DE2063161C3 - Process for the production of water-thinnable synthetic resins based on nitrogen-containing polyethers - Google Patents

Description

The object of the present invention is to provide a process for the production of water-dilutable to provide water-dispersible, air-drying or stoving synthetic resins, which have all the necessary lacquer-related properties and have significantly improved drying properties

a) have compounds with the general formula shafts with excellent film quality and are also characterized by great storage stability and excellent flow properties.

The invention relates to a process for the production of synthetic resins based on nitrogen-containing polyethers by converting

CH, CH-CH, -

■ \ /
O

- <f V "Ο - CH ₂ -CHOH-CH ₂ -CH,

0-CH ₁ -CH

-CH,

where η represents the values 0 to 11 and a molecular weight between 380 and 3500 with

b) nitrogen-containing compounds by heating in the presence of catalysts, characterized in that that as b) b 'alkanolamides of unsaturated fatty acids and / or b "oxazolines of unsaturated fatty acids the general formula

H ₂ C C-

! S.

N
C.

C-X

where R _{2 is} a hydroxymethyl or alkyl radical with 3 carbon atoms, where at least one R ₂ must be _{a hydroxymethyl radical, R 3 is} a mono- or polyunsaturated hydrocarbon with 16 to 18 carbon atoms, and XH ₂ or = CH ₂ means to be used and etherified by heating to temperatures of about 40 to 150 C in the presence of catalysts and

c) the etherification products with such amounts (i./i-ethylenically unsaturated mono- and / or polycarboxylic acids, and if they exist, their anhydrides and / or half-esters with monoalcohols with 1 to 4 carbon atoms in the presence of other vinyl or vinylidene compounds, converted by heating be that the reaction products have at least an acid number of 25, and

d) then the reaction products containing carboxyl groups with such amounts of ammonia and / or strong organic nitrogen bases are added to complete or partial neutralization, until the reaction products are sufficiently water-dispersible or water-dilutable.

The invention also relates to the use of the synthetic resins produced according to the invention as Binder for water-thinnable, air-drying or oven-drying coating agents.

The invention also relates to the use of the according to one or more of claims 1 to 7 synthetic resins produced as binders for electrophoretically separable air-drying or oven-drying coating compounds.

The invention also relates to a water-thinnable, air-drying or oven-drying coating agent, which as a binder is a nitrogen-containing polyether composed of components a). b) and c) contains.

In BE-PS 7 24 922 a process for the production of water-thinnable is already by the same applicant Synthetic resins based on nitrogen-containing polyethers have been described that thereby is marked that one

a) plasticizing, hydroxyl-group-bearing, optionally also epoxy-group-bearing polyethers with the general formula

(OHL

(CH ₇ -

-CH-CH, -O — 1 —Z—

- O - CH, - CH - CH, - O - R

OH

I. Z is an alkyl, aryl or cycloalkyl radical when either η is O and n " is 1 or when ri ' is O and n" is 1, or II. Z is an alkylene, arylene or cycloalkylene radical means when μ and n "is equal to 1 or when / j is equal to O and n" is equal to 2, or when η is equal to 2 and n "is equal to O, or

III. Z is the remainder of the following formula

(R ₁ -O-CH ₂ -CH-CH ₂ -O-R ₁ \ OH

means when η is O and n " is 2, or when η is 2 and n" is O or when η and n " is 1, where / I ₁ is O or a small number up to 5 and where R _{1 represents} an aliphatic or aromatic radical, or

R "

IV. Z = R - C - CO

R "

is when η is 1 and n " is O, where R" R "and R" are each alkyl radicals, it being possible for the alkyl radicals to be identical or different,

b) methylol groups, preferably alkoxymethyl groups Aminoplast condensation products, selected from reaction products of aminotriazines of the general formula

NH,

N N

⁵ N "

NH,

where R _{2 is} NH ₂ , alkyl, cycloalkyl or an aryl radical, with aldehydes of the general formula

R ₁ -CHO

where R, H, represents an alkyl radical with 1 to 4 carbon atoms or the CH - ('H ₂ -RcSt, c) oxycarboxylic acids of the general formula

R ₄ (COOH) ₁₁₄

where R _{4 is} an alkyl radical with I to 20 C-Alomcn, «,, the number 1 or 2 and / I ₄ the number 1 or 2, or instead of these oxycarboxylic acids, their esters ίο with monohydric alcohols with I to 6 carbon atoms are used, reacted jointly by heating and / or component a) with component b) and the intermediate product then with d> jr component c) by heating and or by first reacting components b) and c) with one another by heating and then reacting the intermediate product with component a), and'or by first reacting component a) with component c) and then reacting this intermediate product with component b),

d) if appropriate, the products, insofar as they contain oxycarboxylic acid ester groups contain, stirred into the free carboxylic acids by saponification and

e) by adding ammonia and / or organic nitrogen bases to the water-dilutable Transferred state.

The prior art cited BE-PS 7 24 922 relates to synthetic resins for the production of oven-drying resins Lacquers, wogegc.i with the invention Manufactured synthetic resins prepared paint solutions of the present invention at room temperature fully or practically fully develop their valuable properties. The paints that come with the Nitrogen-containing polyethers are produced according to BE-PS 7 24922, have no air drying Properties and can therefore only be fully cured by using higher temperatures. The nitrogen-containing polyethers of the present invention allow such air-drying coatings that are dust-dry after just 2 hours and that are highly resistant to Mark salt spray, d. H. so great resistance to corrosion and are therefore extremely well suited for corrosion protection primers.

! n the comparative tests given at the end of the patent description to prove the These properties are proven with the technical progress achieved.

The aqueous paints to be produced according to the invention are distinguished in particular by the fact that the coatings produced from them at room temperature or at relatively low baking temperatures fully or practically fully develop their valuable properties. Furthermore, from such Aqueous air-drying lacquers or stoving lacquers with improved adhesive and To maintain shock resistance and paintwork with particularly pronounced elasticity, hardness and resistance to saponification. If desired, coatings can also be obtained which also have other properties, such as flexural strength. Solvent resistance and have a particularly high temperature resistance. The aqueous paints of this invention are preferred as primers used.

