DE2021141A1 - Process for the production of soluble organic copolymers - Google Patents

Description

DR. WALTER NtELSCH Patent attorney I Hunburg 70 P.O. Box 10814

Telephone: 9520707

Reichhold-Albert-Chemie Aktiengesellschaft in Hamburg 70

Process for the production of soluble organic copolymers.

The object of the present invention is to provide a process for the production of soluble organic copolymers and their use as a binder component, but the flat structures which can be produced therefrom have properties which are considerably improved in various directions. This includes that the paint applied to a metallic substrate, which contains the new soluble organic copolymers in combination with organic polyisocyanates, ^{should cure after three to four days of air drying at temperatures around 20 °} C. in such a way that the film under the action no longer swells from water and cannot be removed mechanically by scratching, even if the film is briefly exposed to water at temperatures of 50 - 70 ° C.

The present invention relates to a method for Production of polyhydroxy compounds in the form of soluble copolymers containing hydroxyl groups based on vinyl compounds and vinyl aromatics in inert solvents in the presence of polymerization initiators, optionally chain terminators, characterized in that they are selected from:

0G9849 / 188S

a) 38 - 70 % styrene or alkyl styrene, the alkyl of which

groups have 1 to 3 carbon atoms or a mixture of such alkyl groups,

b) 0-25% by weight of acrylic acid and / or methacrylic acid

esters containing 1 to 12 carbon atoms in the saturated alcohol residue,

c) 3-15 Gew.Jf an α 0-ethylenically unsaturated

Mono- or dioarboxylic acid

and implementation with esterification with

d) 10 -. 40% by weight of glycidyl ester of a-Allcylalkanmonoearbon-

acids and / or α, α-dialkylalkanemonocarboxylic acids the following sum formula

^{C12-l4 Ii} 22 "-26 ° 3 ^woöe 3. The amounts of the compounds a) to d) up to 100 wt.% Must complement

produced by heating.

A special embodiment of the invention is characterized in that one

a) 45 -.! 60% by weight styrene or Viny toluene,

b) 0-20 ßew. $ acrylates and / or methacrylates saturated

ter monoalcohols with 1 to 12 carbon atoms,

c) 5-10 wt. Acrylic acid or methacrylic acid,

d) 15-35 wt. Glycidyl ester a-alkylalkane mono carbon

acids / or α and, α-dialkylalkane monocarboxylic acids of the following empirical formula P ^ _12-1 Hp _2- PGO ,, wherein the amounts of the compounds a)) to d must add up to 100 wt.%,
converted by heating.

A particularly preferred embodiment of the invention is characterized in that one

a) 50 - 60% by weight of styrene.

b) 0-10 wt. Butyl acrylate or butyl methacrylate,

e) 6 ₃ 6 wt.% of acrylic acid or

Wt.% Methacrylic acid,

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d) 22 per weight unit of glycidyl ester α-alkylalkane monocarbon

acids and / or <*, α-diet hy lalkanmonocarbonsäure the following empirical formula

^C 12-l ^l l ^H 22-26 ^O 3 * ^where i the amounts of compounds a) to d) have to add up to 100 wt.
converted by heating.

Suitable solvents for the preparation of the copolymers are those which do not contain any active hydrogen atoms contain - such as alkylbenzenes such as toluene, xylene, esters such as ethyl acetate, butyl acetate, Ether esters of diols such as methyl glycol acetate or ethyl glycol acetate.

Components a) are very suitable, followed by styrene of α, ο-, m- and p-methylstyrene as well as halogenated ones Styrenes "When polymerized in, they give the surface structures made from them a high level of saponification" · durability and good pigment absorption if the copolymers can be used together with organic polyisocyanates as a reactive varnish.

For the use of the copolymers in the reactive coating, it is essential that the content of styrene, α-, ο-, m-, and p-methyl styrene, and halogenated styrene singly or in admixture of at least 33 wt. JS and not more than? 0 wt.% based on the solids content of the copolymer, preferably Ί5 to 60 wt.? amounts to. These quantities must be used to give the pigmented films the gloss, the film hardness, the flexibility and the anti-corrosive properties of the reactive lacquer. With a lower content of styrene or alkyl styrenes, the hardness of the film decreases. Furthermore, there is a decrease in the chemical resistance and the anti-corrosive properties of the reactive lacquers

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obtained films.

In general, methyl acrylate, ethyl acrylate, propyl acrylate , isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate and dodecyl acrylate are particularly suitable as components b). When using esters of methacrylic acid such as methyl methacrylate, butyl methacrylate, isobutyl methacrylate for the purpose of polymerizing in, the light resistance of the coating and hardness can be favorably influenced, while when using the acrylate

esters with Ά to 8 carbon atoms in the saturated alcohol residue, the elasticity and flexural strength is favorably influenced, with special adaptations being made by appropriate mixtures of acrylates and / or methacrylates.

