CS379591A3 - Binding agents for fluorine-containing varnishes - Google Patents

Abstract

The fluorine-containing paint binder contains a) 5 to 80% by weight, based on the sum of the components a) + b), of a finely divided low molecular weight polyfluoro-olefin, derived from fluoro-olefins of the formula CF2=CFX, in which X is F or Cl, with a melt viscosity of 10<1> to 10<6> Pa.s, b) 95 to 20% by weight, based on the sum of the components a) + b), of a fluorine-containing copolymer, which is composed of copolymerised units of a fluoro-olefin of the general formula CF2 = CFY, in which Y is F, a perfluoroalkyl radical having 1 to 8 C atoms or Cl, of copolymerised units of a vinyl ester of a highly branched carboxylic acid with an acyl radical of 9 to 11 C atoms and of copolymerised units of a vinyl monomer containing OH groups, and c) 20 to 300 parts by weight, based on 100 parts by weight of the sum a) + b), of a customary paint solvent. c

Description

v?:. · PF? a4s.

Fluorine-containing varnish binders. i <J to zn

Technician Area · /

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lacquer binder comprising fluorinated compounds.

Background Art

[0008] Varnishes based on fluorinated copolymers containing cross-linking hydroxyl groups are known. Such systems generally contain a high proportion of pigments which provide a high covering power of the resulting coating, for example a facade. The pigment particles deposited in the system behave to some extent as foreign bodies that disrupt the coating structure and can even open the fine channels through the coating layer to the substrate. This adverse effect is particularly pronounced for metal substrates, where it can cause corrosion and at the same time form rust particles on the substrate surface. These particles reach the surface of the coating, which causes a discoloration. This is dealt with most in such a way that the hay of its own paint takes another final, which contains little or no pigment at all. But this is yet another additional work step, while increasing costs.

SUMMARY OF THE INVENTION

It has now surprisingly been found that said drawbacks are eliminated when so-called fluorinated hydrocarbon wax is added to the lacquer-forming system. Accordingly, the present invention provides a lux binder, a)? a: 30 Ϊr o reduced fluoroelastics of a) and b), fine-grained fines. ta? 3xo to the polyoxyethylene fluorinolefin formula

C 2 = CFX wherein X is fluoro or chloro, with a melt viscosity of 101 to 10 ° Pa s, b) 95 to 20 wt. based on the sum of components (a) and (b), a fluorocarbon copolymer consisting of copolymerized fluorolefin units of formula F 2 = GFY, wherein Y is fluoro, a perfluoroalkyl radical having 1 to 8 carbon atoms or chloro, of copolymerized vinyl ester units carboxylic acids wherein the acyl contains 9 to 11 carbons and copolymerized units of the vinyl monomer containing hydroxyl groups and c) 20 to 300 parts by weight based on 100 parts by weight of the sum of components a) and b), a conventional lacquer solvent »

Component a) is a low molecular weight homopolymer of trifluoro-chloroethylene or preferably tetrafluoroethylene. The so-called fluorocarbon waxes, also occasionally referred to as microflora, have a low molecular weight, lower than conventional high molecular weight polytetrafluoroethylene (PTFE) or polychlorotrifluoroethylene (PGTFE), resulting in lower viscosity melts, ranging from icA to 10 ° Pa s, preferably 10 ^ to 1, in x you * 4- - - V. · J '-Λ J_ k- · J! -L ivi JO J.3C; V γ t j j j j j j j j j j j j j j j j j j j

1 v * * j.x w,, X x x C ii v J V i c L · 1 J

Qu ',? said fluorinated wax bvlv fine waxes. A suitable form appears to be a powder having a mean particle size of primary grain of 0.1 to 10 µm, preferably 0.1 to 10 m.

Such low molecular weight fluorinated hydrocarbon waxes (PTEE and PGTES) can be prepared in two different ways. One of these is the degradation of a high molecular weight PTFE or PCTFE material with a shorter chain, particularly high molecular weight wastes. The second approach is to form relatively short chains by telomerization of tetrafluoroethylene or chlorotrifluoroethylene in the presence of suitable proteases.

