DE2065960A1 - REACTION VARNISHES FOR THE PRODUCTION OF COATS OR COATINGS - Google Patents

Description

Eliminated from P 20 54 239.6-43

Hoe 69 / RO16 B
File: R 2195 A

HOECHST Aktiengesellschaft, 6230 Frankfurt (Main) 80

Reactive lacquers for the production of coatings or Coatings

Numerous proposals have become known to produce solvent-resistant and alkali-resistant paints by reacting polyisocyanates and copolymers containing hydroxyl groups and to process them into sheet-like structures. In German Auslegeschrift 1 2k ^r (a process for producing alkali-resistant sheet material according to the polyisocyanate polyaddition process is described, which are obtained from hydroxyl-containing copolymers and the like. Polyisocyanates, however, to four days of reaction time at 20 ⁰ C are three for a not sufficiently water resistant. These coatings obtained by this known process are therefore not suitable as topcoats for weather-resistant exterior paintwork, since blistering occurs after a very short time and the adhesive strength of the paint on the various metallic substrates decreases and the paint is thereby lifted from the substrate.

It is also known that polyhydroxy compounds of

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- / a

Poly oils rait polyisocyanates are crosslinked to cure Lacquer coatings with good resistance properties obtain. These combinations also show insufficient water resistance and lower weather resistance of the cured paint layers. The object of the present invention is to -

to provide a reactive lacquer for the production of primers, flat structures and top lacquers by the polyisocyanate polyaddition process, but the flat structures obtained have considerably improved properties in various directions and are particularly suitable for galvanized iron sheets or zinc as a substrate. This includes it, that is to harden on a metallic, preferably zinc plated, ground applied primer or topcoat after seven days of air drying at temperatures of about 2O ⁰ C, so that the film no longer swells under the action of water, nor mechanically by scratching is removable. In addition, after seven days of drying, the primer or top coat must be resistant to condensation water at ^ 0 ⁰ C and at 90 ° relative humidity.

The present invention relates to reactive lacquers for the production of coatings or coatings from hydroxyl groups Copolymers and polyisocyanates in solvents without active hydrogen atoms by shaping with removal of the solvent, characterized in that that these

A. 65-90% by weight of copolymers containing hydroxyl groups made of:

a) 20 - 50 wt. 5f styrene or alkyl styrene, the alkyl of which

groups of 1 to 3 carbon atoms

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or a mixture of such alkyl groups,

b) 10 - 40 wt .- /? Acrylic and / or methacrylic acid

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

c) 3-18 wt. one a, ß ~ ethylenically unsaturated

Mono- or dicarboxylic acid

and implementation with esterification with

d) 10 - 50 wt .- /? Glycidyl esters of the a-alkylalkane monocarbon

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

^C 12-14 ^H 22-26 ^O 3 ' ^where * ^d ^ ^e amounts of

Connections a) to d) become 100

Weight # must be added

and
B, 10-35 wt% organic polyisocyanate, where A

and B together are numerical values of 100% by weight

must surrender
contain.

A special embodiment of the invention is thereby marked that this

A. 65 - 90 wt. copolymers containing hydroxyl groups made of:

a) 25 - kO weight? Styrene or vinyl toluene,

b) 15 - 35 wt. Acrylate and / or methacrylate ester ge

saturated monoalcohols have 1 to 8 carbon atoms,

c) 7 - 12 wt. Acrylic acid or methacrylic acid and

d) 20 - 40 wt. Glycidyl esters of the a-alkylalkane monocar-

acidic acids and / or the α, α-dialkylalkanemonocarboxylic acids with the empirical formula

^C 12-14 ^H 22-26 ° 3 » ^where ^ - ^d ^ ^e amounts of the compounds a) to d) add up to 100% by weight? need to supplement and

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B. 10-35 wt. SS organic polyisocyanate, where A and

B together numerical values of 100 wt. -5? must surrender

contain.

