JPS6012378B2 - Water-dispersible flake metal pigment composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel flaky metal pigment composition for use in aqueous media, which has significantly improved corrosion resistance, metallic luster, and sharpness in aqueous media.

Flake-like metal pigments, which are manufactured by finely pulverizing metal powder by the Hall method, dry stamp mill method, Hametag method, etc., are made water-dispersible by adding a surfactant and can be used as pigments for various water-based paints or water-based inks. Although these conventional products are used as metal pigments for aqueous media, they not only have insufficient sharpness by themselves, such as exhibiting a muddy color tone when used in coatings, but also gradually degrade in aqueous media. It has a serious drawback in that it generates hydrogen gas in response to water, reducing its metallic luster.

Conventionally, attempts have been made to add various corrosion inhibitors to overcome this drawback, but a fully satisfactory solution has not yet been achieved.

As a result of intensive research to resolve the above-mentioned difficulties in the prior art, the present inventors discovered that dimer acids, which are dimers of unsaturated higher fatty acids (monenoic acid, dienoic acid, and trienoic acid) with a carbon number of 1. The present invention was achieved based on the finding that addition and mixing in a fixed amount is extremely effective in improving the image clarity and corrosion resistance of water-dispersed flaky metal pigments.

Here, any method of adding and mixing dimer acid to the flaky metal pigment can be adopted, such as addition and mixing to conventional products or semi-finished products, but in terms of industrial production, the manufacturing method of the flaky metal pigment It is advantageous to add and mix in the dimer acid at some stage during each step of the dry or wet process known as .

Therefore, the structure and effects of the present invention will be explained in more detail below with reference to typical production examples that are advantageous for industrial production of the composition of the present invention. The most common work steps for dry or wet production of flaky metal pigments are summarized as follows. Dry method 1 Raw metal powder such as atomized powder or shredded foil powder is processed in a pole mill, stamp mill, vibration mill, attritor, etc. in the presence of a grinding aid such as saturated or unsaturated higher fatty acids, and other various additives if necessary. A surfactant is added and mixed to the obtained mixture mainly consisting of flaky metal powder, and then the mixture is divided into dry flaky metal pigment products.

In this case, other additives such as a corrosion inhibitor, a leveling agent, a thickener, a leafing stabilizer, etc. may be further added and kneaded into the mixture after the setsubun. 2. To the mixture obtained by pulverization in the same manner as in 1, various hydrocarbon solvents such as mineral spirit and solvent naphtha are added together with a surfactant.
Alternatively, a medium liquid consisting of another solvent is added to form a metal base, and the mixture is treated in the same manner as in 1 below to obtain a paste-like flake metal pigment product.

The overflow method raw metal powder is crushed in a crusher in the presence of a crushing medium such as a crushing aid, an aliphatic or aromatic hydrocarbon solvent, and other various additives as necessary, and then crushed in the same medium as the crushing medium. The flaky metal powder mixture is taken out of the pulverizer using liquid, separated into streaks under wet conditions, solid-liquid separated using a filter press, etc. to form a filter cake with a solid content of about 70 to 80%, and then mixed with surfactant. At the same time, a liquid medium is added and kneaded to obtain a pasty flake metal pigment product having a desired solids content (usually about 65%).

In addition, in this mud kneading process, depending on the purpose, various additives such as corrosion inhibitors, leveling agents, thickeners, leafing stabilizers, etc. may be added or mixed, or other grades of metal pigments may be added to control color tone. Addition, kneading, etc. are performed. The compositions of the invention are advantageously prepared by adding the dimer acid at any stage during each step of the dry or green process summarized above.

