JPS60260664A - Manufacture of cathode-depositable electodeposition paint binders - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing cathodically depositable electrocoating paint binders based on and self-crosslinking reaction products of epoxy resin-amino-adducts with formaldehyde and phenols. . If necessary, formaldehyde and phenols may be partially substituted with formaldehyde-reactive amino compounds or substituted phenols (7) b) and oxidation products (9).

Cathodic deposition paint binders based on reaction products of Mannich bases and epoxy resins are disclosed in a number of references. German Published Patent Application No. 2033770,
No. 2620601, No. 2357045, No. 2419
No. 179, No. 2541801, No. 2554080,
According to Nos. 2,711,385 and 3,045,251, Mannich bases obtained from polyhydric phenols, secondary amines and formaldehyde react with epoxy resins.

The phenols, like the epoxy resins, are thereby subjected to various modifications, for example with semi-blocked diisocyanates, other phenols or other metal salts.

As can be seen from the cited references, this type of binder also has a resistance of about 19
Although it requires a stopping temperature of 0 DEG C., its resistance to salt water spray, for example, does not meet the requirements of actual use.

The product is accompanied by separation of formaldehyde and amines which have an adverse effect on the surroundings during crosslinking. Therefore, many of the improvements described in the literature do not serve to enhance film properties, but rather to reduce separated materials. For example, in the case of modification with semi-blocked diisocyanates, German Published Patent Application No. 255 (DE-O8)
As clearly disclosed in No. 4080, the isocyanate groups make little contribution to crosslinking and serve only to supplement free amines.

PCT International Publication No. WO83/D0872 (PCT
Publication A Wo 85100872)
discloses cathodically deposited electrodeposition paint binders obtained through the cocondensation of partially defunctionalized epoxy resins with phenolic resoles and the simultaneous or subsequent reaction of primary or secondary amines with epoxy groups. ing. An essential drawback in the production of these products is the need to produce phenolic resols, which is known to require considerable time and generate relatively large amounts of waste water containing phenol and salts. . Salt residues remaining in the resin can be problematic for electrodeposition.

If the epoxy resin-amino-adduct with secondary amino groups is formaldehyde or a substance that separates formaldehyde under the reaction conditions, and phenols, optionally formaldehyde-reactive amino compounds or amino-alkylation of substituted phenols. If condensed in one reaction step with phenols partially substituted by the product,
It has now been discovered that cathodically depositable electrocoat binders are obtained which provide optimum conditions for corrosion protection at stopping temperatures of 150 DEG to 160 DEG C. and which allow production in a simple manner.

The present invention therefore relates to a method for producing cathodically depositable electrocoat binders based on modified epoxy resins. This method uses at least two epoxy groups and 180
to 1000 epoxy equivalent weight (epoxy equi
0 of primary monoalkylamines and/or primary alkylene diamines and/or primary/tertiary alkylene diamines per individual available epoxy group at temperatures between 50°C and 120°C. .6 to 1.0 moles of primary amine groups,
and 0 to 0.4 moles of carboxylic compound or secondary amine per available epoxy group until practically zero, and the resulting epoxy resin-amino-adduct is reacted at a temperature of 50 to 90°C. , calculated per mole of NH-groups, from 0.5 to 1.0 mol of aminoalkylation products of mono- or polynuclear phenols and/or -substituted or trinuclear phenols, or optionally partially.

Formaldehyde of the urea, melamine or guanamine type - 0.25 to 0.9 per reactive site. Preferably 0.6 to 0.8 mol of form, 1 (aldehyde) is reacted, and the reaction product is then partially or totally neutralized with an acid and optionally a water-tolerant organic solvent (water-tolerant organic solvent).
tolerantorganic 5olvents
) is characterized by dilution with added water.

The method of the present invention is characterized by a simple method of implementation. A notable advantage is that no unusable by-products are generated.

The coating compositions prepared in a suitable manner from the binders prepared in accordance with the present invention have outstanding performance with respect to electrodeposition and the bath material formed therefrom.
al) shows remarkable stability. The reason is believed to be the resistance to hydrolysis of the molecules formed through direct crosslinking between the epoxy resin, amine and phenol. At low stopping temperatures, such as 150 DEG C., the product yields films with optimal corrosion resistance even without the combined use of catalysts. The amount of decomposition products that separate during stopping is small and consists essentially of water and a small amount of formaldehyde.

Suitable epoxy resins for carrying out the present invention are commercially available di- or polyepoxy compounds obtained through the reaction of polyhydric phenols, particularly bisphenol A or shrimp chlorohydrin, with phenolic novolacs. If necessary, other epoxy resins can be used, for example resins based on polyols. Typical products are known to the specialist and are disclosed in many documents.

Preferred epoxy resins for the process of the present invention are based on phenolic novolacs or bisphenol A having an epoxy type of 180 to 1000.

In the first reaction step, the epoxy resin is reacted with a primary amine, preferably in the presence of an aprotic solvent, to form an epoxy resin-amino-adduct having secondary amino groups.

per available epoxy group of the epoxy resin, 0.6 to 1.
0 moles of primary amino groups are used, which amino groups are either primary monoalkylamines, preferably amines having 4 or more carbon atoms in the alkyl group, or primary alkylene diamines. or diamines having a tertiary amino group in addition to a dialkylamino group, for example, in addition to a dialkylamino group. Preferred representative examples of this group are normal- and iso-butylamine, hexylamines, 2
- primary/tertiary diamines such as ethylhexylamine, ethylenediamine and homologs thereof, and dimethylaminopropylamine, diethylaminopropylamine and homologues of this series. Particularly preferred are mixtures of alkylamines and alkylene diamines. The reaction is 5o
The temperature is between 90°C and 90°C.

