino group is. According to their structure, such esters are esters of boric acid or a dehydrated boric acid, for example metaboric acid and tetraboric acid c. although they are not necessarily made up of these acids must be made. In most of them babble

sintipreehen the used Bofeslef one of the or Formulas

RC)

OK

KO H K

in which R denotes the same or different organic radicals. R can be practically any organic Be remainder, for example a hydrocarbon radical or substituted hydrocarbon radical which is not more than Contains 20 carbon atoms, preferably not more than 8 carbon atoms. The preferred used Esters contain alkyl radicals or polyoxalkyl radicals. At least one of these organic residues contains one Amip.ogruppe.d. H. a group of the formula

K.

in the Ri and R. · for hydrogen or, preferably, for Methyl, ethyl or another lower alkyl radical, but also be any other organic radical can, provided that this does not adversely affect the desired reaction. It depends less on the nature of the residues used in each case, rather than the presence of the nitrogen atom of an amino group. Because of this, higher alkyl. Aryl, alkaryl and substituted radicals of this type are present be. If both Ri and R2 are hydrogen can be, d. H. when the amino group is a primary amino group, it is preferred to use it at least one alkyl radical or another organic radical, so that the amino group is a is secondary or tertiary amino group.

The boric acid esters or boron esters used with preference correspond to the formula

XOR ₁ N

R,

in which X is the formula

R ₄

C)

25th

ίο K ,.

Has. In these formulas, Ri and R> have the above Meaning and Ri and R; stand for two-valued organic 'radicals, for example alkylene radicals or substituted alkylene radicals such as oxalkylcn- or Poly (oxylene) residues. or, less desirable, aryl, alkarylene or substituted arylene radicals and R-. and Rh stand for alkylresie, substituted alkyl, aryl, alkaryl radicals or another radical consisting of a any monohydric alcohol can be derived by removing the hydroxyl group. Ri and R * can be the same or different.

As examples of boric acid esters of the class mentioned are mentioned:

2- (beta-dimethylaminoisopropoxy) -4,5-dimethyl

1.3,2-dioxiborolane.

2- (beta-diethylaminoethoxy) -4,4,6-trimethyI-

1,3,2-dioxaborinane,

2- (beta-dimethylaminoethoxy) -4,4,6-trimethyl-

1,3,2-dioxaborinane,

2- (beta-diisopropylaminoethoxy) -

1,3,2-dioxaborolane,

2- (beta-dibutylaminoethoxy) -4-methyl-

1,3,2-dioxaborinane,

2- (beta-diethylaminoethoxy) - 1,3,2-dioxaborinane,

2- (gamma-aminopropoxy) -4-methyl-

1,3,2-dioxaborinane,

2- (beta-methylaminoethoxy) -4,4.6-trimethyl-

1,3,2-dioxaborinane.

2- (beta-ethylaminoethoxy) 1.3.6- trioxa

2-boracyclooctane,

2- (Gammadimethylaminopropoxy) -1.3,6,9-tetra-

oxa ^ -boracycloundecane.

? - (Beta-dimethylaminoethoxy) -4- (4-hydroxy-

butyl) -]. 3.2-dioxaborolane and

40 the implementation test
Lactic acid. B201 and neopentyl glycol.

It is a series of amino acid esters containing amino groups known. Many of them are described in US Pat. No. 3,301,804 and 3,257,442, for example. Man can be prepared by adding at least one mole of boric acid (or an equivalent amount of boric oxide) converts three moles of alcohol, at least one mole of the alcohol being an amino-substituted alcohol. Man füh.'t the implementation usually in such a way that the starting materials are refluxed and Removal of the water that has formed is boiling.

To convert the amino salts with the epoxy compound the two components are added at a moderately elevated temperature, for example at one temperature between 70 to 110 "C, together. If one tertiary amine is used, one can, according to a less common embodiment, the amine add to the epoxy compound and to the mixture of both those for the preparation of the desired salt If necessary, add the acid used later in the solubilization stage. Using a Solvent is not necessary, although a solvent is often used to improve the reaction to be able to control. As solvents are aromatic hydrocarbons and monoalkyl ethers of the ethylene

glycols suitable. The quantity ratio / wipe the Aminosil / and the epoxy compound can vary. The optimal proportion is determined by the type of raw materials used in each case. In the As a rule, 1 part by weight to 50 parts by weight of the salt is used per 100 parts by weight of the epoxy compound. manure. The quantity ratio is usually based on the nitrogen nic-ngc, which normally / wipe 0.05 to about 16 percent by weight of the total weight of the amino salt and the epoxy compound. There the amino salt with the epoxy groups of the epoxy resin to form an epoxy group-containing resin reacts, must be the stoichiometric amount of the used Amine must be less than the stoichiometric equivalent of the epoxy groups present. so that is Har / an average of one epoxy group per molecule contains.

The starting materials, their proportions and the

Rr »; il <tinn <.hprlinCTiinapn <.nllipn n:» rh Rirhtlininn tinw; ihlt

prevent the cm gelling of the product and are known to the person skilled in the art. For example, no extremely severe reaction conditions should be used will. Similarly, compounds with reactive substituents should not work with Epoxy compounds can be used with these substituents under the given conditions could react adversely.

That contained in the dispersions according to the invention Epoxy resin can be crosslinked to a certain extent. However, it must be in certain organic Solvents remain soluble and heat-curable. It is essential because of its epoxy content and characterized by its content of chemically bonded quaternary ammonium groups.

If at least part of the salt / acid with a Dissociation constants of more than 1 ■ IO 'are used, one needs the product to produce a no solubilizing agent to be added to a suitable aqueous electrically depositable preparation, although one as desired an acid or an acidic agent as can use solubilizing agent. Using boric acid salts and boron compounds of the above Kind in the absence of a salt of an acid with a dissociation constant of more than 1 x 10 "for the manufacture of the Har / cs used, one can Preparing dispersions of the type according to the invention by adding such an acid, whereby the stronger acid replaces the boron compound in the Har / and the boron compound, which is essentially one forms undissociated boric acid in an aqueous medium remains and is at least partially deposited with the resin.

The acids present in the dispersions according to the invention as partners of the quaternary ammonium groups with a dissociation constant. which is greater than I · 10 ⁵ have a stabilizing effect on the resin, since the epoxy resin tends to polymerize further on storage under strongly alkaline conditions. In some, the acid also helps the resin to dissolve to a greater extent. Moreover, it is desirable to adjust the coatings from an acidic or slightly basic solution, for example at eienm pH-value between 3 and 8.5, electrically deposit and around the desired pH, the _Ü5 addition of an acid is often useful.

If a carboxylamine is used to make the epoxy resin, the resin will contain a dur. η d-.c Reaction between the quaternary group formed and the carboxyl group present Zwitterion or inner salt. Here, the carboxyl group must have a dissociation constant that I · 10 - 'exceeds. The resin obtained is an inherently soluble product; h it takes to make it soluble make, not the use of a special remedy.