A particularly preferred embodiment of the invention, which is intended for primers and top coats, is characterized by the fact that this

A. 70 - 7 ^, 5 wt. SS copolymers containing hydroxyl groups made of:

a) 30-37.5 parts by weight of styrene,

b) 20 - 30 wt. n-butyl acrylate, n ~ butyl methacrylate

or 2-ethylhexyl acrylate,

c) 8-12 wt. Acrylic acid or methacrylic acid and

d) 30 - 36 wt. JS glycidyl esters of a-alkylalkane monocar-

carboxylic acids and / or the a _s ot-dialkylalkanemonocarboxylic acids with the empirical formula

^C 12-1 ^{ I ^H 22-26 ^O 3 * where the amounts of the compounds a) to d) are 100% by weight? need to supplement and

B. · 25.5 - 30% by weight? organic triisocyanate, which

'by reacting three moles of toluene diisocyanate and one mole of trimethylolpropane was obtained, A and B being numerical values of 100 wt must surrender

contain.

A particularly preferred embodiment of the invention, wherein the reactive coating _TO made r are determined by topcoats, is characterized in that this A. 75-80 parts by weight of hydroxyl-containing copolymers SS prepared from: a) 30 to 37.5 parts by weight of Si Styrene,

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b) 20-30% by weight? n-butyl acrylate, n-butyl methacrylate or

2-ethylhexyl acrylate,

c) 8-12 wt. 5? Acrylic acid or methacrylic acid and

d) 30 - 36 wt -.% glycidyl ester of α-Alkylalkanmonocar-

carboxylic acids and / or the α, α-dialkylalkanemonocarboxylic acids with the molecular formula

^C 12 ^H 22-26 ^O lii 3 ^{»wherein the Men} S ^s ~ ^{Ver the} compounds a) to d) up to 100 wt -.%

need to supplement,
and

B. 20-25 wt .- # organic triisocyanate, which by

Reaction of three moles of hexamethylene diisocyanate and one mole of water was obtained, with Λ and B numerical values of 100 wt -.% Must give contain.

Although it is in the resolution of the 32nd Senate of February 9, 1997 I - 32 W (pat 29/70, published in BPatGer K 12, Pages 112 to 115 - stated that the establishment of a material claim - here reaction varnish - by marking different starting materials reacting with one another violates Section Paragraph 1 Clause 5 of the Patent Act if during the course of the reaction Products are created that can no longer be traced back to the starting materials and therefore compared to products can be delimited according to the state of the art.

As the Senate (ibid. On page 114 in the last paragraph) continues executes, in the case decided, "the reaction varnish" does not contain the identified components, but already, immediately after the mixing, their reaction products, which are constantly being converted, are not carried out more closely chemical composition or physical values clearly defined characteristics.

The present case is different.

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Namely, the claimed reactive lacquers of the invention contain no crosslinking catalysts when used. The claimed reaction lacquers of the invention are thereby at Storage stable for about 2 days at room temperature; i.e. the increase in viscosity and the reactions taking place in it, which in the Decision (loc. Cit. On page 114) are reproduced by the equation given there, run in the reactive lacquers of the invention not with a strong reaction and also not with accelerating heat development of the reaction, so that during During this time, the starting components in the paint are definitely determinable through chemical-physical investigations. at The reaction lacquers of the invention remain in storage at 0 to -5 ° C in usable condition 10 to 14 days. Also for such a reaction varnish stored at a lower temperature Invention, the above statements apply with regard to the possibility of determination the components contained therein that contain free OH or NCO groups.

The invention also relates to the use of the reactive lacquers for the production of coatings, primers on substrates made of zinc, galvanized sheet steel or aluminum.

Suitable solvents for the preparation of the copolymers those that do not contain any active hydrogen atoms, 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.

Styrene is very suitable as component a), followed by α-, ο-, m- and p-methylstyrene and halogenated styrenes. You lend if polymerized into the fabrics, they have a high resistance to saponification and good pigment uptake.

It is essential for the reactive lacquers produced according to the invention required that the content of styrene α-, ο-, m- and p-methylstyrene individually or in a mixture at least 20 wt. and

at most

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50 wt -.% Beisogen on the solid content of the copolymer, preferably from 25 to kO wt -.% Is. 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.

In general, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-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, n-butyl methacrylate, isobutyl methacrylate for the purpose of polymerizing in, the light resistance of the coating and hardness can be influenced favorably, while when using acrylate esters with 4 to 8 carbon atoms in the saturated alcohol residue, the elasticity and flexural strength are favorably influenced Special adaptations are possible through appropriate mixtures of acrylate and / or methacrylate esters. 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 10 - 40% by weight - based on the body content - in the copolymer. The best film hardness, chemical resistance and anti-corrosive properties of the reactive lacquers are shown when the content of acrylic and / or methacrylic acid esters, which contain 1 to 8 carbon atoms in the alcohol residue, is 10-25% by weight, based on the body content of the solid Copolymer is. With an increase of over 25 percent Acrylatesteranteils -.%, The film elasticity and increases Pigmentaufnahmefähig-

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Acrylic acid or methacrylic acid, maleic acid or fumaric acid is used individually or in a mixture as component c). Acrylic acid or methacrylic acid is preferably used.

