DE1769189A1 - Molding and coating compounds - Google Patents

Description

"Molding and coating compounds" without priority The invention relates to molding and coating compositions for use in the production of moldings, protective coatings and painting. In particular, the invention relates to such masses on the Basic hardening organic polymer with a content of certain active ingredients, the preferably for applying dry, smooth, uniform and impermeable Schutsfilsen are intended for objects.

Protective films made from itbertugemaasen based on organic polyderers can be applied to objects in various ways. If the subject immersed in the coating mass and then taken out should the protective film must be uniformly distributed on the surface. Practical one finds however, that a dry, uniform, impermeable protective film in this way cannot be produced because the process of immersion causes air to enter the Film becomes trapped and bubbles form, which occurs as it cures and dries manifests itself in the formation of a defective film surface. As the hardening or drying treatment usually inconsistent, wrinkling or "feather patterning" often occurs and leads to the formation of irregular surfaces. It can even form streaks or an uneven color, which makes the surface even more imperfect will.

When applying protective films by brushing on with a brush or the like, holes are usually formed similarly to the dipping process Air bubbles and the application becomes uneven, which is not acceptable when an area completely protected by a uniform, impermeable film shall be. The same disadvantages occur with other conventional coating processes like spraying or flow coating.

It has been found that a drier, smoother, more uniform impermeable Protective film made of organic polymeric coating compounds on counter-strength in the immersion process, by spreading, Spraying, flow coating or other means Desired process can be obtained if coating compositions are used1 which contained a small amount of a certain polyve ether.

It has also been found that # plastic products made from molding materials Can be produced that are extremely smooth and uniform so far Unavailable or possible surface properties if the molding compounds contain a polyvinyl ether additive. Are plastic products made from polymerizable Molding compounds produced using Pormen or Gie # forms, with. a catalyst addition to the formation of the polymer in the mold, it is often felt that the general appearance and surface of the manufactured article a haze that was released during the polymerization is spoiled Air is to be returned. This air comes from the cold molding compound in which it is is included and during the heating caused by the polymerization is released. A wrinkled or holey surface is also often formed, which does not satisfy if high demands are placed on the smoothness and uniformity of the Surface. The formation of fog and surface irregularities, such as wrinkles or dents do not occur when molding compositions with the invention Addition can be used. In particular, was found that here the problems associated with the inconsistent distribution of dyes do not occur.

The molding and coating compositions according to the invention based on curable organic polymers are characterized by a content Bn of a small amount of a polyvinyl ether with calibrated structural units of the formula wherein R is a branched hydrocarbon chain having a molecular weight of at least 100,000.

As organic polymeric molding and coating compositions, which the invention Contain additives, in particular alkyd resins, drying oils, aminoalkyds, nitrocellulose and other cellulosic resins, butadiene polymers and copolymers, styrene polymers and -copolymers, chlorinated rubbers, polymerized coal tar resins,: polyolefins such as Polymers and copolymers of polyethylene and the like in question. These polymerizable Masses can optionally be used together with additives such as pigments, plasticizers, Solvents, dyes and the like in the form of paints, laek paints, lacquers, Cardiac solutions, polymerizable porous masses made entirely from Pestetoffen or the like curable can be present, the duroh according to the invention by the additives Additional benefits were not achieved be affected. The expression "Polymeric molding and coating compositions" include the polymers themselves as well as polymerizable ones Masses, and under "curable" is meant the conversion of liquid polymeric or polymerizable Masses of solid moldings and coatings are understood, which by drying, Oxidation processes, baking, catalytic hardening and the like is caused.

