DE1918023A1 - Process for the production of planar structures - Google Patents

Description

File 2122

REICHHOLD-ALBERT-CHEMIE AKTIENGESELLSCHAFT Hamburg 70 »Iverstrasse 57

Process for the manufacture of sheet structures

Numerous proposals have become known to produce solvent-resistant, alkali-resistant paints by reacting polyisocyanates and copolymers containing hydroxyl groups. In German Auslegeschrift 1 2 ^ 7006 a process for preparing alkali-resistant sheet material according to the polyisocyanate polyaddition process is described, which are obtained from hydroxyl-containing Mispolymerisaten and polyisocyanates, but not after 3 to 4 days reaction time at 20 ⁰ C sufficiently water resistant are. These coatings obtained by this 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 polyols are to be cured with polyisocyanates in order to obtain crosslinked lacquer coatings with good resistance properties. These combinations likewise show insufficient water resistance and lower weather resistance of the cured paint layer.

The object of the present invention is to provide a process for the production of alkali-resistant sheet-like structures by the polyisocyanate polyaddition process, the sheet-like structures obtained having, however, considerably improved properties in various directions. For this it is important that the paint applied to a metallic substrate ^{should harden after 3 to 5 days air drying at temperatures around 20 °} C. in such a way that the film no longer swells under the action of water and cannot be mechanically removed by scratching itself when the film is briefly exposed to water ^{at temperatures of 50-70 ° C.}

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The present invention relates to a method of manufacture of flat structures made of polyhydroxy compounds based on sulfur-containing copolymers based on hydroxyl groups having polymerizable compounds with carbon double bonds and vinyl aromatics and polyisocyanates in Solvents without active hydrogen atoms by shaping with removal of the solvent, characterized in that as sulfur-containing copolymers those from

A.) 60 - 94 wt. L copolymers containing hydroxyl groups,

made of

a) 20 - 70 wt. i styrene or vinyl toluene,

b) 10-50 wt.% methacrylic ^ which in the alcohol radical

Contain 1-4 carbon atoms,

c) 5-30 Qev.% Hydroxylalkyl ester of acrylic acid or

Methacrylic acid, which contains 1-4 carbon atoms in the alcohol residue,

d) 0-30 wt.! Acrylic acid alkyl esters, which contain 1 - 8 carbon atoms in the alcohol residue, ... .. '' ■ '

e) 0.1-5 wt.% SH-groups that od® as aliphatic and / or heterocyclic and / or aromatic mono- * · PoIymerkaptane present, the amounts of the monomers

be a) to d) and the SH-groups sized mÜB & @ n _s that this up to 100 Gem.% Suppl "".

«) 1-20 wt. * Of polyhydroxy compounds of the following formula "

- ^R 2

where R ₁ = -H ₉ -CH ₃ , -CH ₂ - (Oi

R ₂ s -CH ₂ - (O-CH ₂ -CH) n -OH

CH,

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CH ₃

R, = -H, -CHj ₄ -CH ₂ - (O-CH ₂ -CH) _n -OH

CH ₃

Rf, * -CH ₂ - (O-CH ₂ -CH) _n -OH, CH ₃ -CH ₂ -, _{- (O-CH 2} -CH) _n -OH

means _t Where η is equal to 1 to 30.

O - 1 öew. £ of an organometallic compound and / or a tertiary **

DvI 5 - 3 © wt. Si organic polyisocyanate, where A to D must result in counter values of 100 wt.

are built up. In the above embodiment, the aliphatic mono- or poly mercaptans are preferred. A special embodiment of the invention is characterized in that
A.) 70 - 84 wt. HydroxyI-containing copolymers made from

a> 20 - 40 wt.? Styrene or vinyl toluic oil ₉

b) 20 ^ - 40: weight i methyl methacrylate, -,

c) 15 - 25% by weight of hydroxyethyl acrylate or hydroxyethyl ·. -

methaerylate,

d) 15-25 wt. of butyl acrylate or 2-ethylhexyl acrylate,

e) 0.5 ¹ ^ 1 * 5 wt.? SH groups in the dodecyl mercaptan

or lauryl mercaptan are present.

B.) 1-5 wt. 5t of a ^^ poly hydroxyl compound obtained by reacting 1 mole of glycerol and propylene oxide. with an average molecular weight of ^j 3000 and a HydroxyizaM of e &. 5δ ei » ¹ » _-: was held.

