DE2065770A1 - Soluble organic polymer mixtures useful as - binders - Google Patents

Abstract

Mixture of (a) 38-70% wt. of styrene or C1-3 alkyl styrene e.g. vinyltoluene; (b) 0-25% of an ester of C1-12 alcohol and acrylic and/or methacrylic acid; (c) 3-15 % wt. of alpha, beta-unsatd. mono- or dicarboxylic acid e.g. acrylic or methacrylic acid, are heated and then reacted with (d) 10-40% of glycidyl ester of alpha-alkyl-alkano monocarboxylic and/or alpha, alpha-dialkyl alkano mono carboxylic acid of formula C12-14H22-26O3 (a) and (d) together form 100%.

Description

Eliminated from P 20 21 141.0-44

R 2171 A

Reichhold-Albert-Chemie Aktiengesellschaft in Hamburg 70

Process for the production of soluble organic copolymers. I.

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 0} C so that the film under the action of Water no longer swells 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 process for the preparation of polyhydroxy compounds in the form of soluble copolymers containing hydroxyl groups which can be crosslinked with organic polyisocyanates and are based on mixtures of polymerizable vinyl compounds, the ct, ß-äthyleniseh unsaturated mono- or dicarboxylic acids and vinyl aromatics

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_M ρ -

or their derivatives contain and glycidyl esters by heating in inert solvents in the presence of polymerization initiators, optionally chain terminators, characterized in that these are selected from:

a) 38 - 70 wt. 5 & styrene or alkyl styrene. whose alkyl

groups have 1 to 3 carbon atoms or a mixture thereof Alkylstyrenes,

b) 3 ~ 15 wt. y? one ot, ß-ethylenically unsaturated

Mono- or dicarboxylic acid

and implementation with esterification with

c) 10 - 40 wt .- # glycidyl ester of a-alkylalkane monocarbon

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

Need to supplement% and the conversion of the components b) and c) between in equivalent proportions -. ^'Where ^ ^e ^ · the amounts of the' compounds a) to c) to 100 parts by ^ ^ 12-1 22-26® Ί of the carboxyl group and the glycidyl group, so that the products have acid numbers between 2 and 12, produces.

A special embodiment of the invention is thereby marked that one

a) 45-60% by weight styrene or vinyl toluene,

b) 5-10% by weight acrylic acid or methacrylic acid,

c) 15-35% by weight glycidyl ester of a-alkylalkane monocarbon

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

^C 12 -14 ^H 22-26 ° 3> ^where i the amounts of the compounds a) to d) add up to 100% by weight &

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- χ -

must supplement, and component b) in relation to component c) in equivalents Ratios between the carboxyl group and the glycidyl group is used, converted by heating.

Another embodiment of the invention is thereby marked that one

a) 56.5 wt -.% styrene,

b) 10.0 wt .- # acrylic acid and I.

c) 33.5% by weight glycidyl ester of a-alkylalkane monocarbon

acids and / or α, α-diethylalkanemonocarboxylic acid the following empirical formula

^C 12 ^H l4 ~ 22-26 ° 3 ^{wobe i: i} - ^the quantities of compounds a) to d) up to 100 wt -%.

must supplement, and component b) is used in relation to component c) in equivalent proportions between the carboxyl group and the glycidyl group,
converted by heating.

Numerous proposals are known to be solvent-resistant urtd alkali-resistant paints by reacting polyisocyanates and those containing hydroxyl groups Produce copolymers and process coatings. In the DT-AS 1 247 006 is a method for Production of alkali-resistant fabrics using the polyisocyanate polyaddition process described that of hydroxyl-containing copolymers and polyisocyanates can be obtained, but not sufficiently water-resistant after a reaction time of three to four days at 20 ° C are. These coatings obtained by this known process are therefore not suitable as topcoats for weather-resistant

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dense exterior paintwork, as blisters form after a very short time occurs and the adhesive strength of the paint on the various metallic substrates decreases and thereby the paint stands out from the substrate.

It is also known that polyhydroxy compounds of Polyols are to be cured with polyisocyanates in order to obtain crosslinked lacquer coatings with good resistance properties. These combinations also show insufficient water resistance and lower weather resistance of the cured paint layers.

In FR-PS 1 556 309 a coating agent is described, which contains solvents and as film-forming components

A. a copolymer consisting of

(1) 2 - 50 parts by weight of an additive product im Ratio 1: 1 of a carboxyl group of an α, ethylenically unsaturated acid and an epoxy group of a glycidyl ester of an aliphatic carboxylic acid with tertiary carbon atoms, in which the aliphatic tert. Contains group 4-26 carbon atoms, and

(2) 98-50 parts by weight of unsaturated copolymerizable Monomer, and where the total amount of (1) and (2) added to 100 parts by weight and

B. at least one polyisocyanate, which is at least 2 Contains isocyanate groups in its molecule and wherein the polyisocyanate to the copolymer in an amount of 0.2-5 equivalents based on the hydroxyl groups of the copolymer.

As the examples in this FR-PS in Table 1 Page 5 show that the copolymers described there contain at least one acrylate or one methacrylate - in

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in most cases even methacrylates and acrylates at the same time r polymerized.

However, these known coating agents provide films, which are very flexible and therefore do not have great resistance to solvents.

In FR-PS 1 390 572 a process for the preparation of copolymers is described in which one takes place in a solvent an α, β-unsaturated carboxylic acid or one of its Derivatives copolymerized with one or more other vinyl monomers in the presence of a catalyst and simultaneously or successively the reaction product with a glycidyl ester of the formula:

- R

- R

COOH + CH ₂ - CH - CH ₂ - C.
if 0 0 - C
η ^ O I!
0 I ■
Ö 0
Μ - Il
CO- CH ^ * ™ OJtI
OH - CH ₂ - C
Il
0 0 CH
ι ₂ OH C-O- CH - CHp - Ω - R.

converts, in which R is an aliphatic or aromatic radical, which can also be substituted, which is either

is saturated or contains one or more ethylenically unsaturated bonds.

As the examples of this FR-PS 1,390,572 show , the copolymers contain, in addition to styrene, several acrylates or mixtures of acrylates and methacrylates or several methacrylates. In addition, it is mentioned in the résumé of this French patent under the letter D that the copolymers described there can be used for coating agents which, by mixing together with an isocyanate

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prepolymers or a polyisocyanate. The coating agents of the type described there also have a relatively high elasticity after curing and are therefore still vulnerable to solvents.