The content of acrylic acid and / or methacrylic acid esters ^ which contain 1 to 12 carbon atoms in the saturated alcohol residue, may only be within the limits of 0-25% by weight - based on the body convolution of the solid - in the copolymer. The best film hardness, chemical resistance and anti-corrosive properties are obtained with the new copolymers when used in reactive varnishes if the content of acrylic and / or methacrylic acid esters]! / Which contain 1 to H carbon atoms in the alcohol residue is below IO weight /? based on the body content of the solid - in the mixed polymer is »With one. If the acrylate ester content is increased above 25% by weight, the disadvantages such as film softness, film swellability and poor chemical resistance become apparent.

Acrylic acid or methacrylic acid, maleic acid or fumaric acid is used singly or in a mixture as component c). Acrylic acid or methacrylic acid are preferred.

Glycidyl esters of alkyl alkane are used as components d)

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monocarboxylic acids and / or α, α-dialkylalkane ^{monocarboxylic acids of the following empirical formula c} i2-lU iI 22-26 ° ⁱ 3 used individually or in a mixture. Since the glycidyl radical in the glycidyl -'-, ester of a-alkylalkane monocarboxylic acids and / or α, α-dialkylalkane monocarboxylic acids has the empirical formula C, H, -0, the ot-alkylalkanoic acids and α, α-dialkylalkanoic acids are mixtures of such monocarboxylic acids, the one Cq, C ₁₀ and C ₁₁ chain included. The manufacturing processes for the manufacture of the aforementioned ct-alkylalkane monocarboxylic acids are based on the pioneering work of Dr. H. Koch from the Max Planck Institute for Coal Research in Mühlheim, Federal Republic of Germany. The acids are completely saturated and are very heavily substituted on the carbon atom. Acids with two hydrogen atoms on the ot carbon atom are absent and only 6-7% of these acids contain one hydrogen atom. There is also cyclical material (Deutsche Farben Zeitschrift 10/16 year. Page 435).

For the use of the copolymers according to the invention in reactive varnishes, it is necessary that the content of the glycidyl esters of α- ^{alkylalkane monocarboxylic acids and / or α, α-dialkylalkane monocarboxylic acids 10 to 1} JO% by weight » preferably 15 to 35% by weight, based on the Solids content in the copolymer is. With the use of 10 to 20 wt. $ Glycidyl esters of a-Alkylalkanraonocarbonsäuren and / or α, α-dialkylalkanemonocarboxylic acids in the copolymer of HydroxyIgehalt is 0.7 to 1 _S 4 Gew.?L Get such copolymers in combination with the polyisocyanates used _s this results in less cross-linking and thus greater elasticity of the reactive lacquers. In this way, an increase in elasticity is achieved without increasing the content of acrylic acid esters in order to increase elasticity, which would result in the disadvantages already described.

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The copolymers obtainable by the process therefore show very nosh when used in reactive lacquers good anti-corrosive properties and good condensation tests, but the hardness of the pilm surface has decreased somewhat.

If such copolymers are used in the production of the reactive ^{varnish, the 20 to 1} JQ wt. % _S preferably 20 to 35 wt. ψ sat contain, used for the combination, where the amount of polyisocyanate characterized by the MCO content is used in equivalent amounts corresponding to the hydroxyl groups in the copolymer, the increase in the hydroxyl group content in the copolymer results in greater crosslinking due to the increased polyisocyanate additive an increase in the film surface hardness and also resistance of the films to chemicals and condensation water, however, the elasticity of these films decreases somewhat, but is still sufficient when they are on rigid substrates. The required increase in elasticity must then be achieved when the coating is applied to decimable substrates, e.g. leather, by using up to 25 wt. Cc acrylic acid esters with an alcohol residue of H to 12 carbon atoms. '*

The reaction for preparing the new copolymers is carried out in such a manner that the carboxyl groups of the components c) α with the glycidyl groups of the s-alkylalkanemonocarboxylic acids and / or ot-dialkylalkane monocarboxylic acids of the components d) reacting ₉ so DAT under Esterbildung a free hydroxyl arises _s «Left with later use for networking, for example

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the organic polyisocyanates is necessary. sales takes place in equivalent proportions between the Carboxyl and glycidyl groups.

The copolymers produced in this way result Acid numbers between 2 and 12; those are preferred 2 -4. .

