DE1745336A1 - Process for the production of water-dilutable, air-drying or burn-in synthetic resins - Google Patents

Description

DR. WALTER NIELSCH 17 May

Patent attorney

2 Hamburg 70 file: 2095

StWoßjtroße 112-Postfach 10914 ^S Telephone: 652 97 07

REICHHOLD CHEMIE AKTIENGESELLSCHAFT, Hamburg 70, Iversstrasse 70

Process for the production of water-thinnable, air- drying or stoving synthetic resins

It has long been known to produce synthetic resins by boiling phenolic resins with unsaturated oils (see: The wood oil from E. Ponrobert, Berliner Union, Stuttgart). These products, which are only soluble in organic solvents, are characterized by excellent properties, in particular the film properties. In the present invention, on the basis of this reaction, air-drying, water-thinnable synthetic resins are synthesized which, in particular, are able to meet the high requirements placed on the storage stability of such products. )

The invention includes a method for producing air-drying or stoving, water-thinnable, saponification-resistant synthetic resins in the form of their arrmonia and / or amine soaps, characterized in that these obtained by at least one of the following methods:

1. By heat conversion of at least one phenolic resin (i) with at least one ethylenically unsaturated Fatty acid (il), with at least 14 carbon atoms.

2. By heat reaction in stage A of at least one Phenolic resin (i), with at least one ester (ill and IV) Ethylenically unsaturated fatty acids, with at least one monohydric and / or polyhydric alcohol and the following Cleavage of the esters in stage B and, if appropriate, separation of the alcohols released and, if appropriate any inorganic salts present.

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" ^2. 17A5336

3 · By blocking any phenolic hydroxyl groups still present in the products according to 1 and / or 2 by reaction with compounds containing oxirane rings, the are capable of reacting with phenolic hydroxyl groups, the reaction of the products obtained according to 2 with the compounds containing oxirane rings preferably according to the stage ο Λ as stage A-, and the Cleavage of the ester is then carried out.

4. By copolymerization of the products according to 1 and / or 2, and / or J>, which in the latter cases can optionally also take place after stage A or A, with vinyl (V) and / or vinylidene compounds (Vl) in the warm, preferably in the presence of polymerization catalysts and cleavage of the esters in stage B, provided that products according to 2 or 5 were copolymerized in stage Λ or A, the copolymerization preferably not taking place until after stage B in the preferred variant.

5. By modifying the products according to 1 and / or 2 and / or 5, which in the latter cases Dv.oh after stage Λ or A, and / or the products h with cyclopentadiene or v /. Dicyclopentadiene (VIl) in the heat.

6. By heat reaction of at least one phenolic resin (i) with at least one with vinyl (V) and / or Vin; -lidenverbindungen (VI) copolymerized in the heat, preferably using polymerization catalysts Ethylenically unsaturated fatty acid (II) with at least 14 carbon atoms.

7. By heat reaction of at least; a phenolic resin (l) with at least one with cyclopentadiene bsw. Dicyclopentadiene (VIl) in the heat modified ethylenic unsaturated fatty acid (II) with at least 14-C ~ .Aton: 3n.

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8. By heat reaction in. Stage A of at least one phenolic resin (i) with at least one with vinyl (V) and / or vinylidene compounds (VI) copolymerized esters (III and IV) of ethylenically unsaturated Fatty acids (il) with mono- and / or polyhydric alcohols and subsequent cleavage of the esters in stage B and, if appropriate, separation of the released ones Alcohols and any inorganic salts present.

9. By heat shares in level A of at least a phenolic resin (i) having at least one with cyclopentadiene or dicyclopentadiene (VIl) heat-modified esters (III and IV) of ethylenically unsaturated Fatty acids (il) with mono- and / or polyhydric alcohols and subsequent cleavage of the Esters in stage B and optionally separation of the released alcohols and any alcohols present inorganic salts.

10. Implementation of the products according to 1 to 9 with α, g -ethylene unsaturated dicarboxylic acids. or so far exist, their anhydrides (VIII) in the Würrna.

The resols formed by the alkaline condensation of phenols with formaldehyde are particularly suitable as phenolic resin I. These resols already have more or more increased molecular weight due to heat condensation in an alkaline and / or acidic medium, so it is necessary, however, that the phenolic resins are selected in such a way that, after their reaction with the fatty acids (II) and / or fatty acid esters (III and IV) homogeneous products are created. This homogeneity is achieved particularly easily in so-called oil-soluble, preferably oil-reactive, phenolic resins. Resole based trifunktionoller simple phenols are therefore wenicon for IHI ¹ Cr pronounced alcohol solubility only in verhältnisr.äßig, particularly favorable cases at the implementation n \ it

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17A5336

unsaturated fatty acids. Most suitable are alkylphenol resins which can easily be condensed with unsaturated fatty acids or their esters.

Without difficulty, the so-called oil-reactive Alkylphenolic resins can be used. Resoles, which can only be obtained by appropriate etherification of the methylol groups in their Solubility behavior of the alkylphenol resins have been adjusted in terms of their boilability with the Fatty acids (il) must be checked carefully.

In the present invention in the first I inie Suitable phenolic resins I include those produced by alkaline condensation of phenols of the general formula Aldehydes, preferably formaldehyde, formed resoles. These are preferably in largely anhydrous form used.