The essential aprotic solvent in various cases when carrying out the reaction is an aromatic hydrocarbon such as doluol or quidyol or a glycol diether such as diethylene glycol dimethyl ether. The amount of solvent ranges from 10 to 50%, calculated based on the epoxy resin-amino-adduct.

If necessary, the epoxy resin-amino-adduct can be modified by carboxyl compounds such as saturated or unsaturated fatty acids, polyesters containing carboxyl groups, or corresponding prepolymers based on acrylates or carboxyl groups containing polyesters. Based on calculations, up to 40 mol% can be modified. Preferred fatty acids are monocarboxylic acids having 7 to 20 carbon atoms of synthetic or natural origin. For example, benzoic acid.

These are isooctanoic acid, isononanoic acid, α-branched synthetic monocarboxylic acids with alkyl groups having 8 to 12 carbon atoms (KOCH-acid) or oily fatty acids and tall oil fatty acids. Epoxy resin - amino -
Other monocarboxylic acids suitable for the modification of the adducts are half-esters of monoalcohols and dicarboxylic acids having 6 or more carbon atoms or carboxylic acids modified with oxazolidines. For example, the preparation of
5,946). There, oxazolidines additionally serve as formaldehyde carriers.

The reaction with the carboxyl group containing the modifier is advantageously carried out at a temperature of 90°C to 120°C prior to the reaction with the amines.

In a particular embodiment of the invention, the carboxylic compounds used in addition to the primary amino compounds and which are particularly advantageously used include the addition of maleic anhydride to unsaturated oils and/or unsaturated hydrocarbon compounds. It is a thing. The anhydride portion opens the ring by forming half-esters with the monohydroxy compound, and the free carboxy group optionally partially reacts with the monoepoxy compound.

Through this modification, the film surface and the flexibility of the film can be substantially improved.

Carboxylic compounds of this type which are suitable for the modification of epoxy resin-amino-adducts are tung oil, linseed oil, dehydrated castor oil, soybean oil.

It is formed in a known manner through the addition of maleic anhydride to unsaturated oils such as sunflower oil and similar natural oils. Hydroxyl-free synthetic esters of the fatty acids contained in the oils mentioned above and of tall oil fatty acids and polyols are also suitable as starting materials. Preferred polyene compounds for reaction with maleic anhydride are unsaturated low molecular weight hydrocarbon polymers or oligomers. Examples of this class of compounds are the so-called polybutadiene oils, ie liquid oligomers of butadiene with various stereospecific structures or the corresponding pentagenes or cyclopentagenes.

These compounds usually have a molecular weight between 400 and 6000.

It is clear that mixtures of these starting materials can be used in the adduct formation with maleic anhydride.

The amount of maleic anhydride is 60 for carboxylic compounds.
to 15 CP"9 KOIF [g, preferably from 65 to 80" f KOW9.

For the formation of half esters, the maleic anhydride adduct is 50
React with the monohydroxy compound in a known manner at a temperature of ~150°C.

Suitable monohydroxy compounds are saturated or unsaturated monoalcohols having 1 to 8 carbon atoms, such as methanol and its homologs, fatty alcohols, allyl alcohols, and the like. Other suitable monohydroxy compounds are glycol monoesters of (meth)acrylic acid, such as hydroxyethyl (meth)acrylate and its further homologs and isomers.

When unsaturated monohydroxy compounds are used, it is advantageous to carry out the reaction in the presence of an inhibitor such as hydroquinone.

A possibility to reduce the number of carboxyl groups in the half-esters is the reaction of these groups with monoepoxy compounds such as esters or glycidyl esters or ethers of epoxidized fatty acids. Examples of compounds well suited for this purpose are the glycidyl esters of cottofoic acids, especially those having at least one fatty acid group having 8 or more carbon atoms at the tertiary carbon atom.

The reaction between the epoxy groups of the epoxy resin and these groups of the carboxylic compound is carried out at temperatures of 90 to 150°C.

It is advantageous to carry out the reaction until complete crosslinking of the modifying compound occurs.

More suitable modifiers are secondary amines, especially secondary alkylamines. The resulting tertiary amino groups can influence the solubility of the product.

The reaction step to obtain the epoxy resin-amino adduct is carried out until the epoxy value is practically zero. That is, the obtained epoxy resin-amino adduct does not have epoxy groups.

4tEl*x<-+y4i[-y'ii-Hm*, ,
, optionally modified with a carboxylic compound, in the first step formaldehyde or a compound which separates formaldehyde under the reaction conditions, and - substituted amino-alkyl mono- or di-hydric phenols. and/or alkylphenol.

or optionally with formaldehyde-reactive compounds of the urea, melamine or guanamine type. In this case, 0.5 to 1.0 mol of phenol and formaldehyde are reacted per mole of NH groups of the epoxy resin-amino adduct. The reaction is carried out at 50-90°C,
and to reach as substantial a crosslinking of formaldehyde as possible.