The degradation of high molecular weight polytetrafluoroethylene can be carried out pyrolytically at temperatures usually above 400 ° C, optionally under reduced pressure and in the presence of inert gases as catalysts. This process and the products prepared by it are known, for example, from U.S. Pat. Nos. 2,496,973, 3,223,739 and 4,076,760. Similarly, the pyrolytic degradation of polychlorotrifluoroethylene is described, for example, in U.S. Patent Nos. 2,543,530, 2,664,449 and 2,854,490. The preparation of the necessary low molecular weight fluorocarbon waxes can also be accomplished by degradation of high molecular weight polytetrafluoroethylenes or polychlorotrifluoroethylenes by the action of ionizing radiation, such as gamma radiation in particular, Newtons or neutron radiation. Such a process and the compounds obtained therein are described, for example, in British Patent Specification 75S 554, U.S. Pat. Nos. 3,766,031, 3,838,030, 4,029,370, 4,036,718, 4,052,278, and in European Patent 4,752,031;

Furthermore, the respective fluorinated hydrocarbon waxes for use in the binders of the present invention may be prepared by telomerization of tetrafluoroethylene or chlorotrifluoroethylene in void body genes or also by oligomerization. In doing so, telomerization can be carried out either in the telogen itself or in a mixture thereof with another organic solvent. The process may also be carried out in the aqueous phase in the presence of a telogen and a surfactant. In the first case, solid granular or crystalline waxes are formed, in the second, colloidal aqueous dispersions from which the coagulation is waxed off. This produces grape-like agglomerates of particles with a primary granular structure. Such waxes formed by thermoforming are described in U.S. Pat. Nos. 2,694,701, 2, 700,661, 3,067,262, 3,102 S62, 3,103,490, 3,105 S24 and 3 956 000.

For the purposes of the present invention, the appropriate fluorinated waxes, which are also available in the shop, must be formulated with the necessary forms by gentle milling. The particles must have a mean particle size of 0.1 to 15 m, preferably 0.1 to 10 m. In the case of agglomerates, this is the particle size of the primary grain. The melt viscosity T of these waxes is 10 to 10 mbar, preferably 10 to 10 mbar. For fluorine-containing copolymers constituting component b), those which contain copolymerized fluoroolefins are suitable for use in the lacquer binders according to the invention. Units of formula 0-2 = CFY, where Υ is chloro. They are perfluorohexene fluorine, perfluoroalkyl with, for example, fluorobutene

1 and perfluorisobutene. Z to 6 hydrocarbon ;; or 1, perfluorooctene-1, others particularly preferred cniortriiluorethylene, hexafluoropropylene and tetrafluoroethylene. The respective copolymers further comprise copolymerized units of vinyl ester of a strong branched carboxylic acid which is resistant to saponification. These are vinyl esters of formula (I1)

CH 2 X CH - O - CO - C 1 - R 11 R-, wherein R 1, R 1 or R 4 are branched chain or alkyl chain alkyls and the entire acyl contains 9 to 11 carbons. At most one of the radicals R @ 1, R @ 4 and R @ 4 may be hydrogen. Preferred are branched acyls of the above formula having 9 carbon atoms and, in addition to one quaternary carbon, further quaternary carbon or one to two tertiary carbons per one residue. They further comprise copolymerized units of vinyl monomers having hydroxyl groups required for crosslinking the entire lacquer system. These monomers may contain hydroxyl groups per se, or these hydroxyls may be formed by the already prepared copolymer of functional groups which form hydroxyls by hydrolysis or alcoholysis. The first group of vinyl monomers include, for example, hydroxyalkyl vinyl ether with a hydroxy-alkyl group containing 1 to 6 carbons. Such copolymers are known, for example, from U.S. Pat. No. 4,659,755. The second group preferably consists of vinyl esters of carboxylic acids. In particular, they are carboxy-short chains which can be saponified. ον e xysenny, ^ icíe acyl 003ζ · '. ·; 3 «