The polyvinyl ethers used according to the invention with repeating structural units of the formula have branched hydrocarbon chains R, which are preferably branched alkyl chains with 3-10, preferably 3-8 carbon atoms. The polyvinyl ether can have a medium or high molecular weight, so that satisfactory results can still be obtained, and should preferably have a molecular weight of from about 100,000 to about 1,000,000 or higher, in particular from about 200,000 to about 600,000. It is possible to use polyvinyl ether with a grate R su which contains a hydrocarbon residue with an iso grouping such as an isopropyl, isobutyl or isoamyl group or the like. The group R can also contain secondary or tertiary carbon atoms. Commonly used branched polyvinyl ethers are polyvinyl isobutyl ether, polyvinyl isopropyl ether, polyvinyl isoamyl ether, polyvinyl 2-ethylhexyl ether, polyvinyl sec, polyvinyl butyl ether, polyvinyl tert-butyl ether and the like.

The molding and coating compositions according to the invention can be used in a known manner Whiteness can be made according to its intended use, e.g. as paints, clear paint films and the like. tht according to the invention # to achieve the desired effect, it is necessary that a small amount of the active polyvinyl ether be mixed in will. It has been found that satisfactory results are obtained when the amount of polyvinyl ether is about 0.00025 to about 0.5 weight percent based on total weight. Particularly beneficial results are obtained at an amount of from about 0.0025 to about 0.1% by weight received.

The admixture takes place directly or in the form of a dispersion or Dissolution of the polyvinyl ether in a suitable medium or solvent. Examples suitable solvent used without altering the desired results are hydrocarbons such as xylene, benzene or kerosene.

In addition, the introduction of the polyvinyl ether in the form or be carried out in a manner known per se «is not critical.

The invention will. explained by the following example, where the Polyvinyl ether in the form of a 5% solution in xylene is used and the amounts by weight are based on the total mass.

Example t It becomes a paint of the following composition manufactured: 1. pigment. a) Titanium dioxide 200 g b) Chrome green 50 g 2. Carrier a) With Ester rubber modified phenolic resin 11 g b) Tungdl 172 g c) Banzin 232 g d) Reine Phenolic resin loo g e) linseed oil 170 g 3rd polyvinyl isobutyl ether (5% in xylo @) 2 g medium Molecular Weight (Lutanol J60) The pigments are first in part of the carrier ground in, using a thorough mixture of ingredients a three-roll mill to a smooth, homogeneous paste. In this paste will dor the rest of the carrier material and desiccant in the form of 3 g cobalt naphthenate (6% cobalt) and 5 g lead naphthenate (24% lead) below Stir introduced until a smooth paint is obtained. The polyvinyl ether is also thoroughly mixed into the solution in xylene.

The viscosity of the paint mixture will soak up to a suitable spreading consistency of 67-70 K.U. on the Vickosimeter according to Stormer by adding a diluent depending on the pigments used and carrier materials.

The paint obtained is applied to the smooth surface of a plastic plate brushed on and after drying gives a uniform, smooth film surface. The color remained evenly distributed over the entire coating.

Another mixing device can also be used, e.g. a ball mill, a paint bar kit stone balls or a high-speed or colloid mill keits-dispersing device / instead of the roller mill can be used.

The pigment can also be added in another way, for example in the form of pre-ground dispersions in linseed oil or in another compatible form, like it in the manufacture of ANTI agents often happens.

Comparative Example According to Example 1, a paint is produced, However, no polyvinyl ether was added. After spreading on a similar Surface will keep an irregular and pocky surface after drying The color scheme is also inconsistent.

Example 2 According to Example 1, a paint is produced, however, the following ingredients are used: 1, Pigments a) Chrome Green loo g b) Titanium dioxide 45 g c) Calcium sulfate loo g 2. Carrier a) Extended with soybean oil Alkyd resin (24% phthalic anhydride) 350 g b) Bensin 235 g 3. Polyvinyl isobutyl ether (5% in xylene) lititanol J60) 1 g after spreading on a test area and Drying gives the same results as in Example 1 and also a uniform coloring is achieved.

Comparative example A paint produced according to Example 2 without the addition of polyvinyl ether resulted in and after spreading on the test area Dry a pooky film surface with blotchy coloring. The color scheme of the film was decidedly dissimilar.