CJ 0; - 0.2 wt / l tin dibutyl dilaurate and.

Dr-i "-15 - 24 ^ aew.3i organic triisocyanate» which by conversion

■ Formation from 3 moles of hexamethylene diisocyanate

and 1 mole of water was obtained,

A to D give count values of 100 wt. # have to,

are used «.

As methacrylic acid ester 'b, which in the alcohol radical 1 -4 carbon, contain atoms, such esters come into question in which methyl, "Üthyl- or Isöpröpyl- or Butyialkohole are incorporated.

Under hydroxyalkyl esters he e of acrylic acid or ifethaeryic acid, which contain 1 * 4 carbon atoms in alcohol is e.g. Mydroxyäthyiacrylät, Hydroxybutylacryiät, Hydroxyathyimethacrylät and hydroxybutyl methacrylate, which contain a primary hydroxyl group at the end.

As “other acrylic acid esters to be used” if necessary the i - 8 carbon atoms in the alcohol residue come butyl acrylate, Ethyl acrylate ^ methyl ethyl ether, isobutyl aylate, hexyl acrylate> Öötylacrylat or 2-Äthylhexylaeryiat, for example in question *

As organic polyisocyanates may be used, for example tolylene-2, 4-diisocyanate, tolylene-2, _{6-diisocyanate;} Cyclobexylene-1,4-diisocyanate, diphenylmethane-4,4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4-, 4,2-triphenylmethane triisocyanate, such as 1- (isocyanatophenyl) ethyl isocyanate or the xylylene diisocyanates, fluorine -substituted diisocyanates, ethylene glycol diphenyl ether-2,2'-diisocyanate, diethylene glycol diphenyl ether-2,2'-diisocyanate, 1,1'-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4 '-diisocyanate, benzophenone-3,5 ¹ -diisocyanate, fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, pyrene-3,8-diisocyanate, chrysene-a ^ e-diisocyanate, l-methylbenzene ^^^ -triisocyanate, naphthälin-l ^^ - triisocyanate, biphenylmethane-2,4,4'-triisocyanate, triphenylraethane-4,4,4 "-triisocyanate, J'-methoxyhexane diisocyanate, octane diisocyanate, 'ω, ω ¹ - Diisocyanac-l ^ -diethylbenzene, ^, _ifl | -diisocyanate-1,4-dimethylnaphthalene, cyclohexane-liJ-diisocyanate, l-isopropylbenzene-2,4-diisocyanate, l-chlorobenzene-2,4-diisocyanate, l-pluobenzene- 2,4-: di-isocyanate, l-Ni + -. Robenzene-2,4-diisocyanate, l-chloro-4-methoxyoe benzene-2,5-diisocyanate, azobenzoi-4,4'-diisocyanate, benzene-azonaphthalene-4,4i-diisocyanate, diphenyl ether ^^ - diisocyanate

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and diphenyl ether-4, k diisocyanates, further isocyanate group-containing reaction products of polyhydric alcohols with polyisocyanates, for example the reaction product of 1 mole of trimethylolpropane with 5 moles of toluene diisocyanate, and also trimerized or polymerized isocyanates, such as those described in German patent 951 168.

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

Organic metal compounds in the context of the invention are, for example usable dimethyltin dichloride, dbutyltin laurate, Tin octoate.

As tertiary amines can be used in the present invention the following are used to produce the hydroxyl-containing copolymer: triethylamine, triethylenediamine, N-methylmorpholine and others.

The polyhydroxy compounds of the general formula mentioned

' ^R l

R ^ -C R2

from polyols are obtained by reacting 1,2-propylene glycol, glycerol, trimethylolpropane, pentaerythritol or bisphenol A with propylene oxide. The number η indicates how many moles of propylene oxide have been added. Mixtures of such polyhydroxy compounds,, can also be used «

NS

Most preferred compound of the formula mentioned

are the reaction products of glycerine and trimethylolpropane with propylene oxide, where η is a number from 10 to ^ O.