Especially preferred are vinyipropionate and particularly preferred vinyl acetate. Preferred amounts are 10 to 50 moles of branched carboxylic acid and 20 to 50 mol%. hydroxyl-containing vinyl monomer. The fluorinated olefin complements the sum of the three components to 100 mol%. The fluorinated olefin portion is at least 10 mol%, preferably 20 mol%

The copolymerization to prepare the copolymers described above is preferably carried out in organic solvents in which the copolymers formed dissolve. Such suitable solvents are, in particular, perfluorinated solvents, fluorinated perchlorinated solvents, or partially halogenated solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane, perfluorocyclobuccin, perfluoro-n-pentane, -isopentane, -n. -hexane, -isohexane, l, l, 1,2-tetrafluoroethane or 1,1,2,2-tetrafluoroethane. In addition, alkanols such as tert-butanol, carboxylic acid esters such as butyl acetate or n-propyl acetate, aliphatic or cycloaliphatic ketones such as methyl isobutyl ketone or cyclohexanone, alkylaromates such as toluene or xylene and mixtures thereof are also suitable. solvents with ethanol.

The copolymerization leading to the preparation of the said component b) copolymers can also be carried out in the aqueous phase by the suspension polymerization process in the presence of buffers, suitable radical-forming initiators and optionally in the presence of small amounts of emulsifiers; or it may be carried out in aqueous colloidal dispersions by the process of emulsion polymerization in the presence of suitable surface active agents, preferably fluorinated, as emulsifiers.

Laxes may be present in both the free and non-aqueous copolymerization of the chain transfer agent.

According to the method chosen, the copolymer is obtained in the form of a viscous solution, granular powder or an aqueous colloid dispersion. The formation of the colloidal dispersion must be enhanced by the addition of a suitable coagulating agent or by high shear forces. The coagulum 3e formed is then washed and dried.

The copolymer thus formed - when it contains short-chain carboxylate carboxylate units as hydroxyl-forming moieties - is subjected to further treatment to saponify the vinyl ester units. The term "saponification" as used herein refers to the cleavage of ester groups by hydrolysis and / or alcohol. The pulverulent copolymer is initially dissolved in an alcohol containing 1 to 4 carbon atoms and then precipitated with water. Saponification can also be carried out by treatment with aqueous alkali or quaternary ammonium hydroxides.

To process the copolymers that are in solution, the following procedure may be useful: (a) first remove the major portion of the solvent by distillation of the malformed pressure, (b) then remove the monomer residues by vacuum distillation with highly viscous copolymers c) These highly viscous copolymers will dissolve in a mixture of 1 to 4 carbons and solvents, the mixture also having to saponify the product; d) saponification is carried out with the addition of an alkaline agent; optionally, the solvent of process c) is removed by distillation and the residual viscous copolymer is dissolved in the lacquer solvent and then e) the resulting copolymer solution is filtered.

As described above, it is possible to convert the units of the methyl ester to the hydroxyl groups in a proportion of 50 to 100%, preferably 50 to 30%.

The copolymers of the present invention obtained by the process described above are soluble in a number of organic solvents and solvent mixtures commonly used in the paint industry. These solvents, in amounts of 20 to 300 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the components a) + b), are components c) of the paint binder according to the invention.

Solvents are generally selected from the following groups: Aliphatic alcohols having 1 to 8, preferably 4 to carbon atoms, polyglycols such as ethylenediglycol, ethylentriglycol, propylendiol glycol, propylentriglycol; mono- and diethers of these glycols such as ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl ether; glycol esters or glycol ether esters such as ethylene glycol acetate or ethylene glycol acetate ethyl ether, propylene glycol acetate ethyl ether and methyl ether; they are furthermore alkylated and dialkylated aromatics such as xylene and diethylbenzene or isomers of alkylated aromatics in the mixture as designated Solvesso or Shellsol; then ketones such as methyl isobutyl ketone, cyclohexanone and iso-foron; carboxylic acid esters, in particular acetic and propionic esters with alcohols having 1 to 6 carbons; since all mixtures of such solvents are homogeneously miscible.