That is, according to the present invention, since dimer acid has a sufficient function as a grinding aid, it can be used as a grinding aid alone or as a grinding aid mixed with conventional aids such as various higher fatty acids. obtain. Alternatively, the raw metal powder may be pulverized using a conventional pulverizing aid, and dimer acid may be added and kneaded to the pulverized product, or a predetermined amount of dimer acid may be added in portions to both the pulverizing process and the kneading process. good. On the other hand, the dimer acid used in the present invention is a dimer of unsaturated higher fatty acids (monoenoic acid, dinic acid, trienoic acid) with a carbon number of 1 a, as described above, but usually the dimer acid as the main component is In addition to acids, they can be used in the form of fatty acid mixtures containing trimer and monomer acids. Typical examples include dimer acids derived from oleic acid and linoleic acid having 18 carbon atoms, which have a dimer acid content of 7.
Versadim is commercially available as a 0-98% fatty acid mixture.
Japan Mineral Mills Co., Ltd. (Enbor; Emery Co., Ltd., etc.). Further, the amount of dimer acid in the composition of the present invention is selected within the range of 0.81/true specific gravity of metal to 81/true specific gravity of metal (parts by weight) based on 100 (parts by weight) of metal particles. Below this lower limit, the effect of improving image clarity and corrosion resistance will be insufficient; on the other hand, if above the upper limit, the strength of the paint film will be inhibited. The surfactant is not particularly limited as long as it can make the product water-dispersible, and may be appropriately selected from various known surfactants.

Or, its effective addition amount is usually 100 parts by weight of the metal particles (81 parts by weight) to 81/true specific gravity of the metal (
(parts by weight). Some preferred surfactants in the present invention are illustrated and summarized as follows: Anionic surfactants: fatty acid soap, long mirror alcohol sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene alkyl phenyl ether sulfate ester salt, polyoxyethylene nysooctyl phenyl ether sulfonate, alkylbenzene sulfonate, polyoxyethylene alkyl phenyl ether phosphate ester salt , polyoxyethylene alkyl ether phosphate ester salt, nonionic surfactant: polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkylamide, polyoxyethylene fatty acid ester, polyoxy Ethylene sorbitan fatty acid ester and solpitan fatty acid ester. The composition of the present invention does not interfere with the coexistence of any substances included in the subordinate flaky metal pigment composition, such as grinding aids, grinding media, liquid media, and various additives. However, some of these and other conditions advantageous in carrying out the present invention are summarized and exemplified below.

1 Atomized powder and shredded foil powder made of raw metal powder AI, Cu, Ni, Zn, Fe and their alloys such as Cu-Zn alloy and stainless steel.

2 Grinding media or medium liquid Other conventional grinding media excluding aliphatic hydrocarbon solvents such as mineral spirits, aromatic hydrocarbon solvents such as solvent naphtha, and water.

3 Grinding aids Saturated or unsaturated higher fatty acids having 8 or more carbon atoms, their esters, amides, alcohols, etc. More specifically, the following can be exemplified: oleic acid, stearic acid,
Behenic acid, palmitic acid, myristic acid, lauric acid, linoleic acid, isostearic acid; stearic acid butyl ester, oleic acid methyl ester, stearic acid amide, oleic acid amide, stearyl alcohol and oleyl alcohol O4 Other additives penzotriazole, etc. Corrosion inhibitors: Whitening agents such as silicone and fluorosurfactants; Thickeners such as montmorillonite and leafing stabilizers.

Although the present invention has been described above by illustrating typical embodiments and aspects, the present invention is not limited to these in any way, and the present invention is not limited to these. As the activator and various additives, other desired additives may be selected and used as desired.

The remarkable effects of the present invention can be more clearly understood from the following description of non-limiting examples and comparative examples.

Example 1 Atomized aluminum powder (A manufactured by Toyo Aluminum Co., Ltd.)
AIOI) 1.0k9 Mineral Spirit 1.25 Dimer Acid (Empollo Pine, manufactured by Emery Co., Ltd.) 50ml were placed in a ball mill with a diameter of 50mm and pulverized for 2 hours and 30 minutes.

After grinding, the slurry was treated with dimer acid for 4 nights/100 minutes.
It was washed out with 8 sleeves of mineral spirits and passed through a 325 mesh screen. Thereafter, solid-liquid separation was performed using a pan filter to obtain a filter cake having a metal content of 8% by weight. This filter cake has a hidden power of 94
It contained about 1.5 parts by weight of dimer acid per 10 parts by weight of metal. Using this filter cake, the following composition was kneaded for 1 hour to obtain a water-dispersible aluminum paste pigment. Aluminum pigment filter cake 1250 polyoxyethylene alkyl phenol ether (Emulgen 906 manufactured by Kao Soap Co., Ltd.)
30 Tapolyoxyethylene alkyl ether (
Kao Soap Co., Ltd. Emulgen 408)
60 evening mineral spirit 1
98ta total 153
Comparative example 1 Atomized aluminum powder (AAIOI manufactured by Toyo Aluminum Co., Ltd.)
1.0k9 mineral spirit
1.25 Oleic acid 5
09 was placed in a pole mill with a diameter of 50 mm and ground for 2 hours and 3 minutes.