A paint was prepared according to Example 2, but one equivalent amount of polyvinyl ethyl ether used instead of polyvinyl isobutyl ether. It got the same unfavorable results including the uneven Coloring after drying a sample streaked on a test area obtain.

Example 3 According to example 1, a paint is produced under Use of the following ingredients 1. Pigments a) Titanium dioxide 245 g b) Carbon black 5g 2. Carrier a) Oil-extended alkyd resin (24% phthalic anhydride and 65% oil) 35o g b) Gasoline 235 g 3. Polyvinyl tsobutyl ether (5% in xylene), high molecular weight (Oppanol C KV 125) 20 g After drying one coat of paint a smooth, uniformly colored film obtained.

Similar results are obtained if instead of the high molecular weight Polyvinyl isobutyl ether one with a medium molecular weight (Oppanol C KV 115), high molecular weight polyvinyl isopropyl ether or polyvinyl isooctyl ether high molecular weight can be used.

If, on the other hand, polyvene ether is not used, this is done after you have dried it film obtained from a paint on the test area is defective and shows defective ones Spots and uneven coloring.

Example 4 Following the procedure of Example 1, an anesthetic color is obtained manufactured with the following components: t. Pigment.

.) Titanium dioxide 50 g b) Chrome yellow 100 g c) Chrome orange loo g 2nd carrier a) Medium soybean oil modified alkyd resin (24% phthalic anhydride and 57% oil) 255 g b) betaine 170 g c) Dehydrated castor oil 80 g d) Ester gum 80 g 3rd polyvinyl isobutyl ether (5% in xylene) medium molecular weight (Oppanol C KV 115) 0.5 g. After drying a spread on the mixing surface was a smooth, evenly colored film is obtained.

Conversely, if no polyvinyl ether additive is used or equivalents are used Quantities of low or high polyvinyl ethyl ether or polyvinyl methyl ether Molecular weight used in place of the polyvinyl isobutyl ether is the dried one Film on the test area irregular and unsatisfactory.

In addition, the coloration is uneven.

Example 5 According to Example 1, a paint becomes the following Composition prepared: 1. Pigments a) Titanium dioxide 200 g b) Ru # 2g c) Chrome green 48 g 2nd carrier a) Oil extension tea alkyd resin (24% phthalic anhydride and 65% oil) 350 g b) gasoline 235 g 3. polyvinyl isobutyl ether (5% in xylene) (Oppanol C KV 115) 2 g after drying a paint on a test area a smooth, evenly colored film is obtained.

If, on the other hand, polyvinyl ether is not used or is not used in the paint instead of polyvinyl isobutyl ether, a polyvinyl ethyl ether is used the paint film obtained after drying is irregular and unsatisfactory, example 6 According to Example 1, a paint with the following composition is produced: 1. Pigment a) Titanium dioxide 240 g b) Phthalocyanine blue lo g 2. Carrier a) @offloröl-modified Polyurethane varnish (50% solids in gasoline) (Spenkel F-78-50) 585 g 3. Polyvinyl isobutyl ether (5% in xylene) (Oppanol 0 KV 125) 0.5 g After drying a paint on the A smooth, uniform film was obtained on the test surface. The coloring was even.

A similar result is obtained using an equivalent amount High molecular weight polyvinyl isoootyl ether instead of polyvinyl isobutyl ether obtain.

If, on the other hand, polyvinyl ether is not used in the paint, then After a coat of paint has dried, an irregular and faulty film received.

The color is uneven.

Example 7 According to Example 1, a paint of the following Composition prepared: 1. Pigments a) Titanium dioxide 240 g b) Lamp black lo g 2. Carrier a) Oil-extended alkyd resin (24% phthalic anhydride and 65% oil) 285 g b) Modified polyurethane varnish (Spenkel F-78-50) 300 g 3. Polyvinyl isobutyl ether (5% in xylene) (Lutanol J 60) After drying one coat of paint becomes smoother Evenly colored film was obtained on the test area.