A coupling solvent is expediently added to the electrically depositable preparations. Through this one can improve the appearance of electrodeposited films. As such solvents are Hydrocarbons, alcohols. Suitable for esters, ethers and ketones. Preference is given to using monoalcohols. Glyc «lc and polyolc as well as ketones and ether alcohols In particular, the coupling solvents are isopropanol, butanol, isophorone. 4-methoxy-4-methylpentanone-2. Ethylene and propylene glycol. the monomethyl ether. Monoäthyläthcr and Monobutyläther des Ethyl glycol. Called 2-ethylhexanol and ethylene glycol monohexyl ether. The coupling solvent currently preferred is 2-ethylhexanol. The amount of solvent is not essential to the invention in the strictest sense. Generally applies the dispersant in an amount of 0.1 to 40 percent by weight, preferably 0.5 to 25 percent by weight at.

Even if the dispersions according to the invention contain the ungelled epoxy resins with quaternary ammonium groups contained essentially as the only resin component, it is often used for improvement and to modify the appearance and / or the properties of the film obtained, the electrically depositable preparation non-reactive and reactive substances or resins such as Plasticizers, for example N-cyclohexyl-p-loluenesulfonamide. Ortho- and paratoluenesulfonamide. N-Ethy! Ortho- and N-Ethylparatoluenesulfonamide, aromatic and aliphatic polyether polyols, phenolic resins, for example phenolic resins containing allyl ethers, liquid epoxy resins. Tetrakis- (2-hydroxypropyl) -äthylendnmin and polycaprolactones; Triazine resins, for example melamine resins and benzoguanamine resins, in particular ren their alkylated formaldehyde reaction products: Urea-formaldehyde resins, acrylic resins, polyesters containing hydroxyl and / or carboxyl groups and to add hydrocarbon resins.

In a preferred embodiment contains the aqueous dispersion according to the invention as a resinous material other than the non-gelled epoxy resin with quaternary ammonium groups a melamine formaldehyde resin or a urea formaldehyde haiz in lower amounts than the epoxy resin.

Other additives are esters, for example

Butyl benzyl phthalate, dioctyl phthalate,

M ethylphthalylethyl glycolate,

Butyl phthalyl butyl glycolate,

Cresyl diphenyl phosphate,

2-ethylhexyldiphenyl phosphate,

Polyethylene glycol-200-dibenzoate and polyester

and2,2,4-dimethylpentanediol monoisobutyrate,
called.

In most cases, the resin preparations are also given a pigment and, if necessary, one Oxidation inhibitor, a surface treatment agent or a wetting agent such as a commercially available one containing a hydrocarbon oil Diatomaceous earth and glyco-substituted acetylenes.

Sulfonates, sulfonic acid camides and alkyfphenoxypolyoxyalkylene alkanols to. The pigments used are those of the conventional type, for example Iron oxides, lead oxides, slronliumchromal, soot, titanium dioxide, Talc and barium sulfate, as well as color pigments such as cadmium yellow, cadmium red and chrome yellow.

When using the dispersions according to the invention These preparations are used for the electrical coating of electrically conductive substrates an electrically conductive anode and an electrical conductor (ends Brought into contact with the cathode, the surface to be coated serving as the cathode. When the current flows between the anode and the cathode is deposited in contact with the bath containing the coating compound A firmly adhering film of the coating compound forms on the cathode.

The conditions under which toarhctiri vuirrl ^ during the electrical deposition with the dispersions according to the invention are generally those which are used in the electrical deposition of coatings of a lesser nature. The voltage applied can fluctuate greatly and, for example, wipe I volt to several thousand volts. normally, the voltage between 50 and $ 00 volts. the current density is usually between 1.0 A and 15 A per 929 cm ^2. It tends during the electric deposition to lower.

The resin freshly deposited on the cathode contains quaternary ammonium groups. The one that forms the salt Acid group migrates at least in part towards the anode. The electrodeposited resin contains lerner boron bound to the basic groups. The amount bound to the deposited film Bors grows depending on the number of basic groups in the concentration and the basicity of the basic groups with the concentration of the boron in the bath until a degree of saturation is reached.

The film, even if it can be crosslinked to a certain degree, remains in certain organic Solvents soluble.

The dispersions according to the invention can be used for coating conductive substrates of any type be used. Metals such as steel and aluminum are particularly suitable as substrates. Copper and Magnesium. After the deposition, the coating is hardened, usually at an elevated temperature. Man now hold it at a temperature between 121 and for 1 to 30 minutes for this purpose 260 ° C. During the hardening, especially if this takes place at elevated temperature, at least a substantial part of the quaternary ammonium base is broken down into tertiary amino nitrogen. This contributes to that Crosslinking of the coating, which after curing is infusible and insoluble. The presence of Boric acid in the film increases the rate of crosslinking and lowers the temperatures at which a desired degree of hardness can be achieved in a commercially acceptable time can and leads to coatings of greater hardness and corrosion resistance.

The epoxy groups can be determined by the well-known pyridine hydrochloride method. One A description of this method can be found, for example, on p. 242 of the »Quantitative Organic Analysis Via Functional Groups «by S i g g i a, published in 1963 by John Wiiey & Sons, in New York is.

The total amount of those present in the polymer basic groups, d. H. of the quaterniti'un groups and the amino groups can be determined on another resin sample. Usually the Harz.probc neutral. If the I larz is basic, it should

Sample of an amount known as salt in the pot any acid present can be neutralized. If the acid present in the resin as a salt is a weaker acid than HCI is. is the resin with HCI titricri and with Sodium hydroxide in an automatic titration device! ';

ίο z.backiitricri. By titrating with HCl, the Total amount of base groups present while going through the back litricren with sodium hydroxide separates the quaternary groups from the amino groups. An analysis that is typical for this. leads

For example, you can do this in the following way: Man carries out a 10 ml sample of approximately 10% solids Containing deposition baths with the pipette in 60 ml Tetrahydrofuran and then titrate the sample with 0.1

th acid is the set of quaiernary groups and of the amino groups equivalent. The sample is titrated then back with 0.1 n-nainum hydroxide, so that a Titration curve with several end points is created. In this typical example, the first corresponds to the endpoint

2s excess hydrochloric acid. When titrating with HCI the second end point corresponds to the neutralization of the weak acid, for example lactic acid, and des Amino hydrochloride. The volume difference between the two endpoints denotes the volume

\ o the standard base, which is equivalent to the weak acid and thus to the amine content of the sample.

