DE2600431A1 - Delustering agent for varnishes - prepd. by hydrogenating ethylene and carbon monoxide polyketones and freeze drying polyalcohol prod. solns. - Google Patents

Abstract

Delustering agent for varnishes consists of a finely-divided modified polyolefin wax. The wax has mol. wt. 1000-8000 and contains 1.5-15 OH gps./1000 mol. wt. units. Delustering agents can be used for all lacquers contg. organic liqs. or water as solvents or dispersants. The delustering agents disperse well on stirring and neither agglomerate, nor settle, even in combination with pigments and fillers. In an example, delustering agent was prepd. by hydrogenating a copolymer of 80% C2H4 and 20% CO; dissolving polyalcohol prod. in p-xylene, cooling to 12 degrees C and sublimating xylene at 4 Torr.

Description

2G00431

BASF Aktiengeselischart

Our sign O ₀ Z ₀ 31 771 Dd / MK 67OO Ludwigshafen, January 6th, 1976

Matting agent for paints

The invention relates to a varnish matting agent based on a finely divided polyolefin wax containing hydroxyl groups, and a process for its production by hydrogenating a copolymer of ethylene and carbon monoxide and subsequent freeze-drying of a solution of the hydrogenation product β

Paint coatings are usually clear and high-gloss "For some applications _s Z _n B ₀ in the furniture industry, but matt surfaces" desirable It is known that one can achieve a matting effect when finely divided the paint polyolefin zusetzte Thus, "B _o in is DT-PS 1 059 134 describes the use of low molecular weight, finely crystalline polyethylene for matting the varnish. »The fine particle size required to achieve the desired matting effect is achieved by stirring a solution of polyethylene in aromatic hydrocarbons into the varnish and thereby the wax in microcrystalline form fails "The disadvantage of this process is that large quantities of highly flammable, aromatic liquids have to be handled, which are introduced into the paint and lead to undesirable environmental pollution when they evaporate."

Therefore, it has also tried to add polyolefin the paint system in ground form "Thus, Z ₀ B ₀ after the DT-PS 1,246,916 polypropylene in a finely divided solid form incorporated into paints ₀ can order however not sufficiently uniform distribution reach, so that only coatings with a coarse surface structure are obtained from the paints. Furthermore, the pulverized polyolefins tend to form irreversible clumps during storage ₀

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o.z. 31 771

The object of the present invention is to show matting agents which can be produced in a reproducible manner in a simple manner and do not have the disadvantages outlined above.

This object can surprisingly be achieved in that one modified polyolefin waxes as matting agents used which have a molecular weight between I ₀ and 8 OOO "000 and 1 = 000 molecular weight units is about 1.5 to 15 hydroxyl groups,"

Such Lackmattierungsmittel preferably prepared by a copolymer of 95 to 60 percent by "$ ethylene and 5 to 40 GeWo ^ monoxide hydrogenated under conventional conditions and then a 50 to 90 wt _o - # - solution of hydrogenation product in an organic solvent frozen between -10 and + 8O ⁰ C and sublimed in a "vacuum, freeze-dried wirdo

Copolymers of ethylene and carbon monoxide, so-called polyketones, can be known, under conditions of high-pressure polymerization of the monomers to produce., Depending on the choice of the process conditions, molecular weights can be between 200 and 20O0OOO and adjust the CO concentrations between 0.1 and 50%, such as zobo in the chapter "Olefin-Carbonmonoxide Copolymers" in "Encyclopedia of Polymer Science and Technology", Vol ₀ 9, Interscience 1968, pages 397 to 402, is described , preferably 10 to 30 $ Gewo carbon monoxide having a molecular weight of 1,000 to 80OOO, preferably 2 to 6 _{0 0} 000 000 "

Such polyketones can now be hydrogenated to polyalcohols under customary conditions (s _o z ₀ Bo V ₀ Morishima, "European Polymer Journal" 1973, pages 669 to 675). It is preferred to work in solvents such as alcohols or aromatic hydrocarbons; Usual hydrogenation catalysts are used, such as Raney nickel or palladium sponge, the temperature can be from 110 to 180 ^° C. »

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The polyalcohol can be freed from the solvent by distillation and then converted into finely divided form by grinding. Can be the hydrogenation product, however, stir directly as a solution in toluene in the paint ,, In a preferred embodiment of the invention, the modified polyolefin wax, however, from a 30 to 90 wt _o - # - obtained solution of the polyalcohol by freeze drying = Suitable solvents are those in question that solidify between -10 and + 80 ° C and sublime in a vacuum, e.g. benzene, cyclohexane, para-xylene, naphthalene, tert-butanol, 2,2-dimethylpropanol, pentamethylethanol, neopentyl alcohol, cyclohexanol, butanediol 1,4, 1-menthol, phenol, para-cresol, meta-cresol, promoform, ethylene bromide, trichloroethanol, trichloro-tert-butanol, ^ -chlorotoluene, 1,4-dichlorobenzene, 1,4-dioxane, ethylenediamine, pyrimidine , Pyrazole, pyrazine or piperazine »Preferably tert" -butanol or para-xylene are used, the solution that is expediently used during the hydrogenation "

Freeze-drying gives a particularly finely divided powder whose mean particle size is between 5 and 10 μm and in which more than 99 % of the particles have a diameter between 0.1 and 20 μm, preferably between 1 and 15 μm.