These new copolymers can be used as component A in Reactive lacquers can be used together with a polyisocyanate component B. . .

As component B, for example, the following polyiso- » cyanates are used:

Toluylene-2,4-diisocyanate, tiuylene-2,6-diisocyanate, cyclohexylene-l ^ -diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthylene-ljg-diisocyanate, 4,4'- * 4 _# 2-triphenylmethane triisocyanate, 1 ~ (Isocyanatophenyl) ethyl isocyanate or the xylylene diisocyanate, fluorine "substituted diisocyanate, ethylene glycol diphenyl ether 2.2 * - diisocyanate, diethylene glycol diphenyl ether-2,2'-diieocy * anate, 1,1'-dinaphthyl-2,2'- diisocyanate. diphenyl-2, V-diisocyanate, biphenyl ¹ * »4-diisocyanate, 3-diisocyanate BenEophenon ^f" 3, Pluoren-diisocyanate 2,7-anthraquinone-2,6-diisocyanate, pyrene-3 8- ₉ diisocyanate, chrysene-2,8-diisocyanate, 1- ^ ϊethylbenzene-2,4,6-triisocyanate, naphthalene- !, 3, 7 -triisocyanate, biphenylmcthan-2,4,4'-triisocyanate _a tri-phenylmethane-4 , 4 ', 4 ^M -triisocyanate, 3'-methoxyhexane diisocyanate, octane-diiso-ω _J u-diisccyanate-1,4-diethylbenzene, ω, ω-diisocyanate-1,4-dimethylnaphthalene, cyclohexane-1,2-diisocyanate, l-isopropylbenzene -2, 4-diisocyanate, 1-chlorobenzene-2,4-diisocyanate, l-fluorobenzene ^^ - diisccyanate, l-Nitroben ^ ol-2,4-diisocyanate, l-chloro-4-methoxybenzene-2,5-azobenzene-4,4 diisoeyanat _s ^f diisocyanate, Benzolazonaphthalin-4,4'-diisocyanate, diphenyl ether-2,4- diisocyanate and diphenyl ether ¹ }, 4 ^f -diiscyanate.

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Instead of the polyisocyanates, it is also possible to use polyisocyanates Cleaving compounds are used, as well as isocyanate groups containing reaction products of polyhydric alcohols with polyisocyanates, for example that Reaction product of 1 mole of trimethylolpropane with 3 moles of tolylene diisocyanate, also trimerized or polymerized Isocyanates, such as those described, for example, in German patent specification 951 168.

In addition, a reaction product of 1 mole of water and 3 moles of hexamethylene diisocyanate with an NCO content of 16-17 % by weight is also possible. The last-mentioned reaction product of water and hexamethylene diisocyanate is particularly preferred. The NCO content of the reaction product applies to a 75% solution in xylene / ethyl glycol acetate.

The new copolymers are produced by solvent polymerization, the monomers a) to c) and the glycidyl ester d) in the reaction vessel together with the solvents, the initiators, possibly also in the presence of chain terminators to react, with the condensation reaction and polymerization reaction run together. In a preferred embodiment, the glycidyl ester is dissolved in the solvent and adds at elevated temperature - about 80 to 170 '"C - the monomers a) to c) with the initiators and Chain terminators added and condensed and polymerized together. Examples of initiators are: Azo compounds, peroxide compounds, for example Denzoylpercxyl, cumene hydroperoxide or di.-tert.-butyl peroxide. By using chain terminators such as mercaptans and aldehyde, the degree of polymerization be adapted to the required conditions.

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Viscosities for 50% resin concentrations in aromatic solvents such as toluene or xylene or in ether esters such as ethyl glycol acetate according to the Gardner-Holdt scale from K - Z ^ are aimed for. The viscosity range from U to Z ₂ at 20 ^° C. is preferred.

The new polymers should preferably have molecular weights from about 5,000 to 20,000. These should preferably have a hydroxyl group content of 0.7 to 3 Ω 1.5 to 2.8 wt. * #. The hydroxyl group content refers to the proportion of pesticides in the copolymer.

The implementation of the hydroxyl-containing copolymers A when using in.Reaction paints with the organic Depending on the intended use, polyisocyanates B can contain 0.5 to 1.1 NCO groups per hydroxyl group. The implementation Is preferably carried out so that the amounts of the organic Polyisocyanates based on the total hydroxy1 content of the components present in the reaction mixture in an amount of 0.7 to 1.0 isocyanate groups per hydroxyl group available.