As aliphatic mono- or polymercaptans in the present Invention as a chain terminator, but in the copolymer are mostly incorporated, the following compounds can be used: butyl mercaptan, pentyl mercaptan, hexyl mercaptan, Octyl mercaptan, decyl mercaptan, dodecyl mercaptan in straight and branched chain form. Di- and polymercaptans with a carbon chain of 3 to 12 can also be used C atoms that contain 2 to 4 mercapto groups in the molecule. In addition, aromatic or heterocyclic mono » or polymercaptans with β to 12 carbon atoms in the ring can be used if one to three mercapto groups in the molecule are present, but must be aliphatically bound <,

The following can also be used as mercaptans:

η-butyl-, n-amyl-, n-hexyl-, n-heptyl-, n-octyl-, n-nonyl-, i-propyl-, 2-methyl-propyl-, 1-methyl-propyl ™, 1 , 1-Dimethyläthyl-, 1-methyl-butyl, 2-methyl-butyl, 4-methyl-butyl- ₉ n-dodecyl, n-hexadecyl mercaptan. ....

As dimercaptans, for example, there are dimercaptans with the following Formulas useful:

HS (CH ₂ ) ₃ SH, HSCCHg ^ SH, HS (CH ₂ ) ₅ SH, HS (CH ₂ ) gSH, BS (CH ^) ₁

As mercaptocarboxylic acids are compounds with the general Formulas:

HS-CH ₂ COO-CH ₃ , HS-CH ₂ COO-C ₂ H ₅ , CH ₃ -CH-COOH

-, SH suitable.

- 7 As heterocyclic mercaptans are e.g.

2 ~ mereaptothiazoline, CH ₂ -Nv

J C-SH

2-mercapfcöbenziwidazole,

r ii

S-SH

2,5-Di «ercapfcö-i, 3, iJ ~ thiadia2öi, N N

HS-C C-SH

Other specific examples of the coating linings of the present invention Invention are composed on the following basis :

(A) is a copolymer of Hyäröxyäthylmethacrylat, Methylmethacrylatι styrene and lauryl mercaptan with the Implementation product of glycerine and propylene oxide (B), the Reaction product of tin octoate (C) and the decomposition product of 5 moles of hexamethylene diisocyanate and 1 mole of water (D) is combined «

(A) is a copolymer of Hydroxyäthyimethacrylat, Methyl methacrylate, styrene, butyl acrylate and lauryl mercaptan, which is converted into glycerine; and propylene oxide (B), the conversion product of tin octoate (C) and the dissolution product of 3 moles of hexamethylene diisoeyanate and 1 mole of water (D) is combined.

(A) is a copolymer of hydroxyethyl methacrylate, methyl methacrylate, styrene and butyl mercaptan, which is mixed with the reaction product of glycerol and propylene oxide (B), the reaction product of tin octoate (C) and the reaction product of 3 moles of hexamethylene diisocyanate and 1 mol of water is combined.

191δ023

(A) is a copolymer of hydroxyethyl methacrylate, methyl methacrylate, styrene, butyl acrylate and butyl mercaptan, that with the reaction product of glycerol and propylene oxide (B), the reaction product of tin octoate (C) and the reaction product of 3 moles of hexamethylene diisocyanate and 1-mole of water (D) is combined.

(A) is a copolymer of hydroxyethyl methacrylate, ' Methyl methacrylate, styrene, butyl acrylate and pentyl mercaptan, that with the reaction product of glycerine and propylene oxide (B), the reaction product of tin octoate (C) and the um ^ - Settlement product of 3 moles of hexamethylene diisocyanate and 1 ^ mole of water (D) is combined.

(A) is * a copolymer of hydroxyethyl _{methacrylate s} methyl methacrylate, styrene and pentyl mercaptan, that with the reaction product of glycerol and propylene oxide (B), the reaction product of tin octoate (C) and the reaction product of 3 moles of hexamethylene diisocyanate and 1 mole. Water (D) is combined.

(A) is a copolymer of hydroxyethyl methacrylate, methyl methacrylate, styrene and Hexyimerkaptan, which with the Reaction product of glycerol and propylene oxide (B), the reaction product of tin octoate (C) and the reaction product of 3 moles of hexamethylene diisocyanate and 1 mole . Water (D) is combined ..

(A) is a copolymer of hydroxyethyl methacrylate,, methyl methacrylate, styrene ^ butyl acrylate and hexyimercaptan, the mit.dem reaction product of glycerine and propylene oxide (B), the reaction product of tin octoate (C) and the reaction product of 3 moles of hexamethylene diisocyanate and 1 mole of water (D) is combined. . ■

(A) is a copolymer ^: äus Hydroxyethyl methacrylate, methyl methacrylate, styrene and octyl mercaptan, which with the reaction product of glycerol and propylene oxide (B), the reaction product of tin octoate (C) and the reaction product of 3 moles of hexamethylene diisocyanate and 1 mole of water (D) is combined.