R = alkyl radical with 2 to 20 carbon atoms or aryl radical

The phenols of the general formula bind in the lace, up to 2 moles of formaldehyde per mole of phenol zn. Resoles containing 1 to 2 mol of formaldehyde per mol of phenol are preferred. The molecular weight of the resoles can already have been increased to a greater or lesser extent by condensation in an alkaline and / or acid medium, so that so-called phenolic resins are present. However, it is necessary that the phenolic resins are selected in such a way that homogeneous products result after their reaction with the fatty acids (II) and / or fatty acidic esters (III and IV). Among the phenols of the general formula, p.-tert-^ ucylphenol is very particularly suitable. Phenols of the general formula substituted with longer alkyl chains contribute to the deficiency of the films produced from the synthetic resins according to the invention. However, the films also get softer and have

.. ,, .... ν «20981 3/1 354

a lower water resistance. To establish the desired properties, a mixture of different phenols of the general formula with substituents R of different chain lengths is therefore recommended. Phenols of the general formula in which R = C ₅ H ₁₁ , CgH ₁ ^, C ₇ H ₁₅ , CgH ₁₇ , C ₉ H _{19 are} particularly suitable for elastification. The phenolic resins and / or resols can also have already been etherified with alcohols in a known manner.

Phenolic resins based on can also be used Bisphenol-A, but preferably with a low charge with formaldehyde (phenolformaldehyde 1: 0.8 to 1: 1.5) In the case of bisphanol resins, etherification may occur if a high charge with formaldehyde is sought with monohydric alcohols with 1 to 4 carbon atoms advisable. Phenolic resins based on are also suitable Phenolcarboxylic acids, the phenolcarboxylic acids however still having at least one free phenolic hydroxyl group must contain and should at least be bifunctional,

i.e., the Ph ^ nolcarbons- ^ u ^ a i.; uß 2 Hol formaldehyde to accumulate capital. The use of cresol and xylenol resins, optionally etherified cresol and xylenol resins, must be checked on a case-by-case basis.

In addition to the phenolic resins mentioned, other phenolic resins such as terpene phenolic resins can also be used as admixtures and oil-soluble phenolic resins, which are reaction products of phenol-formaldehyde condensation products with natural resins are used. The use of terpene phenolic resins can be beneficial for viscosity regulation impact.

Suitable unsaturated fatty acids (II) are: eleostearic acid, Licanic acid, parinaric acid, linolenic acid with isolated and conjugated double bonds, linoleic acid with isolated and conjugated double bonds. These acids are known to be present individually or as a mixture. The total of the multiple unsaturated fatty acids in the reaction product of I and

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II should be 20-90% , preferably 40-75 %. These ratios also apply if, instead of the free fatty acids, their esters III and IV are used. In addition, fatty acids with 10 to 50 carbon atoms which have at least one unsaturated carbon double bond in the chain are suitable as admixtures with the acids mentioned above, all unsaturated fatty acids occurring in natural fatty oils, such as palmitoleic acid, petroselic acid, oleic acid, elaidic acid, erucic acid, Arachidonic acid, clupanodonic acid, etc. The total content of these at least monounsaturated fatty acids must not, however, exceed 60 wt. # (Based on the reaction products I and II). However, the content of these fatty acids is preferably below 30 wt. The proportion of saturated fatty acids that is always present when fatty acid mixtures, such as those obtained by saponification of natural oils, are used, should not exceed 20% by weight, if possible even below 10% by weight. The polybasic acids obtained by dimerization or obligomerization of unsaturated fatty acids can also be used as unsaturated fatty acids (II). It is preferred to use unsaturated fatty acid mixtures such as are obtained from natural vegetable and animal unsaturated fats by saponification. Such natural unsaturated fatty oils are, for example, cottonseed oil, lupine oil, corn oil, rapeseed oil, sesame oil, grapeseed oil, walnut oil, perilla oil, linseed oil, wood oil, oiticica oil. Of these, wood oil, oiticica oil and linseed oil are preferred. In particular, mixtures of wood oil and oiticica oil with linseed oil, whereby the linseed oil content should not exceed 60% by weight. Furthermore, fatty acids from dehydrated castor oil which contain a high proportion of conjugated linoleic acid are also suitable. Additions of natural resin acids (rosin) up to a maximum of 30 %, based on the reaction product I with II, can be added under certain circumstances.

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Instead of fatty acids, however, it is often advisable to use fatty acid esters. Both fatty acid esters of monohydric and polyhydric alcohols can be used. The inexpensive fatty acid methyl esters, which are obtained by transesterification of natural, unsaturated oils, are recommended as fatty acid esters of monohydric alcohols. Like the fatty acids, they represent fatty acid mixtures. Natural oils, ie glyceride esters of unsaturated fatty acids, are primarily suitable as fatty acid polyol esters. The fatty acids contained in the esters (III and IV) correspond to the fatty acids mentioned under (II) including the selections and proportions made there. The use of difatty acid esters _VO n glycols, especially Kthylenglykol and propylene glycol may be advantageous to control the viscosity during the course of the reactions.

The reaction of the phenolic resins (i) with the fatty acids (II) and / or fatty acid esters (III and IV) takes place at an elevated temperature, generally between 200 and 270 C. When using fatty acids or fatty acid glyceride esters of highly unsaturated fatty acids, there is usually a little A lower temperature, i.e. around 200 to 240 ° C., is advantageous, while a higher temperature between 250 and 270 ° C. may be necessary for less strongly unsaturated fatty acids. When ptenol resins are reacted with highly unsaturated oils (wood oil, linseed oil, oiticica oil), temperatures and reaction times must be adhered to very precisely, as this reaction - as is well known - can very easily lead to gel formation. As a reference value can be said that (measured # 66 in white spirit) in the reaction between phenol resins and highly unsaturated fatty oils max. A viscosity of about 1000 centipoise / 20 ⁰ C can be obtained. A gelled batch can also be worked up on a laboratory scale, since the subsequent saponification of the reaction product causes the gel to split, but this operation cannot be carried out technically.