To use the new copolymers one brings the mixtures of solvent-containing hydroxyl groups Copolymers A and B polyisocyanate The easiest way possible, for example after adding known ones Auxiliaries, such as leveling agents, pigments or dyes, by spraying, dipping, pouring, brushing or others take appropriate measures on the relevant documents and dry the fabrics at room temperature; in special cases, for example when using isocyanate cleavers, the coatings can be baked in, which essentially depends on the type of coating used Documents and the requirements made by practice aimed at the coatings. Also the use

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of reactive melamine resins can be beneficial. You can use the reactive melamine resins in amounts from 1 to to 10 Gew.Jf, based on the weight of the binder grain, component, so that in particular an increase in gloss can be observed in the fabric.

Monomethylolpentamethoxymethylene melamine and dimethylol-tetramethoxymethylene melamine, for example, can be used as reactive melamine resins or trimethylol-trimethoxymethylene melamine individually or as a mixture.

ψ When the new copolymers are used in the reaction lacquers already explained, the reaction and the application of the surface structure to the substrate take place in solution. Suitable solutions are, for example, ethyl acetate, butyl ester, ether ester, diethylglycol diacetate and aromatics such as benzene, toluene or xylene. The concentration of the solutions may vary within wide limits and depends essentially on the solubility of the components, preferably solutions with a solids content of 20 -. 80% by weight is used.

However, polymer solutions are also available for special purposes with a lower hydroxyl group content, which leads to a weaker crosslinking, of Interest, for example for coatings on movable substrates. Such copolymers are with the in practice typical hydroxyl group-containing polyesters and polyethers can and can be mixed in any ratio therefore are blended with these. Also the conversion products such blends with polyisocyanates deliver alkali-resistant coatings with similar properties * shafts like those already described above, whereby the relatively fast drying time is particularly noticeable.

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The copolymers obtainable by the process can be used for the production of coatings in the reaction lacquers already explained together with Polyisocyanates on various types of substrates, e.g. Porous or non-porous substrates such as textile fleeces, leather or plastics can be used. Particular emphasis should be placed on the manufacture of upper layers on wood or metals. In any case, high-gloss, very surface-hard, pore-free elastic ones are obtained and solvent-resistant coatings that you can use with both can treat strong inorganic acids as well as strong alkalis without the coatings being attacked even to the slightest extent. Show such covers also excellent weather resistance and yellowing resistance.

It should be emphasized in particular that the coatings or coatings produced in this way on aluminum sheets as single-layer coatings have excellent adhesive strength. The coatings and coatings can advantageously enough, be done on aluminum, by, after application of the coatings the coating by a temperature treatment at UO - 50 ⁰ C freed for about 30 minutes from the solvent, and the resulting coating or the coating in a tack-free state is present , so that the surface does not absorb dust and is no longer sensitive to impact or other mechanical pressure, so that these painted objects can be subjected to further processing. After curing for three to four days at room temperature, the maximum properties are then achieved. The maximum properties are also achieved by increasing the temperature to 120 ^ C in 30 minutes. When using the new copolymers in reactive paints, components A and B are preferably used in the following amounts:

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A. 70 - 9 ¹ *% by weight of copolymers containing hydroxyl groups

te made from:

a) 38 - 70 Qew.J? Styrene or alkylstyrene, the alkyl of which

groups have 1 to 3 carbon atoms or a mixture of such alkyl groups,

b) 0-25 wt. l acrylic and / or methacrylic acid esters,

which contain 1 to 12 carbon atoms in the saturated alcohol residue,

c) 3-15 Qevi.% of an α, B-ethylenically unsaturated

Mono- or dicarboxylic acid,

and implementation with esterification with

d) 10 - MO weight? Glycidyl ester ot-alkylalkane monocarbon

acids and / or α, α-dialkylalkanemonocarboxylic acids the following empirical formula

^C 12 ^H lM ^d 22-26 ⁰ 3 ^'wobe * * ^e & amounts ü ^r compounds a) to d) up to 100 wt.?

need to supplement
and

B. 6-30 wt. % Organic polyisocyanate, where A and D

together must result in numerical values of 100 wt.

A specific embodiment of use comprises: A. 75-90% by weight of hydroxyl-containing copolymers produced from.:

a) iJ 5 - 60 wt / l styrene or vinyl toluene,

b) 0-20 wt.% acrylates and / or methacrylates saturated

Monoalcohols with 1 to 12 carbon atoms,

c) 5-10 per weight unit of acrylic acid or methacrylic acid,

d) 15 -. 35% by weight of glycidyl ester of a-Alkylalkanmonocarbonsäu * ·

ren and / or α, α-dialkylalkanemonocarboxylic ^{acids of the following empirical formula C} 12-1 ¹ J ^H 22-26 ^O 3 * where * ^d * ^e amounts of the

009849/1868

compounds a) to d) up to 100 wt.% must complement,
and

B. 10-25 wt. % Organic polyisocyanate, where A and B

together numerical values of 100 wt.? must result in:

A particularly preferred embodiment of the use includes?

