US 4,750,933 AGrant
Floor Polish Emulsions Based on Ethylene Copolymer
Issue Date:1988-06-14
•1 Claims
Abstract
An aqueous wax dispersion for floor care contains a mixture of an aqueous secondary dispersion of an ethylene copolymer wax, having a specific MFI, and an aqueous primary dispersion together with plasticizers, leveling agents and water, and an ethylene copolymer wax in the form of an aqueous secondary dispersion is used for floor emulsions.
Metadata
Assignee
- BASF Aktiengesellschaft
Inventors
- Franz Brandstetter
- Walter Ziegler
- Wolfram Dietsche
- Stefan Weiss
- Albert Hettche
- Otto Kuehneweg
Application Information
Application Number:US 9145095
Filing Date:1986-10-02
Priority Date:1984-05-30
Art Unit:115
Classifications
IPC:
C09G 108
Field of Search:
10652452510501;515;522;523227;240;241
Patent Drawings
This patent does not have any drawings.
Description
The Examples which follow illustrate the invention. Parts are by weight, unless stated otherwise.
I. Preparation of ethylene copolymer wax
EXAMPLE 1
A mixture of 349 kg/h of ethylene, 10.5 kg/h of acrylic acid and 0.5 kg/h of propionaldehyde was passed continuously, at 35.degree. C., through a 10 l stirred autoclave maintained under 2,300 bar. The temperature in the autoclave reactor was kept at 216.degree. C. by the continuous addition of 202 g of tert.-butylperpivalate per hour (as a rule, in a suitable solvent). When the reaction mixture was let down, the polymer was obtained in an amount of 49 kg/h, corresponding to a conversion of 16.9%, based on the ethylene throughput. It contained 17% by weight of acrylic acid and had a melt flow index MFI 190/2.16 of 220.
Examples 2 to 8 below were carried out as described in Example 1, differing preparation conditions and the product parameters being summarized in Tables 1a and 1b.
The copolymer waxes prepared in Experiments 1 to 8 were emulsified using non-ionic emulsifiers, such as alcohol oxyethylates or alkylphenol oxyethylates, in the presence of an alkali metal hydroxide solution, such as KOH or NaOH, to give highly transparent emulsions, the alkali metal hydroxide solution being used alone or together with ammonia or with amines, such as diethylethanolamine (DEE), dimethylethanolamine, triethanolamine or 2-amino-2-methylpropan-1-ol.
II. Preparation of a secondary dispersion
EXAMPLE 10
To emulsify the wax described in Example 1, 20% by weight of wax, 2.9% by weight of a non-ionic emulsifier (C.sub.13 /C.sub.15 -oxoalcohol with 8 EO (ethylene oxide) units or straight-chain or branched C.sub.9 /C.sub.11 -fatty alcohols with 7 EO units or an alkylphenol oxyethylate with 10 EO units), 1.4% by weight of potassium hydroxide and 74.4% by weight of water were stirred in a closed autoclave at from 150.degree. to 160.degree. C. under from 5 to 6 bar to give a homogeneous melt. In order to obtain a satisfactory speck-free, finely divided emulsion, this temperature was maintained for one hour. The wax emulsion was then cooled rapidly. An optimum method of discharging the emulsion, which was under pressure, was via an intensive cooler. After cooling to room temperature, a very finely divided emulsion was obtained, which could readily be recognized from the blue color of the product discharged.
When diluted 1:400, the resulting emulsion had transparency to light of 77%, measured in a 5 cm cell at 533 nm. The emulsion did not exhibit any creaming even after prolonged storage. Coatings on a glass plate formed speck-free, clear, glossy, very tough, scratch-resistant films at room temperature, as are desirable for the floor polish sector.
Examples 10 to 21 are summarized in Table II.
The emulsions 11-21 were prepared by a method essentially similar to the preparation method (10). In some cases, in contrast to the method described above, the stock emulsion method was employed. In this method, which is used in particular for waxes which are rather difficult to emulsify, emulsification is initially carried out using only from 30 to 60% by weight of the envisaged amount of water. The remaining amount of water is generally forced in only toward the end of the emulsification process.
For the preparation of novel floor polish emulsions for the end user, the wax emulsions described in Table II are preferably mixed with a primary dispersion based on acrylic acid/styrene/acrylate, as described in, for example, European Patent 6547. The mixture is applied onto linoleum or a PVC covering and is dried in the air, and the resulting thin, highly glossy and scratch-resistant film is subjected to the conventional walk-on test.
III. Example of the preparation of a primary dispersion
An emulsion consisting of 250 parts of water, 160 parts of methyl methacrylate, 80 parts of butyl acrylate, 80 parts of ethyl acrylate, 36 parts of styrene, 36 parts of methacrylic acid, 8 parts of N-methylolmethacrylamide, 0.2 part of dodecylmercaptan, 6 parts of Na dodecylsulfate and 70 parts of a 4% strength potassium peroxydisulfate solution was metered, in the course of 2 hours and at 95.degree. C., into a stirred solution consisting of 260 parts of water and 0.4 part of potassium peroxydisulfate. A further 20 parts of peroxydisulfate solution of the above concentration were then added in the course of 1 hour at the same temperature, and stirring was continued for a further 2 hours at 85.degree. C.. The mixture was cooled, after which 10.5 parts of zinc ions (=2.5%) in the form of an ammoniacal zinc acetate solution were added, and the pH was brought to 9 with ammonia.