In the book H. Wagner and HP Sarx "Lackkunstharze", Carl Hanser Verlag Munich 1959, page 170, 1st paragraph, it is stated that those monomers which result in very hard pure polymers, such as vinyl chloride, styrene, etc. are copolymerized with such monomers, which in turn give very soft pure polymers, such as butyl acrylate, vinyl isobutyl ether, etc. In addition to changed solubility, the products obtained show particularly advantageous film elasticity. In this case, one speaks of "internal plasticization" of the hard film formers. However, it is not evident from this information how the object of the present invention can be achieved in practice. In the book William v. Fischer "Paint and Varnish Technology ¹ 'Verlag Reinhold Publishing Corp., New York 19 ^ 8, page 222, 2nd paragraph, the properties of acrylate resins and methacrylate resins are mostly thermoplastic and very variable between soft, tough, semi-liquid to solid and hard Solids with the characteristic of colorless transparency and excellent aging properties as well as resistance to sunlight, oxygen and ozone described, the properties of the acrylates and methacrylates depend on the molecular weight of the polymers the polymerization temperature, the catalyst concentration of the polymerization solvent used and the copolymers are possible to produce synthetic resins with any degree of flexibility, which eliminates the need to use plasticizers en how the object of the present invention can be achieved in practice

can.

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In the brochure of the company Röhm & Haas GmbH Darmstadt "Plexigum, Plexisol, Plexalkyd, Plextol, Rohagit, Acriplex; Properties, differences and relationships to one another "Delivery program 1963, is given on pages 6 and 7, that polyacrylic esters and polymethacrylic esters are characterized by the following properties: They are colorless and clear, lightfast, resistant to yellowing even at high temperatures, extremely resistant to weathering and aging, excellent chemical resistance and physiologically harmless. The individual polymers differ mainly in mechanical properties and solubility. The following applies: 1. The hardness decreases when the number of carbon atoms in the alcohols used for esterification increases. 2 «Branched alcohols produce harder polymers than linear ones (poly-n-butyl methacrylate and poly-iso-butyl methacrylate).

3. Polymethacrylic acid esters are harder than polyacrylic acid esters. But also from these general remarks is not apparent how the object of the present invention could be achieved.

US Pat. No. 3,330,814 already contains hydroxyl groups Copolymers which are built up from monoethylenically unsaturated monomers have an acid number ^

up to 40 and at least 5 percent by weight ethylene unsaturated carboxylic acid units with active hydrogen atoms, which have a structure from the selected Groupings consisting of

Il

-CH ₀ -CH-CH ₀ -OCR 2, 2 OH

HO-CH ₂ -CH-CH ₂ -OCR

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where R is a tertiary aliphatic hydrocarbon radical with the structure

is where R. is -CH, and Rp and R-. Alkyl groups with 1 to Represent 12 carbon atoms and wherein according to claim 6, the monoethylenically unsaturated monomers styrene and Are acrylic acid and the polymer has an acid number of 5 to 40.

These known copolymers can be used alone as stoving coating agents (loc. Cit. Column 1, lines 56-61) Find. The combination of these copolymers with amino resins (loc. Cit. Column 3 »lines 52 - 62), Phenol-formaldehyde resins (op. Cit. Column 3, lines 63 - 66) indicated, in addition, epoxy polyethers (op. Cit. Column 3, lines 67 - 75) can also be used. These coating agents are baked at 121 to 205 C for 30 to 120 minutes. However, the use of these copolymers together with polyisocyanates is not considered. The US PS 3,330,814 corresponds to GB-PS 1 009 217.

In addition, there are no technical rules for action in the production of the copolymers described above indicated, which stipulate that the ethylenically unsaturated carboxylic acid units in equivalent proportions must be used between the carboxyl group and the glycidyl group of the glycidyl ester. Implementation of the Copolymers which are described in GB-PS 1 009 217 are specifically for the reaction with polyisocyanates not provided at all. This is shown by the examples in GB-PS 1 009 217 on the page are shown as example 10. A solution of the copolymer prepared according to Example 1 is namely produced there has been to one over with a melamine formaldehyde solution

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traction means processed. A.a.O. on page 12 will then the solution of the copolymer, which has been obtained according to Example 1, with hexamethoxymethylmelamine with a Epoxy resin based on epichlorohydrin and diphenylpropane with an epoxy equivalent weight of 450 to 525 and an esterification equivalent weight of about 145 processed in a coating agent.

That this example 1 is also not suitable for the preparation of a coating composition by combining with a polyisocyanate is suitable and was also not intended for it, it follows that the solution of the copolymer obtained after the copolymerization with butanol is diluted to a body content of 50%. Since butanol compared to " If polyisocyanate is very reactive in a known manner, the copolymerization solution prepared according to Example 1 GB-PS 1 009 217 has been produced, result in unusable preparations, so no suitable coating agent.

In order to show that Example 1 of the British patent, even if the butanol is omitted in order to obtain a copolymer solution that can react with Polyisocyanates is suitable to provide coatings that are much worse than those with the copolymers of the present invention have been prepared, is based on the results of the I given after the examples Comparative studies pointed out.

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.

As components a) are very suitable styrene followed by α, ο-, m- and p-methylstyrene. They lend a poly-

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merizes the fabrics produced from it high saponification resistance and good pigment absorption, when the copolymers are used together with organic polyisocyanates can be used as a reaction varnish.

For the use of the copolymers in the reactive coating, it is essential that the content of styrene, αϊ ο- m-, and p-methyl styrene, individually or in admixture at least 38 wt -.% And at most 70 wt .-% based on the solids content of the copolymer, preferably 45 to 60 wt .- / S. These amounts have to be used in order to impart the glossiness of the pigmented films, 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 films obtained from the reactive lacquers.

Acrylic acid or methacrylic acid, maleic acid or fumaric acid is used individually or in a mixture as component b). Acrylic acid or are preferred. Methacrylic acid.

As component c) glycidyl esters of ct-alkylalkane monocarboxylic acids and / or α, α-dialkylalkane monocarboxylic acids of the ^{formula c i2-14 H} 22-26 ° "3 ^e ^ - ^{n2e: j} - ^{n or} in a mixture. Since the glycidyl radical in the glycidyl ester of α-Alkylalkanemonocarboxylic acids and / or α, α-Dialkylalkanmonocarbonsäuren the empirical formula C, H (-0 is assigned, the α-alkylalkanoic acids and α, α-dialkylalkanoic acids are mixtures of such monocarboxylic acids, which have a Cg, C _1Q and C ^ chain 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.

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- li -

The acids are completely saturated and are at the α position Very heavily substituted carbon atom. Acids with two hydrogen atoms on the a-carbon atom are not present and only 6-75? these acids contain a hydrogen atom. In addition, there is cyclical material (German colors magazine issue 10/16 year. Page 435).