Glycidyl esters of α-alkylalkane monocarboxylic acids and / or α, α-dialkylalkane monocarboxylic acids with the empirical formula ^c i2-li | are used as components d) ^H 22-26 ^O: 5 used individually or in a mixture. The Cg-C ^ acid contained in the glycidyl ester of the a-alkylalkane monocarboxylic acids is based on the pioneering work of Dr. H. Koch from the Max Planck Institute for Coal Research in Mühlheim, Federal Republic of Germany. The a-alkylalkanoic acids therefore mainly represent a group of Cg-, C ^ ₀ - and ^., - monocarboxylic acids. The acids are completely saturated and are very strongly substituted on the a-carbon atom. Acids with two hydrogen atoms on the α-carbon atom are absent and only 6-755 of these acids contain one hydrogen atom. In addition, there is cyclical material ... (Deutsche Farben Zeitschrift, issue 10/16. Year. Page 435)

The glycidyl esters of ct-alkylalkane monocarboxylic acids used as component d and / or α, α-dialkylalkane monocarboxylic acids with the empirical formula

^C 12-IU ^H 22-26 ° 3
are used by the company SHELL in the company fonts? called "Cardura E".

This is a product that through

the following formula: ' ^!

O p
CH ₂ -CH-CH ₂ -O-R '

can be represented in which R ^{1 is} an aliphatic hydrocarbon radical with 8-10 carbon atoms and

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represents a branched chain. Such a commercial product is made by reacting the epichlorohydrin with a mixture of saturated, essentially tertiary carboxylic acids containing 9 - H carbon atoms obtained, this acid mixture still being about 10 $ secondary May contain acids.

For the reactive lacquers produced according to the invention, it is necessary that the content of the glycidyl esters of cc- alkylalkane monocarboxylic acids and / or α, α-dialkylalkane monocarboxylic acids 10 to 50 wt .- /?, Preferably 20 to HO wt .- SS, based on the solids content, im Copolymer is. When using from 10 to 20 wt .- # glycidyl esters of cc-alkylalkane monocarboxylic acids and / or α, α-dialkylcane monocarboxylic acids in the copolymer, the hydroxyl content is 0.7 to Ι, Ί wt .- 55. If such copolymers are used in combination with polyisocyanates in a weight ratio of NCO: OH = 0.7-1.1: 1, less crosslinking occurs and thus greater elasticity of the reactive lacquers is achieved. This results in an increase in elasticity without increasing the content of acrylic acid esters in order to increase elasticity.

The reaction lacquers obtained here still show very good anti-corrosive properties and good results in Testing of condensation water, however, the film surface hardness has decreased somewhat.

If 20 to ¹ JO wt .- / 5 glycidyl esters of α-alkylalkane monocarboxylic acids and / or α, α-dialkylalkane monocarboxylic acids, based on the solids content in the copolymer, for the combination with polyisocyanates in the weight ratio NCO: OH = 0.7-1, When used 1: 1, the reaction lacquers obtained show greater crosslinking due to the increase in polyisocyanates and thus an increase in the film surface hardness and likewise good loading

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resistance of the films to chemicals and condensation water; however, the elasticity decreases somewhat, but is sufficient when the paint is applied to rigid sub-surfaces. found out. The elasticity must decrease when the coating on extensible substrates, for example leather, is applied, by use of 20 to 35 wt -% acrylate are achieved with an alcohol residue of 4 to 8 carbon atoms..

The implementation for the preparation of the according to the invention The copolymers used in 'varnishes' * takes place in such a way that the carboxyl groups of components c) are mixed with the glycidyl groups of the α-alkylalkanemonocarboxylic acids and / or α, α-dialkylalkane monocarboxylic acids of components d) react so that a free hydroxyl group is formed with ester formation, which is responsible for the Crosslinking with the organic polyisocyanates is necessary. By polymerizing the monomeric components c and condensation of component d into the copolymer, the copolymer contains groups the following formula

OR ¹
R-CH ₂ -CHOH-CH ₂ -OC

or R-CH-CH ₂ -OCR ¹
CH ₂ OH

where R ^{1 has} the meaning already explained and R represents the remainder of the component c used. The hydroxyl group formed during the reaction can be clearly seen in the formulas. The conversion takes place in equivalent ratios between the carboxyl and glycidyl groups.