Water is used as the solvent for the paints produced according to the invention.

E η A a i;

ü F r b Ii

To achieve sufficient water solubility. improvement the flow properties and gloss of pigmented paints, it may be necessary to organic solvents that are unlimited or at least largely miscible with water, at Dissolve with water to use. These organic solvents can be used in amounts from about 0 to 30 percent by weight, preferably 2 to 15 percent by weight, Find use and serve to paint with a when diluted with water Obtain body content of around 30 to 70 percent by weight. As such are z. B. mono or Diether of ethylene glycol, diethylene glycol with lower monohydric alcohols, such as. B. methyl glycol, Ethyl glycol, propyl glycol, isopropyl glycol, butyl glycol, diethylene glycol diethyl ether and ethanol, n- and i-propanols, n- and i-butanols, and also acetone alcohol. lower ketones such as acetone. Methyl ethyl ketone and, in small amounts, methyl isobutyl ketone.

The aqueous lacquers produced according to the invention can, if desired, granulate those in the case of aqueous lacquers usual additives such as pigments, siccatives. soluble dyes, optical brighteners, and promotional agents the gradient and shine included. In particular, the paints can be used in addition to the polyether resins other usual lacquer binders. such as alkyl resins. Aminoplast resins. Phenolic resins, epoxy resins. Rosins, drying and nondrying oils and other polyether resins that are not identical to the main binder (polyether resin of the type indicated), dissolved and or contained dispersed. The weight ratio of the polyether resin to the other additional lacquer binders should in general expediently be greater than 1, in particular greater than 2. It has also generally proven to be useful if the weight ratio of the water to the total amount of binder in the paints from about 0.4 to 3, in particular from about 0.5 to 1.5 amounts to.

To produce paintwork, the aqueous paints can be used using the customary Methods are applied to the objects to be painted, e.g. B. by spraying. Spreading, Pouring on, rolling on, cn. Floods. Dipping or soaking and by means of electrodeposition z. B. Electrophoresis. The drying or stoving of the coatings can in general expediently be carried out at room temperature or during stoving at temperatures from about 80 to 180 ° C., in particular about 100 up to 140 C and. depending on the temperature, over a period of about 5 to 120 minutes, in particular take about 20 to 40 minutes. The valuable properties of the paintwork are coming in particular on metals such as iron, aluminum, magnesium and alloys of these metals Validity. The water-based paints are also particularly suitable for painting objects made of wood, Masonry. Concrete. Paper. Sheet metal, e.g. B. Body parts. Ships and ice boxes, as well as from Cans. Jugs, vats and appliances for industry and household. The paints can be used equally use for making base and top layers; because of their adhesive strength they are suitable also very good for the production of single-layer coatings on metals, with the high surface gloss generally makes repolishing unnecessary.

As those containing epoxide groups, possibly also containing hydroxyl groups Compounds suitable for building up the reaction products are: epoxidized olefins, Diolefins. Oligo olefin. such as 1,2,5,6-diepoxihexan and 1,2,4.5-diepoxihexan. Other epoxy compounds are derived from glycols. such as ethylene glycol, diethylene glycol, triethylene glycol. Propylene glycol-1.2. Propylene glycol-1,3. 1.4-butylene glycol, 1.5-pentanediol. 1.6-hexanediol and especially diphenols, like resorcinol, catechol. Hydroquinone, 1,4-dihydroxynaphthalene. Bis (4 - hydroxyphenyl) methane. Bis - 4 - (hydroxyphenyl) - methyl - phenylmethane. Bis (4-hydroxyphenyl-tolyl) methane. 4,4-dihydroxydiphenyl and 2,2-bis-4-hydroxyphenyl propane. Polyethers containing epoxy groups come at an end general formula for:

CH ₂ CH-CH ₂ - (OR ₁ -O-CH ₂ -CHOH-CH ₂ I _n -OR ₁ -O-CH ₂ -CH CH ₂

O O

Here, R _{1 is} an aliphatic or aromatic carbon radical, and 11 is 0 or a small integer from 1 to 8.
Particularly noteworthy are polyethers of the general formula containing epoxy groups

CH, -

CH-CH, -

O-CH ₂ -CHOH-CH

O-f "-C- / VO-CH ₁ -CH CH,

which contain 2,2-bis (4-hydroxyphenyl) propane as a starting compound, of which in turn are preferred

compounds containing epoxy groups T alkanolamides unsaturated? Fatty acids and, or OxT zohnc of the formula I! are used which contain at least _{one athenic double bond E r} 2, however, those alkanolamides and oxazolines of the Fo, S U are used which contain several ethylenic double bonds, in the preferred embodiment at least some of these double bonds K ₀ T in a jugged arrangement target

Suitable alkanolamine components of the fatty acid alkanolamides are preferably those with 1 to 6 C-mo , for example di- or TrJ - vorzui, "we, semonoalkanolamines. Such as Mono, Dili hanoKS" Amme der Propanol, der Butanol or Hexan "? Vvae Isopropanolamin, DimethylaminopropanoTödei 2-Amino-2-hydroxy-methyl-1,3-propanediol

These alkanolamines can be z. B. in the presence of catalytic amounts of a sodium alcohol such as sodium methylate at temperatures of up to 100 μm. The unsaturated, preferably drying fatty acids. However, this production is not preferred. The Amir NSF dt be fatty acid, brought higher temperatures for reaction, the water by azeotropic "S la on with recycling of dewatered in a particularly bevoSuS embodiment LösunS-by w removed approx. Suitable fatty acids _s Td.-'- is preferred per

Ζ * " ^{frcien Saurcn can} ™ also those of the Ϊ, Γ T"? ^{alcohol can be reacted with} the alkanolamines ^and the alkanolamides.