Phenol as a phenolic component.

It is used in the form of a cloth. For example, phenol liquefactum (90
%)) and alkylphenols are methyl.

higher phenols such as butyl or nonylphenols or the formula Ph-R-p
Diphenols represented by h are used. R in this formula is a straight-chain or branched alkylene group having 1 to 5 carbon atoms, preferably bisphenol A. The phenols must have at least two formaldehyde-reactive sites to achieve the desired properties. In another method, which allows for a reduction in the amount of acid necessary to obtain sufficient water solubility, the aforementioned phenols are substituted entirely by amino-alkylation products of monosubstituted or trinuclear phenols. or partially replaced. The substituent is an alkyl or aralkyl group having at least 4 carbon atoms, and the amine has at least 2 amino-hydrogen atoms and at least 4
carbon atoms.

In addition to improved solubility, these structures introduce additional flexibility-imparting and flowability-enhancing groups into the binder molecule.

In this way, the use of high-boiling solvents in paint formulations becomes almost unnecessary.

The amino-alkylated products used in this alternative process are formed in the sense of Mannich reactions from phenols, amines and formaldehyde based on Mannich bases (cathodic deposition) as mentioned in the description of the state of the art. In contrast to possible binders, the Mannich reaction in this case is only an additional modification of the phenolic component.The use of primary, higher molecular weight amines eliminates the decomposition products formed in the stopping process. The amount increases only at a dependent rate due to this modification.

Suitable monosubstituted mononuclear phenols for the preparation of the intermediates used according to the invention are primarily alkylphenols, the alkyl group having at least 4 carbon atoms.

Typical of this group are butylphenols and their higher homologues, preferably those having 8 and more carbon atoms in the substituent, such as p-isooctylphenol or p-nonylphenol. Other suitable substituents are aralkyl groups, such as those shown as benzylphenol or cumyl(26)phenol.

Among the trinuclear phenolic group.

Bishydroxyarylalkanes such as bis-(4-hydroxyphenyl)methane or preferably 2,2-biS-(4-hydroxyphenyl)propane (bisphenol A) are mentioned as examples.

Suitable amines as intermediates have at least two
amino-hydrogen atoms and at least 4 carbon atoms.

Some of these compounds include primary (alkanol) amines such as butylamines, their higher congeners such as ethylhexylamine, corresponding alkanolamines, and corresponding primary (alkanol) amines such as hexamethylene diamine. Diamines or N,N-diethylaminoproetby
= yo, 1:5 tx*-R/1XEH*7
”, y, , i. Appropriate a(24) minos can also be made through the reaction of acrylic acid esters or monoepoxy compounds (2 moles) with primary diamines (1 mole). Particularly suitable compounds are the reaction products of hexamethylene diamine with butyl acrylate and 2-ethylhexyl acrylate, or with glycidyl esters of chosfoic acids.

Suitable intermediates for the process of the invention are prepared in such a way that the amines are heated together with the phenols to a temperature of 70° to 80°C. 80 to 1'50° after addition of formaldehyde, preferably in the form of paraformaldehyde
The reaction is carried out at a temperature of C and water is eliminated with the aid of an entraining agent. Depending on the type of reactant, the reaction upon addition of formaldehyde will be more or less exothermic. The reaction is completed when 1 mole of water produced in the reaction per mole of phenol is entrained and separated.

Products with substantially identical properties are obtained with this alternative method. The aminoalkylation of the phenol is then carried out in the presence of an epoxy resin-amino adduct. This alternative method is called the "one-reactor-pro" method.
cess). After the preparation of the epoxy resin-amino-adduct, the amine to be subjected to alkylation, phenol and formaldehyde are added and condensed at a temperature of 70-90°C for 1-3 hours. The water produced remains in the reactor. After this reaction time, the expected amounts of phenol and formaldehyde are added and the reaction is carried out at a temperature of 55-80° C. until the formaldehyde content is below 0.5% (alternative method B).

In a further process (C) it is possible to combine both reaction steps. In this method, the epoxy resin-amino-adduct is mixed together with the 7-mino component and the expected total amount of phenol and total amount of formaldehyde. The reaction is then carried out at a temperature of 60-75°C until the formaldehyde eventually reacts.

If desired, the mono- or polyhydric phenols and/or alkylphenols used according to claim 1 can be partially replaced by other formaldehyde-reactive compounds. Phenols bring about further improvement of their solubility properties, such as urea and thiourea.

It can be partially replaced by melamine or guanamine type amino compounds.

This alternative method involves adding 0.1 to 0.4 moles of a phenolic compound to urea, thiourea, or imidourea.

Formaldehyde-reactive amino compounds of the type melamine, acetoguanamine or these compounds are substituted and a joint reacti
on 5tep) with an amino compound and a secondary amino group containing formaldehyde.

This method improves not only the dissolution properties but also the adhesion of the deposited film to the substrate as well as to the subsequently coated film.

In particular, formaldehyde-reactive compounds within the meaning of the invention include compounds of the type urea, thiourea, iminourea, melamine, acetate and pendiguan(27)amine or mixtures of these compounds. The phenolic compound can be replaced by the aforementioned amino compound at a level of 0.1 to 0.4 mole of phenol.