Mixing components a), b) and c) of the fluorinated binder can be effected in various ways. In the case where the fluorinated copolymer (b) is in a solid powder form, it is preferable to dissolve the copolymer with stirring in a component component c) and then add a low molecular weight polyhalogenolefin (fluorocarbon wax) component a) and using a mixing device. However, it is also possible to mix the powdered copolymer b) and the solid hydrocarbon wax (component a) first in a suitable mixing device and then introduce solvent c) and then homogenize the mixture on a suitable apparatus. In the case where the fluorinated co-polymer (b) is prepared as a solution in the solvent of component (c), fluorocarbon wax is admixed thereto using conventional mixing and homogenizing devices such as bead and ball mills, shakers, sand mills, three-roll jet mills. -mills, kneaders and the like. Bead mills are preferably used. Pigments and other additives are added in the same manner.

The lacquer binders according to the invention contain copolymers with OK groups which allow chemical curing of the lacquer during its application. According to the selection of the crosslinking mechanism, curing can take place at temperatures of 10 to 300 ° C, preferably at 15 to 50 ° C. In the case of the lacquer binder of the present invention, various curing agents, for example aminoplasts such as melamine or urea resins, as well as polybasic acids and their anhydrides or blocked polyisocyanates can be added to the heat-curable lacquer composition; these compositions are single component coating systems. - 1?.

These compositions provide excellent coatings and primer coatings that are elastic, tacky, stable to corrosion, weathering, and especially water, give surface coatings and single-coat coatings. Firing temperatures of at least 30 3 are required to cure these modified varnishes.

The crosslinking reaction can be accelerated by the addition of an acid catalyst such as p-toluenesulfonic acid or its salts.

Typical examples of aminoplasts are condensation products of compounds containing amino groups such as melamine, urea, acetoguanamine or benzoguanamine, with aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde or glyoxal, and products resulting from the etherification of these condensation products with alcohols. Preferably, alcohols having 1 to 4 carbons are used herein. Examples include hexamethylethyl methylolmelamine, hexabutyletherified methylolmelamine, methylbutyl etherified methylolmelamine, methyl etherified methylolmelamine, butyletherified methylolmelamine and isobutyl etherified methylolmelamine. In view of the compatibility with the copolymers of the present invention, methyl etherified methylollamines are preferred, among them penta-bis-hexamethyletherified methylol-melamine.

Typical examples of polybasic acids include acrylic resins with at least two carboxyl groups in the molecule and aromatic polybasic acids such as trimellitic acid or pyromellitic acid.

Typical examples of polyhydric acid anhydrides are succinic anhydride, trimellitic, pyromellitic, and anhydride-bearing avinyl polymers. II -

Typical blocked polyisocyanates are obtained when the polyurethane chemistry known in the art also acts by conventional blocking agents such as alcohols, compounds with phenolic OH groups, oximes, lactams, ethyl esters of acetic acid and h-monosubstituted it is also possible to thermoresign isocyanate blocking by dimerization of the isocyanate functional groups nauretdione. If the fluorinated lacquer binder is used to prepare a lacquer composition in which the curing is to take place at room temperature, the non-blocking polyisocyanate is used as the crosslinking agent. In this application, the hardener is mixed in a separate manner prior to use and a two-component coating system is used,

Typical examples of polyisocyanates are aliphatic diisocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate tetramethylene diisocyanate; alicyclic diisocyanates such as xylene diisocyanate, methylcyclohexane-2,4- or -2,6-diisocyanate, isophorone diisocyanate and 4,4Z-methylene-bis-cyclohexyl isocyanate, biuret branched polyisocyanates which are obtained by reacting polyisocyanates with water; and finally, polyisocyanates with an iso · cyanurate ring formed by the polymerization of said diisocyanates

The isocyanate addition moiety can be accelerated by a number of catalysts, the most important of which are those having the properties of allo-donors (Lewis bases) or electron acceptors tertiary amines, such as triethylamine, diethylethanol amine, dimethylethanolamine, 1,4- diaza-bicyclo- (2; 2,2) -octane and cyclo-hexyidimethylanine are also active catalysts as Lewisow base. Also, 4-dinethylaminopyridine, known as the acylation catalyst, acts catalytically on the reaction of isocyanates, catalytically acting Lewis acids being the most important tin compounds. Any effective catalyst is a tetravalent compound such as dibutyltin dilaurate and diacetate, or divalent tin compounds such as tin dioctanoate.