i, ^her ? ^{lel un} « ^vo » oxazolines is known and described SÄT ^ ', ", ΐ" ^USA - ^P ^ n.schnften 25 04 951, ν ί ^{23 7241} °. ^Verathe _A ^{run "is} in this case, upstream by heating, '" ^Anwescnhei t of per se known ysatoren m such a way that there is always conducted {£ "* y ^dro yl groups the alkanolamides ungesättieter überthnn ^{Un. d / or} oxazolines of the formula Imm <t ™ ^ ν u ^{"d 'e E x} P °''dgruppen the cpoxidunSr"^"Vei are b'ndungen. In alkanolamides FNRM ^beUsuUTCn and oxazolines or f of ho, Γ -μ ^{eS reserve} - the excess not so ί _Γ ^ * · ^Η ί "· ^{Dabd should,} however, also include a epoxide," F, T at ^{least 1} ^ hydroxyl groups. _M J ^ Y- P " ^nzi P ^ie » also possible in such _t ^m _r ^en | ^e _t " ^behave unsaturated with alkanolamides _u I f ^Γ °" ^U " ^d ° of ^the o ^ zolines of the formula II," _η ? η ^{SrUppCntragenden} connections to arbei- "zur'A ^{T? W} ^^ group e _{P e} oxide roup F _nn ^A T ^ ^{endun picking od} he possibly also the" _ru "n ^" ™ ^over on the hydroxyl \ ZZ "^ ^{However, with} such

eh h Il ^Men g ^env conditions in general, o GeL Λ ° ^{86 product} ^ "" d the danger of

Si ¹ SS ^ ^{is ih i}

^l i ^nSäl i ^r - ^{oleic acid E1} ^ ^d insäure. 9 ρ-ΐ- ^ "oleic acid (in ice, cis-trans and

F ^enSaUre ' ^{Elaeost earic} acid, Lig // o- ^E _p ^urucaic acid -arachidonic acid. Clupfno- "" ^annar ^ ^aUre "- ^Lica nic acid or its ^{mixture V}

werder »
Plantlets

^sch · ^Vo ^^-looking _e ^{W 's it from} natural ^FeUcn · ^as cotton' f ^{tIC oil} - ^olive oil, Mohnö, ⁴ T ^{PerlaÖ1 Ra} P ^{SOE1 'So} "" ene ^ra X, ^ubenkernö1' sardine oil.

Fetuiet
Fe tin 1η ₅ £ ΓοΓ, ΐ
säu en oÄ S
tΓ

^ ^W " ^{d by heating the Com} P °" U ^{0 b) to} temperatures of 40 to 150 C

fu ^W ° ^{at the} temperature range of 60 is preferred. Working with United ^{a 'alysatoren is} bevorzust. For example, ^Borlriflu ° nd adducts. z. "b. boron trifluoride ^Or ^ ^African tin compounds, eg., di- ·? ^urate '^ ^ate ™ ary Ammoniumvcrbindun- ² _hl? * ^{T" m} "hylbenzylainmonium. as Katalysah ^ ^{aUChbarDiebeidi} "he implementation incurred", "ff ^r ° ^{Dukle still need} ^" oreanischen "^ i ^{1 as} Mthliblkl XII

? AS

^{Chcmisch hair} ndelten ν '? ^{6 Ricinu oil} fat ^process container deIte ₅ o k
_{D e}

^{n in} ab ^ scnhei, of solu.- - ^rt , however, the presence of Spanish solvents is permissible V ^{enes Ρο1} >' ^{ίί {} ^ _Γ are then with

OxaLne der S ^PrOZ 2 ^et) award. As Atiivl pM " ^{SOwic the} corresponding methyl, Prechenden ^huma ^^ 2- Hydroxy-3-chlorpropyI-

acrylate, 2-hydroxy-1-phenylethyl acrylate, 2-hydroxy-3-butoxypropyl acrylate and the corresponding ethacrylates and phenylethylate, but also other polymerizable vinyl ¹ and vinylidene compounds. such as vinyl toluene, styrene, styrenes substituted in the core, styrenes substituted in the side chain, such as K-methylstyrene. «-Ethylstyrene and u-chlorostyrene. Of these monomers, preference is given to using: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate. 2-hydroxypropyl acrylate as well as styrene, '/ -methylstyrene and vinyltoluene, alone or as a mixture.

Suitable monomers containing carboxyl groups are: acrylic acid, methacrylic acid, cinnamic acid, benzoylacrylic acid. Crotonic acid; furthermore r <, / i-ethylenic unsaturated polycarboxylic acids or their anhydrides, insofar as they are capable of forming such as maleic acid. Fumarsiiuie, citraconic acid. Itaconic acid, methaconic acid. Aconitic acid or monoesters of the aforementioned polycarboxylic acids with saturated, straight-chain acids Monoalcohols with 1 to 4 carbon atoms, preferably methanol. Maleic monomethyl ester, halogen-substituted Acids such as chloromaleic acid. Among the preferred "./iethylenically unsaturated carboxylic acids" include: acrylic acid, methacrylic acid. Maleic anhydride. Maleic acid and fumaric acid.

The monomers bearing carboxyl groups can alone, in a mixture with one another, alone in a mixture with the first-mentioned, no carboxyl groups Monomers or in a mixture with these with the etherification product from step b) for Reaction to be brought. As admixtures, the monomer mixture, individually or as a mixture, other partially polymerizable monomers can be added, such as acrylamide. Methacrylamide, acrylonitrile and methacrylonitrile. The vinyl and / or vinylidene content in the synthetic resin depends on what is intended Area of application of the paint. However, it should be 10 percent by weight, based on the weight of the End product, generally do not fall below. For lacquer coating agents that are after the electrophoretic Application methods are applied, end products that are 10 to 30 percent by weight are particularly suitable contain polymerized onto vinyl and / or vinyl male compounds. With such binders Particular care must be taken to ensure that the reaction with the polymerizable monomers is complete i? t. d. h .. that the remainder of the monomeric fraction is very small. If the residual monomer content is too high! can difficulties arise with the deposition and with regard to pigment compatibility.