For the use of the copolymers according to the invention in reactive lacquers, it is necessary that the content the glycidyl ester of a-alkylalkane monocarboxylic acids and /

or α, α-Dialkylalkanmonocarbonsäuren 10 to 40 Gew. - ?, Ä

is preferably 15 to 35% by weight , based on the proportion of pesticides in the copolymer. With the use of 10 to 20 wt -.% Glycidyl esters of ctAlkylalkanmonocarbonsäuren / or α and, ct-dialkylalkane monocarboxylic acids in the copolymer is the hydroxyl content of 0.7 to 1.4 wt -.%. If such copolymers are used in combination with the polyisocyanates, less crosslinking and thus greater elasticity of the reactive lacquers emerges.

The copolymers obtainable by the process therefore still show a lot when used in reactive lacquers good anti-corrosive properties and good condensation f

test, however the film surface hardness has decreased somewhat.

Are such copolymers in the production of the reactive varnish, the 20 to 40 wt .-?, Preferably 20 to 35 wt .-? copolymerized glycidyl esters of a-alkylalkanemonocarboxylic acids and / or a, a-dialkylalkanemonocarboxylic _s based on the solid content in the copolymer include, used for the combination, wherein the amount of the polyisocyanate characterized by the NCO content in equivalent amounts in accordance with the hydroxyl groups in

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Copolymer is used, show by the increase in the hydroxyl group content in the copolymer reaction lacquers obtained as a result of the increased polyisocyanate addition larger cross-links and thus an increase in the film surface hardness and also good resistance of the films against chemicals and condensation; however, the elasticity of these films decreases somewhat off, but is still sufficient if these are on rigid surfaces.

The reaction for the preparation of the new copolymers takes place in such a way that the carboxyl groups of the components b) with the glycidyl groups of the a-alkylalkane monocarboxylic acids and / or α, α-dialkylalkane monocarboxylic acids of the components c) react so that a free hydroxyl group is formed with ester formation, which in the later Use for example for crosslinking with the organic polyisocyanates is necessary. The turnover takes place in equivalent proportions between the carboxyl and the glycidyl group.

The copolymers produced in this way result

Acid numbers between 2-12, preferred are those between

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

The following polyisocyanates, for example, can be used as component B:

Toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, Cyclohexylene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, Naphthylene-1,5-diisocyanate, 4,4'-, 4,2-triphenylmethane triisocyanate, l- (Isocyanatophenyl) ethyl isocyanate or the xylylene diisocyanate, fluorine-substituted

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ierte diisocyanates Äthylenglykoldiphenyläther-2,2'-diisocyanate, ^2,2-f Diäthylenglykoldiphenyläther diisocyanate, l, l'-binaphthyl-2,2'-diisocyanate, Bipheny1-2,4'-diisocyanate, biphenyl-4,4 ' -diisocyanate, benzophenone-3,3'-diisocyanate, fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, pyrene-3,8-diisocyanate, chrysene-2,8-diisocyanate, l-ethylbenzene-2, 4,6-triisocyanate, naphthalene-1,3 > ~ 7-triisocyanate, biphenylmethane-2,4,4 ^f -triisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, 3'-methoxyhexane diisocyanate, octane diiso-ω, ω -diisocyanate-1,4-diethybenzene, m ^ -diisocyanate-1,4-dimethylnaphthalene, cyclohexane-1,2-diisocyanate, l-isopropylbenzene-2,4- ⁽ 3iisocyanat _y i- |

Chlorobenzene-2,4-diisocyanate, l-fluorobenzene-2,4-diisocyanate, l-nitrobenzene-2,4-diisocyanate, l-chloro-4-methoxybenzene-2,5-diisocyanate, Azobenzene-4,4'-diisocyanate, benzolazonaphthalene-4,4'-diisocyanate, Diphenyl ether-2,4-diisocyanate and diphenyl ether-4,4'-diisocyanate.

Instead of the polyisocyanates, it is also possible to use compounds which split off polyisocyanates, and also isocyanate groups containing reaction products of polyhydric alcohols with polyisocyanates, for example the Reaction product of 1 mole of trimethylolpropane with 3 moles Toluylene diisocyanate, also trimerized or poly-

merized isocyanates, such as those found in German No. 951 168 can be described.

% In question - In addition, a reaction product of 1 mole of water and 3 moles of hexamethylene diisocyanate comes with an NCO content of 16 - 17 wt.. 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.

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The production of the new copolymers is carried out by solution polymerization, wherein one b is the monomers a) and) and the glycidyl ester c) in the reaction vessel, possibly _s brings together with the solvents, the initiators in the presence of chain terminators to the reaction, wherein the condensation reaction and polymerization reaction together expire. In a preferred embodiment, the glycidyl ester is dissolved in the solvent and, at an elevated temperature - about 80 to 170 ° C. - the monomers a) and b) with the initiators and chain terminators are added and condensed and polymerized together. Examples of initiators are: azo compounds, peroxide compounds, for example benzoyl peroxide, cumene hydroperoxide or di-tert-butyl peroxide. By using chain terminators such as mercaptans and aldehyde, the degree of polymerization can be adapted to the required conditions.

There are 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-Zj. strived for. The viscosity range from U to Z ₂ at 20 ^° C. is preferred.

The new polymers should preferably have molecular weights of about 500-20,000. These are a hydroxyl group content from 0.7 to _3} 0, preferably 1.5 to 2.8 wt -% having _i.. The hydroxyl group content relates to the proportion of pesticides in the copolymer.

The implementation of the hydroxyl-containing copolymers A when used in reactive lacquers with the organic polyisocyanates B can depending on the intended use of the products with 0.5 to 1.1 NCO groups per Hydroxyl group can be carried out. The implementation will

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preferably carried out so that the amounts of the organic polyisocyanate based on the total hydroxyl 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-containing copolymers A and polyisocyanate B are conceivable the simplest way, for example after adding known auxiliaries such as leveling agents, pigments or dyes, by spraying,, | Dipping, pouring, brushing or other suitable measures on the corresponding documents and dries the Flat structures at room temperature j in special cases, for example when using isocyanate releasers, stoving the coatings are carried out, which essentially depends on the documents used and the practice requirements placed on the coatings. The use of reactive melamine resins can also be used by Be an advantage. You can use the reactive melamine resins in amounts of 1 to 10 wt .- ^, based on the weight the binder component, which in particular increases the gloss in the fabric -

can. · ™

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

When the new copolymers are used in the reactive lacquers already explained, the reaction takes place and applying the fabrics to the substrate in solution. Suitable solutions are e.g. ethyl acetate, Butyl ester, ether ester, diethyl glycol diacetate and

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Aromatics such as benzene, toluene or xylene. The concentration of the solutions can vary within wide limits and depends essentially on the solubility of the components. Solutions are preferred with a Peststoffgehalt 20-80 wt -.% 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-containing polyesters and polyethers can be mixed in any ratio and can therefore be blended with them. The reaction products of such blends with polyisocyanates also provide alkali-resistant coatings with similar properties as those already described above, whereby in particular, the relatively fast drying time is noticeable.