Formaldehyde is preferably used as paraformaldehyde, one of the commercially available forms with a formaldehyde content of 80 to 100%. In addition, the compounds can be used as formaldehyde donors to separate formaldehyde under the reaction conditions. Such compounds are, for example, oxazolidine compounds used in the form of carboxylic derivatives or as amines for modifying epoxy resins. Formaldehyde is 25 to 90. Preferably a molar amount of 1.1"%l, corresponding to 60 to 80 mol%
-$11.1゛*m""゛"Pa 1.7.1 (Formaldehyde of enolic component - Reactivity Used in an amount of 60 to 80 mol% calculated based on 0 site. Self-crosslinked structure In order to obtain (28) it is advantageous to use at least a 30% additional molar amount of formaldehyde based on the NH- groups.

In order to achieve water solubility, the basic groups of the reaction product are partially or totally neutralized with an acid, preferably with formic acid, acetic acid or lactic acid. dilution capacity (dil) as actually used
10 to 40% of basicity for utab order 1ty)
The degree of neutralization is sufficient and corresponds to an amount of about 20 to 60 mmol per 100 g of resin.

The binders are further diluted with deionized water to the desired concentration. Optionally, prior to neutralization or dilution, or in a partially diluted state, the binders are mixed with coating materials, fillers and other additives to give a pigmented paint.

The formulation of such paints and their application to cathodic deposition processes are known to the expert and disclosed in the literature. When used as a primer, the deposited film is cured for 10 to 60 minutes at a temperature of 150 to 180°C. If the binders do not contain sufficient levels of crosslinking, further crosslinking components such as blocked isocyanates or amine resins or phenolic resins can be used. With appropriate formulations, the product can also be used in other methods such as dipping, roller coating, and jetting. If desired, the binders can also be treated with organic solvents.

The following examples illustrate the invention without limiting the scope of the invention. Parts and percentages are by weight unless otherwise specified.

The following abbreviations are used in the examples.

EPHL Jepoxy resin based on bisphenol A,
Epoxy equivalent weight approximately 190EP
HI [Jepoxy resin based on bisphenol A, epoxy equivalent weight approx. 474 EPHI Epoxy resin based on polypropylene glycol, epoxy equivalent weight approx. 20 DEAPA Diethylaminopropylamine EHA 2
-Ethylhexylamine NBA n-Butylamine T (MDA) Hexamethylenedimine DEA Diethylamine BPA Bisphenol A PH Phenol, liquefied 91% (like-fact
um 91%) NPH nonylphenol P T B p-tert-butylphenol B180
Liquid polybutadiene oil (approx. 75% 1.4-cis, approx. 2
4% 1,4-trans about 1% vinyl-double bond 1 molecular weight about 1500±15%, iodine value about 450 g/1000,9) MAA maleic salt anhydride CP 1.1'; Methyl n -(C7-C' 9) - A (6
1) Industrial mixture of glycidyl esters of lucancarboxylic acids PF91 Paraformaldehyde, 91% IM[)A7
'BUACI (MDA and n-) tylacrylate (
1:2 mol) reaction product 1 (MDA/CE HMDA and CB (1: 2 mol) reaction product EI (X 2-ethylhexanol EGL ethylene glycol monoethyl ether HEGL ethylene glycol monohexyl ether DPME dipropylene glycol Monomethyl ether PME Propylene glycol monomethyl ethyl DEGM Diethylene glycol dimethyl J-lG・Til T Doluol (52) 'I'EX 2,2,4-1 Limethylpentane-1,3
-Diol-Monoisobutyrate (Texanol) Examples 1-5 These examples concern the reaction of phenols or alkylphenols with epoxy resin-amino-adducts.

Preparation of epoxy resin-amino-adducts A1 to A5 Adduct A1: EPHI, 190 parts (1 equivalent, IV
al) with 132 parts of doluol and heated to a temperature of 60°C. Then, DEAPA, 59 copies (0,4
5 mol) and EHA, 58 parts (0.45 mol), are added gradually, the reaction temperature being maintained at 75-80° C. with necessary cooling. Epoxy value is practically 0
Hold the temperature until it drops to .

The adduct solution can be further processed directly. The adduct contains 0.8 moles of N H calculated on resin solids.
- contains a group.

Adduct A2: A solution of 475 parts (1 equivalent) of EPHII in 254 parts of doluol is reacted with 59 parts of DEAPA and 58 parts of EHA (0.45 mol each) in the manner described in AI. . The reaction product contains 0.8 mol of N H-groups (relative to resin solids).

Adduct A3: DBGM by the method described in AI
, a solution of 640 parts (2 equivalents) of EPHI in 71 parts is reacted with 117 parts (0.9 mol) of EAPA and 66 parts (0.9 mol) of NBA. The product is 8 parts of resin solids.
Contains 1.6 moles of NH- groups in 23 g.

Adduct 4: Doluol, by the method described in A1
A solution of 760 parts (4 equivalents) of EPHI in 362 parts of DEAPA, 260 parts (2 moles) and 114 parts of HMPA
The product is 1134.9 parts (1 mo J).
It contains 4.0 moles of NH- groups in the resin.

Adduct 5: doluol by the method described in A1,
FilFT-II, 190 copies (1 equivalent) in 475 copies
A solution of DEAPA, 78 parts (0.6 mol) and DBA
, 21 parts (0.6 mol.