When using a solvent such as propylene glycol, for example together with tetrahydrofuran, In order to keep the sample homogeneous, the boron present also has a titrating effect, since it interacts with the Propylene glycol forms an acid complex. Boric acid differs under the conditions mentioned from the weak acid, for example lactic acid, through a further neutral point in the pHTitra tion curve. | c depending on the strength of the amino group present, this appears either in that of the weak acid, such as lactic acid, or in the part of the titration curve corresponding to the boric acid.

Excess weak acid or excess amine salt can be titrated with in the deposition bath alcoholic KOH can be determined. For this purpose, a 10 ml sample of approximately 10% solids is carried out containing deposit bath with a pipette in 60 ml of tetrahydrofuran and titrated potentiometric with 0.1 π alcoholic KOH to the first end point. The amount of KOH consumed is the acid or the dem Amine salt equivalent in the sample. In the case of neutral preparations, titration with KOH determine the amount of amine present in the form of an amine salt, since the quaternary base is a strong one Base is not titrated.

If salts of strong acids are present in the sample, other methods must be used to reduce the acidity. and to determine amino groups as well as the quaternary groups. For example, if the resin is Hydrochloride of amines and quaternary hydrochloride groups, it can, for example, in a mixture of Glacial acetic acid and tetrahydrofuran are dispersed, whereupon the chloride with mercury-II-acetate one Forms complex and the sample to determine the total amount of amino groups and the quaternary Groups is titrated with perchloric acid. One

herev, in called diinhgeluhne titration of, ilkoholisi Her KOH gives the amount of amino groups present. because the quiitern.tren groups are one of the alcoholic KOII have comparable strength.

Boron can be determined by the method described in the RS Br .ι ma η in Volume 7. on pages 334 to 423 of the KDS η e! I and Hilton at John Wiley & Sons. Inc .. New York, published "Encyclopedia of Industrial Chemical Analysis" under the title "Boron Determination". The boron can be determined on a separated sample, for example by taking a! "I. The canonical deposit bath containing substance is introduced into the pipette in bO ml of distilled water, the pH is lowered to about 4 by the addition of a sufficient amount of HCl, the sample using an automatic titration apparatus of the Metrohm Potentiograph E-4 36or similar device with 0.1 normal Nalriumhydro Md uul urinary kiiiniTi makes the first neutral point of the pH Tilrationskurvc / solution by dip addition of 7 e mannitol acid and titrating up / um / wide Neuiralpunkl the pH titration curve fortsel / t. i / ie amount of The base consumed between the first and the long endpoint is the measure of the number of moles of the boric acid complex formed in the sample.

In the preceding part of the description, a procedure is shown as an example, according to which the Har / the dispersion according to the invention contained Groups can be determined according to quantity and type. Ir; In particular, the procedure can be used as a Adjust resin to be analyzed. However, it is general spoken, in accordance with the description for the exact coordination of the chemical contained in the resin fiii ·; p-.n a suitable method for each case bk

Raw materials

In the list, some starting materials are cha rocketed. those used in the following examples will.

741.6 parts of dimethylethanolamine are charged. 714 parts of lactic acid and 300 parts of toluene in a reaction vessel equipped with a thermometer, a stirrer, a desnllation device with reflux condenser and water trap and means / ui production of an inert gas cushion and heats the reaction mixture for 4 hours at 105 to 110 ° C. A total of 120 parts of water are added a refractive index of η 1,377. 245 parts of boric acid and 728 parts of neopentylglycol are then added and the reaction mixture is heated to 115 to 128 ° C. for about 4 hours, with a further 205 parts of water with a refractive index of π Ι.386 being collected the likely formula

(Il (>

\ (II (H. () ((H (II. ("H ₁

The product is used in the examples as a boron compound A denotes.

In several examples there are oxalkylene groups containing Monoalkoholc used by lim put of ethanol with ethylene oxide in the presence of potassium hydroxide as a catalyst. In the The following examples are "mono alcohol A" the reaction product of 5 moles of ethylene oxide and 1 mole of ethanol .j <; and "Mono alcohol B" is the reaction product of 10 moles of ethylene oxide and 1 mole of ethanol

Example I.

200 parts of a Lpoxyharzcs prepared from I pichlorhvdrin and v> bisphenol A with an epoxy equivalent of 210 to 335 and a molecular weight of 580 to 670 in a reaction vessel, put 58.5 parts of monoalcohol A. 2.3 parts of tin chloride and 28 parts of the dimethyl ether of Diethylnglycol is added and the mixture is heated to 145 to 150 ° C. for 3 hours. An epoxy compound modified by oxalkylene groups and having an epoxide equivalent of 890 is obtained Minutes, parts of 2- (13eta-dimelhylamino-ilht) -xy) -4-methyl-1,3,2-dioxaborinane are added, the temperature increasing to 92.degree. Then after 5 minutes with stirring, 1719 parts of deionized water are added together with formic acid in such an amount λ5 / u. that the solution assumes the pH value 4.4. A colloidal dispersion with a content of 9.1% non-volatile solids is obtained

B (iCll.i.

O CII ₁

According to analysis, none contains quaternary ammonium groups and boron The dispersion was unier the following conditions on steel electrodes:

Bath temperature 21.1 C

pH 4.4

Deposition time 180 seconds

Voltage 225 volts

Sirom strength 1.5 to 0.2 Amp

A permanent bond is obtained on the cathode Coating that is hardened at 204.4 C for 20 minutes. in the When analyzed wet, the electrodeposited film shows a quaternary borate content and quarantine hydroxide is in the hardened state the 0.0254 mm thick coating hard, smooth and firm. He hai cmc excellent resistance against acetone. Salts and alkalis

Example 2

You work according to Example I. used in the sub However, this was decided by an Alumimumkathodc Man obtained the same results as in Example I. dtirth deposit made upper / ug adheres firmly aluminum and other satisfactory properties.

Example 3

Use as epoxy resin! one in this example Including product from pichlorohydfin and bisphenol A mn with a molecular weight of hbt) to 7e0 imtt an Fpoxidäquivak'iii of 5 JO Ins JKO

030 2. (0/118

O 1

1 Λ%

445 files of this Hur / es with 12% of monoalcohol B, 9.5 parts of 90 "/ niger formic acid and 63 parts of diethylene glycol dimethyl ether ν SiuiuUn at 150 to 155 ° C. are used. 16.3 parts of 2- (beta-dimethylaminoathoxy) -4-methyl-1,3,2-dioxaboiinane are slowly added to 200 parts of the Umseuungsproduktes obtained, which has an epoxide equivalence of 737. By adding formic acid and Wjismt, m.in produces a solution with a pII value of 4% and a solids content of 38% from this mixture. From this solution, coatings with suitable properties are obtained by electrical deposition.

Example 4

Example 3 is used in the same way here / u but monoalcohol A and acidifies the reaction product with acetic acid to a pH value from 5.6 onwards, coatings are obtained from the solution equally good properties.