The copolymers obtainable by the process can be used to produce coatings in the reactive 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. Particularly highlighted be it the production of coatings on wood or metals. In any case, you get high-gloss, very Surface-hard, pore-free, elastic and solvent-resistant coatings that can be seen with strong inorganic materials Can treat acids as well as strong alkalis without attacking the coatings even to the slightest extent will. Such coatings also show excellent weather resistance and resistance to yellowing.

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It should be emphasized in particular that the coverings or coatings produced in this way on aluminum sheets as single-layer coatings have excellent adhesive strength. The coverings and coatings can advantageously be made on aluminum by removing the solvent from the coating after applying the coatings by means of a temperature treatment at 40 ° -50 ° C. for about 30 minutes, after which the coating or the coating is in a tack-free state so that the surface does not absorb any dust and is also no longer sensitive to impact or other mechanical pressure, so that the objects painted in this way can be subjected to further processing. The maximum properties are then achieved after curing for three to four days at room temperature. 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:

(A) 70 - 94% by weight of copolymers containing hydroxyl groups made of:

a) 38-70 wt. 55 styrene or alkylstyrene, the alkyl of which

groups have 1 to 3 carbon atoms or a mixture of these Alkylstyrenes,

b) 3-15 wt -.% of an α, β-ethylenically unsaturated

Mono- or dicarboxylic acid,

and implementation with esterification with

c) 10-40 wt. Glycidyl ester of o ^ alkylalkane monocarbon

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

^ 12-14 ^ 22-26 ^ 3 'where the quantities of Compounds a) to c) add up to 100 percent by weight

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must supplement and the other condition is that component b) with respect to component c) was present in equivalent proportions between the carboxyl group and the glycidyl group, so that a free hydroxyl group is formed as a result of the ester formation that has taken place
and

(B) 6-3O wt -.% Of an organic polyisocyanate, where (A)

must result in% - and (B) together numerical values of 100 wt..

A special embodiment of the use includes:

(A) 75-90% by weight of copolymers containing hydroxyl groups,

made of:

a) M 5 - 60 wt. ~ # styrene or vinyl toluene,

b) 5-10 weight percent acrylic acid or methacrylic acid,

c) 15 - 35 wt .- Ji glycidyl ester of a-Alkylaikanmonocarbon-

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

^σ ΐ2-ΐ4 ^Η 22-2β ^Ο 3 ^{ϊ where} i ^d i ^e amounts of the compounds a) to c) must add up to 100 Ge \ i .-% and the further condition is j that the component b) with respect to the Component c) was present in equivalent proportions between the carboxyl group and the glycidyl group, so that a free hydroxyl group was formed as a result of the ester formation that took place,
and

(B) 10-25% by weight of organic polyisocyanate, where A and B.

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

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A particularly preferred embodiment of the use includes:

(A) 76 to 85 wt -.% Hydroxyl-containing copolymers

made of:

a) 56 ₃ 5 wt .- $ styrene,

b) 10.0% by weight acrylic acid,

c) 33.5 wt. JS glycidyl ester of ot-alkylalkane mono-

carboxylic acids

and / or α, α-diethylalkane monocarbon

acids of the following molecular formula

^C 12-14 ^H 22-26 ° 3 ' ^{wol) e} i & i- ^e quantities of

Compounds a) to c) to 100 wt - must% t supplement and is the further condition that the component b has) been present with respect to the component c) in equivalent proportions between the carboxyl group and the glycidyl group, so that by the. If ester formation occurred, a free hydroxyl group was formed
and

(B) from 15 - 24 wt -.% Organic triisocyanate which is obtained by

Implementation from 3 moles of hexamethylene diisocyanate and 1 mole of water was obtained, J.

where A and B numerical values of 100 wt -.% must result.

Example 1:

Production of the copolymer 1:

In a flask equipped with a stirrer, reflux condenser and thermometer, 528 g of xylene and 268 g of glycidyl esters of α, α-dialkylalkanemonocarboxylic acids of the ^{formula C 12-14 H} 22-26 ⁰ "5 ^m ^ ^e ^ ^nem epoxy equivalent of 240-250, in the following only referred to with glycidyl ester α, α-dialkylmonocarboxylic acids, heated to 140 ° C and a

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Mixture consisting of 452 g styrene, 80 g acrylic acid and g di.-tert.-butyl peroxide added uniformly in two hours and about 8 to 10 hours at this temperature polymerized and condensed. The product has a body content of 60 wt. <- #, a viscosity according to Gardner-Holdt from X-Y of the 60% solution in xylene and an acid number of 4.2. The hydroxyl group content is 2.3 wt. based on the solids content in the copolymer.

Example 2:

Reaction lacquer based on 80.3 wt -.% Copolymer 1 and 19j7 wt -.% Organic triisocyanate, both based on the Pestkörpergewicht.

I.) 53 * 1 g of copolymer 1-xylene solution (dissolved plague body 60% by weight ) are rubbed with 600 g of titanium dioxide (rutile), 200 g of xylene and 100 g of ethyl glycol acetate to form a varnish.

II) 150 g of the above pigmented lacquer formulation I containing the copolymer 1, 61.5 g of the unpigmented copolymer 1-xylene solution (dissolved solids 60% by weight ) and 23.1 g of a 75% by weight solution a triisocyanate with an NCO content of 16.5 to 17> 0 wt -% in a mixture of xylene / Äthylglykolazetat. 1: 1 dissolved, which has been obtained by reaction of 3 moles of hexamethylene diisocyanate and 1 mole of water to be on with xylene Spray viscosity diluted and applied to aluminum sheets with a dry layer thickness of 45 - 50 μ and dried in the air. Tack-free is achieved after 30 - k0 minutes. The pendulum hardness measured according to König (Din 53 157) shows 110 seconds after 3 days, 137 seconds after 7 days, 175 seconds after Ik days, stored at 20 ^° C. The water resistance after four

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■ days of drying at 2O ° C on aluminum sheets is · tested as follows: "production of a cross-section, then heating the sheet to 60 to 70 ⁰ C and 10 - 15 mins long exposure to hot water, Result: No swelling at the cross cut, no scraping of the still warm film possible with the fingernail.