(as a denaturing agent). The product is a resin solid 2
Contains 0.5 mol of N)i groups in 89 g.

Example 1: 60 parts of A1,439 parts (0.8 mol NH)
Warm to ℃ and stir to remove BPA.

182 parts (0.8 mol) and PF91, 75.8 parts (2
, 3 mol CH20) and then heated to 80°C. 0
．． The temperature is maintained with stirring until a formaldehyde value of below 6% (calculated on the formaldehyde used) is achieved. The reaction product is 135~KOT-p, 9
It has an amine value of It depends on further processing.

The product can be diluted with further auxiliary solvents such as EGL, HEGL or 'rEX. It can then be used in this form or after addition of the partial or total amount of acid required for protonation (65) for the preparation of a dough paste.

In preparing the binder alternative low solvent, add the expected amount of acid and then slowly add deionized water and stir until a low viscosity dispersion is obtained. At 60-60°C most of the organic solvent separates from the dispersion.

Examples 2-5: Formulation 1 reaction conditions and details are shown in Table 1. Preparation is similar to Example 1.

5, (G. (36) Table 1 Example 2 6 4 5 Amine adduct A2 A5 A4 A5 amine value, ~K
oH/9 95 114 203199 (37) Example 6: 8180.700 parts at 200°C in the presence of 0.05 parts of diphenylparaphenylenediamine inhibitor)
1MAA at a temperature of

100 parts of MAA is reacted in a known manner until complete reaction. After cooling to 100°C, 130 parts of EHX is added and esterification is carried out at 120°C until MAA is completely reacted. After cooling to 100 °C, 130 parts of EHX are added and the esterification is carried out at 120 °C until the theoretical half-ester is reached (MADA). 80%
It is reacted in solution with 212 parts of BPHI at 120° C. until the practical acid number is 01=.

DGMFt, 108 parts, DEAPA, 59 parts (0,45
mol) and EHA, 59 parts (0.45 mol), the batch was effectively reduced to an epoxy value of 0.
The reaction is carried out at 65 to 70°C until Once this value is reached.

BPA, 114 parts (0.5 mol) and PF.

(38) 50 parts (1.5 mol) are added and the reaction is carried out at 60° C. to a free formaldehyde content of 0.5-1%.

After addition of 1/0 part of DGME, the batch is neutralized with 65 mmol formic acid per 100 g resin and diluted with deionized water in portions. The solids content in the opaque dispersion is 65%.

Example 7: MADA, 930 parts to 081125 parts (0
, 5 mol) at 120°C.

60ηK OH/, react to an acid value of 9.

(MADB) 317 parts of MADB are reacted with 219 parts of EPHI in an 80% solution in PME at 120° C. to an acid number of practically 0.

After addition of 146 parts of PMB, 59 parts (0.45 mol) of DEAPA and 29 parts (0.4 mol) of NBA, the batch is reacted at 65-70° C. to an epoxy number of practically 0.

After reaching this value, BPA, 114 parts (0,5 mol), P
H, 21 parts (0.2 mol) and PF (69) 91.66 parts (2.0 mol) are added and 0.5%
The reaction is carried out at 60°G with the following free formaldehyde contents: After addition of 160 parts of PME, the batch is neutralized with 40 mmol formic acid per 100 g of resin solids and diluted in portions to 40% solids via addition of deionized water.

Examples 8 to 16: These examples are.

-Reaction of epoxy resin-amino-adducts using amino-alkylated products of substituted phenols.

The amine and phenol were heated to 70°C in a reaction vessel equipped with a receiver, condenser, thermometer and stirrer, and a little formaldehyde was added at 6°C. ,.

Do not exceed. The reaction water has a boiling point range of 980-130°C (e.g. suitable white spirit).
Remove with the help of entrainment agents.

(40) Continue the reaction until the corresponding reaction water is eliminated. After removing the solvent in vacuo, the product is diluted with DBGM. The following table shows the compositions of intermediates MVP1-5.

MVP 1 2 3 4 5 DEAPA 130 -- -- -- -- -- HMDA
--11(S -------BHA ---129
----- HMDA/13UAC---368--HMDA
/CE---616MPH440880-
-220220 PTB ----300---- BPA -------22B 228 PF91 66 132 66 66 66 (41) Preparation of epoxy resin-amino-adduct Adduct A6: 0.700 parts of 8180.700 parts. 0.5 parts of diphenylparaphenylenediamine in the presence of 100 parts of MAA at 200° C. in a known manner. This is done until the MAA has completely reacted.

After cooling to 100° C., 130 parts of EHX are added and esterified at 120° C. until the theoretical acid number of the half ester is obtained. (MADA) 110 parts of MAD A (corresponding to about 0.12 C'00H-group) with 212 parts of EPHI.

80% solution in DGMB at 120°C.

The reaction is made to have an acid value of substantially zero. DGMJ 108th division (
0.45 mol) and EHA, 59 parts (0.45 mol), the batch was brought to an epoxy number of practically 0 by 65 to 7.
Let the reaction take place at 0°C.

Adduct A7: DEG BPHI, 190 parts (1 equivalent) in a reactor equipped with a stirrer, thermometer and reflux condenser.
M, dissolved in 132 parts (42) and warmed to 60°C. Furthermore, DgAPA.

59 parts (0.45 mol) and EHA, 58 parts (0.45 mol)
mol) mixture gradually.