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When using fatty acids (II) or fatty acid esters of monohydric alcohols (III), in particular fatty acid methyl esters, the reaction with the phenolic resins is less critical. The viscosity can vary within wide limits here, but it has proven to be beneficial if. the viscosity of the reaction products between 100 and 500 centipoise / 20 ⁰ C (50% in butyl glycol) is measured. The reaction temperature should be about 270 ° C.

Since phenols are known to act as antioxidants and can therefore cause a delay in drying in paint films, the reaction product of phenols with unsaturated oils and / or fatty acid monoalcohol esters with compounds containing oxirane rings which are capable of reacting with phenolic hydroxyl groups, preferably ethylene oxide or propylene oxide, be implemented in order to etherify any phenolic hydroxyl groups that may still be present. This reaction takes place in such a way that at an elevated temperature above the boiling point of the ethylene oxide or propylene oxide, optionally under pressure, the reaction is carried out with about 10 % ethylene oxide or propylene oxide (based on the batch). The reaction is complete after about 2 hours, after which the excess ethylene oxide or propylene oxide is distilled off, if necessary under vacuum. It has been found, however, that this conversion is not absolutely necessary in every case.

To achieve solubility in water, it is necessary that the reaction product bearing carboxyl groups is made from fatty acids and phenolic resins are neutralized with ammonia and / or strong organic nitrogen bases. Preferably is suitable for air-drying, water-thinnable coating compounds aqueous ammonia solution, since synthetic resins neutralized with aqueous ammonia solution films with the slightest Yellowing tendencies result.

When converting phenolic resins (i) with fatty acid esters (ill and IV) is to achieve water dilutability first saponification of the ester bonds is necessary.

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This saponification can be carried out in the normal way with aqueous alkalis in the heat; if the saponification is carried out flat, the reaction mixture is acidified with mineral acids, which causes the resin to precipitate and the aqueous salt solutions can be separated off. For complete removal of existing salts mehrm is · I sodium washing with water is required. Much more expedient than alkaline saponification is saponification with water, optionally with the addition of small amounts of acidic catalysts, which is carried out in a known manner at a higher temperature under pressure. In this case, it may not be necessary to wash out the resins, so that the reaction product can be neutralized directly with ammonia or strong organic nitrogen bases. Pressure saponification with aqueous ammonia solution at approx. 8o to 100 ° C is also sufficient in m
dilutable.

100 C is sufficient in some cases to achieve water

The products obtained in this way (1,2 and 3) are already as a water-thinnable binder for production well suited for air-drying coating compounds. In particular in terms of drying speed and water resistance of the dried films, they leave or through a copolymerization with vinyl or vinylidene compounds (4,6,8) and / or through a Addition of cyclopentadiene or dicyclopentadiene, even better (5 * 7 * 9)

The copolymerization gives synthetic resins which give films with very short drying times, which were not achieved by the modification with cyclopentadiene or dicyclopentadiene. Ss therefore becomes the Copolymerization is preferred over modification with cyclopentadiene.

However, since the modification with cyclopentadiene is a a mixture of synthetic resins modified with cyclopentadiene with those, which by copolymerization with vinyl and / or vinylidene

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connections have been obtained.

A subsequent reaction (10) of the anhydrous or largely anhydrous (water content <5 $) products with α β äthylenisctfi unsaturated dicarboxylic acids at temperatures between 100 and 220 ° C, with an adduct formation taking place in a known manner, can increase the hardness of the films and to Improving the water solubility of the synthetic resins may be beneficial, but this method is not part of the preferred embodiment.

The best products were obtained according to method 4 if products according to 2, preferably after? after stage B were copolymerized in anhydrous medium, wherein the vinyl and / or vinylidene compounds were characterized by an admixture of acrylic acid.

The conversion of vinyl and / or vinylidene compounds takes place in the heat, preferably under the action of Polymerization catalysts. The reaction is preferably carried out with a vinyl or vinylidene monomer mixture carried out, the at least one acid equivalent (expressed in grams) in 1,800 g of one for copolymerization with the Contains unsaturated carboxylic acid capable of vinyl or vinylidene compounds. The reaction is preferably carried out with Vinyl and / or vinylidene compounds carried out in an anhydrous medium (water content < $ 5).

When using relatively weakly polar monomers, such as styrene, α-methyl-styrene, vinyl toluene, in l800 g, preferably 2 to 4 acid equivalents be included.

The copolymerization temperature depends on the catalyst system used. As the cheapest areas are Reaction temperatures between 120 and 160 ° C. are preferred using di-tert-butyl peroxide, if appropriate in combination with a chain terminator, preferably lauryl mercaptan. At lower temperatures is the reaction mixture for easy processing

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often too highly viscous. In addition, the speed of reaction, which can be followed by the increase in solids content, for many monomers slow. At high temperatures, products with a lower viscosity are obtained, even with purely thermal polymerization, however, these are poorer in terms of their film properties.

The rate of reaction can be increased by cobalt (II) chloride in amounts of > to 6 parts per million. However, the same reaction times are also achieved in the presence of V4A material. The use of monomers containing carboxyl groups increases the solubility of the system as a whole in water. The content of vinyl monomers based on the total solids ^? "* Body content of the reaction product, can reach 50 #. The total amount, however, depends on the type of monomers used.