IV. The general method below is intended to describe the preparation of novel floor polishes from a primary dispersion and a secondary dispersion, but is not intended to restrict the invention
30 parts of the novel secondary wax dispersion described in Examples 10 to 20, 25 parts of a primary dispersion according to Example III, 41 parts of water, 5 parts of methyldiglycol, 0.9 part of tributoxyethyl phosphate, 0.6 part of tributyl phosphate and 1 part of a fluorine-containing surfactant were mixed to give a homogeneous mixture.
V. Testing of performance characteristics
In the general method IV above, instead of using 30 parts of secondary dispersion, the latter is used in each case in an amount corresponding to 7.5 parts of wax (acrylic acid/ethylene wax or comparative wax) in pure form. If necessary, the amount of water to be added is adjusted in order to obtain the same solids content. This ensures that the total mixture always contains the same amount of wax with the same amount of primary dispersion.
The results are summarized in Table III.
The polish mixture is applied onto a standard PVC floor covering with a fine-haired brush. The emulsion forms a glossy, tough polish film at room temperature.
The scratch resistance, toughness and soilability of the film are tested by a practical walk-on test. To do this, 50.times.50 cm hard PVC sheets are coated with the polish emulsion, dried, and placed in a room where they can be walked on very frequently.
After being exposed for 3 weeks, the soilability, formation of heel marks and scratch resistance are assessed. The comparative secondary dispersion used (a dispersion based on a polyethylene oxidation product) is a commercial formulation based on a hard wax which has been used to date in the floor polish sector.
To characterize the film produced on the PVC substrate, the gloss is measured at an angle of 85.degree., and the static friction is measured using a cobbler's apparatus conventionally used in the floor polish sector. The characteristics in the walk-on test, the gloss and static friction of the film could not be related to one another directly. ln contrast, there was a clearly recognizable relationship between the nature of the wax and the result of the walk-on test. (E denotes ethylene and AA denotes acrylic acid).
The most advantageous mixtures, which received the figure of merit 1 in the walk-on test, were those of Examples 26, 27 and 30; these consist of the wax from Example 2 with 21.5% by weight of AA (MFI at 190.degree. C./2.16 kp =125), the wax from Example 3 with 23.9% by weight of AA (MFI at 190.degree. C./2.16 kp =32), and the wax from Example 4 with 20.6% by weight of AA (MFI at 190.degree. C./2.16 =3.5).
Examples 22, 24 and 28 in the walk-on test received the figure of merit 2. These are waxes according to Example 1 (17% of AA; MFI at 190.degree. C./2.16 kp =220) and according to Example 4 (20.6% of AA; MFI at 190.degree. C./2.16 kp =3.5). Comparative Example 34 containing a polyethylene oxidation product and, for the composition investigated, the wax examples 1, 2, 4, 6 and 8, are rated with figure of merit 3 in the walk-on test.
The comparisons, a wax according to German LaidOpen Application DOS No. 3,044,519 and a commercial lowviscosity E-AA wax, for which it was impossible to determine an MFI under the stated conditions, received figures of merit 4 and 5.
The fact that ethylene/acrylic acid copolymer waxes having a high AA content and a high molecular weight (low MFI) can be used for the preparation of outstanding floor polish emulsions must be regarded as surprising and unforeseeable. These products are furthermore substantially superior to the polyethylene oxidation products having a high molecular weight, as is shown by the comparative example. The Table shows that the waxes with an MFI of from 5 to 500, measured at 190.degree. C. and under 2.16 kp, are preferred.
Claims
We claim:
1. A wax dispersion for floor polishes, which contains a mixture of, based on the total weight of the wax dispersion, (a) from 5 to 20% by weight of an aqeuous secondary wax dispersion of from 5 to 40% by weight, based on the secondary wax dispersion, of an ethylene copolymer wax consisting of from 15 to 24% by weight of acrylic acid or methacrylic acid or mixture of these, and from 85 to 76% by weight of ethylene and having an MFI, measured at 190.degree. C. and under 2.16 kp, of from 5 to 500, from 1 to 5% by weight, based on the secondary wax dispersion, of an alkali metal hydroxide, ammonia, an alkanolamine or a dialkylalkanolamine or a mixture of these, optionally with I to 5% by weight of a non-ionic or anionic emulsifier, and water to make up to 100% by weight, based on the weight of the secondary wax dispersion, (b) from 20 to 50% by weight of a conventional aqueous film-forming primary dispersion for floor polishes, which has a solids content of from 20 to 70% by weight and consists of a water-insoluble copolymer of from 70 to 90% by weight of one or more alkyl acrylates or methacrylates, where alkyl comprises 1 to 4 carbon atoms, from 5 to 20% by weight of styrene, from 8 to 12% by weight of acrylic acid or methacrylic acid or a mixture of these, from 0.5 to 2.5% by weight of N-methylolacrylamide or N-methylolmethacrylamide, and from 0.4 to 3% by weight of zinc ions, (c) from 1 to 8% by weight of at least one plasticizer selected from the group consisting of methyldiglycol and tributoxyethyl phosphate, (d) from 0.2-2% by weight of a fluorine-containing surfactant as a leveling agent, and (e) from 73.8 to 20% by weight of water.
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| US4417035 | 1983-11-01 | Oeder et al. | |
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