The copolymers produced in this way give acid numbers between 2 to 8, with preference being given to those with Acid numbers between Ί to 8 produced.

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

Toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, cyclohexylene-lj ^ -diisocyanate, diphenylmethane-^ J, fl-diisocyanate, naphthylene-1,5-diisocyanate, ^, 4-, * I, 2- Triphenyl methane triisocyanate (the above polyisocyanates are preferred because they have a good reaction time to the hydroxyl groups and allow the process of the invention to be carried out in an economically advantageous manner), (isocyanatophenyl) ethyl isocyanate or the xylylene diisocyanates (the two above diisocyanates are preferred if the coatings to be produced according to the invention should be low-yellowing). Pluorsubstituierte diisocyanates Äthylenglykoldiphenyläther-2,2-diisocyanate ^1, Diäthylenglykoldiphenyläther-2,2'-diisocyanate (the latter three diisocyanates are preferred when flexible coatings are especially be produced). 1,1 '-Dinaphtyl ^2,2-f diisocyanate, biphenyl diisocyanate 1-2,4'-biphenyl-JJ ^ l'-diisocyanate, benzophenone-3,3'-diisocyanate, 2,7-diisocyanate-Pluoren , Anthraquinone-2,6-diisocyanate, pyrene-3,8-diisoeyanate, chrysene-2,8-diisocyanate, 1-methylbenzene-2, H , 6-triisocyanate, naphthalene-1,3,7-triisocyanate, biphenylmethane-2 , 4.4 ^l -triisocyanate, triphenylmethane ^ l, ^ ·, ^ f "-triisocyanate (The above polyisocyanates are preferably used if the hardness of the coatings to be produced is to be increased), 3'-methoxyhexane diisocyanate +, octane-diisccyanat ^ cue-diisocyanate-l ^ -diäthylbenzol, ω, ω-diisocyanato-l, ^ί} -dimethylnaphthalin, cyclohexane-1,2-diisocyanate +, l-isopropyl-2, ⁱ i + diisocyanate (The, with + marked above polyisocyanates produce non-yellowing coatings), l-chlorobenzene-2,4-diisocyanate, l-pluobenzene-2, ^ - diisocyanate, l-nitrobenzbl-2, ² } -diisocyanate, l-chloro-Jl-inethoxy-benzene ~ 2,5-diisocyanate, azobenzene-JJ, 4 '-diisocyanate, benzolazonaphthalene- ² !, 4' -diisocyanate at, diphenyl ether-2,4-diisocyanate and diphenyl

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Λ5

ether- ^ U-diisocyanate .; instead of the polyisocyanates can Compounds which split off polyisocyanates are also used, as well as reaction products containing isocyanate groups of polyhydric alcohols with polyisocyanates, for example the reaction product of one mole of trimethylolpropane with three moles of tolylene diisocyanate. This conversion product is particularly suitable for primers or for those topcoats that contain non-white pigments are offset. Also suitable are trimerized or polymerized isocyanates, such as those in German No. 951 168 can be described.

% In question - In addition, a reaction product coming out of a mole of water and three moles of hexamethylene diisocyanate with an NCO content of 16 - 17 wt.. The reaction product of water and hexamethylene diisocyanate is particularly preferred for topcoats. The NCO content of the reaction product applies to a 75% strength by weight solution in xylene / ethyl glycol acetate.

The copolymers are produced by solvent polymerisation, the monomers a) to c) and the glycidyl ester d) in the reaction vessel together with the solvents, the initiators, possibly also reacts in the presence of chain terminators, the condensation reaction and the polymerization reaction run together.

A preferred embodiment is obtained when the glycidyl ester is dissolved in the solvent and the monomers a) to c) with the initiators and chain terminators are added ^{at an elevated temperature - about 80 to 170 ° C. - and condensed and polymerized together.}

Examples of initiators known per se are:

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Azo compounds, peroxide compounds, for example benzoyl peroxide, cumene hydroperoxide or di.-tert.-butyl peroxide.