A. 80-90% by weight of copolymers containing hydroxyl groups

made of: .

a) 50 - 60% by weight of styrene.

b) 10 -. 22% by weight of butyl acrylate or butyl methacrylate,

% of acrylic acid c) 6.6 wt. or

Weight!? Methacrylic acid,

d) 22 wt.% glycidyl ester of a-Alkylalkanmonocarbon-

acids

and / or α, α-diethylalkane monocarbon

acids of the following molecular formula

^C 12 ~ l4 ^H 22-26 ° 3 ' ^where ^ ^d ^ ^e amounts of compounds a) to d) must add up to 100 wt.
and

B. 10-20 wt. % Organic triisocyanate, which by

Implementation from 3 moles of hexamethylene diisocyanate and 1 mol of water was obtained, A and B being numerical values of 100 wt. must surrender.

Example 1:

Production of the copolymer 1

In a vessel equipped with a stirrer, reflux condenser and thermometer 528 ρ xylene and 268 g of glycidyl ester are ο, o-dialkylalkane monocarboxylic acids of the following formula ^C-i2-H iii '22 -26 ⁰ 3 ^m i ^k a .Epoxyäquivalent of 2 * 10250 "in following only with glycidyl ester α, α-dialkyl

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. - IU -

called monocarboxylic acids, heated to 140 ° C and a mixture consisting of * f52 β styrene, 80 g acrylic acid and 12 g di.-tert-butyl peroxide added uniformly in two hours and polymerized and condensed at this temperature for about 8 to 10 hours. The product results in a body content of 60 wt.% ₉ a viscosity according to Gardner-Holdt of the XY 60 Üigen solution in xylene and an acid number of 4.2 * The hydroxyl group content is 2.3 wt% based on the _K Peststoffanteil in the copolymer.

Example 2:

Preparation of copolymer 2 In the same manner as described in the preparation of the interpolymer 1, 528 g of xylene and L8L g glycidyl ester of α, a-dialkylalkanemonocarboxylic acids are heated to 145 ° C and the following mixture consisting of ¹ 116 g of styrene, 64 g methacrylic acid, 139 p> Butylmetfoaei'ylat and 10 g tert-butyl peroxide Di.-uniformly added in two hours and the mixture polymerized together about 9 to 11 hours under heating to about l4o ° C and condensed. The body content is 60.2 wt. The viscosity measured according to Gardner-Holdt in xylene is Z ₁ - Z ₃ . The acid number reaches a value of 4.9. The hydroxyl group content is 1.56 wt.% Based on the Peststoffanteil in the copolymer.

Example 3:

Production of the mixed polymer 3 In the same way as for the production of the mixed polymer 1 ', 528 g of xylene and 180 g of glycidyl ester: α, α-dialkylalkanemonocarboxylic acids are brought to 140 ° C heated and the following mixture evenly in two hours added: 452 g styrene, 54 g acrylic acid, 113 β

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Butyl acrylate and 10 g of di-tert-butyl peroxide. After eight to ten hours nemeinsamer polymerization and condensation at li "0-150 ⁰ C, the body content of the solution 60.4 wt 'g, while the acid value is 3.6 and the viscosity measured in xylene at 20 ⁰ C, according to Gardner -Hold t Y is. The hydroxyl group content is 1.5% by weight based on the solids content in the copolymer,

Example *":

Reaction varnish based on 8O »3 wt * J? Copolymer and 19.7 wt.% Organic Triisoeyanat, both based on the Festkörperpewicht.

Ι.) 53Ί K mixed polymer-l-xylene solution (dissolved solids 60% by weight) are rubbed into a varnish with 600 β titanium dioxide (rutile), 200 ε xylene and 100 μl ethyl glycol acetate.

II.) 150 π of the above pigmented paint batch I, which contains the copolymer 1, 61.5 e of the unpigmented copolymer-1-xylene solution (dissolved solids 60% by weight) and 23.1 g of a 75% by weight solution of a triisocyanate with an NCO content of 16.5-17.0 wt.? Dissolved in a mixture of xylene / Äthylplykolazetat 1: 1, which has been obtained by reacting 3 moles of hexamethylene diisoeyanate and 1 mole of water, are diluted to spray viscosity with xylene and applied to aluminum sheets with a dry layer thickness of 15 - 50 μ and dried in the air . Tack-free is achieved after 30 - ¹ JO minutes. The pendulum halves measured according to König; (Din 53 157) zips after 3 days 110 seconds, after 7 tares 137 seconds, after IH days 175 seconds, Re * "is stored at 20 ^° C. The water resistance after four-

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Daily drying at 20 ^° C. on aluminum sheets is tested as follows: making a cross cut, then heating the sheet to 60 to 70 ^° C. and allowing hot water to act for 10-15 minutes. Result: No swelling at the cross cut, no scraping off of the still warm film. the pingernail possible.