The temperature is then maintained at 75-80° C. with necessary cooling. The temperature is held until the epoxy number drops to practically zero. The adduct solution can be further processed directly. The adduct contains 0.8 moles of N, calculated on resin solids.
Contains H group.

Adduct A8: EPHIT, 475 parts (1 equivalent) to D
Dissolved in 254 parts of EGMj.

DEAPA, 59 parts (0.45 mol) and EHA, 58
(0.45 mol) at 70-75° C. until an epoxy number of practically 0 is reached. The adduct contains 0.8 mol of NH-groups, calculated on the resin solids.

Example 8: In a reactor equipped with a stirrer, a thermometer and a reflux condenser, 6,628 parts of adduct A (0.8 mol of N
corresponding to the H-group) (43) until the formaldehyde content falls to 0.5-1% (calculated relative to the formaldehyde used).
114 parts (0.5 mol).

MVPl, 149 parts (80%, 0.2 mol) and PIi
91.76 parts (2.6 moles) at 60°C. The batch is diluted with 170 parts of PME and neutralized with 65 mmol of formic acid per 100 g of resin solids. After 1 hour of homogenization, 975 parts of deionized water are slowly added with vigorous stirring. The resulting dispersion is approximately 65
% solids content.

Products with substantially identical properties are also obtained alternatively (B) using the "-reactor method".

For this method, adduct 6A, 628 parts, NPH, 88 parts (0.4 mol) at 90°C.

DEAPA, 26 parts (0.2 mol L PF91゜13 parts (°゛4''''') and 0°ON.
After addition of 14 parts (0.5 mol) and 76 parts of PF'91.degree., the temperature is set and maintained at 70.degree. C. until the free formaldehyde (44) content falls below 0.5%. The remaining operations are the same as in Example 8.

Example 9: As described in Example 6, 7,439 parts of adduct A (corresponding to 0.8 mol of NH groups)
After addition of DEGM, 130 parts at 65°C, BP
A.

91 parts (0.4 mol) t MVP, 392 parts (80%:
0.6 mol) and PF91. 66 parts (2 mol) until the content of free formaldehyde falls below 0.5%.

After addition of 192 parts of PME and 35 mmol of formic acid per ioog of resin solids, a 40% dispersion is prepared by gradual addition of deionized water.

Example 10: As described in Example 6.

DEGM, at 65° C. after addition of 130 parts.

439 parts of adduct A 7 (corresponding to 0.8 mol of NH groups) with MVP 3.39 < 5 parts (80%.

0.7 mol) and 43 parts (1.3 mol) of PF.

The reaction is allowed to proceed until the free formaldehyde content drops to 0.1-1% (45). After addition of 36 parts of PMB and 60 mmol of formic acid per 100 g of resin solids, a 36% dispersion is prepared by slowly adding deionized water in portions.

Example 11: As described in Example B.

adduct) 6,628 parts (corresponding to 0.8 mol of NH group) were mixed with bisphenol A, 91 parts (0.4 mol), M'V
P4,296 parts (85%; 0.3 mol) and PF91.
66 parts (2 mol) and the free formaldehyde content is 0.
The reaction is carried out at a temperature of 60° C. until the concentration falls below 5%.

PMEj 122 parts and 60 per 100.9 resin solids
After addition of mmol of formic acid, a 36% dispersion is formed via addition of deionized water.

Essentially equivalent final products are also obtained according to the alternative method <C) using the "-reactor method". Can be formed from the same raw material.

In this case, 6,628 parts of adduct A was DEGM.

(110 parts) NDA/
BUAC, NPH, 66 copies (0.3mo JL).

(AA) After addition of 159 parts (0.7 mol) of BPA and 86 parts (2.6 mol) of PF9, the reaction is carried out until the free formaldehyde content falls below 0.5%. The remaining operations are the same as in Example 9.

Example 12: As described in Example 6.

8,846 parts of adduct A (corresponding to 0,8 mol of N H-groups) were added to MVP 5,6 after addition of 88 parts of DEGM.
80 parts (80%: 0.5 mol).

BPA, 68 parts (0.6 mol) and PF91°79 parts (2.4 mol), free formaldehyde content 0.5
% (value calculated for formaldehyde used)
React at 65°C until the temperature drops below. A 36% dispersion is prepared by adding deionized water gradually after addition of 35 mmol formic acid per 10og of resin solids.

Example 13: With the apparatus described in Example 8.

1 -1111111------ In the presence of 6,628 parts of adduct A (containing 0.8 mol of NH- groups), 23 parts of HMDA are mixed with 51 parts of BUAC and 1
React (47) at 7°C to 75°C for a period of time. BPA, 160 parts (0.7 mol).

NPI (,44 parts (0,2 mol) and PF'91°66
After the addition of 1 mol; corresponding to 61 mol %, the value calculated for formaldehyde-reactive sites, the batch was heated until the free formaldehyde dropped to practically 0.
Maintain temperature between 0 and 65°C. A 40% dispersion is prepared after addition of 40 mmol formic acid per 100 g of resin solids.

Partial replacement of phenols by urea and melamine is described.

Example 14: In a reactor equipped with a thermometer, stirrer and reflux condenser, 1064 parts (5,6 equivalents) of EPHI
was dissolved in 694 parts of DPME and heated until the epoxy value reached 0.
M.D.A.