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(A) is a copolymer of hydroxyethyl methacrylate, Methyl methacrylate, styrene, butyl acrylate and octyl mercaptan, which with the reaction product of glycerine and propylene oxide (B), the reaction product of tin octoate (C) and the reaction product of 3 moles of hexamethylene diisocyanate and 1 mole of water (D) is combined.

(A) is a copolymer of hydroxyethyl methacrylate, methyl methacrylate, styrene and decyl mercaptan, which with the Reaction product of glycerol and propylene oxide (B), the reaction product of 3 moles of hexamethylene diisocyanate and 1 mole of water (D) is combined.

(A) is a copolymer of hydroxyethyl methacrylate, methyl methacrylate, styrene, butyl acrylate and decyl mercaptan, that with the reaction product of glycerol and propylene oxide (B), the reaction product of tin octoate (C) and the reaction product of 3 moles of hexamethylene diisocyanate and 1 mole of water (D) is combined.

The production of the copolymers containing hydroxyl groups from the monomers as the starting material for the process according to the invention takes place according to known methods and is in organic inert solvents such as aromatics, esters or ether esters in the presence of free radical-forming catalysts such as Peroxide, such as benzoyl peroxide, lauroyl peroxide or cumolhy-

droperoxide or of the azo type, such as azoisobutyric acid dinitrile. the usual polymerization temperatures preferred, but carried out at 50-150 ^o C, wherein is imperative that in the polymerization aliphatic and / or aromatic and / or heterocyclic mono- or polymercaptans must be present. The peroxide catalysts are used in an amount of 0.5-2.02 based on the monomers;

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The aliphatic and / or aromatic and / or heterocyclic mono- or polymercaptans can be reduced by quantity Mood and variation of the inflow time as a regulating measure: can be used.

Only polymers with molecular weights of about 4,000-20,000 can be used for the process according to the invention. These have a hydroxyl group content of 1.0 to 5 * 0, preferably 2 to 4 #.

The reaction of the copolymers containing hydroxyl groups as a mixture with the polyhydroxy compounds B.) with polyisocyanates Depending on the intended use, the reaction products can contain 0.5 to 1.1 NCO groups per total hydroxyl groups be performed. The reaction is preferably carried out in such a way that that the amounts of the polyisocyanate based on the total hydroxyl content of the components present in the reaction mixture, 0.7 to 1.0 isocyanate groups are present per hydroxyl group are. -

The mixtures of solvent-containing hydroxyl compounds are introduced and polyisocyanate in the simplest possible 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 relevant documents on and dries the fabrics at room temperature; in special cases, for example when using isocyanate releasers, the coatings can be baked in, which is essentially the case based on the documents used and the requirements placed on the coatings in practice. Also the use of reactive melamine resins can be beneficial. ■■ The reactive melamine resins can be added in amounts of up to 10% by weight, which increases the gloss in particular Fabrics can be observed.

The implementation and application of the flat structure to the substrate takes place in solution. Suitable solutions are e.g. ethyl acetate, butyl ester, ether ester, dietary glycol

90984771114

diacetate and aromatics, such as benzene, toluene or xylene. the The concentration of the solutions can fluctuate within wide limits and depends essentially on the solubility of the components. It is preferred to use solutions with a plague content. from 20 - 80 wt.

The process can be used for the production of coatings on various types of substrates, e.g. porous or non-porous substrates, such as textile fleeces, leather or Plastics'. Particularly noteworthy is the production of ypn coatings on wood or metals. You get in any case, high-gloss, pore-free, very hard surface elastic and solvent-resistant coatings * that can be also with strong inorganic acids as well as with strong ones Can treat alkalis without affecting the coatings even in the slightest Dimensions are attacked. Such coatings also show excellent weather resistance and yellowing resistance.

It should be emphasized that the coatings produced or coatings on aluminum sheets as single-layer finishes have excellent adhesive strength. The above-, Cables and coatings can advantageously be applied to aluminum can be done by, after applying the coatings, the coating by a temperature treatment at Λ0. - 50 ° C freed from the solvent for about JO minutes, whereupon the, coating or the cover in a tack-free Condition is present so that the surface does not absorb dust and no longer against impact or other mechanical pressure sensitive, is so that the objects painted in this way are a Further processing. After hardening from three to four days at room temperature then the maximum properties achieved. The maximum properties are also achieved by increasing the temperature to 120 ° C in 30 minutes. ..