A film on aluminum sheets dried in the air for ten days shows ^{no blistering in the condensation water test at 50 °} C. after 25 days. The shine is still completely preserved.

Example 3: "

Reaction lacquer on the basis of 85 wt .-% copolymer 1 and 15 wt -.% Organic triisocyanate, both based on the weight of solids.

I ·) 534 g of copolymer 1-xylene solution (dissolved solids 60% by weight ) are rubbed with 600 g of titanium dioxide (rutile), 200 g of xylene and 100 g of ethyl glycol acetate to form a varnish.

II.) 150 g of the pigmented varnish I of this example, which contains the copolymer 1, 68.4 g of the unpigmented copolymer-1-xylene solution (dissolved ä solids 60 wt. %) And 17.7 g of a 75 wt. -JSigen solution of the triisocyanate described in Example 2 with an NCO content of 16.5-17 wt is, is diluted with xylene to spray viscosity and applied to aluminum or steel sheets with a dry film thickness of 40 50 μ and air-dried. The coating is also used in a further experiment at

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Burned in at 130 ° C. The pendulum hardness of the at 2Ο ° £ air-dried film is 97 seconds after 3 days, 122 seconds after 7 days and 145 seconds after 14 days. The water resistance tested as in example 2 gave the following result:

No swelling and no scraping of the still warm film with the fingernail possible. A burned at 13O ⁰ C in 30 minutes paint on a phosphated iron plate shows after 60 hours in boiling wash liquor with a detergent content of 3 wt .- #, and a pH-range of 10-13 j wherein, during 60 hours cooking time, the liquor was replaced six times by freshly prepared washing liquor, no blistering and no loss of gloss. The best self-hardening acrylate resins used for the same purpose show a heavily swollen film after the third change of wash liquor in the test test, while after the fourth change of wash liquor the film was already destroyed and detached from the sheet metal.

Example 4: -.

Reaction lacquer on the basis of 76 wt -.% Organic copolymer 1 and 24 parts by weight JS triisocyanate, both based on the weight of solids.

g of the pigmented lacquer formulation I mentioned in Example 2, paragraph I, which contains the copolymer 1, 38 g of the unpigmented copolymer 1-xylene solution (dissolved solids 60% by weight ) and 21.5 g of a 67% by weight. - # igen solution of a triisocyanate with an NCO content of 11.5 wt-i, dissolved in a mixture of xylene / ethyl glycol acetate 1: 1, which has been obtained by reacting 3 moles of tolylene diisocyanate and one mole of trimethylolpropane, are with a Mixture of xylene / ethyl glycol acetate diluted 1: 1 and applied by spraying onto steel sheets and

509829/0737

baked for 30 minutes at 13O 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 5:

Reaction varnish on the basis of 70% by weight! 1 copolymer, 22 wt -.% Organic triisocyanate and 8 wt -.% Of a mixture of monomethylol-pentamethoxymethylenmelamin λ and Dimethyloltetramethoxymethylenmelamin.

150 g of the pigmented lacquer formulation I, according to Example 4, paragraph I, which contains the copolymer 1, 61.5 g of the unpigmented copolymer-1-xylene solution (dissolved pest body 60% by weight ) ₃ 11.5 g of a mixture ( about 80:20 wt -.% to 20:80 wt -.%) of monomethylol and dimethylol pentamethoxymethylenmelamin tetramethoxymethylenmelamin 70 parts by weight · JSig in Äthylglykolazetat dissolved and 29 g of a 75 wt .- $ of the solution described in example 2 Triisocyanate are diluted to spray viscosity with a mixture of xylene and ethyl glycol acetate and applied to steel sheets with a dry film thickness of 45 - 50 μ f 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 use according to the invention already dry physically, so that - depending on the solvent used - within

509 8 29/0737

.III 1

dust drying occurred halfway through 15 - 30 minutes is.

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

The best results are achieved using the copolymer 1 received.

Example 6:

Reaction varnish based on 76% by weight? 1 copolymer and 24 wt -.% Organic triisocyanate _9, both based on the weight of solids.

It is worked according to Example ¹ J, paragraph 1, but notwithstanding the coated by spraying coating film is baked at an elevated temperature not ₉ but at a temperature of 20 - 25 ° C for 10 days dried in air. The results obtained are shown in the table below.

In the drawings, FIG. 1 shows the pendulum hardness in see (DIN 53 157) as a function of the baking temperature in ⁰ C with a constant baking time of 30 minutes, the test film according to Example 2 being used.

FIG. 2 shows the results of the "reverse impact test" as a function of the stoving temperature in ⁰ C with a constant stoving time of 30 minutes, the test film according to Example 2 being used.

3 shows the results of the Erichsen cupping (DIN 53 156) in mm as a function of the baking temperature in ⁰ C with a constant baking time of 30 minutes, the test film according to Example 2 being used.

5 09829/073 7

Flg. 4 gives the increase in viscosity (4 DIN 53211 / 2O ° C) in see depending on the pot life in hours at constant temperature, namely 20 ° C, again; also with this one An approach according to Example 2 was used for testing.

Resistance tests of a lacquer coating produced according to Example 6

Agents 1 week 2 weeks 5 weeks - 1 LG 40% caustic soda 0 0 O - 1 Sulfuric acid 50% O 0 0 - 1 MV Hydrochloric acid 10% O 0 O - 1 LV Acetic acid 10 # ig O 0 0 - 2 ink 0-1 1-2 LV 1 0 lipstick 0 O 0 LV red wine 0 0 0 mustard 0 0 0 Tomato paste 0 0 LV 0 butter O 0

Valuation:
Film hardness:

Discoloration:

Shine:

0 = no pilm attack LV = slight discoloration LG = slight loss of gloss

1 = paint surface MV = medium discoloration. MG = medium loss of gloss

with frequent SV = severe discoloration. SG = severe loss of gloss

Scratching hardly vulnerable

2 = paint surface at

Frequent scratching easily vulnerable

3 = paint surface at

Frequent scratching very easily injured

4 = film swell

509829/0737

Comparative examination to prove the technical port step achieved:

To determine the "pot life", the copolymer according to the invention listed in the table below was tested in comparison with the copolymer (Example 1) of GB-PS 1 009 217 in combination with an aromatic polyisocyanate. The lacquers were set to 20 sec. ₃ measured in a DIN beaker with a 4 mm opening, with a solvent mixture xylene / ethyl glycol acetate in a ratio of 1: 1.