Finally, crosslinking is also possible with epoxy resins. This is done by heat in the presence of catalysts, in particular the presence of lithium salts and quaternary ammonium salts. Furthermore, in the lacquer compositions of the invention, any of the conventional pigments and reagents, but also cadmium sulphide and zinc sulphide, lead white, barium sulphate, can also be added to the lacquer industry. pyrogenic acid, siliceous, bentonite and chalk and remotely is given by the ratio of components (1: 0 to 1: 1 expressed in the advantages of the proposed system influenced by

The envisaged lacquer formulations such as cross-linking agents, UV-absorbers, to enhance the gloss and the matt adhesion promoter. phthalocyanine dyes. Pigmenta- + b) pigment and should be in bulk. Otherwise, the present invention may further include conventional additive process, disproportionate, or adjuvanting agents.

Lacquer compositions formulated with the addition of cross-linking agents provide surface coatings that can be applied to the most diverse substrates. According to the crosslinking component used, they can be cured at room temperature or wcaled for teclot; vyszi. u2> 3 knives are especially suitable for these paints, especially metals such as iron, steel, aluminum, honey, brass and bronze, but also other hard surfaces such as glass, ceramics, concrete or wood. and the surface of synthetic materials. The storage may optionally be pre-treated with the means. In the case of poorly adhering materials, it is advisable to pre-coat the substrate.

The application can be carried out in all common ways such as spraying, wiping, brushing, rolling, dipping, pouring, coating and painting. The coating compositions containing the binders of the invention are particularly suitable for cold-cured coatings of objects exposed to weathering. It is also suitable for use as an industrial firing lacquer by the coil coating method.

The varnishes containing fluorocarbon wax according to the invention increase weather resistance and corrosion resistance compared to known binders without this wax. In addition, they improve slipperiness and reduce adhesion, especially as regards ice in and snow coming to the surface of the paint. They reduce soiling and increase the self-cleaning effect, especially for paints exposed to weathering. They also cause aesthetic matt effect on white, color and colorless varnishes. EXAMPLES OF THE INVENTION

The invention is illustrated in the Examples which follow. The following test methods and tests are used in the examples:

Dust drying corresponds to the drying degree 1 according to DIN 53 150 "Determination of the degree of drying of paints".

Non-tack drying corresponds to drying rate 2 according to DIN 53 150. - x4 -

Hardness secured by a shuttle device according to KOnig: norm Lin 53 157

Erichsen trenching test: Impact: EGGA (European Goil-Goater * see reference standards ilSTPencil hardness: EGGA T 4

T-Send Test: ISO 1520s Association Regulation) T 5j Response D 2794-69 and ISO R 291

The varnish is applied to the aluminum plate (Bonder AI 722). The film thickness of 100 µm corresponds to 20-22 m after drying, 1 cm wide strip of this lacquered sheet metal on the outside is folded bent by ISO0. This procedure is repeated with the same strip (for simultaneous enlargement of the bending angle) until the film no longer tears (the T film breaks on the first bend; the T-film breaks on the second bend and so on). Example 1

Mixture - a bead mill - a copolymer of 37 mol%. of copolymerized units of tetrafluoroethylene, 31 mol% of copolymerized branched carboxylic acid vinylester units with a 9 carbon acyl, wherein the acyl is a mixture of isomers containing 28 mol% of carbon chains with 2 quaternary carbons, 68 mol% of hydrocarbon chains of 1 quaternary and 2 tertiary carbons and 4 mole% of carbon chains with 1 quaternary and 1 tertiary carbon; 32 mol% of copolymerized units of vinyl acetate; number of CH groups after saponification 115 (50 wt.% solution in butyl acetate) amount of 200.0 g - tetrafluoroethylene based wax (melt viscosity 1.8.