Binders containing 30 to 50 percent by weight vinyl or vinylidene compounds are particular suitable as air-drying lacquers. If the reaction is carried out with «, / I-ethylenically unsaturated monocarboxylic acids carried out, in this case the use of larger proportions of vinyl and / or vinylidene compounds without carboxyl groups are preferred. The proportion of monocarboxylic acids should in general, based on the monomer mixture. not more than 30 percent by weight, otherwise the resulting end products tend to gel and precipitate relatively easily during manufacture can arise.

When implementing r /, / i-ethylenically unsaturated Dicarboxylic acids or their partial esters, the implementation can also without the use of vinyl and / or vinylidene compounds which do not carry any carboxyl groups can be carried out satisfactorily. However, it is advantageous, especially when using such dicarboxylic acids, which are relatively strong Acids are. d. H. Before the reaction with the polyols, all hydroxyl groups have pK values below 4 to block the polyether, otherwise esterification during the polymerization will not occur can be excluded. This blocking of the hydroxyl groups can be achieved by reaction with acid anhydrides, such as B. acetic anhydride or by reaction with isocyanates, e.g. B. tolylene diisocyanates, which easily react with hydroxyl groups can be carried out. When using weaker acidic «, / f-ethylenically unsaturated carboxylic acids there is no such risk. The implementation of the polyethers with the carboxyl groups Monomers for the purpose of partial polymerization takes place in the heat, preferably with the action of polymerization catalysts. The reaction temperatures depend on the catalyst system used. Reaction temperatures between 120 and 180 ° C are preferred as the most favorable ranges, using di-tert-butyl peroxide. optionally in combination with chain terminators, preferably Lauryl mercaptan. When using low temperatures, around 120 C. The reaction mixture is often too viscous for easy processing. In addition, the reaction speed is which can be followed by the increase in the solids content, in the case of many monomers quite slow. When using high temperatures, approximately above 180 "C., low-viscosity products are obtained even with purely thermal partial polymerization. Especially when using '/ ,, - (- ethylenically unsaturated dicarboxylic acids or their anhydrides, it is advantageous to carry out the initial polymerization without the use of a polymerization catalyst, to be carried out only by thermal action at 180 to 220 C. The speed of reaction can by adding cobalt (II) salts, e.g. B. Cobalt) 11) chloride. in amounts from 3 to 6 parts per million, can be increased. However, the same reaction times are also achieved by presence obtained from stainless steel material. The reaction can also be carried out in suitable solvents be performed. Ethylene glycol ethers are particularly suitable as such solvents. like ethyl glycol. Isopropyl glycol or butyl glycol suitable. Also aromatic solvents like xylene. toluene or benzene, although they can be used, they generally have to be used after the reaction has ended be removed again.

The viscosities of the reaction products should be between 95 and 800 cP, measured in a weight ratio of 1: 1 in butyl glycol at 20 ^° C. This can be achieved on the one hand by appropriate selection of the monomer mixture and also by controlling the viscosity through the temperature and the use of appropriate solvents.

Furthermore, the viscosity can also be adjusted by adding what are known as known regulators, as has already been done has been explained above, are also controlled. The reaction products are then added by adding of ammonia and, or strong organic nitrogen bases, such as. B. trimethylamine, triethanolamine. Triisopropanolamine. Diglycolamine, diethylamine, Piperidine, morpholine. Diethanolamine. n-dimethylethanolamine and n-methylethanolamine in their salts

13 14

convicted. Reach fusible state under strong organic nitrogen. It is also bases should be secondary or tertiary amines not absolutely necessary that the admixed are understood to be those in 50 weight percent aqueous condensation products for themselves water-soluble Solution have a pH value of at least 9. It is only necessary that you reach. It is not necessary that the carboxyl 5 hydrophilic character is sufficient to combine groups of the reaction product completely to new with the plasticizing effect according to the invention neutralize, but it is sufficient to add as much amine, produced water-soluble polyether acid resins that the products are at least dilutable with water. to give sufficient tolerance, d. i.e., a-It is advantageous, the water dilution in counter-baked clearcoat films must be homogeneous, and War of so-called hydrophilic solvents in the water-based paints may also be used when applying. As such hydrophilic solvents, working concentrations do not cause separation of the bonds z. B. suitable: Ethylene glycol ether, such as medium proportions.

Ethyiglycol, isopropylglycol, butylglycol, also ethers Examples of suitable thermosetting, hydrophilic,

of diethylene glycol, such as diethylene glycol diethyl ether, low molecular weight condensation products are Phe-

Diethylene glycol dimethyl ether, but also alcohols. 15 alcohols and phenolic polyalcohols, d. h .. still

such as methanol, ethanol, propanols, butanols, secondary low molecular weight, obtained by condensation

Butanol, tert-butanol and also octonene alcohols. such as products of mono- or polyhydric phenols with

Diacetone alcohol. Aldehydes such as formaldehyde, acetaldehyde, croton

The novel polyether resins are available as sole binder aldehyde, acrolein, benzaldehyde and furfural, or medium or in a mixture with other binders in formaldehyde-yielding compounds, such as paraforms Baked enamels included. A preferred veraldehyde, paraldehyde, trioxymethylene. Preferred The application of the new polyether resins consists of aldehyde is formaldehyde or a formaldehyde Use as a sole binder or in a mixture with a supplying compound that is used in an alkaline medium in other binders, is obtained in an electrophoretically deposition known manner, such as. B. Hexabars Lacquers. Another preferred embodiment is methylene tetramine. Suitable phenols are phenol, form consists in the use of the new type of synthetic resins substituted in the o-, o'-p-position, but with form synthetic resins as a binder for air-drying paints. aldehyde condensable phenols such as cresol or

The paints produced according to the invention can xylenol. Phenols that are unpigmented from alkyl are very suitable or be pigmented and / or filler phenols, such as propyl, butyl, in particular p-tert-substances contain. For example, they can be obtained on wood, butylphenol. There are also resols Concrete, masonry, plaster or even on iron and made of binuclear phenols, such as diphenol and bis-steel, as well as on non-ferrous metals, or without phenol A, suitable. In particular, such resols are Pretreatment, such as passivation, phosphating, based on bisphenol A suitable, the per mole of biselectrochemical Treatment. Zinc plating, tin phenol A 1.75 to approx. 2.5 "Mo1 formaldehyde formulation or other metallizations after various 35 stored.