As can be seen from the table below, the copolymer according to Example 6 according to the invention is the copolymer according to example 1 of GB-PS 1 009 217 superior.

509829/0737

Used
Copolymer

according to the invention
Example 6
unpigmented

dito .
pigmented

example 1
the GB-PS

ι 009217

unpigmented

dito
pigmented

Monomer composition

56.5 / S Styrcü $ 10 acrylic acid

33.5 * glycidyl ester

the Versatic fatty acid

Styrene acrylic acid glyidyl ester ■ the Versatic fatty acid

Combination ratio

Reaction varnish from:

76 weight -.% Copolymer and 24 wt -.% Organic triisocyanate, which has been ten preserver by reacting 3 moles of toluylene diisocyanate and 1 mole of trimethylolpropane.

"pot life"

after 50 hours = seconds +

after 40

Hours; = 100 sec. +

after 20 hours gel

after

16

Hours.

gel

Erichsen recess on sheet steel

o μ dry film

5 mm

mm

2 mm

1.5 mm

"pot life" at 20 ⁰ C.

The clear lacquer was flown out in the DIN cup for 20 seconds with a 4 mm opening with xylene / ethyl glycol acetate in a ratio of 1: 1 and the increase in viscosity as a function determined by time.

Further comparative tests with pigmented paints

The reaction materials were, based on the Pestkörpergewicht, on the basis of 80.3 wt -.% Copolymer and 19.7 wt -%, organic triisocyanate which is obtained by reaction of 3 moles of hexamethylene diisocyanate and 1 mole of water produced, and. ir. Ratio 1: 0.7 binder: titanium dioxide pigmented and with a dry film thickness of approx. 50 μ on phosphated steel sheets

509829/0737

upset. The values were determined after drying for 10 days at 20 ° C.

As can be seen from the table below, the copolymer produced according to the invention is according to Example 1 superior to the copolymer according to example 1 of GB-PS 1,009,217.

Investigations
with pigmented
ten paints:
Copolymer shine
after
Gard
ner "reverse impact"
Impact depression
on the back side
of the painted
Sheet metal, measured
as inch x pound
50 y dry film Erichsen-
Cupping Resistance to washing lye:
Liquid Dixan solution 8 hours
cook = 1 round; for
every additional round was
freshly prepared Dixan
solution set invention
according to
example 1 95 % 90 9.0 mm after 10 rounds it was
Paint still undamaged
and showed a shine
measured according to Gardner ₃
by 86 % example 1
the GB-PS
1 009 21? 85 % HO 6.0 mm after 10 rounds it was
Paint completely destroyed
and leafed from the tin
away. Strongest adhesion
loss .

509829/0737

Further comparative tests with unpigmented paints

The reactive lacquers were in the unpigmented state on the basis of 80.3 wt .- / δ copolymer and 19.7 wt organic triisocyanate, which by reaction from 3 moles of hexamethylene diisocyanate and 1 mole of water, both based on the pest body weight, with a dry film thickness of approx. 50 u on a steel sheet applied, and the impact indentation of a clear lacquer which had cured after drying for 10 days at 20 ° C. was made

determined.

As can be seen from the following table, the copoly- | merisat according to the invention Example 1 the copolymer according to example 1 of GB-PS 1 009 217 superior. In addition, the copolymer produced according to the invention shows compared to the copolymer of this GB-PS a more favorable "pot life" in relation to a slower increase in viscosity or gelation, which suggests that the paints can be processed much more favorably.

509829/0737

Investigation with unpigmented paints

Used Monomer "reverse impact" "pot life" at 20 ° C. Copolymer together Impact depression The clear coat was settlement on the back on 30 min. 4 sec. te of the painted with xylene / ethyl Sheet metal, measured glycol acetate im as inch x pound Ratio 1: 1 Layer thickness set 50 μ dry film inventive 56.5% according to Styrene, 160 after 30 hours example 1 $ 10
acrylic 110 min. 4 sec. acid, $ 33.5 Glycidyl ester d. Versatic fatty acid example 1 60% 80 after 50 min. gel the briti Styrene, patent 11% font acrylic 1 009 217 acid, 29% Glycidyl ester d. Versatic fatty acid

509829/0737

Further comparative tests with unpigmented paints

The reaction materials were in the unpigmented state on the basis of 80.3 wt -.% Copolymer and 19.7 wt -.% Organic triisocyanate which is obtained by reaction of 3 moles of hexamethylene diisocyanate · and 1 mole of water, both based on the Pestkörpergewicht applied with a dry film thickness of about 5Oy, on a glass plate and determines the dust drying and after drying at 20 ⁰ C lOtägiger the König pendulum hardness and the resistance to xylene. |

As can be seen from the following table, the inventive Copolymer 1 is superior to the comparative examples of PR-PS 1,390,572 and the adapted example. aside from that shows the copolymer 1 used according to the invention compared to the examples of FR-PS 1 390 572 a more favorable "pot life" in relation to a slower increase in viscosity or gelation, which infer more favorable processability of the paints which can be used according to the invention leaves.

S09829 / 0737

Investigations with unpigmented paints

Monomer After 10 ί Dust- Pendulum "pot life" at together- dayj? I. dry hardness 20 ⁰ C. The clear one settlement Dry tion after varnish was on at king 20 sec. 20 ⁰ C was after time in DIN de the lOday. cher with 4 mm Xylene Dry opening with constant- tion Xylene / ethylgly- speed at Kolacetat in ver after 10 20 ⁰ C ratio 1: 1 Min. Beτ represents and the vis burden increase in cost in checked Dependence on determined by time. Invent 56.5% 1 45 146 after 30 hours dung s ge
should s Styrene,
10? Min. Sec. 110 min. 4th sec. example 1 acrylic acid $ 33.5 Glyci- dylester d.Versa- ticfett- acid Example 7 30.8% 3 57 96 after 6 hours the PR-PS
1390572 Styrene,
15.35% Min. Since. gelled Meth acrylics. 15.35% Butyl acrylate 38.5% Glycidyl ester d. Versatic fat. Example 8 27.6 "* 4th 88 60 after 30 hours the PR-PS
1390572 Styrene
13.8% Min. Sec. gelled acrylic acid 13.8% Ethyl- acrylate l \ 5% glyci- dylester d Versaticfs