For the. For the production of high-resistance coatings by the process according to the invention, it is expedient to use the copolymerization

SJQ 9.S 47 M-TU ^:

of the starting material to be carried out in inert solvents so that a hydroxyl group content of the copolymers of preferably 3-4 % is achieved. For special purposes, however, polymer solutions with a lower hydroxyl group content, which leads to weaker crosslinking, are / are of interest, for example for coatings on movable substrates. Such copolymers can be mixed with the hydroxyl-containing polyesters and other polyethers typical in practice in any ratio and can therefore be blended with them. The reaction products of such blends with polyisocyanates also give alkali-resistant coatings with properties similar to those described above, the relatively fast drying time being particularly noticeable.

Manufacture of a starting material

Mixed polymer 1.

465 g of xylene are heated to boiling under reflux temperature and a mixture of

126 g hydroxyethyl methacrylate,

140 g methyl methacrylate,
4 ^ 4 g styrene,
20 g lauryl mercaptan and

8 g of di-tertiary butyl peroxide

added in 4 hours and polymerized to a body content of 6l - 62 %. According to Gardner-Holflt, the viscosity is Z ^ - Z ₅ .

Mixed polymer 2

Under the same conditions as described for copolymer 1 is in

465 g of xylene added the following mixture within 4 hours;

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126 g of hydroxyethyl methacrylate, 140 g of methyl methacrylate, 250 g styrene,

84 g butyl acrylate,

16 g lauryl mercaptan and 8 g ditertiary butyl peroxide

are polymerized to a body content of 62% , a Gardner-Holdt viscosity of Z ₂ - Zj being reached.

Mixed polymer> As described for mixed polymer 1, in

The following mixture was added to 470 g of xylene over the course of 4 hours :

132 g of hydroxyethyl methacrylate, 224 g of methyl methacrylate, 210 g of styrene,
142 g of butyl acrylate, 16 g of lauryl mercaptan and 8 g of di-tertiary butyl peroxide

are polymerized to a body content of the solution of approx. 6l to 62 %. According to Gardner-Holdt, the viscosity is then Z ₂ -Z ₅ .

Mixed polymer

The procedure is carried out under the same conditions as described for the preparation of the copolymer 1. However the following approach is used:

to ^ 65 g of xylene becomes a mixture within 4 hours consisting of

126 g hydroxyethyl methacrylate 140 g methyl methacrylate 350 g styrene
84 g of butyl acrylate

9098 * 7/1114 ..

14 g of tert-dodecyl mercaptan 8 g of di-tert-butyl peroxide

gradually added, and it is polymerized to the solids content of 62 $, a Gardner-Holdt viscosity of Z ₂ -Z is reached.

Mixed polymer

The procedure is carried out under the same conditions as described for the preparation of the copolymer 1. However the following approach is used:

to 470 g of xylene a mixture is formed within 4 hours the end

132 g of hydroxyethyl methacrylate, 224 g of methyl methacrylate, 210 g of styrene
142 g of butyl acrylate 12 g of octyl mercaptan 8 g of di-tert-butyl peroxide

Gradually added and it becomes solid polymerized from $ 62, with a viscosity according to Gardner-Holdt from Zg-Z, is reached.

example 1

555 g of copolymer 1 are mixed with 310 g of titanium dioxide (rutile) and 200 g of xylene pigmented.

A mixture consisting of 180 g pigmented copolymer corresponds to 58 g · hydroxyl gruppenhaltigem copolymer, 198 a 7 g 5% solution of a triisocyanate with an NCO content of from 16.5 to 175 * in a mixture of xylene ÄthylglyXolacetat 1: 1, which has been obtained by reaction of 3 moles of hexamethylene diisocyanate and 1 mole of water, 4 g of a polyhydroxy! compound which is obtained by reaction of 1 mole

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Glycerine and propylene oxide with an average molecular weight of 3000 and an exner hydroxyl number of about 56 and 8 g of a 5% solution of zinc octoate were dissolved in xylene is diluted with xylene to a spray viscosity of 22 DIN 4 seconds and on aluminum sheets with a Dry film thickness of 40 <μ applied and 30 minutes dried at 500 C.

König pendulum hardness (DIN 53 15β) after one day 67 seconds, after three days 110 seconds, after ten days 150 seconds.