The matting agents according to the invention can be in the form of their Powder can be stirred directly into the lacquer; however, as is customary with other matting agents, they can also be used together with Solvents, plasticizers or resin solutions are mixed with the paints »

The matting agents are used depending on the desired matting effect generally in amounts from 1 to 20, preferably from 2 to 10% by weight, based on the solids content of the paint, added »They can also be mixed with other substances commonly used in the paint industry, such as polyolefin waxes, can be used with natural waxes, as well as with esters or amides of long-chain carboxylic acids »Combinations with inorganic matting agents such as finely dispersed silicas or silicates.

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The matting agents are suitable for all conventional lacquers which generally organic liquids, such as Z ₀ as aliphatic or aromatic hydrocarbons, alcohols, esters, ethers, ketones or even water containing as a solvent or dispersant.

The paints for which the invention Matting agents are advantageously used, the usual, such as amino resins, alkyd resins, acrylate resins, Polyurethanes, nitrocellulose or vinyl chloride copolymers, and mixtures of the binders mentioned. The matting agents can be used for clear coats as well as for pigmented ones Paints in question, the paints may contain other additives and auxiliaries customary in the paint industry, such as leveling agents, dyes, silicone oils, surfactants, deaerating agents, thixotropic agents, catalysts and activators. The lacquers are processed in the usual way.

Compared to known matting agents, those according to the invention are distinguished in particular, that the matting agent without additional measures by simply stirring into a state of optimal dispersion passes and neither itself nor in combination with pigments and fillers to agglomeration or tends to settle.

The parts and percentages given in the examples are based on weight.

Examples

A Manufacture of matting agents

1. A copolymer of 80% ethylene and 20% carbon monoxide having a molecular weight of 2,500 is hydrogenated in 50 # strength solution in ethanol at 130 ⁰ C under 200 bar hydrogen pressure over Raney nickel. After removing the catalyst with a magnetic filter, ethanol is distilled off and the polyalcohol is dissolved in paraxylene 70% -lg by heating

Solution will then

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8O ⁰ C dissolved. The solution is then ^{cooled to 12 0} C,

whereby it solidifies. The xylene is at one pressure sublimed from <■ 4 Torr. It will be a loose powder with it an average particle diameter of 5 to 10 µm.

2. Example 1 is repeated, but after removing the catalyst and the solvent of the polyalcohol by cooling with liquid nitrogen in a vibrating mill with iron balls Grind for 4 hours. A powder with an average particle size of 5 to 10 μm is obtained.

3. (Preferred method)

Example 1 is repeated, except that the hydrogenation is carried out in 50% strength solution in terto-butanol The solution obtained is filtered, cooled to 25 ° C. and in vacuo at < 20 Torr dried »A loose powder with an average particle diameter of 5 to 10 to receive.

B paint formulations

4. 2 parts of the polyalcohols prepared according to Example 2 are dissolved in 20 parts of white spirit ^{at 80 to 100 ° C.} The hot solution is added to the following paint formulation while stirring slowly:

100 parts of an air drying alkyd resin, 60 S? In

White spirit,
30 parts white spirit,

2 parts of a hardener based on a Co / Pb / Mn phthalate, 0.5 part of an anti-skinning agent.

5. (Preferred embodiment)

2 parts of the finely divided polyalcohols prepared according to Example 1 are mixed with a slowly rotating stirrer entered in the following paint formulation:

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Parts of a urea / formaldehyde condensate etherified with butanol, 60 / S-ig in butanol, 38 parts of ethanol / Ä "thy lglycol 2:? 1, 0.6 part silicone oil, 1 pound in toluene,

12 parts of a solution of hydrogen chloride in ethanol as acid curing catalyst "

(Preferred embodiment)

Parts of the finely divided polyalcohol produced according to Example 3 are entered in the following paint formulation:

12 parts nitrocellulose / butanol 2: 1,

20 parts of a urea / formaldehyde P etherified with butanol räk on de ns at e s,

30 parts of ethyl glycol,

24 parts of toluene,

50 parts of butyl acetate,
2 parts of phosphoric acid, 10 # in ethyl alcohol "

ORIGINAL INSPECTED

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Claims (1)

ο.ζ. 31 771 Claims Matting agent for paints based on a finely divided, modified polyolefin wax, characterized in that that the polyolefin wax has a molecular weight between 1,000 and 8,000 and in the molecule to 1,000 molecular weight units contains about 1.5 to 15 hydroxyl groups » Lacquer matting agent according to claim 1, characterized in that the mean particle size of the modified polyolefin wax is 5 to 10 µm and more than 99 % of the particles have a diameter between 0.1 and 20 µm. A method for producing the Lackmattierungsmittels according to claim 1, characterized in that a copolymer of 95 to 60 percent by "# ethylene and 5 to HO Gew.iS carbon monoxide is hydrogenated under conventional conditions and then a 30 to 90 wt _o -% - solution of the hydrogenation product in an organic solvent that ^{solidifies between -10 and +80 0} C and sublimed in a vacuum, freeze-dried » BASF Aktiengesellschaft _OB , G1NAU INSPECTED 709829/0845