509829/0737

Monomer After 10 5098 j Dust- I. Pendulum "pot life" at 20 ⁰ C. together day dry .9 / 073 hardness The clear coat was settlement Drying tion after for 20 sec. at 20 ^° C king time in the DIN Beeher was the after with 4 mm opening Xylene lOday. with xylene / ethyl gly- constantlyk. Dry colacetate in the ratio after 10 tion set to 1: 1 Min at and the viscosity burden 20 ⁰ C increase depending checked from the time determined. at 32.2% 4th 70 83 after 30 hours game
10 Styrene,
12.9% Min. Sec. 170 min. 4 sec. the Meth PR-PS acrylics. 1390- 19.3% 572 Butyl acrylate 35.6% Glycidyl ester d. Versatic fat. at 3 68 92 after 30 hours b. game Styrene Min. Sec. Clears temperature 12 d. 18.8% 320 min. 4 sec. FR-PS Meth 1390 acrylics. 572 4.7% Butyl acrylate 53% Glycidyl ester d. Versatic fatty acid at 21.5% 68 35 after 6 hours game
13 d. methyl
met h- Min. Sec. gelled PR-PS acrylate 1390 37% 572 Ethyl- acrylate 12.9% Meth acrylics. 28.6% GIy- cidyl ester d.Versatic fatty acid 7th

After 10 34 - Pendulum 2065770 Monomer day dust hardness. "pot life." at 20 ⁰ C. together- Drying dry after The clear coat was settlement at 20 ^° C tion king for 20 sec. was the after time in the DIN Beeher Xylene 10day. with 4 mm opening with constantlyk. Dry Xylene / ethyl glycol after 10 tion aeetat in proportion Min at set to 1: 1 burden 20 ⁰ C and the viscosity checked increase depending on from the time ermit 1-2 125 telt. the 5OJS 57 Sec. after 30 hours PR-PS styrene
1390 10? Min. 145 min. 4 sec. 572 acrylics. an- 6.5? matched butyl By-acrylate game 33.5? Glycidyl ester d. Versatie fatty acid Further comparative tests with pigmented paints

The reactive varnishes were, based on the weight of the target body, on the basis of 80.3 percent by weight of copolymer and 19 »percent by weight of organic triisoeyanate, which was obtained by reacting 3 moles of hexamethylene diisocyanate and 1 mole of water, and in a ratio of 1: 0.7 Binder: pigmented titanium dioxide and applied to phosphated steel sheets with a dry film thickness of approx. 50 μ. After drying for 10 days at 20 ^° C., the values were determined.

As can be seen from the following table, the inventive Copolymer 1 of the comparative examples of French patent 1390572 and the adapted example think.

509829/0737

he"

CD 00 NJ CO • ^ »O

co

Investigations
with pigmented
Lacquers Shine n.
Gardner Pendulum hardness
n. king Bucbholz-
Hardness after
DIN 53153 Eriohsen
Cupping Resistance to washing lye:
Liquid Dixan solution 8 hours
cook = 1 round. For every
another round was fresh
prepared Dixan solution
puts after 6 rounds it was
Paint destroyed to about 50% inventive
according to example 1 95% I60 sec. 118 9.0 mm after 10 laps the paint was off
still undamaged and showed
a gloss measured according to
Gardner of 86% Example 7 of the
FR-PS I390572 90% l40 sec. 100 8.0 mm i after the 4th round completely
• j destroyed Example 8 of the
PR-PS I390572 902 120 sec. 83 <
8.4 mm j completely after the 4th round
I destroyed the FR-PS
1390572 adapted
example 92g 145 sec. 111 1 9.0 mm

VJTI I

N) O

cn cn

Further comparative examinations to prove the achieved technical port step compared to coatings, which according to the technical rules of PR-PS 1 390 572 have been produced:

1) Procedure according to the invention and results obtained: A copolymer is at I was prepared in accordance with the information in this patent description of the present invention. Then, a reactive varnish was prepared according to Example 1 of the present invention. Iron sheets were then sprayed with a lacquer layer thickness of ¹ IO - 60 μ and stored for 14 days at room temperature.

a) The sheets were then subjected to a fluoride test. After a 12 month ploridate test period
only a decrease in gloss of 8% on the paint films was found.

b) Another part of the sprayed iron sheets was

70 hours in boiling 10% strength by weight sodium hydroxide solution and no damage to the coatings was found.

c) Another part of the sprayed iron sheets was at room temperature (about 20 ° C) 1000 hours in one 40% strength by weight aqueous sodium hydroxide solution stored. The Laekschicht showed no attack afterwards.

2) Working method according to PR-PS 1 390 572 and achieved results:

Under the same conditions as in the copolymer I and Example 1 of the present invention indicated, a reactive varnish was produced using the same iso-

509829/0737

cyanate and, as described above under item 1 (a to c), tested.

In this case, copolymers were used which had the following compositions:

0-72% by weight styrene,

5-85 wt .- / S acrylic and / or methacrylic acid esters, which contain 1 to 4 carbon atoms in the saturated alcohol residue,

3-15 wt -.% Acrylic or methacrylic acid and reacting under esterification with - 40 wt -.% Glyeidylester of α, α-Dialkylalkan-

monocarboxylic acids with the following empirical formula ^C 12 -14 ^H 22-26 ° 3 ^m ^ ^e i ^nem epoxy equiva- *

12-14 ^H 22-26 ° 3
lent from 240 - 250, the quantities

of compounds a) to e) must add up to 100% by weight.

a) In the Florida test, the coatings obtained showed a decrease in gloss of between 20 and 30%.

b) When treated with 10% strength by weight boiling sodium hydroxide solution the films were destroyed after 1 1/2 to 2 1/2 hours.

c) When tested in 40 wt .- # ä aq sodium hydroxide solution, the resist layers 25 were according to

Already swollen after 45 hours of exposure and cracking or hole formation had occurred.

These comparative tests show that in the case of the present invention, there is a jump in various directions technical progress is achieved which would not have been expected by the average person skilled in the art.