As vinyl and vinylidene monomers come primarily Vinyltoluene, α-methylstyrene and styrene are possible. The co-use of aerylic acid esters cannot be avoided in some cases in order to achieve sufficient elasticity of the To achieve movies. Preferred acrylic acid esters are therefore those which are relatively stable to saponification.

Suitable alkyl esters of α, 3-unsaturated monocarboxylic acids methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, Lauryl acrylate and the corresponding Meth-y A'th-, Phenyl acrylates, propyl orotonate, butyl crotonate and the like, also hydroxyl alkyl esters, α, β-unsaturated Carboxylic acids, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, S-Hydro ^ butyl acrylate, 3-Hydroxybutyl acrylate, 6-hydroxyhexyl acrylate and the corresponding methacrylates, Ethacrylate, phenyl acrylate, 2-hydroxyethyl maleate, Di- (2-hydroxypropyl) maleate or the corresponding fumarates, 2-hydroxy-J-chloropropyl acrylate, 2-hydroxy-1-

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-Phenylethyl acrylate, 2-hydroxy-3-butoxypropyl acrylate and the corresponding meth-, A'th- and phenyl acrylates. Furthermore, styrenes substituted in the core (ortho-metha-, para, methyl-, ethyl-, propyl-, butylstyrene, 2,4-2, I ) -, 2,5-dimethylstyrene, 2,4-, 2,3-, 2,5-dichlorostyrene) substituted in the side chain. Styrenes such as α-methyl styrene, α-'thy is tyro 1, α -chlorostyrene, etc. are possible. The vinyl monomers which are stable to saponification and esters susceptible to saponification are preferably used only to the extent that is absolutely necessary for the elasticization of the films, preferably 2-ethylhexyl acrylate. As monomers bearing carboxyl groups, which must be capable of copolymerization with the above-mentioned monomers, acrylic acid and / or methacrylic acid, cinnamic acid, β-benzoylacrylaic acid, crotonic acid etc. are also suitable able to form, such as maleic acid, fumaric acid, citraconic acid, itaconic acid ,, mesaconic acid, aconitic acid or monoesters of the polycarboxylic acids mentioned with saturated, straight-chain monoalcohols having 1 to 4 carbon atoms, preferably methanol. The preferred α , ß-ethylenically unsaturated monocarboxylic acids include acrylic acid and methacrylic acid. The monomers bearing carboxyl groups can be reacted alone, in mixtures of lower insiders or alone, or in mixtures with the monomers bearing no free carboxyl groups.

As far as compatibility is achieved in the overall system, can the monomer mixture individually or as a mixture other polymerizable Monomers can be added, such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and the like. The total proportion of polymers of vinyl or vinylidene compounds in total resin can be $ 0 to $ 50. It was however, found that the best results in terms of water resistance of the mushrooms are when the total content of polymers made from vinyl and / or vinylidene compounds 28 to 35 Gev. $ N =! I-protrudes. Will the polymerization not driven up to a high fixed tipper, so it is advisable the removal of the excess monomer content

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Vacuum distillation. As already stated, aqueous ammonia solution is particularly suitable for neutralization. However, if the tendency of the film to yellow, as is the case with primers, for example, strong organic nitrogen bases can also be used for neutralization. Volatile alkylamines are particularly suitable such as triethylamine, diethylamine, trimethylamine, tertiary, secondary or primary alkylolamines such as triethanolamine, diethanolamine, monoethanolamine, N-dimethylethanolamine, N-methylethanolamine, N-diethanolamine, monoisopropanolamine, di-isopropanolamine, triisopropanolamine should generally be used under strong organic nitrogenous bases those are understood, the 0.05 normal aqueous solutions of which have a pH value> 10.0, measured at 25 ^° C. The neutralization with aqueous ammonia solution and / or strong organic nitrogen bases should take place at room temperature or only moderately elevated temperatures is it, di e to carry out neutralization in the presence of water.

In a particular embodiment, the coating agents according to the invention contain strong organic ones Nitrogen base at least one compound according to the general formula:

-O fa H H -C-
, ' C.
j H H

F 1

- (Y) _x -C -N

R ₁ 'HH

where the substituents and symbols. following meaning to have:

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Y = CH ₂ -, C ₂ H ₄ -, C ₃ H ₆ , C ₄ H ₈ -, CH ₂ -N-CH ₂ -;

R ₂

= H 1 CH ₃ -, C ₂ H ₅ -, CH ₂ -COR ₅ -;

-, CH ₂ -COR ₃ -;
H

-, C ₂ H ₅ -;

GH I

= H-,. (CH ₉ -CH ₀ -O-) -H; - <CiL-C - 0) - H and

^CH 3 "C

IU = H, (CH ₂ -CH >> -0.) _X -H; = (CH ₂ - "C- 0) _χ - H and

Zero or
χ = -Q an integer between 1 and 6.