By using chain terminators known per se like mercaptans and aldehydes, the degree of polymerization can be adapted to the required conditions.

There are viscosities for 60 wt .- # ige resin concentrations in aromatic solvents such as toluene or xylene or in ether esters such as ethylglycol acetate according to the Gardner-Holdt scale from K-Zj. strived for. The solutions having the viscosity range from U to Z ₂ at 2O ⁰ C. are preferred

For the process, polymers with molecular weights of about 5,000-20,000, preferably from 8,000 to I ^ 000 are used. These should have a hydroxyl group content from 0.7 to 3.0, preferably 1.5 to 2.8 wt .- ^, have. The hydroxyl group content is related on the proportion of pesticides in the copolymer. ■ ", -

The implementation of the hydroxyl-containing copolymers A with the organic polyisocyanates B takes place in a ratio of 0.5 to 1.3 NCO groups per hydroxyl group. the The reaction is preferably carried out in such a way that the NCO: OH ratio is 0.7-1.1.

The mixtures of solvent-containing hydroxyl groups are brought in Copolymers A and polyisocyanate B in the simplest possible way, 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 cleavage

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tern, the coatings can be stoved in, which essentially depends on the documents used and the requirements placed on the coatings in practice. The use of reactive melamine-formaldehyde resins can also be advantageous. Can be the reactive melamine-formaldehyde resins in amounts up to about 10 wt -.% Enforce, in particular an increase in gloss can be observed in the fabric thereby. The implementation and application of the flat structure to the substrate takes place in solution. Suitable solvents are, for example, ethyl acetate, butyl acetate, ether esters, ethylglycol acetate and 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 with a solids content of 20-80% by weight are preferably used. For special purposes, however, polymer solutions with a lower hydroxyl group content, which leads to weaker crosslinking, are also of interest, for example for coatings on movable substrates. Such copolymers are miscible in any ratio with the polyesters and other polyethers that are typical in practice and contain hydroxyl groups and can therefore be blended with them. The reaction products of such blends with polyisocyanates also provide corrosion-resistant coatings with properties similar to those described above, the relatively fast drying time being particularly noticeable.

The reaction varnishes can be used for the production of coatings or Coatings on various types of substrates, e.g. porous or non-porous substrates, such as textile fleeces, Leather or plastics, find use. The production of coatings should be particularly emphasized Wood or metals. In any case, you get high-gloss,

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AZ

very hard surface, pore-free, elastic and solvent-resistant coatings. Such coatings also show excellent weather resistance and yellowing resistance.

It should be emphasized in particular that the coatings produced on galvanized iron sheets, zinc and aluminum sheets as single-layer coatings have excellent adhesive strength. The coatings and coatings can advantageously be carried out on zinc or aluminum by removing the solvent from the coating after the application of the coatings by means of a temperature treatment at 0 ° -50 ° C. for about 30 minutes, whereupon the coating or the coating is in is in a tack-free state, so that the surface does not absorb dust and is no longer sensitive to impact or other mechanical pressure, so that the objects painted in this way can be subjected to further processing. After curing for seven 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.}

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 ester of the ctjCt-dialkylalkane monocarboxylic acids with the empirical formula ^c i2-li | ^H 22-26 ° ' ^: 5 ^m: ^ ^e ^ ^nera epoxy equivalent of 2k0 - 250, hereinafter referred to only as glycidyl ester of α, α-dialky! Monocarboxylic acids, heated to 125 C and the following mixture consisting of: 250 g styrene, 80 g of acrylic acid, 202 g of n-butyl acrylate, 3 g of dodecyl mercaptan and 8 g of di.-tert.-butyl peroxide were added uniformly over the course of two hours, and the mixture was polymerized and condensed together for about 8 to 10 hours while being heated to about 125 ° C.

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The body content is 60.2 wt .- #. The viscosity as measured by Gardner-Holdt in xylene at 2O ⁰ C is Y. The acid number reaches a value of 7j2. The copolymer has a hydroxyl number of 85.