Erichsen cupping 4.5 mm after ten days.

Example 2:

A mixture consisting of:

180 g of the pigmented copolymer from Example 1, 19.8 g of the triisocyanate described in Example 1, 8 g of the polyhydroxyl compound described in Example 1 and 8 g of a 5% solution of zinc octoate is dissolved in xylene

as described in Example 1, applied to aluminum sheets and dried for 50 minutes at 50.degree.

König pendulum hardness (DIN 53 156). 42 seconds after one day, after four days 110 seconds, after ten days 140 seconds.

Erichsen cupping 6.8 mm after ten days. Example 3s

555 g of copolymer 2 are pigmented with 310 g of titanium dioxide (rutile) and 200 g of xylene.

A mixture consisting of:

180 g of the pigmented copolymer 2 corresponds

58 g of the copolymer containing hydroxyl groups, 19 g of the triisocyanate described in Example 1, 3 g of the polyhydroxyl compound described in Example 1 and 8 g of a 5 igep solution of zinc octoate, dissolved in xylene as described in Example 1 applied to aluminum sheets

909847 / 11U

and dried at 50 ° C for 30 minutes. ■

König pendulum hardness (DIN 53 156) after one day 55 seconds, after four days 120 seconds, after ten days 150 seconds.

Erj.chsen cupping after ten days 6.9 mm.

The film shows against water after four days after one No swelling for ten minutes at 50 ° C.

Example 4;

A mixture consisting of:

180 g pigmented copolymer 2 from Example 3 * 18.5 g of the triisocyanate described in Example 1, 6 g of the polyhydroxyl compound described in Example 1 and 8 g of a 5% solution of zinc octoate is dissolved in xylene

applied to aluminum sheets as described in Example 1 and dried at 50 ° C. for 30 minutes.

9098A7 / 1114

König pendulum hardness (DIN 53 156) after one day 50 seconds, after four days 110 seconds, after ten days 144 seconds.

Erichsen cupping 7.4 mm after ten days. "

The film shows after curing for four days after exposure no swelling of ten minutes at 50 ° C.

Example 5:

A mixture consisting of;

180 g of the pigmented copolymer 2 from Example 3, 18 g of the triisocyanate described in Example 1, 9 g of the polyhydroxyl compound described in Example 1, 8 g of a 5% solution of zinc octoate dissolved in xylene is applied as described in Example 1 to aluminum sheets and dried at 50 ° C for 3 minutes. Pendulum hardness according to König. (DIN 53 156) after one day 32 seconds, after four days 90 seconds, after ten days 120 seconds.

Erichsen cupping after ten days 8> 0 mm. .

Inventive comparison example 6:

555 g of Misah polymer 3 are mixed with 310 g of titanium dioxide (rutile), 2QQ g xylene and 1.5 ml of a liquid solution of silicone oil AL pigmented.

A mixture consisting of:

180 g of the pigmented, copolymer 3 corresponds 60 g of hydroxyl-containing copolymer, 19> 8 g of the triisocyanate described in Example 1, 1 g of the polyhydroxyl compound described in Example 1 is applied to aluminum sheets as described in Example 1 and dried at 50 ° C for 30 minutes.

Comparison example from 4 German _r Auslegesehrift 1 247 006;

The mixed polymer 3 without the SH groups was obtained Connection Läurylmerkäptan made and a varnish as in Ver same example 6 described prepares and on aluminum sheets

stacked and dried at 50 g for 30 minutes. ^ "

^; ■ 9 Of '«.7 / 11ΊΤ 4 ..: ORIGINAL

^! 318023

- ie,

Tabel

Cross-cut Invention Resistant to kinking - 3 --4- Water resistant after 10 days according to 1-2 ability I after four Drying at game 6 after 10 days daily drying: 20 ° C Comparison ger drying at 20 ° C '■' according to DIN 53 151B example at 200 G II 10 min. A the German effect of what Interpretation 3 - 4 water at 60 ° C font 1 247 006 1-2 1 - 2 2-3

Paint shows

Buckling resistance: Sheet II 1 = jerky over the edge of the table Bend by 90 °, abruptly 2 = ßend by more Bend 90 °

1) no cracking

2) little cracking 3 =

3) Several cracks, paint film has flaked off up to 10%

4) severe cracking, lacquer 4 = film is up to more than 50> i chipped off

no swelling at the cross cut

low swelling at the cross cut, up to 25 % of the varnish can be removed by scratching

there is greater swelling at the cross cut, from scratching the paint up to 50 # too remove

strong swelling, paint is easy to scratch off

From the table it can be seen that the example according to the invention 6 the comparison example from the German interpretation tool 1 24? 006 in the cross-cut, the buckling strength and is clearly superior in water resistance.