Example 5

2500 parts of an epoxy resin are made from the Art. As it is also used in Example I. 441 parts Monoalcohol A and 49 parts of 40% formic acid an epoxy compound containing oxalkylene groups with an epoxy equivalent of 642. One sets 325 parts of this modified epoxy compound at 70 C in the course of 20 minutes a solution of 37.8 Divide the 1 MoI boron oxide (BjOi). 2 moles of dietary glycol and 2 moles of dimethylethanolamine produced Boresters too. This ester is probably 2- (beta-dimethylaminoethoxy) -1.3.6trioxa-2-boracvclooctane from the formula

(II. (H

W (i (ΊΙ. (Il \

(II. <IL

• A mixture of solvents is used as the solvent 37.8 files butyl diethyl glycol acetate and 26.4 parts fsophorane. After completing the fsierzugabc. through the the temperature rises to 90 C, the heating Continued for 2 minutes. Then 89.5 parts of deionized water and 50% strength aqueous acetic acid are added such an amount that a solution with a pH value of 4.6 is formed. One makes from the glycolic acid solution electrodeposited and cured under the conditions set forth in Example I these 20 minutes at 191 ° C. The result is a firmly adhering, hard, flexible and shiny cover train. which has high resistance to acetone.

Example 6

One uses one of 117 parts of the öxalkylcrHHö * difizierlcn epoxy compound according to Example 5 and 55.5 parts of 1 mole of boron oxide and 2 moles of dimethylethylamine and 4 moles of n-hydroxanol obtained oil produced reaction product and acidified this with acetic acid to pH 4.5. At the Bofestef it is probably the Bem-dimethylaminoethyl-di-n-hexylborate from the formula

("II

(..Il

W O (II.C HN

Ml,

(II,

From the with acetic acid to a pH value of 4. ■ acidified reaction product is obtained k'.ir. aqueous solutions.

Example 7

The boron ester used in this example is prepared from 3 mol of 1,3-butanediol, 3 mol of 2-ethylaminoethanol and 1.5 mol of BjOi. This HsIc ^- is probably 2 (beta-ethvlaminoaihoxy) -4 methyl 1.3.2-dioxaborinane of the formula

H.

(Π O Il

(IL η (KII- (Ii. \ (Ιι, (ιι.

(II. O

It also produces an epoxy compound. that you 2000 parts of a obtained by the reaction of epichlorohydrin and bisphenol A Epoxyhar zes with the epoxy equivalent 225 to 290 with 175 parts Polypropylene glycol (molecular weight 425). 150 parts Isophorone and 2.8 parts of dimethylbenzylamine

is 6 '/ 4 hours at 108 to 117 C and that Implementation product with 1.1 parts of 90% formic acid neutralized. It has. Calculated on a 100% substance basis, an epoxy equivalent of 665 You then put 200 parts of the epoxy compound with 17.4 parts of the boron ester in the previous one Examples described way around and makes from the reaction product with water and 50% aqueous Formic acid cmc solution with a pH value of 4.45. It is made out of solution by electrical deposition

4t, coatings and cures them for 20 minutes at 196 "C. The coatings are smooth and glossy and resistant to solvents.

Example 8

In this example one uses one of 2 moles!.? Butanediol. 2 moles of J amino-1-propanol and 1 mole BjOi manufactured boresters from likely formula

( H,

(Il O

Λο (II. I! O (ll _, (II. (HMI.

CH, O

and one through the reaction of 2000 parts of the 6s epoxy resin according to Example 7.825 parts of Cclyathyleneglycöl (Molecular weight 400), 725 parts of isophorone and 14 parts of dimethylbenzylafnine and uses the two components in the

21 63 14

Ratio of 70 parts of the epoxy compound (80% Solid content). One brings the Umseuungsprodukt through the addition of Was-.iT and formic acid in Solution and establishes from this solution by electrical Deposit coatings. the ones after the hard party adhere to their records.

Example 9

In this example one uses one of 2 moles of boric acid, 2 moles of neopentyl glycol, and 2 moles of glycolic acid * and 3 moles of dimethylethanolamine produced boron ester, which is the likely formula

(11,

CU, C) H ₁ C- CC ^- H ₁ B Ο CIW O CH, CH ₂ N

CU ₂ C) CH,

has and at least an ucrmue amount of that of the probable Furmcl

I CW, OO CD

(H ₁ C CH ₁ B

; CH, O O CH,

CH,

N CTI, CH, OH

Πί,

contains corresponding salt.

65 parts of the ester are added in the form of a 60% solids solution in isopropyl alcohol 500 parts of the epoxy compound according to Example 12, this in the form of a solution containing 80% solids. around. itcllt from the reaction product with water and Formic acid is a clear solution with a pH of 7.8 here. applies this to 230 volts through electrical deposition on the cathode and hardens it Cber / ug 10 minutes at 204 C. The uber / ug is hard, flexible and resistant to l.osung'.miii '* !.

Albeit with those described in these examples Preparations associated with the particular benefit. that they. electrodeposited as described can, one can also convcniioncl Apply ler procedure. Furthermore, the / hastiness, although they are usually neutralized to an acidic pH, in many cases they are not neutralized One can furthermore also certain reaction products, which in process / ur electrical Deposits are less desirable, apply different ways and make coatings that work for many Purposes are suitable. These embodiments indicated here are used in the following examples described in more detail.

Example 10

A mixture of 280 files is heated by reacting epichlorohydrin with polypropylene glycol obtained epoxy resins ·, with an epoxy equivalent of 186 and a molecular weight of 372 and 342 parts of bisphenol A 10 hours at 140 to 150 C mi! 11 parts of 85% formic acid and sets 547 parts of the product obtained with 1070 parts of Kpichlorhyclrin in the presence of sodium hydroxide. After removing excess epichlorohydrin, the reaction product obtained is an epoxy compound, which contains oxalkylene groups in the polymer chain and has an epoxy equivalent of 528.

It constitutes Epoxyverbindurig mixed with 42 parts Äthylenglycolmonobutyläiherac2tat with 30.4 parts of 2- (Beta-dimethylaminoäthoxy) -4-methyl-1,3,2-dioxaborinane in the manner described above and to the säuer ¹ Umsetz.ungsprodukt with aqueous acetic acid on the ÖH-Wefl 5.2. The colloidal solution obtained can be used with good results

Deposit JS electrically. It is the deposited on the cathode coating 30 to cure mimed a heat of 177 ⁰ C of. It then adheres firmly to its base and, although it is somewhat soft, has good resistance to solvents.

\ o If the IJmsetzu.'gsprodukt contains little epoxy groups, it may happen that the preparation is not linked to the desired extent. In such cases it is often advisable to add another resinous substance to the preparation

is with the hydroxyl groups present in the reaction product or other groups respond. An amino aldehyde, for example, can be used as a coreactive resin resin, e.g. B. hexakis (methoxymethyl) melamine or a other melamine-formaldehyde resin or .. · '· urea-formaldehyde resin or use another resin containing reactive functional groups. It can In some cases it may be useful to add a small amount of an epoxy resin curing catalyst. This is explained in more detail in the following example.