A film on AIu- dried in the air for ten days. In the condensation test at 50 ° C after 25 days, miniumblechen did not show any blistering. The shine is still completely preserved.

Example 5:

Reaction lacquer on the basis of 85 wt. Ji copolymer and 15 wt.% Organic triisocyanate, both based on dae Pestkörpergewicht.

Ι.) 53Ί g of copolymer-l-xylene solution (dissolved plague body 60 wt. £) are rubbed with 600 g of titanium dioxide (rutile), 200 g of xylene and 100 g of ethyl glycol acetate to form a lacquer ^1.

II.) 150 g of the pigmented lacquer 1 of this example, which contains the copolymer 1, 68, Ί g of the unpigmented Mixed polymer l-xylene solution (dissolved Solids 60 wt. JO and 17.7 g of a 75 wt Solution of the triisocyanate described in Example 4 with an NCO content of 16.5 - 17 weight per unit in one Mixture of xylene / ethyl glycol acetate 1: 1 dissolved, which has been obtained by reacting 3 moles of hexamethylene diisocyanate and 1 mole of water, is diluted to spray viscosity with xylene and applied to aluminum or steel sheets with a dry film thickness from Ί0 - 5Oy and applied to the Air dried. The paintwork is also used in a '

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baked in another attempt at 130 ° C. The pendulum hardness of the film, air-dried at 20 ° C., is 97 seconds after 3 days, 122 seconds after 7 days and 145 seconds after 14 days. The water resistance tested as in Example 4 gave the following result: no swelling and no scratching of the still warm film with the fingernail possible. A lacquer baked at 130 ^° C. in 30 minutes on a phosphated iron plate shows after 60 hours in boiling washing liquor with a detergent content of 3 parts by weight and a pH range of 10-13, the liquor being used six times during 60 hours of cooking was replaced by freshly prepared washing liquor, no blistering and no loss of gloss. The best self-hardening acrylic resins used for the same purpose show a heavily swollen film after the third change of wash liquor in the test, while after the fourth change of wash liquor the film was already destroyed and detached from the sheet metal.

Example 6:

Reaction lacquer on the basis of 84 wt.% Copolymer and 16 wt. £ organic triisocyanate, both based on the weight of solids.

I.) 534 g of Miechpolymerisat-2 * xylene-IfÖ8ung (dissolved Peet body 60.2 wt. H) are mixed with 600 g of titanium dioxide (rutile)! 200 g xylene and 100 g xthylglycol acetate ζμ one Paint rubbed. *

II.) 150 g of the above pigmented paint batch I of this example, which contains the mixed polymer at-2-xylene Solution (dissolved solids 60.2 wt.it), 65 g of the

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unpigmented copolymer 2-xylene solution (dissolved solids 60.2% by weight) and 18 g of a 75% by weight? solution of the triisocyanate described in Example 1 are diluted with xylene and applied by spraying on aluminum panels and baked dried for 30 minutes in the air and at 130 ⁰ C. The pendulum hardness of the air-dried film was 116 seconds after 2 days, 137 seconds after 7 days and 161 seconds after 14 days.

Again, the baked at 130 ⁰ C film as described in the verification test in Example 5, shows six changes to the wash liquor, no loss of gloss and no bubble formation.

Example 7:

Reaktionelack organic based on 84 Gew.2 copolymer and 16 Gew.Ji triisocyanate _£ both based on the weight of solids. ··· · ......... _; ......

I.) 267 g of copolymer 3-xylene solution (dissolved solids 60.4% by weight) are combined with 300 g of titanium dioxide (rutile), 100 g of xylene and 50 g of ethylglycol acetate to form one Paint rubbed.

II.) 160 g of the above pigmented paint batch I of this example, which contains the copolymer 3 and 70 g of the unpigmented copolymer - ^ * · xylene solution (dissolved solids 60.4% by weight) and 20 g of a 75% by weight solution of the i "example 4 Triisocyanäts described viscosity be diluted with xylene to spray * and applied to aluminum panels at a dry film thickness of 45 - 50 μ is applied, air dried and stoved at 130 ⁰ C as well.