509829/0737

Claims (1)

Patent claims: Process for the production of polyhydroxy compounds in the form of soluble copolymers containing hydroxyl groups which can be crosslinked with organic polyisocyanates based on mixtures of polymerizable vinyl compounds that are α, β-ethylenically unsaturated Mono- or dicarboxylic acids and vinyl aromatics or their derivatives contain and glycidyl esters by heating in inert solvents in the presence of polymerization initiators, optionally chain terminators, thereby characterized by the fact that one consists of: a) 38 -. ~ 70 weight% styrene or Älkylstyrol whose Alkyl group 1 to 3 carbon atoms have or a mixture of such alkylstyrenes b) 3-15 wt .- # of an α, β-ethylenically unsaturated Mono- or dicarboxylic acids c) 10-40% by weight and implementation with esterification with Glycidyl esters of α-alkylalkane monocarboxylic acids and / or α, α-dialkylalkane monocarboxylic acids of the ^{following empirical formula c i2-l4 H} 22-26 ° V ^whereby ^ ^d * ^e amounts of compounds a) to c) have to add up to 100% by weight and the conversion of components b) and c) takes place in equivalent proportions between the carboxyl group and the glycidyl group, such that the products have acid numbers between .2 to 12, manufactures. 5 09829/0737 2. The method according to claim 1, characterized in that one a) 45-60% by weight styrene or vinyl toluene, b) 5 - 10% by weight acrylic acid or methacrylic acid, c) 15 - 35 wt. SS glycidyl ester of a-alkylalkane mono * carboxylic acids and / or α, α-dialkyl-alkanemonocarboxylic acids following Molecular formula ^c ip-l4 ^H 22-26 ° V ^whereby ^ the amounts of the compounds a) to c) add up to 100% by weight? must supplement and component b) in relation to component c) in equivalen-. f th ratios between the carboxyl group and the glycidyl group is used,
converted by heating. 3 · The method according to claim 1, characterized in that a) 56.5 wt. Ji styrene, b) 10.0 wt. Acrylic acid and c) 33.5 wt -.% glycidyl esters of a-Alkylalkanmonocarbon- acids and / or α, α -dialkylalkane mono- carboxylic acid with the following empirical formula λ ^C 12 ^H l4 22-26 ° 3 ⁱ wherein the amounts of compounds a) to c) to 100 weight - need to supplement% and the component b) with respect to the component c) in equivalent proportions between the carboxyl group and the. Glycidyl group is used,
converted by heating. 4. The method according to any one of claims 1 to 3 »characterized in that the production by solution 509829/0737 medium polymerization takes place, whereby the monomers a) and b) and the glycidyl ester c) in the reaction vessel together with the solvents, the initiators, possibly also in the presence of chain terminators to react, the condensation reaction and the polymerization reaction take place together. 5. The method according to any one of claims 1 to 3 _S, characterized in that the glycidyl ester c) is dissolved in the solvent and at elevated temperature - about 80 to 170 ^o C - the monomers a) and b) with the initiators and chain terminators are added and condensed and polymerized together. 6. The method according to any one of claims 2 to 5, characterized in that the reaction is terminated as soon as the new polymers have molecular weights of about 5OOO - 20,000 and a • hydroxyl group content from 0.7 to 3.0, preferably 1.5 to 2.8 wt. SS have, the hydroxyl group content relates to the proportion of pesticides in the copolymer. 7. Use of new copolymers as binder components (A) for reactive lacquers together with organic polyisocyanates as component (B) in the following quantities: (A) 70 - 94 wt. copolymers containing hydroxyl groups, made of: a) 38-70 wt -.% of styrene or alkylstyrene, the Alkyl group have 1 to 3 carbon atoms or a mixture such alkylstyrenes, b) 3-15 wt -.% of an α, β-ethylenically ungesättig th mono- or dicarboxylic acid, and reaction with esterification with 509829/0737 c) 10-40% by weight of glycidyl ester of ct-alkylalkane mono- carboxylic acids and / or α, α-dialkylalkanemonocarboxylic acids following Molecular formula ^c i2-l4 ^H 22-26 ° ^: 5 ^{> where} i the amounts of the compounds a) to c) must add up to 100 wt .- # and the further condition is that the component b) in relation to the component c ) was present in equivalent proportions between the carboxyl and the glycidyl group, so that the ester | formation a free hydroxyl group was formed
and
(B) 6-3O wt -.% Of an organic polyisocyanate, Must result in% - (A) and (B) together numerical values of 100 wt.. Use of components (A) and (B) according to claim 7 in the following amounts: (A) 75 - 90 wt. S5 copolymers containing hydroxyl groups, made of: a) 45 - 60 wt -.% of styrene or vinyltoluene, j b) 5-10 wt .- / S acrylic acid or methacrylic acid, c) 15 - 35 wt .- # glycidyl esters of a-alkylalkane mono- Bonsäure and / or α, α-Dialkylalkanmonocarbonsäuren of the following ^{empirical formula c} i2-l4 ^H 22-26 ^O 3 » ^whereby ^ ^the amounts of the connections a) to c) have to add up to 100 Gew .- / S and the selection condition according to claim 7 applies
and 509829/0737 (B) 10 - 25 wt -.% Of an organic polyisocyanate, Must result in%, for the purpose indicated in claim 7 - (A) and (B) together numerical values of 100 wt.. Use of components (A) and (B) according to claim in the following amounts: . (A) 76 to 85 wt -% hydroxyl-containing copolymers prepared from: a) 56.5% by weight styrene, b) 10.0 wt .- # acrylic acid, c) 33.5% by weight glycidyl ester of a-alkylalkane monocar- carboxylic acids and / or α, α-dialkylalkanemonocarboxylic acids the following sum formula ^c ip-l4 ^H 22-26 ° V ^{wot> e} ^ - ^the amounts of compounds a) to c) need to supplement% and the selection condition applies according to claim 7 - up to 100 wt.
and (B) from 15 - 24 wt -.% Organic triisocyanate which by reacting 3 moles of hexamethylene diisocyanate and 1 mole of water was obtained, with (A) and (B) giving numerical values of 100 wt must and the selection condition according to claim 7 applies to the purpose specified in claim 7. 10. Use of components (A) and (B) according to claim in the following amounts: (A) 7o wt -.% Hydroxyl-containing copolymers and (B) 22 wt -.% Organic triisocyanate and 509829/0737 (C) 8 wt .- /? a mixture of monomethylolpentamethoxymethylmelamine and dimethylol tetramethoxymethyl melamine. 11. Use of components (A) and (B) according to claim 7 in the following amounts: (A) 80.3 wt. S? Mixed polymer and (B) 19.7 wt -.% Organic triisocyanate which by reacting 3 moles of hexamethylene diisocyanate and 1 mole of water has been received. 12. Use of components (A) and (B) according to claim 7 in the following amounts: (A) 85 wt .-% copolymer and (B) 15 wt. organic triisocyanate with a NCO content of 16.5-1756, which is obtained by reacting 3 moles of hexamethylene diisocyanate and 1 mole of water has been obtained. 13. Use of components (A) and (B) according to claim 7 in the following amounts: (A) 76 wt. J? Mixed polymer and (B) 24% by weight of organic triisocyanate with a ™ NCO content of 11.5? », Which is obtained by reacting 3 moles of toluene diisocyanate and one mole of trimethylolpropane has been obtained. 14. Use according to any one of claims 1 to 9> being as further binders 1-10 wt. JS reactive melamine resins, based on the weight of the binder component. 509829/0737 Blank page