Production of the mixed polymer 2 In the same way as for the production of the mixed polymer 1, 528 g of xylene and 265 g of glycidyl ester "^, a-dialkylalkane monocarboxylic acids are heated to 125 ° C heated and the following mixture added evenly in two hours:

295 g styrene, 78 g acrylic acid, 162 g n-butyl acrylate, 8 g di-tert-butyl peroxide and 6 g dodecyl mercaptan. After eight to ten hours of common polymerization and condensation at 125 ° C of the body content of the solution 60, H by weight is -.%, While the acid value of 7.0 and the viscosity of a measured in xylene according to Gardner-Holdt X and the hydroxyl Gives a value of 80. + from

Example 1:

Reaction varnish on the basis of 7 * 1 weight-5? .% Organic triisocyanate, both based on the weight of solids - copolymer and 26 wt.

123 g of mixed polymer 1 solution are mixed with 75 g of titanium dioxide (Rutile), 15 g zinc chromate, 15 g talc, ^ 15 g barium sulfate and 1 g of calcium naphthenate rubbed into a varnish and 38.8 g of a 67 wt .- ^ solution of a triisocyanate with an NCO content of 11.5 wt .- ^ in a mixture of Xylene / ethyl glycol acetate (volume ratio 1: 1) dissolved, the triisocyanate being obtained by reacting three moles of tolylene diisocyanate and one mole of trimethylolpropane has been added and diluted with a mixture of xylene / ethyl glycol acetate (volume ratio 1: 1) and by spraying onto freshly galvanized iron sheets.

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worn and air-dried at room temperature for seven days. The primer was _at% in the condensation ^ tO ⁰ C and 90 # sulfuric humidity (1 Zyclus is 8 hrs. At ² IO ⁰ C and 16 hrs. At room temperature) is checked. Result: after 30 cycles no swelling and no blistering. The cross-cut according to Din 53151 is 1.

Example 2:

Reaction varnish based on 7% by weight copolymer and 26 wt .- /? organic triisocyanate, both sourced on the solid body weight.

123 g of the mixed polymer solution are rubbed with 75 g of titanium dioxide (rutile), 15 g of zinc chromate, 15 g of talc, 5 g of barium sulfate and 1 g of calcium naphthenate to form a varnish and 38.8 g of a 67% by weight solution of a Triisocyanate added according to Example 1 and after dilution to spray viscosity with a mixture consisting of xylene / ethyl glycol acetate (volume ratio 1: 1 ") applied to galvanized iron sheets with a dry film thickness of JJO u and air-dried after seven days. The primer was in the condensation test as described in Example 1. Result: After 30 cycles, the primer showed no swelling and no blistering.
Erichsen depression 5 mm after exposure.

Example 3:

Reaction lacquer on the basis of 79 wt% copolymer and 21 wt ~ -..% Organic triisocyanate, both based on the weight of solids _s as a top coat using a primer according to Example 2.

53 * 1 g of the mixed polymer 2 solution are combined with 600 g Titanium dioxide (rutile), 200 g xylene and 100 g ethyl glycol

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acetate rubbed into a varnish.

150 g of the above pigmented mixed polymer 2 solution (paint) 65 g of the unpigmented mixed polymer 2 solution and 25 »8 g of a 75% strength by weight solution of a triisocyanate with an NCO content of 16.5 to 17% by weight. -% dissolved in a mixture of xylene and Fithylglykolacetat (volume ratio 1: 1), the triisocyanate has been obtained by reacting three moles of hexamethylene diisocyanate and one mole of water, are diluted with xylene to spray viscosity to obtain a topcoat.

First, hot-dip galvanized iron sheets are primed according to Example 1 of this invention, the dry film having a thickness of about 35 to 10 microns. After a drying time of 2k hours at room temperature (20 ^° C.), the topcoat is sprayed on according to Example 3 so that the dry film of the topcoat has a layer thickness of about UO u. . ■

After a drying time of seven days at room temperature (20 ° C) the paint is subjected to various tests.

■ Condensation test.

The panels were hung in a test device with a closed chamber. At the bottom of the chamber there is an open tank with low- HO ° C water. The air humidity adjusts to 90 $ relative humidity. After a test time of 240 hours, the cross-cut according to DIN 53151 shows a fourth of 1. The cross-cut before insertion into the test chamber had a value of zero. This test result shows that the coatings produced according to the invention have excellent properties with regard to adhesion and elasticity.