Example 11

1770 parts of a liquid Lpychlorhydrin are used Bis-phenol A epoxy resin with a viscosity of 30 up to 70 poise and an epoxy equivalent of 193 to 203

so and 302 parts of bisphenol A in a reaction vessel for 45 minutes at 170 to 180.degree. C., cools to 130.degree. are as ⁿ n 790 parts of polypropylene glycol 600 to weight and holds the Reaktionsgemi'.ch at 130 C. until the molecular. at a 50% solids content in

5S a mixture of 90 parts isophorone and 10 parts Toluene measured, the viscosity of L-N according to Gardner · H oldt reached. The one for the general freak tion time to this point is approximately

5 hours. The reaction mixture is then cooled to 120 ° C. to neutralize the amine present

6 parts of a 90% strength solution of formic acid are added, the mixture is cooled further to 70 ^° C. and 318 parts of the boron compound A and 82 parts of isopropanol are added over the course of 20 minutes, the temperature being 70

6y increased to 90 ⁰ C. The mixture is then kept at 95 ° C. for 5 minutes, then 500 parts of water are slowly added and, as soon as the mixture is homogeneous. slowly 15.5 parts of a surface-active agent and 200 parts

Ie 2-ethylhexanol and then a further 840 parts of water.

The product contains 0.225 milliaqtiiv.i per gram learn quaternary groups, 0.213 milliequivalents of lactic acid and 0.228 milliequivalents of boric acid. <

Taking the product from a 10% solids aqueous bath at a temperature of 26.7 ° C and a voltage of 250 volts 90 seconds Electrically deposited on phosphated steel disks, then rinsed and hardened for 30 minutes at 177 C, one obtains. ,, a 0.01524 mm thick film of a hardness exceeding the pencil hardness 6 H. The film is great resistant to acetone and salt mist.

Example 12 ¹ ^

Man full! Place 336 parts of the epoxy resin from Example ii and 113 parts of bisphenol A in a reaction vessel equipped with a stirrer, a thermometer, a condenser, a device for introducing inert gas and a heating device, and heats the mixture to! 80 ⁰ C, wonac ' . the reaction is exothermic. The reaction mixture is kept at 180 to 190 ° C. for 45 minutes, then cooled to 110 ° C. are then 40 parts of isopropanol / u. cools further to 80 C. ·; over the course of 20 minutes at a temperature between 80 and 90X, a solution of 42.7 parts of 2- (beta-dimethylaminoethoxy) -4 · methyl-1.2.3-dioxaborinane in 10.7 parts of isopropanol is added. holding the mixture for 5 minutes at 94 ° C., and thereafter 107 parts of water \ "in the course of 4 minutes / u. A clear, brown resin solution is obtained.

A solution of 2.4 parts of an antifoam agent ¹ ) in 33 parts of 2 ethylhexanol is added to the solution at 74 ° C. and it is adjusted to a solids content of 100%. They have the epoxide number 752 and the hydroxyl number 275.

Example 13

40

The following electrodeposable preparations are made:

A 272 parts of the resin solution obtained according to Example 12 are used 1630 parts of deionized water. With difficulty, a 4s milky dispersion is formed that contains 9.36% solids and has a pH of 9.3. This preparation has a breakdown voltage of 400 volts at 26.7'C. If one such preparation at a bath temperature of 36.7 C 90 Secunder, long lblage at a voltage of 250 volts so on zinc phosphate-treated Slahlplatlen ^r t. a wet, rough film is obtained that is rough and blistered even after curing for 25 minutes at 177 ° C

According to the analysis, the deposit bath contains per ss Milliliters

0.0374 milliequivalents of quaternary base.

0.0038 milliaquivalcnic of amino groups and

0.0444 milliequivalents of boric acid B is prepared from 272 parts of the according to Example 12 fto resin solution obtained, 10 parts of 85% lactic acid and 1630 parts of deionized water electrically depositable preparation that contains 10.3% solids and has a pH of 6.3. That Resin can easily be converted into an almost clear colloid disperse. The preparation has a breakdown voltage of 400 full at 26.7 ° C. One draws up from it a steel slat treated with / mknhosnrial electrical deposit a (Jber / ug fro and whore this 25 minutes at 177 C. The obtained smooth and The solvent-resistant coating has a lead hardness of 6 11. According to the analysis, it contains Deposition bath per milliliter

0.0419 milliaquivalents lean quaternary base 0.0013 milliequivalents of amino groups.

0.0437 milliequivalents of lactic acid and

0.0484 milliequivalents of boric acid. The particle size is determined by the light scattering method according to A and B. In a light source of 4,358 A. shows the dispersion A i-inu unit size of 560 Å and dispersion B has a particle size of 290 A. while in a light source of 5460 A the dispersion A has a particle size of 630 Å and the dispersion B shows a particle size of 300 Å.

Example 14

Adding to an Reaklionsgefa '* · όπ the beschiiebenen in Example 12 Type 1000 "! Rush t poxvhar / Bei play 11 and 335 parts Bispnenol A and the mixture heated to 170 C. and the reaction proceeds exothermically. One obtains the reaction mixture · ΐ5 minutes at 18 (i to 185 C. then cools to 117 C. gibl then } 2j file isopropano! / ti. cools further aiii HO C. Then gives a solution of 230 parts of the boron compound A in isopropano containing 80% solids ! in the course of 20 minutes at a temperature of 80 to 90 C / u. the mixture holds for 5 minutes at a temperature of 90 to 94 C and then sets in the course of 5 minutes 375 parts of deionized water and then, at a temperature of 70 C. A solution of 7b parts of an antifoam agent in 100 parts of 2-ethylhexanol / u The clear brown resin solution obtained has adjusted to a plastic content of 100%, the epoxy number 1125 and the hydroxyl number 29.5.

272 parts of the resin solution thus obtained are added to 1630 parts of anti-ionic water. The Harz IaRt sith disperse lightly to a blue-green colloidal solution that contains 9.74% solids and one The preparation has a breakthrough stress of 410VoIl at 26.7 ° C. Man coats zinc phosphate treated steel plates with it by electrodeposition for 90 seconds at a voltage of 250 volts and a bath temperature of 29.4 C and subjects the film obtained 25 minutes of heat treatment at 177 ° C. A slightly textured, smooth and shiny one is obtained Coating According to the analysis, the deposit bath contains per milliliter

0.0379 milliequivalents of quaternary base.

0.0011 milliequivalents of amino groups.