Process, including electrophoretic dissolving "Very well, phenolic carbon can also be used as resols.

wear-wise, are applied. Pigments and or acid produced by condensation of formaldehyde

Fillers are for example - without the invention or formaldehyde-supplying compounds with

to limit this - iron oxide red, carbon black- suitable phenol carboxylic acids have been obtained.

Use black, lead silica chromate, strontium chromate, Blanc 40. Among the formaldehyde condensing

Fix. micronized types of barite, microtalkum, colloidal phenol carboxylic acids, the 4,4-bis (4-hy-

Dale chalk, diatomaceous earth, china clay, titanium (hydroxyphenyl) valeric acid are preferred positions

dioxide and chromium oxide. a. The most favorable results are also here

The use of strongly basic pigments, as obtained when 1.75 to 2.5 moles of formaldehyde per zinc oxide, zinc chromate, lead carbonate, basic lead, 45 moles of phenol carboxylic acid are bound. The Hersulfate. Red lead, or calcium plumbate, requires a precise examination of the other similar phenol carbonic acid residues. These pigments can become thick, for example in German Auslegeschrift 11 13 775, or they can tend to fail. The described according to the invention. The phenol carbonic acid resoles. Lacquers produced in particular can be stoved at elevated temperatures, those based on 44-bis (4-hydropheny1). When used as one-valeric acid, which are well suited for combination for the firing lacquers, an admixing of water-soluble lacquers to be produced according to the invention, which are suitable for the inventive or at least hydrophilic, low molecular weight Aide- according to the invention as electrophoretic hydrolytic condensation products, ζ. Β. Phenolic resols and / or separable lacquers are determined. It is very pre- or aminoplast-forming condensation products that at least some of the formaldehyde be beneficial. The mixing of the novel condensation products with lower monohydric water-soluble polyethers with relatively low-molecular-weight alcohols with 1 to 4 carbon atoms is ocular, at least hydrophilic, thermosetting ethers, such as ethanol, methanol, propanols, butanols. Condensation products, such as aminoplast-forming. Preferred water-thinnable phenol resols are sol reaction products and / or phenol resols and / before the reaction of phenol resols etherified or etherified with alcohol results in higher phenol aldehyde condensation products with ali-crosslinking of the stoved coating agents and phatic monooxy or dioxycarboxylic acids and thus a further improvement in their lacquer-related esters were obtained and those in the Belgi properties. as hardness, gloss and corrosion see patent 7 24923 are described.
protection. As thermosetting, hydrophilic, low molecular weight.

Among thermosetting, hydrophilic condensation products, aminoplast-forming condensation products apply

on products should also be such condensation aldehyde reaction products of those with alde-

products are understood that, although heated alone, hyden convertible compounds, such as urea,

a relatively high molecular weight, but not yet non-ethylene urea. Dicyandiamide and Aminnirinzinen.

such as melamine, benzoguanamine, acetoguanamine and formoguanamine. The aforementioned compounds can use aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, acrolein, and benzaldehyde Furfural be implemented. Aldehydes should also include aldehyde-forming compounds such as paraformaldehyde, Paraldehyde and trioxymethylene. The preferred aldehyde is formaldehyde; preferred Aldehyde-binding compounds are melamine and urea. The implementation takes place in the usual molar ratios, e.g. B. urea resins in a usual formaldehyde molar ratio of 1: 1.5 to 1.4, for melamine resins in a formaldehyde molar ratio from 1: 1.5 to 1: 6. The aminoplast-forming condensation products are preferred in partially or fully alkylated or alcohol-modified form for use. Have good In the present case the etherification products of the lower half-ethers of Glyku and Diglycol, such as Äthylglvkol, Äthyldiglykol mit dem Methylolmelamin, bewa.m, as they are already in the Austrian Palentschrift 180407 described are. The most preferred positions have low molecular weight condensation products of melamine with Formaldehyde in a melamine / formaldehyde ratio of 1: 4 to 1: 6, which is almost completely with Methanol have been etherified. Ethers containing nitrogen that have been partially esterified with dicarboxylic acids are also suitable Polymethylol compounds such as are used, for. B. by transesterification of hexamethoxymelamine with Adipic acid can be obtained.

Such water-thinnable melamine resin condensation products are particularly preferably used, the reaction of aminotriazine-formaldehyde condensation products etherified with alcohol, which contain at least one mole of volatile alcohol residue in the ether bond, with aliphatic Hydroxycarboxylic acid esters have been obtained by heating, and those in the French patent 1544219 are described.

Preference is given to lacquers which contain combinations of the novel polyether carboxylic acid resins and aminoplast-forming or phenoplast-forming condensation products with 10 to 30 percent by weight, based on the solids content of the binder. For the electrophoretic application process, it is advantageous not only to mix in the thermosetting condensation products of the type already explained above, namely phenoplasts and / or aminoplasts, but to subject the components to a reaction. The reaction, which can be referred to as precondensation, is generally carried out at temperatures of 100 to 150 ° C., whereby, by carrying out the reaction appropriately, care must be taken that the components are not esterified, but rather polyetherification in that the reaction of the components is carried out in the presence of an acidic catalyst known per se, such as, for example, phosphoric acids, p-toluenesulphonic acid or benzoic acid, at temperatures between 100 and 150 ^° C. The heating is stopped immediately when the acid number has decreased by about 10 units compared to the initial value of the acid number of the reaction mixture. This can preferably be achieved by using etherified, low-molecular, thermosetting condensation products as phenoplasts and / or aminoplasts. In order to obtain sufficient etherification, it is also beneficial to the reaction to be carried out under vacuum.