Such polyhydroxypolyamines are preferred according to The above general formula, which is obtained by completely substituting the hydrogen atoms of polyamines with the 2-hydroxypropyl radical are marked. In particular the polyhydroxypolyamines obtained by exhaustive reaction of diethylenetriamine and diethylenetetramine with propylene oxide. *

It may be necessary to achieve sufficient solubility in water be to use organic solvents that are unlimited or at least largely miscible with water. Mono- and dieters, for example, are suitable as such

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of ethylene glycol, diethylene glycol with lower monohydric alcohols such as methanol, ethanol, propanol, Butanol, such as methylglycol, ethylglycol, propylglycol, Isopropyl glycol, butyl glycol, diethylene glycol diethyl ether, also acetone alcohol, lower ketones such as acetone, methyl ethyl ketone and, in small quantities, methyl isobutyl ketone. The water-thinnable synthetic resins should 1; " in water be soluble or at least dispersible. Preferably "colloidal solutions should arise which are clear or cloudy can appear.

To produce air-drying paints, it is necessary to to make the paints siccative. The are suitable as siccatives cobalt, lead, Manganese etc. compounds. Preferred are those that are dispersible in water.

The coating compositions according to the invention can be - non-pigmented or pigmented and / or containing fillers, used ' will. You can, for example, on HoIzV concrete, masonry, Plaster or iron and steel "as well as' on non-ferrous metals, with or without pretreatment such as passivation, Phosphating, electrochemical treatment, galvanizing, tinning or other metallization according to different Methods, including electrophoretic application, are applied. Pigments and / or fillers are for example - without the invention hereby to restrict - iron oxide red, soot black, lead silica chromate, strontium chromate, blanc fix, micronized barite varieties, Microtalk, cloidal chalk, diatomaceous earth, china clpy, Titanium dioxide, chromium oxide green and others.

The use of strongly basic. Pigments, such as zinc oxide, zinc chromate, Bicarbonate, basic lead sulphate, red lead, calcium plumbate require careful examination. These pigments can tend to thicken or precipitate. The ratio of pigment to binder depends on the one used Pigment type and the vorgfce '.- cneri use-

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purpose. In most cases this will be the pigment binder -Ratio of 0.5: 1 to 2: 1. The pigment content can only be used with electrophoretic application are also below 0.5.

Those produced by the process of the invention Synthetic resins can also be baked on at elevated temperatures.

The synthetic resins obtained by the process according to the invention can be provided with the relevant customary additives, e.g. minor amounts of water-soluble organic solvents, in the presence of which the components of the paint have been produced, and / or other solvents, such as monoalkyl ethers of di- and Triethylene glycol, also compounds of the hexavalent Chromium, such as ammonium dichromate, as well as soluble dyes, Pigments, flow improvers, corrosion inhibitors, stabilizers and / or curing catalysts.

Production of the phenolic resin 1

At p.-tert.-butylphenol are in aqueous alkaline Media added in a known manner 1.5 mol of formaldehyde, the temperature should not exceed 70 C. That obtained p.-tert.-butylphenol resol is with sulfuric acid decomposed and excess acid and existing salt removed by repeated washing with water. Afterward the water is distilled off within as short a time as possible, in which case the work may be carried out under vacuum can be. The resin is kept at 115 to 120 ° C until the melting point of about 50 to 60 ° C is reached.

Production of the phenolic resin 2

It is worked wio in the production of the phenolic resin 1, However, instead of p.-tert.-butylphenol, nonylphenol is used. In the case of nonylphenol resin, the condensation

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.sation ends as soon as no Water passes over. The nonylphenol resin is viscous at room temperature.

■ Production of the phenolic resin 3

The same procedure was used for the production of phenolic resin 1, but instead of ρ-tert-butylphenol Bisphenol-A used and only 1.1 mol of formaldehyde used per mole of bisphenol-A. The condensation was ended as soon as a melting point of approx. IGO ° -C had been reached after complete removal of the water.

80 parts by weight of phenolic resin 1 are reacted with 120 parts by weight of linseed oil fatty acid by heating at 250 ° C. for three hours. The viscosity at the end of this experiment, measured 40% in white spirit, is approx. 80 cP / 20 C. A sample of this resin is diluted to 50% with ethylglycol and neutralized with 100% aqueous ammonia solution, based on the acid number . It is diluted to JO % test body content with water. It is siccative with cobalt-containing siccative (Cyclodex, 0.1 $ cobalt based on solids) and a 90% film is drawn on with a doctor blade. This film is bone dry in about two hours.

Example according to the invention_2

Parts by weight of phenolic resin 1 and 66 parts by weight of wood oil

held at 200 to 210 ° G until the viscosity has risen to 6θΟ to 650 cP / 20 ° C. The reaction takes place under inert gas. It is then cooled and reacted at 100 ° C. with 5 parts by weight of propylene oxide. Ca. is maintained for 2 hours at 100 to 120 ⁰ C to reflux. When the reaction has ended, the excess propylene oxide is removed by vacuum distillation. The viscosity is approx. 750 cP / 20 ° C; the saponification number approx. 115.

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With an excess of 10 to 20 % over the theoretical saponification number, the resin is saponified with potassium hydroxide solution, which has mainly been dissolved in ethanol. The saponification takes place under reflux and under a nitrogen atmosphere. After about 5 hours of refluxing, the saponification is complete. It is neutralized with hydrochloric acid diluted 1: 1 with water until the resin precipitates out of the solution. The decomposition water is separated off, whereupon the remaining resin solution is washed three times with water. After neutralization with ammonia, the resin according to Example 2 is suitable as a binder for air-drying, water-soluble paints.

With regard to the drying properties, the resin according to Example 2 can be improved by copolymerization with vinyl compounds. For this purpose, the resin obtained after the third wash is freed from water by azeotropic distillation with xylene. As soon as no more water collects in the water separator, any remaining water and the xylene are removed under vacuum distillation. The temperature can rise to l6o ⁰ C. Sodium chloride still remaining precipitates from the anhydrous resin and is separated off by filtration. The viscosity is between 180 and 250 cP / 20 ° C, 66% measured in white spirit.

