DK147107B - SODPIGMENT PREPARATION AND PROCEDURE FOR ITS PREPARATION - Google Patents

Description

(19) DENMARK

φ (12) PUBLICATION MANUAL od 147107 B

DIRECTORATE OF

THE PATENT AND TRADEMARKET SYSTEM

(21) Patent Application No. 4750/77 (51) Int.CI.3: C 09 C 1/56 (22) Filing Date: 26 Oct 1977 (41) Alm. available: 28 Apr 1978 (44) Submitted: 09 Apr 1984 (86) International Application No: - (30) Priority: 27 Oct 1976 DE 2648639 (71) Applicant: 'DEGUSSA AKTIENGESELLSCHAFT; 6000 Frankfurt 1, DE.

(72) Inventor: Lothar * Rothbuehr; DE, Hans' Schaefer; DE, Edith 'Elsenmenger; DE, Lutz 'Dworowy; THE,

Guenther 'Fuchs; THE.

(74) Plenipotentiary: International Patent Bureau_ (54) Soot pigment preparation and process for its preparation

The invention relates to a soot pigment composition for use in lacquers or inks and its manufacture.

Soot is widely used in the manufacture of black lacquers and inks. In soot, as is well known, there is a correlation between the intensity of the black color and the size of the primary grains. Deep black soot has a large specific surface area and a small size for the primary grains. Soot with a less black color intensity, on the other hand, has a larger primary grain size and a relatively less specific surface area. Soot with large surface area is difficult to disperse in binder systems in general. Therefore, considerable dispersion work must be used to distribute the soot in intermediates for lacquers and inks to obtain the optimum properties of these soot qualities in the dispersion.

Known apparatus used to distribute pigments in thin liquid binder systems are e.g. ball mills or bead mills. Known apparatus used for distributing pigments in viscous binder systems are e.g. discontinuous or continuous kneading machines. However, these appliances have a large energy consumption. Furthermore, there are a number of binders which cannot withstand the high temperature, such as e.g. is developed by kneading, which can decompose slowly or explosively.

In order to remedy these disadvantages, the so-called "binder" type preparations are prepared. These soot pigment compositions can then simply be added to solvents and introduced into the respective lacquer or printing inks without the use of significant shear forces to produce the desired lacquer or printing inks. In order to obtain a good dispersion of finely divided soot without the use of an excessive amount of binder, the addition of wetting and dispersing agents is sought to improve the dispersibility of the finely divided soot. Particularly important is the use of a dispersant in the processing of nitrocellulose binders, as in this case an explosive disintegration of the nitrocellulose may result from excessive mechanical processing in the incorporation of the soot. The quality of the soot binder composition is often crucial to the nature of the dispersant. It is important to choose a dispersant which, in the final system in which it is to be used, does not produce negative properties or changes.

In known soot pigment compositions, mainly amine-containing compounds such as e.g. benzidine and phenyldiamine as dispersant ·. The dispersants used as dispersants have poor solubility in gasoline and xylene. This means that dots and streaks may appear in the lacquer layers if no further work process for clearance is carried out, for example. by centrifugation. Because of their amine content, their use as pigmentation agents is not without physiological risk.

US Patent No. 1,987,980 discloses soot pigment preparations which, in addition to soot, contain nitrocellulose, resin, plasticizer and a copper oleate dispersant. However, the use of this dispersant does not produce as high a gloss as desired.

It has now surprisingly been found that by using alkaline earth octoates, especially barium octate, as dispersants in soot pigment preparations of the kind known from the United States patent, it is possible to achieve a product improvement, since varnish produced from such concentrates gives coatings with improved gloss properties as demonstrated below.

The invention accordingly relates to a soot pigment composition containing a content of nitrocellulose, plasticizer, dispersant and optionally an alkyd resin compatible with nitrocellulose, characterized in that it consists of 10 - 50% by weight of soot 5 - 30% by weight plasticizes 0 - 30 wt% nitrocellulose compatible alkyd resin 30 - 80 wt% nitrocellulose wool 0.5 - 2.5 wt% alkaline earth octoate, preferably barium octoate.

The soot pigment composition of the invention preferably contains from 12 to 25% by weight of soot and 1% of barium octate as dispersant.