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ORIGINAL INSPECTBD

Example 8

It is the copolymer 4 as in Example 3 instead of the copolymer 2 is used. The coating composition obtained is very good Surface hardness and elasticity of the air-dried cured Film.

Example 9

The mixed polymer 5 is used as in Example 6 instead of the mixed polymer 3. The coating composition obtained by the baking at 13O ⁰ C in 30 minutes is distinguished by very good surface hardness and good resistance to aromatic solvents.

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Claims (3)

\ CJ 18023 File: ON 2122 PATENT CLAIMS 1./Process for the production of flat structures from polyhydroxy compounds based on sulfur-containing copolymers based on hydroxyl groups polymerizable compounds with carbon double bonds and vinyl aromatics and polyisocyanates in solvents without active hydrogen atoms by shaping under Removal of the solvent, characterized in that as sulfur-containing copolymers those from A.) 60 - 94 wt.; * Hydroxyl group-containing copolymers, made of a) 20 -.! 70% by weight of styrene or Viny toluene, b) 10 - 5 ^> wt. ^ Methacrylic acid esters, those in the alcohol residue Contain 1-4 carbon atoms, c) 5 - 30 wt. ^ S hydroxylalkyl esters of acrylic acid or Methacrylic acid, which contain 1-4 carbon atoms in the alcohol residue, d) 0 - 30% by weight acrylic acid alkyl ester, the 1 -. contain 8 carbon atoms in the alcohol radical, e) 0.1 to 5 wt. % SH groups, which are present as aliphatic ^ and / or aromatic and / or heterocyclic mono- or polymercaptans, the amounts of the monomers a) to d) and the SH groups being measured in this way must that these add up to 100 wt. #. B.) 1-20 parts by weight of polyhydroxy compounds from polyols or mixtures of such compounds of the following form R _1. ' 909847 / 11U. ORIGINAL -Π 8 O 2 R ₁ = H, -CHj, CH ₂ - (O-CH ₂ -CH) _n -OH R ₂ = CH ₂ - (O-CH ₂ -CH) _n -OH > - ( _{O-CH 2} -CH) _n -OH Rj = H, CH ₅ , CH ₂ - (0-CH ₂ -c4l) _n r0H Rl ₁ . = CH ₂ - (O-CH ₂ -Ck) _n -OH CH ₅ -CH ₂ - CH ₅ ^ y (O-CH ₂ -CH) _n -OH η = 1 to 30 C) O-I wt. # Of an organometallic compound and / or a tertiary amine. D.) 5 - 30 wt. # Organic polyisocyanate, where A to D Numerical values of 100% by weight must result, are constructed, are used. 2. The method according to claim 1, characterized in that A.) 70 - 84 wt. Copolymers containing hydroxyl groups, made of a) 20-40 wt. # of styrene or vinyl toluene ,. b) 20 - 40 wt% of methyl methacrylate. • c) 15-25 Gew.j ^ Hydroxyäthylacrylat or Hydroxy- ' ethy! methacrylate d) 15 '- 25 wt. # of butyl acrylate or 2-ethylhexyl acrylate, e) 0,5 - 1 # 5% by weight of SH-groups in the mercaptan. or lauryl mercaptan are present. B.) 1 - 5 wt. # Of a polyhydroxyl compound, which by reaction from 1 mole of glycerine and propylene oxide with an average molecular weight of JOOO and a hydroxyl number was obtained from approx. 56, 9 0 9 8 4 7/1114 INSPECTiD -'- Π 8023 -aa- ■ C) O - 0.2 wt. ^ Tin dibutyl dilaurate and D.) 15 - 24 Gew.?B organic triisocyanate, which by Implementation of 3 moles of hexarene t hy I end iisocyanate and 1 mole of water was obtained, where A to D must result in numerical values of 100% by weight, can be used. 3. Reaction lacquer, optionally with customary additives for lacquers, as a means for carrying out the process according to Claim 1 or 2, characterized in that it contains the identified components. 909847/1 TU ■ OHfQiNA INSPECTED