677 parts by weight of this dehydrated resin are at 150 ° C within 2 1/2 hours with a mixture From: 142 parts by weight of styrene, 385 parts by weight α -Methylstyrene, 46 parts by weight of acrylic acid, 20 parts by weight of di-tert-butyl peroxide are added.

The temperature is then kept from 150 to 160 ° C until a pest body content of 83 % has been reached (1 g of resin is weighed into a metal dish - 8.5 cm in diameter -, diluted with 2 ml of ethanol and kept at 110 ° for one hour C dried in a drying cabinet). Under

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The excess monomer is distilled off in vacuo. The viscosity is approx. 250 to 280 cP / 20 ° C 1 ·. 1 measured in butyl glycol. A sample of this resin is diluted to 50 % solids content with ethylglycol, neutralized with 100% concentrated ammonia solution (based on acid number 81.5) and diluted to 40% solids content with water. The solution is desiccated with cobalt siccative (Cyclodex), 0.1 % cobalt based on solid resin.

A film drawn on a glass plate with a layer thickness of 90-μ is dust-dry within half an hour. After the film has been dried for four days at room temperature, the film can be moistened with a wet cotton ball for four hours without the film becoming cloudy. The pH of the coating solution was 9.5, the viscosity of the solution 4o $ 1,600 EP / 20 ⁰ C; after three weeks of storage of 4o $ solution in a closed vessel at 50 ° C, the pH was 9.3 * the viscosity of the solution 4Ö $ 1,300 cP / 20 ⁰ C. After a further 21 days of storage, 'a total of 42 Days of storage at 50 ° C, the pH was 9 * 1 * the viscosity 1,250 cP / 20 ° G. Even after 2 days of storage, the film was dust-dry after 30 minutes, also in terms of water resistance after four days of drying in air There was no change in room temperature. Both at the beginning and after 42 days of storage, the material was 1: «water-soluble without the need for post-neutralization.

Invention item _Example 1 _4

150 parts by weight according to the method described in Example J5 dewatered resin according to Example 2 at 150 ⁰ C within 2 1/2 hours with a mixture consisting of:.

25 parts by weight of 2-ethylhexyl acrylate, 4 parts by weight of vinyl toluene, 5.7 parts by weight of acrylic acid and 2.4 parts by weight of di-tert-butyl peroxide are added and this continues for as long

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Maintained temperature until the solids content is approx. 98 fo. The solid kyrpor content is determined at 110 ° C. The product is diluted with ethyl glycol to a solids content of 50% and neutralized with concentrated ammonia solution, 100%, (based on the theoretical acid number) and adjusted to a solids content of 40% with water.

A film drawn on from a sample with a layer thickness of 90μ which had been siccative with cobalt siccative (Cyclodex) 0.1% was dust-dry within 30 minutes and showed good water resistance after storage for 4 days. The 40% resin solution had a pH of 9 * 3 and was 1: 00 water-soluble. Despite the incorporation of the 2-ethylhexyl acrylate, this resin also proved to be storage-stable. After l4tägiger storage at 50 ⁰ C, the pH was 9 * 0 dropped, but the solution was clear and 1: °° water-dilutable. Compared to the resin according to Example 3, the resin according to example 4 results in films with significantly higher elasticity.

Inventive example_5

190 parts by weight of phenolic resin 2 are reacted with 11 parts by weight of linseed oil and 456 parts by weight of wood oil at 220 to 230 ° C. under inert conditions until the viscosity is measured to be 200 to 250 cP / 20 ° C., 66% in white spirit , amounts to. The batch is cooled and reacted at 100 ° C. with 37 parts by weight of propylene oxide. The propylene oxide is fed in at the rate at which the reflux distillation allows. After a two-hour reaction, the excess propylene oxide is removed by vacuum distillation up to 130 ° C. The viscosity is after completion of vacuum distillation, 66fo strength measured in white spirit, about I80 to 220 cP / 20 ° Cj is the Verselfungszahl 125-130.

600 parts by weight of this resin are mixed with 83 parts by weight of potassium hydroxide, which is dissolved in 200 parts by weight of water and ^ ^c 209813/1354

Was dissolved 200 parts by weight of ethanol "■ at about 90 C under nitrogen saponified _'9 5 hours. When the hydrolysis is complete, it is acidified with concentrated hydrochloric acid, the resin precipitating out. After the separation water has been separated off, the resin is washed four times with 500 parts by volume of water each time. The washed resin is freed from water at approx. 150 ° C. with xylene by azeotropic distillation. After the water has been completely removed, the solvent is stripped off in vacuo. The filtered resin solution has a solids content of at least 99%; the viscosity is approx. 80 to 90 cP / 20 ° C, 66% measured in white spirit.

300 parts by weight of dehydrated resin are at 150 C within of 2 1/2 hours with a mixture., consisting of: 83 parts by weight of styrene, 171 parts by weight of α-Kcthylotyrol, 20.5 Parts by weight of acrylic acid and 8 parts by weight of di-tert-butyl peroxide offset. The temperature is held until a solids content of approx. 8 2 to S3% has been reached. If necessary, the surrender of 11 parts by weight of di-tert-butyl peroxide required.