The stoving enamels produced with chemically combined binders can be applied to the objects to be coated using the customary methods; they are particularly suitable for painting sheet metal. It is a particular advantage of the lacquers that they can also be deposited on the metal sheets using the electrophoresis process. The stoving of the lacquers can take place at temperatures from 80 to 200, preferably from 100 to 180 ^° C., and depending on the stoving temperature in a time span of 10 to 80, preferably 20 to 60 minutes.

The lacquers can optionally, and practically in all cases, advantageously as an additional Component at least one which is soluble in the paint system and different from the polyether resin Remove the usual additional resin from the relevant water-thinnable stoving enamels, with the selection Pay attention to the type and quantity of the tolerance wedge.

When using the stoving enamels produced according to the invention, an addition of hydroxyl-containing compounds, in particular hydroxyl-containing amines, preferably polyamines, cheap. In a particular embodiment, those prepared according to the invention contain Varnishes as strong organic nitrogen bases have at least one compound with the general formula

R ₂ HHR ₂

R ₁ -OCC HH CCO-Rj

i i \ I I / i I

HH NC- (Y) _x -CN HH

/ I i \

R ₁ HHR ₁ '

where the substituents and symbols have the following meaning to have:

γ = -CH ₂ -, -C ₂ H ₄ -, -CjH ₆ -,

R ₁
i
-C ₄ H ₈ -, -CH ₂ -N-CH ₂ -

R ₁ = H-, CH, _{-C 2} H ₅ -, CH ₂ -COR.,

I. H

R ₁ '= H-. CH, ~. C ₂ H ₅ -. CH ₂ -COR ₃

RiI fUI C UI

R ₂ '= H-. CH ₃ . C ₂ H ₅ -

R, = H-. (CHj-CH ₂ -O -) .- H.
CH ₃ ^%

CH, -C -O

R ₃ - = Η-, - (CH ₂ -CH ₂ -O ^ -H.

ι CH ₃

CH ₂ -CO

- Η

χ = O or an integer between 1 and 6.

Preference is given to those polyhydroxypolyamines according to the above general formula which by complete substitution of the hydrogen atoms of polyamines are characterized by the 2-hydroxypropyl radical, in particular by exhaustive Reaction of diethylenetriamine and diethylenetetramine with propylene oxide obtained polyhydroxypolyamines. The manufacture of the aforementioned polyhydroxypolyamines is in French Patent 1497222 described.

The vinyl modified polyethers produced according to the invention can also be used for the production of air-drying Varnishes are used. In this case it is necessary to siccativize the paints. as Siccatives are suitable for the production of relevant known cobalt, lead and manganese compounds. Those which are dispersible in water are preferred.

The air-drying paints can optionally, and in practically all cases, advantageously as an additional component, at least one that is soluble in the paint system, of the oxidatively drying component Carboxylic acid resin various, in the case of relevant water-thinnable, air-drying paints contain the usual additional resin, whereby the selection according to Art and amount, the tolerance must be taken into account.

In some cases it has proven to be useful to use the water-dilutable, vinyl-modified polyether with dispersions based on styrene-butadiene copolymers. Vinyl acetate homopolymers and vinyl acetate copolymers as well as pure acrylate copolymers. individually or as a mixture, to be mixed. The quantitative ratios between dispersion and according to the invention The coating compositions produced can be 5 to 95 or 95 to 5 percent by weight.

Polyether resins are used for paints that are preferred to be produced used as conversion products, made from:

1. 41 percent by weight of soybean oil fatty acids, noethanolamide, 29 percent by weight of an epoxy resin based on 4,4'-dioxydiphenylpropane with an epoxy equivalent weight of 240 to 290. 24 percent by weight styrene and 6 percent by weight Acrylic acid.

2. 45 percent by weight of linseed oil fatty acid monoethanolamide. 23 percent by weight epoxy resin, see item 1, 25 percent by weight ethyl acrylate and 7 percent by weight Acrylic acid.

3. 50 percent by weight of the reaction product from 28Og linseed oil fatty acid and 105 g diethanolamine, 28 weight percent epoxy resin, see number 1, 14.5 percent by weight styrene and 7.5 percent by weight acrylic acid.

4. 40 percent by weight of linseed oil fatty acid monoethanolamide, 40 percent by weight of an epoxy resin based on 4.4'-dioxydiphenylpropane and an epoxy equivalent weight of 450 to 525,

ίο 13 percent by weight styrene and 7 percent by weight Acrylic acid.

5. 40 percent by weight of ricin fatty acid monoethanolamide, 30 percent by weight of an epoxy resin, see section 4, 20 percent by weight styrene and 10

: _as percent by weight acrylic acid.

The following are preferred for the production of stoving enamels:

6. The mixture of 30 parts by weight of a p-tert-butylphenol resol and 70 parts by weight of resin according to item 5.

7. The mixture of 30 parts by weight of a phenolic resin based on 4,4'-dioxydiphenylpropane with a formaldehyde charge of about 4 and 70 parts by weight of the resin according to item 4.

8. The mixture of 20 parts by weight of hexamethoxymethylmelamine and 80 parts by weight of resin according to section 4.

9. The precondensate of 20 parts by weight of a p-tert-butylphenol resol which has been etherified with n-butanol and 80 parts by weight of resin according to item 1.

10. The precondensate of 30 parts by weight of a phenol resol based on 4,4'-dioxydiphenylpropane with a formaldehyde charge of about 4 and 70 parts by weight of resin according to item 5.

11. The precondensate of 20 parts by weight of hexamethoxymethylmelamine with 80 parts by weight of resin according to item 5.