After the grinding was completed, the slurry was washed with 8 sleeves of mineral spirit containing oleic acid 4 nights/100 minutes and passed through a 325 mesh screen. Thereafter, solid-liquid separation was performed using a pan filter to obtain a filter cake having a metal content of 8% by weight. This filter cake is Fujibei Power 9
300 parts per 10 parts by weight of metal, approximately 1. It contained phantom parts by weight of oleic acid. Using this filter cake, the following composition was mixed for 1 hour to obtain a water-dispersible aluminum paste pigment. An aluminum base was obtained using the same machine as in Example 1. Aluminum pigment filter cake 1250 polyoxyethylene alkyl phenol ether (Emalgen 906 manufactured by Kao Soap Co., Ltd.)
30 Tapolyoxyethylene alkyl ether (
Kao Soap Co., Ltd. Emulgen 4 female) 6
0ta Mineral Spirit 198
Total: 1,538 days Example 2: Commercially available bronze powder (hidden strength: 3,900 grounds/day) ground in the presence of stearic acid was mixed with the following composition for 1 hour.

Bronze powder (Alcan Metal Powder Co. M-cho 450R
ichC℃ld) 1000 Tadimer acid (Empollo 14 manufactured by Emery) 1 Tapolyoxyethylene sorbitan trioleate (Sorpon T-85 manufactured by Toho Chemical Co.) 12 Ta Comparative Example 2 Commercially available bronze powder ground in the coexistence of stearic acid (Hidden Bay Power 390 reports/night) was drilled for 1 hour with the commissioned composition.

Bronze powder (Alcan Metal Powder Co. M Town 45 plates i
chG℃ld) 1000 taolenic acid 1000% polyoxyethylene sorbitan trioleate (Sorbon T manufactured by Toho Chemical Co., Ltd.)
-85) Comparative Example 3 Using the filter cake used in Example 2, the following composition was kneaded for 1 hour.

Aluminum pigment filter cake 1250 tadimer acid (Versadim 216 manufactured by Japan General Mills Co., Ltd.)
) 350 Sodium dodecylbenzenesulfonate (NOF Newrex R) 300 Mineral Spirits
300ta total
The following tests were conducted on the samples obtained in the Examples and Comparative Examples.

The results are summarized in Table 1. Test 1 A sample metal pigment was dispersed as a metal component in a water/butyl Cellsolp (=1/4) medium 100°C, this dispersion was maintained at 50°C, and the amount of gas generated from the dispersion was measured. did.

The measurement period was one month. Test 2 A water-based metallic paint was prepared with the following composition, and the sharpness of the coating film obtained by doctor-blading the core paint was visually judged.

Further, gas generation from the paint was measured over a period of one month when the paint was maintained at 50°C. The paint after the gas generation test was applied with a doctor blade, and the difference from the painted surface before the test was measured using a color difference meter. Water-soluble acrylic varnish (Arokuton 557N manufactured by Hina Flow Chemical Co., Ltd.)
560 ta water-soluble melamine varnish (Sumimar M-50W manufactured by Sumitomo Ib Gakusha)
150 Taffetalocyanine Blue (Dainippon Ink Co., Ltd. NK
Blue) 32 Yen Distilled Water 90 Yen Sample Metal Pigment (as metal content) 48 Ta Test 3 Sample metal pigments were packed in a tin key and kept in a constant temperature room at 50 CO, and after one month, the presence or absence of aggregation of the samples was examined using a 325 mesh sieve. It was measured with

Table 1

Claims (1)

[Claims] 1 Effective amount of surfactant and metal particles 100 (parts by weight)
1. A water-dispersible flaky metal pigment composition containing dimer acid in a ratio of 0.81/specific gravity of the metal to 81/specific gravity (parts by weight) of the metal.