0.0374 milliaquivalents of lactic acid and 0.0392 milliequivalents of boric acid

Example 15

Filling e ¹ "mixture of 500 parts of hpoxyhar zes of Example 3 and 65 parts of isophorone in a RcaklionsgefäD from that described in Example 12 type and GIBL this mixture in the fluidized. 20 minutes in a beginning at 55 ° C and at 76 ^r C. A solution prepared from 32.2 parts of dirricylethyl alcohol, 2.8 parts of boric acid, 15.5 parts of isopropanol and 20 parts of deionized water is put in at the end of the temperature range C. After the end of the reaction, the control system is wrapped in 5 miniatures

at 76 to 85 C. Dnmich set / l trum in the course of 4 minutes 287 parts of deionized water / u. The solution is obtained at a temperature of 62.degree According to the analysis, they have a plastic content of 100% adjusted Har / Iösung the Kpoxid / ahl 073 and the hydroxyl / ahl93.

The solution is made up of 215 parts 1200 parts of enlionized water create a deposition bath with a pH value of 8.5 and a breakthrough span from 200 full ago. The films electrodeposited from this had are rough and blistered. After Analysis contains the bath per milliliter

0.0602 milliequivalents of quatcrnarcn and
0.0657 milliaquivalcnican boric acid.

The electrically remote F-'ilni abides, like that Analysis shows 0.0% 7 milliäqtiivalenlc per gram quaternary borate groups. The wet film contains 63% solids.

3 parts of an 85% lactic acid and 1200 parts anti-ionized water a deposit bath with a pH value of 8.5. For this bath you can leave the above conditions by electrodeposition films of better appearance produce that during the treatment in the I strand / u cure even coatings. According to the analysis, the deposit bath contains per milliliter

0.0617 milliequivalents of quaternary base.

0.0337 milliequivalents of lactic acid and

0.0693 milliequivalents of boric acid
Analysis shows that the electrodeposited wet film contains 0.1474 milliequivalents of quaternary borate groups per gram. Lr has a solids content of 66.9%.

Example 16

The reaction vessel used in Example 12 is added type described 400 parts of the F.poxy resin from Example 11 and 100 parts of bisphenol A and heated the Mixture to 170 "" C. At this temperature the Reaction exothermic. The reaction mixture is kept at 175 to 184 ° C. for 45 minutes. cools to 155 ° C. gives Add 90 parts of isophorone and cool to 70 ° C. Hereinafter this reaction mixture is called the starting resin.

It is added in the course of 20 minutes within a period beginning at 70 ° C. and ending at 90 ° C. A solution of 55 parts of the boron compound A in 14 parts of isopropanol is maintained at a temperature interval Mixture then 5 minutes at 90 to 96 ° C and continues to use 295 parts of deionized water Course of 10 minutes too. The resin solution obtained has a clear and calm state when stirred pearlescent appearance. According to the analysis, the resin solution has adjusted to a solids content of 100% the epoxy number 578; and the hydroxyl number 141.

A scale bath is made from 215 parts of this starting resin and 1285 parts of deionized water with a pH of 6.7. This bath has a bath temperature of 25 ° C and a voltage of 300 volts a throwing power of 7.62 cm in 90 seconds. This bath is stored at a bath temperature of 25 ° C. a voltage of 20OVoIt and a deposition time of 90 seconds films on with Zinc phosphate treated steel plates and then subject them to a for 30 minutes Heat treatment at 177 to 193 "C. The films obtained have a thickness of 0.01 mm and the Blcistiflhärtc 6 II plus. They are smooth and shiny. To The analysis shows that the sedimentation bath is per milliliter

0.0293 milliequivalents of quaternary bases,

0.0280 milliequivalents of lactic acid and

0.0311 milliequivalents of boric acid.
One gives to the! The mixture holds 55 parts of 2- (betn-dimethylaminoethoxy) -4-methyl-1,3,2-dioxaborihah over the course of 20 minutes within a temperature range beginning at 70 ° C. and ending at 89 ° C. 5 minutes at 89 to 100 and 285 parts of enlionized water are added in the course of 4 minutes From 215 parts of this resin solution and 1285 parts of deionized water, a deposit bath with a pH value of 8.9 is made. This bath has a throwing power of 5.4 cm. This bath is stored at a temperature of 2 ° C. and a voltage of 200 full and a deposition period of 90 seconds, films are electrically deposited on zinc phosphate treated steel plates and subjected to heat treatment. The films obtained have a thickness of 0.0063 to 0.0076 mm and a pencil hardness of 6 H plus. After analysis, the Abla contains bath per milliliter

0.0420 milliequivalents of quaternary bases and

0.0510 milliequivalents of boric acid

Example 17

\ o is filled in 1005 parts of the epoxy resin of Example 11 and 339 parts bisphenol A into a Resktionsgefäß from that described in Example 12 Art. the mixture is heated to l80 C. ^r holds it for 45 minutes at 180-188 'C. it is cooled to 120 "C. uses 114 parts of isopropanol

\ f, to. cools further to 79 ° C. Then, in the course of 20 minutes, at a temperature rising from 79 to 93 ° C., 141 parts of a 75% solids solution of dimethyl ethanolamine lactate in isopropanol are added. holds the reaction mixture for a further 2 minutes at 93 to 97 ° C. and then adds 425 parts of deionized water over the course of 4 minutes. At the end of this time, the reaction lake mixture has a temperature of 75 ° C.

By adding a solution of 7 parts

Antifoam is obtained in 90 parts of 2-ethylhexanol one is a clear, yellow, in the following as the starting resin designated resin solution. With a solids content of 100%, the resin has the epoxy number 1085 and the Hydroxyl number 233.

so one makes from 272 parts of the starting resin and 1630 parts of deionized water prepared a 10% solids sedimentation bath at pH 6.7. A voltage is obtained from this bath by electrical deposition at a bath temperature of 27 ° C of 250 volts and a deposition time of 90 seconds on steel plates treated with zinc phosphate a film of uniform structure. After half an hour of heat treatment at 177 "C, the now glossy film a thickness of 0.011 mm and the pencil hardness 6 H. One from this bath at 300 / olt but otherwise produced under the same conditions by electrical deposition and in the heat treated film is 0.0127 mm thick and has a pencil hardness of 6 H.

One makes one from 272 parts of the starting resin. iö3ü parts deionized water and 6.6 parts Boric acid is another bath with a pH of 6.4. Films that one unler rirn out of this bathroom

21

above conditions electrically on with /.inkphosphat treated steel plates a thickness of O.öl 27 mm with a tension of 25OVoIt and a thickness of 0.0154 mm with a Voltage of JOO volts. In both! - "they all have Film the liability 7 11 plus.