Pa s, the average particle size of the primary grain d ^ 0 0.4 m 13 - 40.0 g

The composition of the lacquer: a batch of 240.0 g of hexamethylene diisocyanate trimer, a 75% by weight, trade name Lesrnodur h 75 52 2 · dibutyltin dilaurate, 1% by weight solution. in xylene 200.0 mg

The coating was cured at 20 ° C. The mixture was applied to a glass plate using a coating machine. The paint was subjected to different. tests. The penetration test was performed with free film.

For these measurements, the glass plate film was previously released. Test results are shown in Table 1.

Table 1 lest result

Drying for dusting 35 min drying nanSepivost 60 min hardness by pendulum 7 d 138 s

Penetration (film thickness 100 m) H 2 O (g / m 2 d) 4.5 02 (cm 3 / m 2 d. Bar 322 hT 2 (cm 3 / m 2 d. Bar 38 CO 2 (cm 3 / m 2 d. Bar) 1455 Example 2

The coating was carried out as in Example 1. To verify the amount of curing agent used on the coating hardness, 2: 1 κ: hexamet7 flax:

Table 2 οη ο z s t v ί v yt v r z ο v a dl a

65.3 N 78.3 g 91.4 g 104.4 g Λ * ’Γ · ':: Ί

'.'V lips t v r d o s t a d 1 o in the yard

i. 4-0 S 156 s158 s 162 s Example 3

Comparative Example - no fluorocarbon wax

Paint composition:

Copolymers as in Example 1 (50% by weight solution in butyl acetate) hexamethylene diisocyanate trimerized by 75% by weight. solution (Desmodur N 75) dibutyltin dilaurate 1 wt. solution in xylene 200.0 g 52.2 g 200.0 mg

The coating was cured at 20 ° C. The preparation of the coating and the performance of the tests was the same as in Example 1. The test results are summarized in Table 3.

Table 3

Test V ^ l / v u. X. test 7 d

Drying to dusting non-tack dryingShipping hardness

Penetration (film thickness 9 H90 (g / m "a) (cm ^ / m2" d.bar) ft'2 (cur / ni ". D" bar) 002 (cmP / m 2. D .bar) 60 164 100 ^ m) 6,412 84,185 mek min min s Example 4

Mixture - bead mill feedCopolymers from Example 1 (50% w / w solution in butyl acetate) butyl acetate wax based on tetrafluoroethylene (obtained by pyrolytic degradation of polytetrafluoroethylene); melt viscosity9 1.2 "10" Pa s, median particle size d50 "9

The composition of the lacquer: the bead of the pearl mill listed aboveexamethylene diisocyanate - trimer · 75% by weight. solution (Cesmodur N 75) 100.0 g43.0 g.-2 ^ .0.Λ 163.0 g 163.0 g 26.1 g

Dibutyltin dilaurate (1% w / w solution in xylene) was added. The addition of additional butyl acetate provided the viscosity for 20 seconds (DIN 53 211 effluent cup) and the spray gun was introduced. The coating was then subjected to some tests. Their results are summarized in Table 4

Table 4

Test Result

Dust-drying 10 min Non-tack drying 40 min Hardness by shuttle test 7 d 158 s Example 5

Mixture - handle for pearl mill:

Copolymers such as Example 1 (50 wt% Butyl Acetate Solution) 200.0 g

Tetrafluoroethylene wax as in Example 1 40.0 g blocked aliphatic isocyanate (25% w / w Solution in methoxypropyl acetate of the trade name Aditol VXL 9946) 241.0 g

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The mixture of the above composition, processed in a bead mill, was deposited on an aluminum sheet (3onder Al 722. The wetted layer was wetted with 100 µm, dry 20-20 mFLT (Peak-metal-temperature): 224-232 ° C. The results are summarized in Table 5 «

Table 5

Test Result Acetone Test? 100

Impact 70 ip T-Bend T 2

Pencil Hardness F Example 6

Mixture - bead mill batch copolymers as in Example 1 200.0 g (50% w / w solution in butyl acetate) Tetrafluoroethylene wax as in Example 40 40 gpentamethyletherified methylol melamine (trade name Maprenal MF 900) 25.0 g p- toluenesulfonic acid 120.0 mg