Comparative investigation to demonstrate the technical progress achieved. For comparison, a copolymer is used which, as a modification of Example 2, however, uses

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2Q6596Ö ·. . . ....

g styrene, 78 g acrylic acid and 2β5 Slycidyiester g _of a, a-dialkyl! is prepared monocarboxylic acids, and this, as described in Example 2 and 3 processes one,

• As a primer and top coat, it will be the same test

. Peeling of the entire paint system was observed after just 100 hours. · '.. ·' · ■ ·

Impact test ( "impact resistance") to the condensation test - test ^objects:

• The condensation test - test items are then subjected to an impact test. After the execution of the single strikes is the deformed impact point on paintwork

φ- den examined. With a setting of 10i, 60 cm / per 0.4536 kg

no cracking is found. This test result shows that the paint system is also excellent Fourth in terms of adhesive strength, elasticity and anti-corrosive properties. '. ..

The reaction lacquers used. are stable in the absence of crosslinking catalysts at room temperature for about 2 days. When stored at 0 to -5 C, the reaction lacquers of the invention in serviceable condition in the absence of Vernetzungskatalysätoren 10 are to Ik days shelf life.

Φ Further comparative tests to prove the technical

Port steps taking into account FR-PS 1 390 572 and the PR-PS 1 556 309

Production of the mixed polymer 1 g according to the invention :

33.6 wt -.% Glycidyl ester having the empirical formula C ₁₂ ^ ^ Ηρ ΛΧ,

. ·. 31.2 percent -.% Styrene, ·

10 wt -.% Acrylic acid and

25> 2 wt -.% Butyl acrylate. ■

Preparation of the copolymer 2 in accordance with the invention. 33.2 wt -% glycidyl ester having the empirical formula C ₁₀ "" H ₀₀ ^ 0,

ie- 14 eLd-da $

36.8 wt -.% Styrene,

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-20659BO

9.8 wt -.% Acrylic acid and - ***
20.2 wt% butyl acrylate.

Discussion of the Prior Art -.

In PR-PS 1 556 309 the following copolymers come closest to the invention:
Example 3 Addition product A = 25% by weight of methyl methacrylate = 35% by weight of styrene. = 35 'wt .- # ■ -

Butyl acrylate = 5 weight percent

In PR-PS 1,390,572, only those copolymers which contain only inert solvents, such as Examples 6 and 13, come into consideration. Composition of the copolymers Example 6: 37.2 wt -% Kthylacrylat.

21, Ί wt. 55 methyl methacrylate

28.6 wt -.% Glycidyl ester with the Sunmenformel C ₁₂ _ _11} H _22-26 O-, '. 12.8 wt% methacrylic acid;

Example 13 28.6 wt -.% Glycidyl ester with the Sunmenformel ^ ₁₂ ^ 2-26 ° -ik 3

21.4 wt. £ methyl methacrylate,

37.2 wt -.% Ethyl acrylate.

12.8 wt -.% Methacrylic acid.

From the comparative copolymerization of FR-PS 1 556 309, example 3, and from FR-PS 1,390,572, Examples 6 and., 13, were in the same way as those made in accordance with the invention Mixed polymers reactive lacquers in the form of primers and Topcoats produced and as a coating on hot-dip galvanized iron sheets applied. The films, which were air-dried after 7 days at room temperature, were subjected to the condensation test on the test panels subjected. '.

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Reaction paints Condensation test
at 40 ° C 240 hours Lattice ^ nitt
according to DIN 53 151 Erichsentiofung
after the load inventive
moderate example 1 no swelling 1 6 mm inventive
moderate example 2 no swelling 1-2 5 mm inventive
moderate example 3 no swelling 1 4 mm Example 3 of the
PR-PS 1 556 309 after 100 hours
chipped about $ 50 0.5 mm Example 6 of the
FR-PS 1 390 572 after 150 hours
about jo% chipped off .3-4 1.5 mm

The above test results show that the present Invention provides coatings which have significantly superior improvements in various directions.