If, on the other hand, no polyvinyl ether is used, it becomes irregular defective film obtained after drying a paint. The coloring of the film is uneven.

Example 8 According to Example 7, using a lettering color made of the following ingredients: 1. Pigments Chromium Green 150 g b) Titanium dioxide 100 g 2. Carrier a) Epoxy, modified with soybean oil fatty acids, 50% solids in Bensin (Epi-Tex 120) 585 g 3. Polyvinyl isobutyl ether (5% in xylene) (Oppanol C K 115) 3 g The paint obtained becomes more even, smoother, drier Film painted onto the test area, Example 9 According to Example 1, a paint is made made with the following ingredients: 1. Pigments a) Phthalocyanine Blue 5 g b) titanium dioxide 245 g 2. carrier a; Epoxy resin (Epotuf 650-75) 290 g b) Cellosolve-acet-xylene 95 g cl polyamide hardener (Versamid 115) 200 g 3. Polyvinyl isobutyl ether (5% in xylene) (Oppanol C KV 115) 0.5 g Example 10 Den in the following Table I listed polymerizable organic compositions 0.05%, 0.5% and 2.5% of a solution of 5% polyvingyl isobutyl ether in gasoline were added.

For comparison, the measurements were in each case without the addition of polyvinyl ether scheduled. The samples provided with the addition and the comparative samples were shaken thoroughly for better mixing and to imitate the processes during Spreading a color. The masses obtained were poured over metal sheets were held in a vertical position until the film formed.

TABLE I Mass. Trade Name Diluent A. Oil Modified Spenkel F-7s-50; aliphatic polyurethane paint (Spencer Kellogg) heavy fuel B. Vinyltoluene - Styresol 4257 aliphatic alkyd resin (Reichhold Chemicals) Heavy gasoline C. Hot-curing Beckasol 12-620; Alkyd urea varnish (Reichhold Chemicals) and Beckamine 3520 (R. C. I.) toluene D. Moisture-curing polyurethane 13-330 polyurethane (Reichhold Chemicals) toluene E. butadiene styrene resin, Pliolite S-5A 'with chlorinated paraf- (Goodyear Co.) and finen modified Chlorowax 40 and 70 (Diamond Alkali Co.) Toluene F. Chlorinated Kautsohuk-Parlon S-20 (Hercules resin, with Chlorinated Powder Co.) and chloro-paraffins modified wax 4o (Diamond Alkali Co.) Toluene G. Modified alkyd resin Plaskin PR-203; Pitts- aliphatic burgh Plate Glass Co.) Heavy gasoline H. Epoxy ester Epi-Tex 120; (Jones-Dabney Co.) Toluene I. With dioctyl phthalate Vinylite VAGH; Methyl ethyl plasticized Poly- (Union Carbids Co.) ketone and toluene vinylohlorid J. Aorylatharz (Rohm & Haas Co.) Toluol K. Nitrooellulo.elack 1/2 sec. Nitrocellu- paint dissolving mixture loose, Alkydhars, dioctyl phthalate (2t1s1) The dry films of the comparative samples and the samples with additive were compared and found in each case that the compounds provided with additives are much smoother, smoother and without surface defects was. The comparison samples showed irregularities, surface stripes, Flow lines, holes or craters, patterned signs of wear and tear and not torn Blow.

Example 11 The procedure was as in Example 10, but as polymerizable Mass of a polyester catalytically polymerized with methyl ethyl ketone peroxide (2%) (R.C.I.33-031) used and the obtained leave with and without the addition of polyvinyl ether by pouring into the lid of a paint can to form disks about 7.5 cm in diameter and about 6.3 mm thick. After drying, the comparative sample showed one pronounced ribbed surface with many large and deep holes of around 0.8 up to 1.5 mm in diameter. The edge of the pane is cleaved from many bubbles that sioh apparently form on drying. In contrast, the masses with the addition of polyvinyl ether dried to even, smooth and uniform discs which, notably, have no surface defects had.