Manufacture of the polyether resin 1

400 g of soy fatty acid monoethanolamide and O. (* G of a 40 percent by weight solution of boron trifluoride in ether are dissolved in 150 g of dioxane. For this purpose, a solution of 280 g of an epoxy resin with an epoxy equivalent weight of 240 to 290 and a viscosity of 500 to 1000 cP is added at 80 C. measured 70 percent by weight in butyl glycol at 25 ° C. and a refractive index of 1.5830, which was obtained in a known manner by condensation of bisphenol A with epichlorohydrin, in 150 g of dioxane. After the addition is complete, the mixture is added dropwise at 80 ° for 1 hour The dioxane is then removed by vacuum distillation and a mixture of 240 g of styrene, 60 g of acrylic acid, 6 g of di-tert-butyl peroxide and 6 g of lauryl mercaptan is added dropwise ^{to the residue at 150 ° C. over the course of 2.5 hours.}

After the addition is complete, the mixture is ^{kept at 150 °} C. until the solid has reached 98 percent by weight. The remainder of the unreacted monomers is then removed by vacuum distillation. The product has a viscosity of 250 cP, measured 1: 1 in butyl glycol at 20 ° C., and an acid number of 32. It is diluted with isopropyl glycol to a solids content of 80 percent by weight.

Manufacture of the polyether resin 2

400 g of linseed oil fatty acid monoethanolamide and 210 g of polyether resin 1 are mixed together. For this purpose, a solution of 0.6 g of a 40 percent strength by weight boron trifluoride solution in ether, in 10 g of linseed oil fatty acid ethanolamide, is added at 40.degree. The mixture is then ^{kept at 80 °} C. for 2 hours. To the resulting product was a mixture of 220 g of ethyl acrylate, 60 g acrylic acid, 5.8 g of di-tert-butyl peroxide and 7.7 g of lauryl mercaptan are added dropwise at i50 C for ^D?} / ₂ hours. The mixture is then held at 150 ^° C. until the solid has reached 98 percent by weight. The remainder of the unreacted monomers is then removed by vacuum distillation. The product has a viscosity of 15OcP, measured at 1: 1 in butyl glycol at 2O ⁰ C, and an acid number of 30. The mixture is diluted with isopropyl glycol to a solids content of 80 weight percent. (The resin neutralized with triethylamine can be diluted with water indefinitely.)

example 1

The polyether resin 2 is neutralized with concentrated ammonia solution and diluted with water to 40 percent by weight solids. The solution is siccative with cobalt siccative, 0.1 percent by weight cobalt, calculated on the solid resin. A film drawn on a glass plate with a layer thickness of 90 μ is dust-dry within 2 hours. In its pigmented state, the coating compound is extremely well suited for corrosion protection primers and is characterized by its high resistance to salt spray. The pH of the application solution is 9.5. After 21 days of storage at 50 ^° C., the pH was 9.4. The drying properties of the product had not changed during this period.

Example 2

The polyether resin 1 is treated with one of the documents laid out in Belgian patent 724923, Example 2, described phenol resin ether carboxylic acid in a ratio of 7: 3, based on the solids, mixed. The preparation of the phenolic resin carboxylic acid is described below. The resin mix is neutralized with triethylamine and reduced to a solids content of 40 percent by weight with water diluted. The paste is then rubbed in a ceramic ball mill with titanium dioxide so that the Pigment binder ratio is 0.5: 1. Thereafter, the paste is mixed with water to a solids content diluted by 10 percent by weight. The solution is poured into a steel basin 1Ox 1Ox 18 cm, and Passivated steel sheets are coated in it by applying an electrical direct voltage at 110 volts. The sheets are then baked at 170 ° C. for 30 minutes, and extraordinary results are produced hard, resistant coatings.

Production of the etherified phenol resol

686.5 g p-tert-Butylphenolresol be dehydrated under vacuum to 90 ⁰ C, then 1650.0 g n-butanol and 835.0 g of toluene are added. The mixture is heated to the boil and the water is removed by azeotropic distillation, the solvent mixture being returned to the reaction vessel. After about 40 g of water has been removed, 8.0 g of 85 weight percent phosphoric acid are added and the azeotropic distillation is continued until no more water passes over. The acid is then neutralized with calcium hydroxide added in solid form. The product is concentrated in vacuo to a temperature of 110 ^° C. and then filtered. The solids content is about 92 percent by weight.

Production of the phenolic resin carboxylic acid

340 g of etherified phenol resol, as described above, are obtained, and 70 g of dimethyl olpropionic acid are obtained mixed and under vacuum to 150 to 160 ° C heated and held until about 100 g of

• 5 stillat (butanol) have passed over. The product then has a viscosity of 150 cp, measured at 1: 1 in butyl glycol at 20 ⁰ C, and an acid number of 90. The product is diluted with "" opropylglykol to 80 weight percent solids The neutralized resin is at pH 8.5!. unlimited water dilution.

Example 3

The polyether resin 1 is with an anioni-2s see melamine resin according to Example 2, as in that interpreted priority document of the French patent specification 1544219, namely the German patent application R451951Vd / 12p described, in the ratio 8: 2 mixed. This mixture is pigmented and as described in Example 2 of this invention just as described there, deposited electrophoretically. The sheets are kept at 150 ° C for 30 minutes burned in. Relatively bright, hard coatings are created.

Manufacture of the anionic melamine resin

390 g of hexamethoxymethylmelamine, 150 g of n-butanol and 140 g of butyl glycolate are mixed and 0.1 g of p-toluenesulfonic acid was added as a catalyst.

The mixture is heated to 100 to 110 ^° C. until no more distillate passes over. Then vacuum is applied and the unreacted portion of alcohol and ester is distilled off. 100 ml of 5N NaOH and 100 ml of water are then added.

It is refluxed for 1 hour. Then the water is azeotroped with benzene as an entrainer Distillation removed. The benzene is then distilled off in vacuo and the mixture becomes a solution of 30 g of oxalic acid in 100 g of acetone at 30 ° C. It is stirred well and then filtered. Then the resin is neutralized with triethylamine. It can be diluted with water indefinitely and can be used for electrophoretic painting.

Example 4

160 g of polyether resin 1 are produced, but the resin is not diluted in isopropyl glycol, but 43.5 g of the etherified phenol resol, the production of which is described in Example 2, is added. 1 g of a 40gewichtsprozentigen isobutanol solution of 80 weight percent phosphoric acid are added, and the mixture is heated under vacuum to 14O ⁰ C and kept at this temperature has reached until the acid number is about 42 and the viscosity of 15OcP, measured at 1: 1 in Butyglykol at 20 ° C. The resin is then diluted to 80 percent by weight with diacetone alcohol

and with diisopropanolamine to a pH of about 8 neutralized. It is suitable as the sole binder for electrophoretic painting.