BAD QRJGiWAL

709832/0776

Claims (5)

Claims: 2 Π 6 R 9 R Π 1. Reaction lacquers for the production of coatings or coatings from copolymers containing hydroxyl groups and polyisocyanates in solvents without active hydrogen atoms Shaping with removal of the solvent, characterized in that this is a mixture consisting of % Hydroxyl-containing copolymers, - A. 65-90 wt. made of: a) 20 - 50 wt. JS styrene or alkylstyrel, its Alkyl groups have 1 to 3 carbon atoms or a mixture such alkyl groups, b) 10% by weight of acrylic and / or methacrylic acid esters in the saturated alcohol '· ...' "contain a remainder of 1 to 12 carbon atoms, c) 3 to 18 wt. of an α, β-ethylenically unsaturated Mono- or dicarboxylic acid and implementation with esterification with d) 10 - 50 parts by weight of glycidyl esters of a-alkylalkane mono- carboxylic acids and / or the α, α-di- ■. '- Alky lalkanmonocarbonsäuren with the ? Molecular Formula ^Ii ^ i -L4 22-26 ° 3 ^s wherein the amounts of compounds a) to d ..) to 100 wt -% complement müs- ";. '.' ■ sen ...-. ' ■ and · ·. B. 10 - 35 wt. organic polyisocyanate where A .. and B together are numerical values of 100 ~ Wt .- $ must result, contain. ■ ■ ".- · .-> 2. Jteaktionslacke rack to claim 1, characterized in that this one Mixture consisting of % Hydroxyl-containing copolymers, - A. 65-90 wt. made of: 709832/0776 a) 25 - 40 wt .- /? Styrene or vinyl toluene, b) 15-35% by weight of acrylate and / or methacrylate ester saturated monoalcohols with 1 to 8 carbon atoms, c) 7 -. 12 wt -.% Of acrylic acid or methacrylic acid and d) 20 - 40 wt. Glycidyl ester of the cc-alkylalkane mono- carboxylic acids and / or the α, α-di- ■ alkylalkane monocarboxylic acids with the '· "Molecular formula ^c ₁ pl ⁱ l ^H 22-26 ^O 3 ^> where •. - '. 'the amounts of the compounds a) to d) fCU 100 percent - sen% supplement müs- ■.
and B. 10 - 35 wt -.% Of an organic polyisocyanate, A and B together are numerical values of -. 100% by weight must be $ 7, contain. · 3. Reaction lacquers according to claim 1, characterized in that these for. Primers and top coats a mixture consisting of A. 70 -% hydroxyl-containing copolymers, - 7 * 1.5 wt. made of: a) 30-37.5 wt .- ^ styrene,. ^; v b) 20 - 30 wt '-.% n-butyl acrylate, n-butyl methacrylate . ■ or 2-ethylhexyl acrylate, c) 8-12% by weight of acrylic acid or methacrylic acid . ■ '· and. . ■ el) 30 - 3 (5 wt. J5 glycidyl esters of the a-alkylalkane ; · ·. · Monocarboxylic acids and / or the α, α-di- ■ alkylalkane monocarboxylic acid with the • ·. Sum formula ^c i2-i2 { ^Ii 22-26 ^O 3 * ^wo " must add up to 100 wt. ~% of the quantities of compounds a) to d), and. . B. 25.5-30 wt. JS organic triisocyanate, which 709832/077 8. • by converting from three moles Toluylene diisocyanate and a hol trimethylolpropane was obtained, where A and B must result in numerical values of 100 wt. contain. 4. Reaction lacquers according to claim 1, characterized in that that these for top coats a mixture consisting of % Hydroxyl Mischpolymeri - A. 75-80 wt. seeds, made from: '' a) 30 - 37.5% by weight of styrene, b) 20 - 30 wt -.% n-butyl acrylate, n ~ butyl methacrylate or 2-ethylhexyl acrylate, c) 8-12 wt .- / S acrylic acid or methacrylic acid and · d) 30 - 36 wt -.% glycidyl ester of ct-Alkylalkan- ■ ·. . monocarboxylic acids and / or eier 0,0-di- ■ '' alkylalkane monocarboxylic acid with the Sum formula ^c i2-l ^Ji l ^H 22-26 ^O 3 ^{i where} "" for the amounts of the compounds ■ '. a) to d) to 100 wt -.% ER .. all have, and B. 20-25 wt .- £ organic triisocyanate, which • by converting from three moles. . . '. ^: · Hexamethylene diisocyanate and a ■ '..' - ... ■ · '·· mole of water was obtained, where A and B numerical values of 100 wt. Ί ·· ■. must result, ■ contain. · '-'. ..- ■ ·· ·. ■ - 5. Use of the reactive lacquers according to one of claims 1 to 4 for the production of coatings, coatings, primers on substrates made of zinc, galvanized sheet steel or aluminum. 709832/0778