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The pendulum hardness is 88 after 3 days at 20 ° C, after 7 days 116 and after H days 153 seconds. The lacquer has after curing in the air and on it following baking at 130 ° C an Ericheen cupping from 8 to 9 mm on steel sheets »The paints that have been fully hardened on aluminum sheets can be bent by 180 ° without cracking the paint.

Example 8:

Reaction varnish based on 76% by weight copolymer · · sat and 2 ¹ IQeW. % organic triisocyanate _f both based on the fetus weight,

100 g dos in Example ¹ J, paragraph I, said pigmented coating approach I which contains the copolymer 1, 38 g of the unpigmented copolymer-1-xylene solution (ge - luster solid Gew.S 60) and 21.5 g of a 67Jtigen solution of a triisocyanate with an NCO content of 11.5 Qew.ff, in an oil of xylene / ethylglycol acetate; dissolved, which has been obtained by reaction of 3 moles Toluylendiieocyanat and one mole of trimethylol propane, be with a mixture of xylene / Äthylglykolatetat diluted 1: 1 and applied by spraying to steel panels and baked 30 minutes at 130 ⁰ C.

The pendulum hardness was 198 seconds. The film showed good elasticity and nail hardness. There was also one very good resistance to shoe polish and lipstick.

Example 9:

Reaction lacquer on the basis of 70 Gew.I copolymer, 22 wt.% Organic triisocyanate and 8 a Gew.J

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Mixture of monomethylol pentamethoxymethylene melamine and dimethylol tetramethoxymethylene melamine.

150 g of the pigmented Lackansatzee I, according to Example ¹ J, paragraph I, containing the copolymer 1, 61.5 S ^d r © unpigmented copolymer-l-Xyiol solution (dissolved Pestkörper Gew.Si 60), 11.5 g of Mixture (about 80: 20 % by weight to 20: 80 % by weight) of monomethylol-pentamethoxymethylene melamine and dimethylol-tetramethoxymethylene melamine 70 Gew.fcig dissolved in Kthylglykolazetat and 29 g of a 75 Gew.5Sigen solution of the triisocyanate described in Example 1 are with a Mixture of xylene and ethyl glycol acetate diluted to spray viscosity and applied to steel sheets with a dry film thickness of 45 - 50 μ and dried in the air.

The experiment was repeated, the lacquer then being ^{baked onto steel sheets at 130 °} C. in 20 minutes. The air and oven-dried film after curing showed an Erichsen cupping of 7-8 mm, very good results in the salt spray test and very good results in terms of gloss retention after two years of weathering in Florida.

The combinations of A and B used in the process according to the invention already dry physically, see above that - depending on the solvent used - the dust drying has occurred within 15-30 minutes.

The curing of air-dried systems is only complete after a few days.

The best results are obtained using copolymer 1. ' *

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Claims (9)