116 parts (1 mol) DEAPA, '564 parts (2,8
-EA) and. □, 163 parts (0,8-E'1 l) at 65-70°C. The adduct contains 5.6 moles of secondary NH groups.

(4 days) Furthermore, after adding 180 parts of DPME, jNPH was obtained.

550 parts (2.5 mol), 84 parts of 50% urea aqueous solution (
0.7 mol of urea), BPA.

251 parts (1,1 mol) and 91,254 parts PF (7,
7 mol) are added and the batch is stirred at 60° C. until the free formaldehyde content (value calculated based on the formaldehyde used) is below 1%.

To prepare the dispersion, the batch was mixed with 272 parts of N-3 formic acid (
(equivalent to 30 mmol per 100 g resin solids),
It is then slowly diluted with deionized water to a solids content of 40%.

Example 15: With the apparatus described in Example 14.

EPHI, 760 parts (4.0 equivalent) to DPME.

490 parts of H until the epoxy value is 0
React with 116 parts (1 mol) of MDA and 260 parts (2 mol) of DEAPA at 65-70°C. Its appendix is 4
Contains moles of secondary amino groups.

(49) Further, after adding 350 parts of DMPJ, NPH.

594 parts (2,7 mol) and melamine, 63 parts (0,5
mol) and the free formaldehyde content was 1%.
(value calculated for the formaldehyde used) until it falls below.

Stir at 55-60°C. 161 parts of N-3 formic acid (10
After addition of 35 mmol (equivalent to 25 mmol/0 g resin solids)
% dispersion is made according to the method described in Example I.

! As mentioned above, low solvent dispersions are produced from the products of this invention. Required amount of acid, degree of neutralization.

The solids content and stopping loss (according to the measurement method given below) of the dispersion are summarized as follows.

(50) 1 50 20.7 68 ' 5.2/16(](5
1) ※) Formic acid (or acetic acid) ※※) 9 dispersion was diluted with deionized water to a solids content of 10% to determine the stopping loss. Dry film thickness 18
The degreased mesh plate was cathodically coated under conditions that yielded a film with a diameter of ±2 μm. The board was pre-dried at 110°C for 30 minutes.

Weighed and calcined (5 toves) for a further 30 minutes at the temperature listed in Table 1. Stopping losses were determined by reweighing the plate.

The stopping temperatures listed are based on over 100 back and forth rubs (do
It ensures sufficient crosslinking characterized by the solubilization resistance of uble-rub).

Similar stopping conditions were used to test resistance properties. In order to measure the resistance properties of Examples 1-7, 14 and 15, colored paints with the following formulations were produced.

Example 8 Coatings 1 to 13 contained a high-boiling solvent (coalescing agent, 'coa
Contains no Iescjng agents).

Nevertheless, the surface is (52) in all cases It was normal.

(53) Kneading paste (1) -91--91--Fusing aid
12 10 - 8 14 - -TFfX TEX
I (EGL τ■ Kneaded paste (1) 91 - - - 91 91
- - Coalescence aid - - 1 - - 1 - (I) (II) 1 0.8 Carbon black 1210 Basic lead silicate milling resin was produced by the following method: Bisphenol A (epoxy Approximately 500) based on epoxy resin 5
00 parts in 214 parts of PME and phthalic anhydride and E in the presence of 0.5 g of triethylamine as a catalyst.
83 parts of the half ester of I-I
It was reacted with an acid value of KOH/9. Then NH-functional oxazolidine 120 of aminoethylethanolamine, 2-ethylhexyl acrylate and formaldehyde
and 2<S parts of DEAPA were added and allowed to react at 80° C. until the batch epoxy value was essentially zero. Batch Propylene Glycol Monoethyl Ether 2
00 parts, and partially neutralized with 97 parts of N-3 formic acid. The (55) solids content of the resulting solution was 5B, 8%.

Under conditions such that after dilution to a solids content of 18%, a film with a dry film thickness of 20±μm is obtained.

The paint was cathodically deposited onto a zinc phosphate steel plate and baked in an oven for 60 minutes at the same temperature used to measure the stopping loss. In all cases, the salt spray test A8TMB117-64 after 700 hours of exposure was
shatch) showed rust of less than 21E11. In a humid chamber (50°C and 100% relative humidity) the coating
It was in good shape after some time.

Giant (56) Continued from page 1 Priority claim 0198 Worship July 12th [phase] Austria [
Phase] 1984? , August 6th [phase] Austria 0198 service November 15th [phase] Austria O Inventor Helmut Hoehni Otsch Tuse 0 Inventor Wolfgang Die Ohmer-Gruer (AT) ■A2243/84 A (AT) [Stock ] A2526/84 A (AT) ■A3608784 Country of Stria, Nie-8010 Grat, Seebacherga 0 Country of Stria, Nie-8010 Grat, Rosenbergter 37 Procedural Amendment Showa. 0 years. July 1st, Commissioner of the Japan Patent Office Gakudon Shiga 1. Indication of the case Showa Application No. 60 Patent 51615 2. Name of the invention 3. Person making the amendment Relationship with the case Patent applicant 5. Subject of the amendment "Description" ”

Claims (1)