Once the solids content has been reached, that will excess monomers distilled off in vacuo. After vacuum distillation the solids content is 99.5%, the viscosity approx. 80 to 90 cP, 50% dissolved in butyl glycol. (|

The acid number of the resin is 89. A sample of the resin is diluted with ethyl glycol to 50% solids content and neutralized with concentrated ammonia solution, 100% (based on acid number) and adjusted to 4-0% solids with water. Cyclodex) 0.1% s ikkcTti fourth sample with 90 μ on the drawn film is dust-dry in approx. 2 hours. The viscosity of the 0% if * en solution is approx. 130 cP / 20 ° C. The water resistance of the films obtained according to Example 5 is not as high as those films obtained from resins according to Example 3 after drying for days.

200813/1364.

Instead of the saponification of the reaction product made from phenolic resins and using potassium hydroxide in Examples 2 to 5 Fatty acid esters can cleave these products with water alone, possibly in the presence of "amounts." Acid, which act catalytically, are carried out.

375 parts by weight of the reaction product of 250 parts by weight of phenolic resin 1,150 parts by weight of linseed oil and 600 parts by weight of tung oil, which is called 230 to 240 ° C to a viscosity of about 400 cP / 20 ⁰ C, 2: 1 was measured in white spirit, brought, are heated with 125 parts by weight of deionized water and 3.7 parts by weight of para-toluenesulfonic acid in a Γ liter autoclave to about 180 C. This temperature was maintained for about 6 to 8 hours. During this time, the reaction components were thoroughly mixed. After 6 hours of saponification, the acid number was 107. After neutralization with concentrated ammonia solution, the resin 1 was dilutable in water.

As in Example 6, the pressure saponification was carried out with concentrated ammonia solution and water. 375 parts by weight of the resin - as in Example G - were with 75 parts by weight of concentrated ammonia solution and 50 parts by weight of water mixed and kept in the autoclave at 100 to 110 ° C for 17 hours. The acid number was after this holding time 50. Mach addition of ethyl glycol in a ratio of 1: 1 based on solids content, it was possible Dilute the resin to a solids content of approx. 20% with water. With wide \ r> When diluted, the resin could only be diluted with water in the form of an emulsion.

209813/1354

- £ .0 ~

Example according to the invention 8

125 parts of phenolic resin 1 are reacted with 75 parts of linseed oil fatty acid methyl ester and 300 g of wood oil fatty acid methyl ester at 270 ° C. under inert gas until the viscosity is 750 to 850 cP / 20 ° C., measured directly. The mixture is then cooled to 150 C and the product, a mixture of 104.5 T styrene, α- methyl styrene and 2S4 T 35 T acrylic acid with I ₉ M-5 T Di-t-butyl are added during 2 1/2 hours. The temperature is maintained until a solids content of approx. 32-83% has been reached. The excess monomer is then distilled off in vacuo. The viscosity is then 110 cP / 20 ° C., 50% in butyl glycol _3, the solids 98.5%, the saponification number is 141.

■ + 06 g of the resin are mixed with a solution of. 78 T potassium hydroxide saponified in 100 parts of water with 100 parts of methanol under nitrogen at about 90 ° C. for 4 hours. Then it is concentrated with Hydrochloric acid acidified, whereby the resin precipitates. The wash water is separated off and the resin with it for so long Washed water until the pH of the wash water is neutral. Then 615 g of the resin with CO g of methyl glycol diluted. The solids content of the resin is 98.5%, acid number 129. The product is treated with concentrated ammonia 100%, based on the theoretical acid number, neutralized and adjusted to a solids content of 40% with ethyl glycol One with cobalt siccative (Cyclodex) 0.1% siccative Sample with 90 µ layer thickness was dust-dry in 30 minutes.

209813/1354

Example 9

100 g of the resin according to Example 3 with a solids content of approx. 98% are diluted with _{butyl glycol to a solids content of 50%, then mixed with M, N, N '9} N ^f -Tetrakis- (2-hydrexypropylEthylenediamine and then completely with ammonia neutralized. .Anschließend is diluted with water to a solids content of 40%. The solution is _Ä covered with Kobaltsiccativ (Cyclodex), 0.1% cobalt on the solid resin. a siccativiert on a glass plate tucked film 90 μ layer thickness is after 2 hours touch dry.

209813/1354

Claims (1)