- 21 -DR, WALTER NIELSCH Patent attorney
Himburg 70 PO Box 10914 claims Telephone: 6528707 CJÖ ¹ ) 'Process for the preparation of polyhydroxy compounds in the form of soluble copolymers containing hydroxyl groups based on vinyl compounds and vinyl aromatics in inert solvents in the presence of polymerization initiators, optionally chain terminators, characterized in that these are made from: a) 38 - 70 wt. yi styrene or alkyl styrene, the Al- alkyl groups from 1 to 3 carbon atoms have or "a mixture of such alkyl groups, b) 0-25% by weight of acrylic acid and / or methacrylic acid esters containing 1 to 12 carbon atoms in the saturated alcohol residue, c) 3 "15 wt. # of an α, 8-ethylenically unsaturated Mono- or dicarboxylic acids and implementation with esterification with d) 10 -. 40% by weight of glycidyl ester of a-Alkylalkanmonocar- Bonic acids and / or a, a-Dialkylalkanmonocarbonsäuren the following empirical formula C ^ 2-l4 ^H 22-26 ° 3 ' ^where ^ ^d ^ ^e amounts of the compounds a) to d) add up to 100 wt.% must be prepared by heating. 2.) Process according to claim 1, characterized in that one . a) 45 · 60 wt.% of styrene or vinyltoluene, • b) 0-20 Gew./f acrylates and / or methacrylates saturated monoalcohols having 1 to 12 carbon atoms, c) 5-10 wt.% of acrylic acid or methacrylic acid, 009849/1868 "2021U1 ά) 15 "35 wt.? Glycidyl ester α-alkylalkane monocar- acids / or α and, α-dialkylalkane monocarboxylic acids of the following empirical formula ^c; i ^ 2-14 22-26 * ^ ^wobe ^ - ^d i ^e quantities of the compounds a) to d) must add up to lOO'Qevi%. converted by heating. 3.) The method according to claim 1, characterized in that that he a) 50 - 60 Qew.i styrene, b) 0 -. 10% by weight of butyl acrylate or butyl methacrylate, % of acrylic acid c) 6.6 wt. or 8 wt. Methacrylic acid, d) 22 wt.% glycidyl-ct Alkylalkynmonocar- Bonsäuren and / or α, α-diethylalkanmonocarbonsäure following sum η-formula ^c n2-14 ^ 22-26 ^ 1 'whereby the amounts of the connections a) to Ί) have to add up to 100 Gew. % , implemented by heating. 4.) Process according to one of claims 1 to 3, characterized in that the preparation by solvent polymerization takes place, the monomers a) to c) and the glycidyl ester d) in the reaction vessel together with the solvents, the initiators, possibly also, in the presence of chain terminators for Brings reaction, the condensation reaction and polymerization reaction taking place together. 5.) Process according to one of claims 2 to 3, characterized in that the glycidyl ester is dissolved in the solvent and at an elevated temperature - about 80 to 170 ^° C. - the monomers a) to c) with the initiators and chain terminators are added and condensed together and polymerized. 009849/1868 6.) The method according to any one of claims 2 to 5, characterized characterized in that the reaction is terminated as soon as the new polymers have molecular weights of about 5000-20,000 and a hydroxyl group content of 0.7 to 3.0, preferably 1.5 to 2.8 wt. 55 have, the hydroxy group content on refers to the solids content in the copolymer. 7.) Use of new copolymers as binder components (A) for Huaktionslacke together with organic polyisocyanates as component (B) in the following amounts: (A.) 70- $ k weight? Copolymers containing hydroxyl groups made from: a) 38 - 70 wt.fc styrene or alkylstyrene, its Alkyl groups have 1 to 3 carbon atoms or a basic structure such alkyl groups, b) 0 - 25 wt. Acrylic acid and / or methacrylic acid esters containing 1 to 12 carbon atoms in the saturated alcohol radical contain, c) 3-15% by weight of an α, ß-ethylenically ungesättig. ten mono- or dicarboxylic acid, 'and implementation under esterification with d) 10 - 40 wt. JE glycidyl ester a-alkylalkane monocar- carboxylic acids and / or α, α-dialkylalkanemonocarboxylic acids following Empirical formula C ^ ₂ ^ H _22- 2ß ⁰ 3 ^{»wol:) e} ^ the quantities of compounds a) to d) must add up to 100 wt. ii, and
009849/1868 (B.) 6-30 wt. Crganiscb.es 1 polyisocyanate, A and B together numerical values of 100 wt.? must surrender. 8.) Use of components (A) and (E) according to claim in the following quantities: A. 75-90% by weight of copolymers containing hydroxyl groups Risate made from: a) 45 -. 60% by weight of styrene or vinyl toluene, B) 0-20% by weight of saturated acrylates and / or methacrylates Monoalcohols with 1 to C atoms, c) 5-10 GtVKZ acrylic acid or methacrylic acid,
D 15 - 35 Cew.n Glycidylestor a-Alkylalkanmonocar- carboxylic acids and / or α, α-dialkylalkanecnocarboxylic acids of the following formula C _n ^. i, H _n " _oi 0 ₇ . where the
Amounts of the compounds a) to d)
must add up to 100 wt.%, and B. 10 - 25 Gev / .i? organic polyisocyanate, where A and B together numerical values of 100 Gev /. 1. must endure for the im
Claim 7 ar.ce given purpose. 9.) Components (A) and (E) according to claim 7 in the following amounts:
(A) 80-90% by weight of hydroxyl-containing copolymers sate herrc-stfclit from:
a5. 50 - 60 wt% of styrene, b) 10 - 22 % by weight of butyl acrylate or butyl methacrylate, c) 6.6 Gev /.? Acrylic acid or Weight? Methacrylic acid, d) 22 wt. Glycidyl ester a-alkylalkane monocar- acidic acids and / or α, α-diethylalkanemonocarboxylic acids the following sum 1868 2021IAI . ■ - 25 - formula C-, 2_ili ^K p2-26 ^^ '4C Mencon of the compounds a) to d) must add up to 100 wt. #, and. (B.) 10-20 wt.% Organic triisocyanate, .which diisocyanate by reaction of 3 moles of hexamethylene ■ and 1 mole of water was obtained, where A and B numerical values must give 100% by weight, for the in claim _7. purpose stated. BATH 009849/1868