Mcis ρ ι el 18

2070 parts of the epoxy resin from Example 7, 875 parts of a polypropylene glycol with an average molecular weight of 400 to 425 and 7 parts of dimethylethanolamine are filled into a cm reaction vessel of the type described in Example 18. The mixture is heated to IJO to 138 ° C hold it at that temperature for five and a half hours. At the end of this time, the reaction product has. measured on a 50% solids solution of the reaction product in a 90% mixture of isophorone and toluene, a Gardner-Holdt viscosity of H. 4.2 parts of 90% formic acid are then used to neutralize the dimethylethanolamine catalyst to. The product obtained has an epoxide equivalent of 800 and a hydroxyl number of 269. It is referred to below as the starting resin according to Example 27.

A mixture of 25 parts of 1-amino-2-propanol is added to 500 parts of this starting resin in the course of 20 minutes within a temperature interval beginning at 70 ° C. and ending at 89 ° C. 35.3 parts of 85% lactic acid and 14 parts isopropanol. the reaction mixture is allowed stand for 5 minutes, with the temperature at 97 ¹ C increases, and then sets by the addition of 315 parts of deionized water produces a pearlescent dispersion. the product contains, after the analysis per gram of 0.159 milliequivalents of quaternary base groups 0.133 Milliequivalents of Ämin and 0.327 milliequivalents of lactic acid.According to analysis, the resin has adjusted to a solids content of 100% and calculates the epoxide / ahl 1590 and the hydroxyl / ahl I 31.

Example 19

1890 parts of the epoxy resin from Example 11 and 180 parts of bisphenol A are poured into a reaction vessel of the type described in Example 12, the mixture is heated to 170 ° C., after which the temperature rises exothermically to 182 ° C. and the mixture is kept between 180 for 45 minutes and 190 ° C, cools to 130 ⁰ C. is a mixture of 875 parts of polypropylene glycol 425 and 8 parts of dimethylethanolamine, heated to a temperature between 130 and 137 ° C and held for about five and a half hours at this temperature to the reaction mixture A solution containing 50% solids in a ratio of 90:10 was measured as a mixture consisting of isophorone and toluene to give a Gardner-Holdt viscosity of J + 9.6 parts of 90% formic acid were then added.

Are then added to 500 parts of the cooled to 70 ⁰ C the reaction mixture in the course of 18 minutes in a beginning at 70 ⁰ C and ending at 90'C temperature interval of 18 parts of a boric acid. 25.3 parts of Dimelhyläthanolamin and 11 parts of isopropanol existing salt solution and then 276 parts of deionized water is added, the mixture keeps 5 minutes at 75 ⁼ C, and then add a solution YPN 2.7 parts of an anti-foaming agent in 34.5 parts of 2-ethylhexanol to. The analysis of the resin shows, based on a 100% residual plastic content, ile kpoxid / ahl 920 and the hydroxyl number 71.

One prepares the I lar / solution from 220 parts. 47.5 parts Butyl benzyl phihalate and deionized water Electrical dissipation barc containing 5.75% solids Preparation with the pH value 7.6 and coated from this at 250 volts and a bath temperature of 27 ° C for 90 seconds one treated with Ziiikphosphhal Steel plate by electrical deposition.

ίο The electrically storable bath contains after dei Analysis per milliliter 0.0074 milliequivalents of weak acid and 0.02) 5 milliequivalents of I3or The wet electrodeposited film was analyzed to contain 75.1% solids and more per gram 0.062 milliequivalents of quartz borate and 0.188 Milliequivalents of amine.

Example 20

11 35 parts of the epoxy resin from Example 11 are used with 108 parts of bisphenol A 50 minutes in one Reaction vessel from that described in Example 12 Kind around. are 525 parts of polypropylene glycol 425 and 4.2 parts of dimethylethanolamine. holds the mixture five and a half hours at I 30 to 137 C. around him. at a 50% solids solution in a 90:10 ratio of isophorone and toluene Mixture measured, a Gardner-Holdt viscosity to give of H + cools to 123 "C. set / · 5.1 parts 90% formic acid to, cools further to 7 ° C. sets also a mixture of 51.6 parts of dimethylethanolamine. 61.3 parts of an 85% lactic acid solution and 60.3 parts of neopenlyl glycol over the course of 20 minutes within a starting at 7 Γ C and at 79 C at the end of the temperature interval, the reaction then mix for 5 minutes at 79 to 91 ° C. and then add 1000 parts of deionized water Analysis showed the resin solution obtained, based on a solids content of 100%, to have an epoxide number of 1270. the hydroxyl number 116 and the acid number 0-. She will be in

_A o hereinafter referred to as the starting resin.

Mη η is made up of 433 parts of this starting resin. 95 parts of butylbenzyl phthalate, 19 parts of 2-ethylhexanol and 325U direct water to an eicKtnscn aDiageroare Preparation with a pH value of 5.6 and coated

^ ₅ steel plates treated with this preparation with zinc phosphate for 90 seconds at 250 volts and a bath temperature of 27 ° C by electrical deposition. The deposited film is subjected to heat treatment at 177 ° C. for 20 minutes. You get a smooth one.

shiny film of pencil hardness H.

From 435 parts of the starting resin according to this example, 95 parts of butylbenzyl phthalate and 8.9 parts are made 1 rimethoxyboroxine, 20 parts of 2-Ä thylhcxanol, 2 parts an anti-foam agent and 3250 parts deionized Water produces a white pearlescent dispersion with a pH of 5.6. One wears out of this Dispersion by electrodeposition for 90 seconds films at 250 full and a bath temperature of 27 "C on steel plates treated with zinc phosphate and then subjects the films for 20 minutes a heat treatment at I77 ° C. The films have one Thickness from 0.021 to 0.025 mm and a pencil hardness of 4 H plus. The dispersion has a deposit capacity of 6.83 cm.

According to the analysis, this deposit bath contains 0.0238 at a dissolution content of 9.2% per milliliter Milliequivalents of quaiernary bases; 0.0243 milliequivalents of lactic acid and 0.050 milliliters of boron.

Example 21

One sclzl in a reaction vessel of the type described in Example 12 is 1890 parts of a liquid Epoxyhafzcs.dascin polyglycidyl ether of bisphenol A inIl a viscosity and 100 to 160 poise and an epoxy equivalent of 185 to 192 and 180 parts of bisphenol A 45 minutes at 175 to 180 ° C to cooled aui i 30 "C ₁ are 875 parts PolypiOpylcnglycol (MG 425) and 7 parts of dimethylethanolamine to which Rcaklionsgemisch heated to 130 his 138 ⁰ C and keeps it 5 StUhdeh at this temperature to give it. on a 50% Solids-containing solution in a mixture consisting of isophorone and toluene in a ratio of 90:10 measured to give a CiardnerUoIdt viscosity of 11 +, cools to 12I ¹ C ". adds 4.8 g of 90% formic acid and cools further to 73 C. At this point the reaction mixture has the oxide number 763 and the hydroxyl number 348. KA ^ _n r _r t. * , i _nm DnnLi; or, s ™ cm! 'i furthermore a salt solution consisting of 106 parts of dimethylethanolamine, 129 parts of an 85% lactic acid solution and 53.9 parts of isopropanol in the course of 18 minutes at a temperature of 73 to 80 ° C., it lasts for 7 minutes at a temperature of 80 to 100 ^r C, add 500 milliliters of deionized water and a solution of 15.5 parts of an antifoam in 208 parts of 2-ethylhexanol and then another 960 parts of water. The resin solution obtained has. according to the analysis, based on 100% solids, the epoxide number 1460 and the hydroxide number 132.5. It is referred to below as the starting resin.