[Claims] 1. An epoxy resin having at least two epoxy groups and an epoxy equivalent type of 180 to 1000
At °C. For each available epoxy group, primary monoalkylamine and/or primary alkylenediamine and/or primary
Primary amino group of class/6th class alkylene diamine 0.6
from 0.0 to 1.0 mole, and from 0.0 to 0.0 mole per available epoxy group.
The resulting epoxy resin-amino adduct is reacted with 4 moles of carboxylic compound or secondary amine until the practical epoxy value is zero, and then the resulting epoxy resin-amino-adduct is
At 0°C, the calculated amount per mole of NH group is 0.
5 to 1.0 mol of aminoalkylated mono- or polynuclear phenols and/or alkylphenols and/or -substituted mono- or dinuclear phenols or optionally partially,
Formaldehyde-reactive compounds of the type urea, melamine or guanamine, and 0.25 per formaldehyde-reactive site until formaldehyde is practically bound.
to 0.9. Preferably, the reaction product is reacted with 0.6 to 0.8 mol of formaldehyde, and then the reaction product is partially or totally neutralized with acid and optionally diluted with water after addition of a water-tolerant organic solvent. Features. A method for producing cathodically depositable electrocoating paint binders based on modified epoxy resins. 2. The manufacturing method according to claim 1, characterized in that an epoxy resin based on bisphenol A and/or phenol novolak is used. 3. The manufacturing method according to claim 1 or 2, characterized in that a primary monoalkylamine having at least 4 carbon atoms is used. 4. The manufacturing method according to any one of claims 1 to 6, characterized in that a mixture of monoalkylamine and/or alkylene diamine and dialkylaminoalkylamines is used. 5. The manufacturing method according to any one of claims 1 to 4, characterized in that the reaction between the epoxy group and the amine is carried out at 50 to 90°C. 6. The manufacturing method according to any one of claims 1 to 4, characterized in that the reaction between the epoxy group and the carboxylic compound is carried out at 90 to 120°C. Z The manufacturing method according to claim 6, characterized in that a monocarboxylic acid having 7 to 20 carbon atoms is used as the monocarboxylic acid. 8. The manufacturing method according to claim 6 or 7, wherein a monoalcohol or a half ester of an oxazolidine compound and a dicarboxylic acid is used as the monocarboxylic compound. 9. As carboxylic compounds, unsaturated oils and/or
or half esters and/or low molecular weight unsaturated hydrocarbon polymers or oligomers without hydroxyl groups of oily fatty acids or tall oil fatty acids contained in these oils and polyols,
using an addition product of maleic anhydride to a diene polymer, preferably having a molecular weight of about 400 to about 6000;
7. A process according to claim 6, characterized in that the anhydride group is ring-opened by forming a half-ester with a monohydroxy compound. 10. Claim No. 2, characterized in that the carboxylic compound has an acid value of 60 to 1301 μH/g, preferably 35 to 81 μH/g. Process according to claim 9 or 10, characterized in that the number of groups is reduced by reaction with a monoepoxy compound.12. Phenol having at least two formaldehyde-reactive sites. 13. The method according to any one of claims 1 to 11, characterized in that bisphenol A is preferably used. 13. 0.1 to 0.4 of the phenolic compound used.
Mol is urea, thiourea, imidourea. replaced by formaldehyde-reactive compounds of the type of melamine, acetoguanamine or benzoguanamine or mixtures of these compounds, and characterized in that they react in the merging reaction step with formaldehyde and secondary amino groups containing amino compounds. A manufacturing method according to any one of claims 1 to 12. 14. Mono- or polynuclear phenols and/or alkylphenols are partially or totally replaced by aminoalkylation products of mono- or di-substituted phenols, the substituents of which are alkyl phenols having at least 4 carbon atoms; or an aralkyl group, and the amine has at least 2 amino hydrogen groups and at least 4 carbon atoms.
The manufacturing method according to any of Item 3. 15. Production method according to claim 14, characterized in that an alkylphenol having an alkyl group having 8 or 9 carbon atoms and/or bisphenol A is used as the phenol. 16. Aminoalkylation 1 mol of an aliphatic oh-diamine, preferably hexamethylene diamine, and an acrylic ester, preferably butyl acrylate, as amine for. 16. Process according to claim 14, characterized in that 2-ethylhexyl acrylate or the reaction product of a monoepoxy compound, preferably a glycidyl ester of cottofoic acid, is used. 1Z The method for producing phenols according to any one of claims 14 to 16, characterized in that the aminoalkylation of phenols is carried out in the presence of an epoxy resin-amino adduct. 18. The production according to claim 16 or 17, characterized in that the aminoalkylation of phenols and the reaction of the epoxy resin-amino-adduct with formaldehyde and phenols are carried out in one reaction step. Method. 19 Claims 1 to 18 characterized in that formaldehyde is used in a molar excess of 60% relative to the N H groups present in order to obtain a self-crosslinked structure of the binder.
The manufacturing method described in any of paragraphs. 20, after neutralization with acid and dilution with water. 20. Process according to any one of claims 1 to 19, characterized in that the co-solvent is at least partially removed in vacuo from the reaction product at 60-60[deg.]C. 21. The manufacturing method according to any one of claims 1 to 20, characterized in that the coloring of the binder is achieved with the aid of a colored stock resin. 22. Electrodeposited binders that can be cathodically deposited, produced by the production method according to claims 1 to 20.