B ei s ρ i e I 5

The resin combination described in Example 4 is instead of diisopropanolamine with N, N, N ', N'-tetrakis - (- 2-hydroxypropy]) ethylenediamine neutralized. The resin works well for spray primers and can be applied in thick layers without hosing down bake in the applied layer.

B e i s ρ i e 1 6

160 g of polyether resin 1 are produced, but the resin is not diluted with butyl glycol, but rather 40 g of hexamethoxymethylmelamine are mixed in. 0.1 g of toluenesulfonic acid is added and the mixture is heated to 120 ^° C. under reduced pressure. As soon as the acid number has fallen to 35, the resin is diluted to a solids content of 80 percent by weight with isopropyl glycol and neutralized with diisopropanolamine. The resin is suitable for electrophoretic painting to achieve light-colored coatings.

Manufacture of polyether resin 3

450 g of an epoxy resin with an epoxy equivalent weight of 450 to 525, a softening point of 65 to 75 ° C., which was obtained in a known manner by reacting bisphenol A with epichlorohydrin, are dissolved in 500 g of xylene. To this end, 400 g of ricin oil fatty acid monoathanolamide are added. A solution of 1 g of boron trifluoride, 40 percent by weight, in ether in 30 g of ricin oil fatty acid monoethanolamide is then added and the mixture is boiled for 1 hour at reflux temperature. The xylene is then removed by vacuum distillation. The resin is then diluted with Athvlglykol to a solids content of 80 percent by weight, and for 3 hours at 140 ⁰ C a mixture of 80 g acrylic acid, 200 2 ethyl acrylate, 90 g of butyl acrylate, 10 g of di-tert-butyl peroxide and 10 g of lauryl mercaptan admitted. The temperature is maintained until the solids content has reached 85 percent by weight.
Example 7

The procedure is as described in Example 1, but the polyether resin 3 is used.

Manufacture of the polyether resin 4

It becomes the same as in the manufacture of the polyether resin 2, but instead of linseed oil fatty acid monoethanolamide the reaction product of 300 g of linseed oil fatty acid and 105 g of diethanolamine 220 ° C used.

Example 8

The procedure is as described in Example 1, but the polyether resin 4 is used. The paint obtained has air-drying properties.

Claims (10)

Patent claims: 1. Process for the production of water-thinnable synthetic resins on the basis of nitrogen-cold ones Polyethers through implementation of a) Compounds with the general formula CH, CH-CH ₁ - -O- CH, -CH, - CH ₃ O-CH, -CH CH, where η represents the values 0 to 11 and a molecular weight between about 380 and about 3500 b) nitrogen-containing compounds by heating in the presence of catalysts, characterized in that as b) b 'alkanolamides of unsaturated fatty acids and' or b "oxazolines of unsaturated fatty acids of the general formula H, C- I. ο -C-R, C-X 35 40 where R _{2 represents} a hydroxymethyl or alkyl radical with 3 carbon atoms, where at least one R ₂ must be a hydroxymethyl _{radical, R 3 is a} mono- or polyunsaturated hydrocarbon with 16 to 18 carbon atoms, and XH ₂ or - = CH ₂ means to be used and by heating to temperatures of about 40 to 150'C in the presence of catalysts, to be etherified and c) the etherification products with such amounts •, / V-ethylenically unsaturated mono- and / or Polycarboxylic acids and, if they exist, their anhydrides and / or half-esters with monoalcohols with 1 to 4 carbon atoms in the presence of other vinyl or vinylidene compounds, by heating be implemented so that the Lmsetzungprodukte have at least an acid number of 25, and d) then the carboxyl group-containing reaction products with such amounts of ammonia and / or strong organic nitrogen bases until complete or partial neutralization 6s are added until the reaction products are sufficiently water-dispersible or water-dilutable are. 2. The method according to claim 1, characterized in that as component b) those unsaturated Alkanolamides are used, the reaction products of monoethanolamine or diethanolamine with unsaturated fatty acids, such as Soybean oil fatty acid, linseed oil fatty acid, tall oil fatty acid and ricin oil fatty acid are. 3. The method according to claim 1, characterized in that as component b) such oxazolines are used, the reaction products of diethanolamine or amines of the polyvalent Propanols or amines of polyvalent butanols with unsaturated fatty acids with 10 to 20 carbon atoms, preferably linseed oil fatty acid. Are tall oil fatty acid and ricin oil fatty acid. 4. The method according to one or more of claims 1 to 3, characterized in that the etherification of components a) and b) is carried out in such a way that the hydroxyl groups are always present of component b) are present in excess over the epoxide groups of component a). 5. The method according to claim 4, characterized in that the etherification is carried out by heating components a) and b) to temperatures of 60 to 120 ^r C. 6. The method according to one or more of claims 1 to 5, characterized in that as component c) methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and styrene, (i-methylstyrene and vinyltoluene. Alone or in a mixture. 7. The method according to one or more of claims 1 to 6, characterized in that that the carboxyl group-bearing component c) acrylic acid, methacrylic acid, cinnamic acid. , / - benzoylacrylic acid, Crotonic acid. Maleic acid. Fumaric acid, citraconic acid. Itaconic acid c. Methaconic acid c. Aconitic acid, its anhydrides, insofar as they are able to form such, or monoesters of the aforementioned Polycarboxylic acids with saturated, straight-chain monoalcohols with 1 to 4 carbon atoms, preferably methanol, monomethyl malcate, chloromaleic acid are used. 8. Use of the synthetic resins produced according to one or more of claims 1 to 7 as a binder for water-thinnable, air-drying or oven-drying coating agents. 9. Use of the synthetic resins produced according to one or more of claims 1 to 7 as a binder for electrophoretically separable air-drying or oven-drying coating compounds. 10. Water-thinnable, air- or oven-drying coating agent made from a synthetic resin as a binder, produced by the process of claim 1, and customary additives.