I) R-WALTERNIELSCh, ! b2 ^Wfl ™ 'AktehOs ^'' ^ϋυ ''"W May 1367 amburg / O ^ 1 τ / rooo ■ ' 112. P.O. Box 10914 Jl 5. I / 4 O O J 652 97 07. PATENT CLAIMS 1) Process for the production of air-drying or stoving, water-thinnable, saponification-resistant synthetic resins in the form of their ammonia and / or amine soaps, characterized in that they are obtained by at least one of the following processes: 1. By heat conversion of at least one phenolic resin (I) ₅ with at least one ethylenically unsaturated fatty acid CII), with at least I ¹ + C atoms, or '■ 2. By heat reaction in stage A at least one phenolic resin (I) with at least one ester (III and IV) Ethylenically unsaturated fatty acids, with at least one monohydric and / or polyhydric alcohol and subsequent cleavage of the esters in stage B and, if appropriate, separation of the alcohols released and any inorganic salts present; or 3. By blocking any phenolic hydroxyl still present groups in the products according to 1 and / or 2 by reaction with compounds containing oxirane rings, the capable of reacting with phenolic hydroxyl groups are, the reaction of the products obtained according to 2 with the compounds containing oxirane rings, preferably after stage A as stage A. and the Cleavage of the ester then takes place 209813/1354 ^2O95 I745336 - 2C- U.By copolymerization of the products according to 1 and / or 2, which in this case preferably takes place after stage A, and / or the products 3, which in this Fall preferably after stage A. takes place with vinyl (V) and / or vinyl oxide compounds (VI) in the heat, preferably in the presence of polymerization catalysts; and cleavage of the esters, provided that products n -'- .h 2 or 3 have been copolymerized in stage A, wherein in the preferred variant, the copolymerization takes place only after stage B; or 5, By modifying the products according to 1 and / or 2 and / or 3, which in the latter case can optionally also take place after stage A or A ₁ and / or the products 4 with cyclopentadiene or dicyclopentadiene (VII) in the heat ; or 6. Through the heat reaction of at least one phenolic resin (I) with at least one with vinyl (V) and / or vinylidene compound (VI) in the heat, preferably using of polymerization catalysts, copolymerized ethylenically unsaturated fatty acid (II) with at least 11 carbon atoms; or 7. By heat reaction of at least one phenolic resin (I) with at least one ethylenically unsaturated one modified with cyclopentadiene or dicyclopentadiene (VII) in the heat Fatty acid (II) with at least 14 carbon atoms; or 209813/1354 2095 8. By heat reaction in stage A of at least one phenolic resin (I) with at least one with vinyl (V) and / or vinylidene compounds (VI) copolymerized esters (III and IV) of ethylenically unsaturated Fatty acids (II) with monohydric and / or polyhydric alcohols and subsequent cleavage of the esters in stage B and, if appropriate, separation of the released ones Alcohols and any inorganic salts present; ■■ or 9. By heat reaction in stage A of at least one phenolic resin (I) with at least one ester (III and IV) of ethylenically unsaturated fatty acids (II) with mono- and / or polyvalent fatty acids modified with cyclopentadiene or dicyclopentadxene (VII) in the heat Alcohols and subsequent cleavage of the esters in stage B and optionally separation of the released alcohols and any Λ inorganic salts present; or 10. Implementation of the products according to 1 to 9 with α, ß-ethylenic unsaturated dicarboxylic acids or, if they exist, their anhydrides (VIII) in the heat, 2) Method according to claim 1, characterized in that the reaction of the phenolic resins (I) with the fatty acids (II) and / or fatty acid esters (III and IV) at elevated temperature generally takes place between 200 and 27O ° C, 209813/1354 where, when using fatty acids or fatty acid glyceride esters of highly unsaturated fatty acids, the ^{reaction is carried out at about 200 to 240 °} C., when using fatty acid methyl esters at about 270 ° C. 3. The method according to claim 2, characterized in that phenolic resins and highly unsaturated fatty oils are converted up to a maximum viscosity of about 1,000 centipoise / 20 ⁰ C (measured 66% in white spirit). 1. The method according to one or more of claims 1 to 2, characterized - _} that when using fatty acids (II) or fatty acid esters of monohydric alcohols (III), in particular fatty acid methyl esters, is preferably reacted by heating until the viscosity of the reaction products is between 100 and measured at 300 centipoise / 20 ° C (50% in butyl glycol). 5) Method according to one of claims 1 to 4, characterized characterized in that during the copolymerization of the products according to 1 or 2 with vinyl and / or vinylidene compounds is converted in the heat, preferably with the action of polymerization catalysts, preferably the reaction with a vinyl or. Vinylidene monomer mixture is carried out, which in 1800 g at least one acid equivalent (expressed in grams) one for copolymerization with the vinyl or. 209813/1354 Unsaturated carboxylic acid capable of vinylidene compounds contains. 6) Method according to claim 5, characterized in that . when using weakly polar monomers such as styrene, ct-Methylstyrcl, vinyltoluene _s g in 1800 are used preferably 2 to H acid equivalents. 7) Method according to one or more of the claims 1 to 6, characterized in that the phenolic resin (I) is a resol made from a phenol of the general formula OH R R = alkyl radical with 2-20 carbon atoms, or aryl radical and formaldehyde, which is practically anhydrous, is used. 8) Method according to claim 7, characterized in that the phenol is p-tert-butylphenyl. 9) Method according to claim 7 and 8, characterized in that that the added formaldehyde content is 1 to 2 moles per mole of phenol. 10) Method according to one or more of claims 1 to 9, characterized in that the fatty acids (II) are fatty acids 209813/1354 ZO 2095 from wood oil and / or oiticica oil and / or linseed oil are used will. 11) procedure after an-odej? several of the claims 1 to 10, characterized in that for the production of amine soaps as an organic nitrogen base at least a compound according to the general formula: R ₃ -OCC MR, H H MY) - C-N is used, where the substituents and symbols have the following meanings: Y = CH ₂ -, C ₃ H ₆ -, -C ₄ H ₈ , CH ₂ -N-CH ₂ -; _; -, CH ₂ -Cl R ₁ = H-, CH ₃ -, C ₂ H ₅ -, CH ₂ -COR ₃ ; H _R R ^ = H-, -CH ₃ , C ₂ H ₅ -, -CH ₂ -COR ₃ ; H
Rn = Η—, -CH--, C ₀ Hr- » R ₂ = H-, -CH ₃ -, C ₂ H ₅ - i R ₀ = H-, - (CH ₀ -CH ₀ -O-) -H, - (CH ₀ -CO) - H and CH. R ₃ '= H-, - (CH ₂ -CH ₂ -O) _x -H; - (CH ₃ -CO) _x H and H χ = zero or an integer between 1 and 6 209813/1364