Di @@@@ ispiele explain that the inventive use of the polyvinyl ether promotes the evenness of the coloring and d5 the surfaces Improved from films made with added polyvinyl ether. @@ e uneven Dyeing at Übergügen @ is known as "swimming" and occurs everywhere when the coating compositions contain more of a pigment or a mixture of pigments than a colorant is used. Attempts have been made to overcome this disadvantage. by using certain Avoid silicono. However, the use of such elements has the disadvantage 1, Adhesion becomes poor, craters appear, and coatings fail to tack will.

The progress achieved according to the invention is shown in Table II specified values explained in more detail, with Ioo @ portions of the paint base of Example 1 Init 0.2 G of the polyvinyl ethers mentioned as a 5% solution in xytol mixed and spread on a closed surface.

TABLE II formulation polyvinyl ether molecular weight alkyl group result Trade name 1 Lutanol J-30 low isobutyl swimming, better than comparative sample 2 "J-60 medium" no swimming 3 Oppanol C KV-115 medium to high "" 4 "C KV-125 high "" "5" A-25 low ethyl pronounced swimming 6 "A-50 high" "" 7 " M-40 high methyl "" 8 * xylene alone - - "" * comparison From the Values in the table; EI clearly shows that when using polyvinyl ethers with a molecular weight of at least 100,000 obtain a uniform color that does not swim. In contrast, there is a pronounced unevenness the color, if no polyvinyl ether or one with too low a molecular weight is used. Similarly poor results are obtained when straight chain Polyvinyl alkyl ethers were used.

The medium molecular weight polyvinyl ethers listed in Table II weren such. having a molecular weight of at least about 150,000 to 200,000, while with the high molecular weight polyvinyl ethers the molecular weight of about 500 Ranged from 1,000 to 600,000.

Claims (12)

Claims 1. Form and coating compositions based on curable organic polymers, characterized by a content of a small amount of a polyvinyl ether with repeating structural units of the formula where R is a branched hydrocarbon chain with a molecular weight of at least 100,000. 2. mold and coating compositions according to claim 1, characterized in that g e k e n n -z It is noted that the curable organic polymer is a polyurethane resin. 3. mold and coating compositions according to claim 1, characterized in that g e k e n n z It is noted that the curable organic polymer is a polyester resin. 4. molding and coating compositions according to claim 1, characterized in that g e k e n n z It is noted that the curable organic polymer is an alkyd resin. 5. molding and coating compositions according to claim 1, characterized in that g e k e n n -z e i h e t that the curable organic polymer Butadiene polymer is 6. molding and coating compositions according to claim 1, characterized in that g e k e n n -z e i c h n e t that the curable organic polymer is a cellulose resin, 7. Shape and Covering compositions according to claims 1-6, characterized in that they are the Polyvinyl ether a polyvinyl alkyl ether with branched alkyl groups of 3 to 10 Is carbon atoms. 8. molding and coating compositions according to claim 7, characterized in that g e k e n -2 e 1 c h n e t that the polyvinyl ether is polyvinyl isobutyl ether. 9, molding and coating compositions according to claim 7, characterized in that g e k e n n -z It is clear that the polyvinyl ether is polytinyl isopropyl ether. 10. Form and coating compositions according to Anspruct 7, thereby g e k e n n -z e i c h e t that the polyvinyl ether is polyvinyl iso- @ octyl ether. 11. Molding and coating compositions according to Claiml @ lo, thereby g e k e n n -2 e i c h n e t that the amount of polyvinyl ether 0.00025 to 0.5 wt .-%, based on the total weight. 12. molding and coating compositions according to claim 11, characterized in that g e -k e n it is noted that the amount of polyvinyl ether is about 0.0025 to 0.1% by weight, based on your total weight, cheating.