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The bead mill composition of the above composition was supported on an aluminum plate (Bonder AI 722). The scraped coating had a wet thickness of 100 [mu] m, a dry coating of about 20 to 22 [mu] m. The layer was fired by two different procedures and then subjected to some tests. The test results are summarized in Table 6. 20

Test Burning conditions 130 ° 0/15 min 33O ° O / 45 acetone test 336> 100 Impact 80 ip 75 ip T-Bend 1 3 T 3 adhesion after test T-5end 0 0 pencil hardness H 4 F Example 7

Mixture - handle for pearl mill:

Copolymer of 47 mol% of copolymerized units of tetrafluoroethylene, 30 mol% of copolymerized units of branched vinyl ester, the acyl radical of which is a mixture of one acyl component R 4 = CH 3, R 4 = O 2 H 2, 3 = and other acyl components in which R = = CH,, R ^ = OH ^, R ^ = CH ^Cl ^, in addition 23% by mol of copolymerized units of>-hydroxy-n-butyl vinyl ether (50% by weight solution in butyl acetate of 200, 0 &amp;

Tetrafluoroethylene wax (as in example 1) 40.0 g titanium dioxide (type CL 310) 50.0 g butyl acetate 86.0 g

Lacquer composition: The pearl mill handle above 376.0 g

Hexamethylendiocyanate trimer, 75 wt. solution (Desmodur N 75) dibutyltin dilaurate (1% w / w solution in xylene)

The film layer, Vxriiaia χόΌα. '2 · i ^ t, r Ό tě r tě ám ám ám ám ám ám ám ám ám ám ám ám, whose results are summarized in Table 7

Table 7

Test Pronunciation

Dust drying n

Non-tack drying 24 h Pendulum test hardness 7 and 73 s Sun test 0 h 69% 250 h 67% 500 h 66% 750 h 66% "Sun test" is based on gloss refinement pov: Reflection according to DIN 67 530 100% irradiated light intensity).

Industrial usability

The waxes of fluorocarbon-containing waxes according to the invention improve the properties of the lacquers of which it is a component, particularly in terms of resistance to weathering, corrosion and soiling. Coatings of these lacquers have, in addition to improved technical properties and advantages, aesthetic effects in painting.

Claims (3)

lt Li '/ —L —j C’1 CLAIMS 1. Binders for fluorine-containing lacquers, characterized in that they comprise a) 5 to 80% by weight, based on the sum of components a) + · o), of a finely divided low molecular weight polyfluorolefin derived from an olefin of the formula IC2 = CFX (I) where X fluorine or chlorine, having a melt viscosity in the range of 10 to 10 Fa; and b. 95 to 20% by weight, based on the sum of components a) + b), of a fluorine-containing copolymer consisting of copolymerized fluoroolefin units of formula II CF2 = GFY (II) wherein Y is fluoro, perfluoroalkyl of 1 to 8 carbons or chloro, copolymerized units of a vinyl ester of a branched carboxylic acid whose acyl contains 9 to 11 carbon atoms of copolymerized units of a vinyl monomer containing hydroxyl groups and c) 20 to 300 parts by weight based on sum a) + b) of a conventional lacquer solvent. The fluorine-containing varnishes according to claim 1, characterized in that component a) is a low molecular weight polytetrafluoroethylene. 3. A varnish composition comprising fluorinated binders and crosslinking agents, characterized in that the fluorine-containing 23 binder comprises a) 5 to 80 c, C mass, based on the comminuted low molecular weight formula I GF2 = GFX (I) sum of components a) + b), a fine polyfluorolefin of general formula wherein X is as defined above, 6 with a melt viscosity of 10 to 10 Pa s, b) 95 to 20% by weight, based on the sum of components a) + b), of a fluorocarbon copolymer composed of copolymerized units a fluorooolefin of the formula II CF 2 = CFY (II) wherein Y is as defined above, by copolymerized units of a branched carboxylic acid vinyl ester having an acyl content of 9 to 11 carbons and a copolymerized vinyl monomer unit containing a hydroxyl group and c) 20 to 300 parts by weight based on per 100 parts by weight of a) + b), a common lactic solvent, the addition of customary pigments in amounts of up to 1 part by weight based on the sum of components a) + b).