This initial resin is made from 220 parts. 47.5 parts of butyl benzyl phthalate and 1630 parts of water an electrically depositable preparation with a pH value of 8.5. were included from this preparation 250 volts and a bath temperature of 27 ° C for 90 seconds electrically on a film with zinc phosphate treated steel plates and then heat-treats the deposited film for 20 minutes at 177 ° C. A smooth, glossy film is obtained which has a thickness of 0.0165 mm and which Pencil hardness 2 H has. The preparation has a Deposits of 5.08 cm.

From 220 parts of the starting resin according to this example, 45 parts of butylbenzyl phthalate and 2 parts are made Boric acid and 1675 parts deionized water. which has a pH value of 5.7, and therefrom electrically deposits films on zinc phosphate treated steel plates in the above manner away. The film obtained after the heat treatment has a thickness of 0.0208 mm and a pencil hardness of 4 H plus. The preparation has a scattering power of 6.99 cm.

From 220 parts of the starting resin according to this example, 45 parts of butylbenzyl phthalate and 6 parts are made Boric acid and 1675 parts deionized water another preparation which, like the previous preparation, also has a pH value of 5.7. and stores therefrom, in the manner described above, films electrically on zinc phosphate treated steel plates away. The film obtained after the handle treatment has a thickness of 0.020 mm and the blcistiflhifte 5 h. The preparation has a throwing power of 7.30 cm.

B e i S ρ i e 1 22

1890 parts of the epoxy resin from Example 11 are used and 180 parts of bisphenol A in a reaction vessel of the type described in Example ^ for 30 minutes at 175

ίο to 180 "C around, adds 875 parts of polypropylene glycol 445, lowers the temperature to 130 ⁰ C, then adds 8 parts of dimethylethanolamine, heated to 130 to 140 ° C", holds five and a half hours at this temperature to allow the reaction mixture, Measured on a 50% solids solution in a mixture consisting of isophorone and toluene in a ratio of 90:10 to give a Gardner-Holdl viscosity of H +, the temperature then drops to II6 ° C. and gives

Q A Toil * »QfI OA irr ** Δ rnF» icpncäiir £ 7ij

ίο 500 parts of the resin solution obtained are used 15 parts of dimethylethanolamine in the course of 9 minutes at 60 to 70.degree. C., leaves a further minute at 73.degree stand, then add 17.8 parts of lactic acid in the course of 10 minutes at a temperature of 73 to 78 C, lets the mixture stand at 75 ° C. for 3 minutes 17.4 parts of ncopentylglycol are added, left to stand for 2 minutes at 7 ° C., 9.8 parts of boric acid are added, left at 75 for a short time to 77 "C and then add 30 parts of deionized water. The resin solution has after

jo analysis, based on 100% solids, the F.poxide number 1285. the acid number 16.4 and the hydroxyl number 107.8. she is referred to below as the starting resin.

440 parts of this starting resin, 95 parts of butylbenzyl phthalate, 19 parts of 2-ethylhexanol, 1.9 parts of an antifoam and 3250 parts of deionized water are used to produce an electrically depositable preparation, which is stored at 250 volts and a bath temperature of 27 ° C. for 90 seconds Electrically deposited a film on zinc phosphate-treated steel plates for a long time, and heat-treated the deposited film at 177 ° C for 20 minutes. A smooth, hard and glossy film is obtained that is 0.018 to 0.02 mm thick and has a pencil hardness of 4 H plus. 500 parts of the resin adduct according to paragraph I of this example 35 are added over 19 minutes within between 70 and 85 ° C lying temperature interval 18.6 parts of 85% lactic acid and 19.4 parts of triethylamine. The reaction mixture is left to ^{stand at 85 to 90 °} C. for 5 minutes. According to the analysis, it has an epoxide number of 2790 and a hydroxyl number of 105.

M an is made from 440 parts of this resin solution, 95 parts of butylbenzyl phthalate, 19 parts of 2-ethylhexanol, 1.9 parts an anti-foam agent and 3250 parts deionized Water produces an electrically storable preparation, stores from this preparation at 250 volts and one Bath temperature of 27 ° C for 90 seconds a film on zinc phosphate treated steel plates electrically and then subject the deposited film to heat treatment at 177 ° C for 20 minutes receives a smooth, shiny film that is 0.0127 to 0.0152 mm thick and has a pencil hardness of 3 egg.

Claims (7)

Patent claims: 1. Aqueous dispersion of a nichigelierien in Water dispersible epoxy resins *, which optionally May contain solvents, thereby characterized in that it consists of at least 1 to 25 percent by weight of an epoxy resin an epoxy group in the molecule and a content of chemically bound nitrogen of at least 0.05% in the form of a salt of a quaternary ammonium base and an acid with a dissociation constant of greater than 1 ■ 10 ·. 0.01 to 8 percent by weight Bur in the form of boric acid and possibly other common resinous materials, plasticizers, couple the solvents. Pigments. Oxidation preventers. Surface treatment rolls and net / average 2 WaUnge dispersion according to claim 1. characterized characterized in that the epoxy resin has a chemically bound nitrogen content of 0.05 to 16 percent by weight in the form of chemically bound nitrogen of a salt of a quaternary ammonium umbase and an acid with a dissociation con Stante greater than 1 10th possession :. i. Waßngi * dispersion according to claim 1 or 2, characterized. that the Lpoxyhar / is a polyglycidyl ether of a poly phenol. 4. Aqueous dispersion according to claim 1 or 2. characterized in that the epoxy resin is made from 1.1 methylene to fj-substituted hydantoin) has been V Aqueous dispersion according to Claim 1 or 2. characterized in that the Lpoxyhar / a is heterocyclic N.N diglyeidyl compound. b. Aqueous dispersion according to one of the claims 1 to 5, characterized in that the Lpoxvhar / additionally 1.0 to 90 Gewiehlsprii / eni Oxyulkvlcn contains groups. 7 Aqueous dispersion according to one of the claims 1 to b. characterized in that they are different hiir / like material a melamine formaldehyde h. or a llarnslofformaldehvdhar / in lesser Quantity as the epoxyhar / enlh.ilt H Use of the dispersion according to one of Claims 1 to 7 / um electrical coating of electrically conductive substrates