The invention further relates to a process for the preparation of the soot pigment compositions which are characterized by mixing nitrocellulose (wetted with isopropanol), plasticizer, alkaline earth octoate and any alkyd resin while adding a solvent to obtain a plastic mass, pre-mixed mass, the product thus produced is rolled out to obtain a further distribution of the soot and to evaporate the solvent and finally the product breaks into chips (chips).

Softeners are plasticizers or plasticizers. These materials are added to a plastic mass (a synthetic resin or natural product) to improve its softness, flexibility, stretchability and workability.

Plasticizers are especially important for varnish and plastic products.

For example, they must provide organic film-forming substances (resins, caustic, butyl rubber, linseed oil, lacquers, polyvinyl products, acetylcellulose, nitrocellulose and the like) adhesiveness, suppleness, elasticity and toughness and by plasticity improve flexibility. Unlike solvents, the plasticizers have a high boiling point (above 250 ° C). They do not evaporate after application, but unite with the film formers to physically uniform masses.

4 147107

An ideal plasticizer should be odorless, colorless, light, cold and heat resistant, non-hygroscopic, water resistant, non-health-damaging, only slightly flammable and as volatile as possible. Furthermore, it must react neutrally, be able to be ground with pigments on rollers and have a good solubility against resins and cellulose esters.

The preferred plasticizer groups are phthalates (phthalic acid esters), such as e.g. dioctyl phthalate (DOP), dimethyl phthalate, diisophthalate, dibutyl phthalate, optionally combined with diethyl phthalate, dicyclohexyl phthalate, high molecular weight esters of decyl and tridecylalbate, butyl ester, butyl ester, butyl ester, butyl ester, butyl ester, butyl ester. , diethylhexyl phthalate, dimethyl glycol phthalate, dicapryl phthalate and the like, phosphates such as tricresyl phosphate and triphenyl phosphate; triphenyl phosphate combined with tricresyl phosphate and phthalates, diphenylcresyl phosphate, diphenyl-2-ethylhexyl phosphate, tri (2-ethylhexy1) phosphate, tris (butoxyethyl) phosphate, acyclic (aliphatic) dicarboxylic acids, e.g. esters of adipic acid and sebacic acid (dioctyl adipate, diacetyl adipate, dicapryl adipate, dibutyl sebacate, 2-ethylhexyl sebacate, dioctyl sebacate, dihexyl sebacate, butylbenzyl sebacate etc.), such as fatty acid esters butyl oleate or butyl stearate, methyl and butyl esters of acetylated ricinol fatty acid, fatty acid glycol ester, triethylene glycol di- (2-ethylbutyrate), and esters of epoxy stearic acid, citric acid esters acetyltributyl citrate and acetyltriethyl citrate, as well as polymeric plasticizers, are e.g. polyesters of dicarboxylic acids (adipic, sebacic or phthalic acid) and glycols (propylene glycol, 2-ethyl-1,3-hexane-diol and the like), partly modified by monofunctional acids or alcohols; molecular weight approx. 850-8000. Also epoxidized oils and butadiene acrylonitrile copolymers may be considered polymeric plasticizers.

Nitrocellulose compatible alkyd resins are found in the ricin alkyd group and in the group of non-drying alkyd resins. Yellow resistance is important to avoid affecting the tint of the soot pigment.

As the solvent, esters or ketones such as e.g. ethyl acetate, butyl acetate, acetone and methyl ethyl ketone. They can be used in amounts of from 0.5 to 10% by weight based on the total amount of the individual components.

5 147107

Both soot furnace as well as gas soda and flame sod can be used as soot. Particularly advantageous is oxidized soot based on flame or gas soda. These are characterized by a volatile content of more than 3%.

The soot pigment composition of the invention is readily soluble in gasoline or xylene. It can be easily dispersed without the formation of dots. The processability of rolls is good. As mentioned, the lacquers made with the soot pigment compositions exhibit a significantly better gloss as well as a greater densitometer value than the known soot-containing lacquers. The soot pigment preparations in question can contain a large proportion of soot, which allows for less transport costs.

The present soot pigment composition can be used as a pigment pigment. For this application, 0.01-20% by weight of soot pigment composition is added to the varnish system.

Liquid and coating agents include liquid pastes or fabric mixtures which, by various methods, such as coating or spraying, apply to the surfaces to be coated and, by physical or chemical drying, provide an adhesive coating to the substrate.

Coating agents are systems composed of various components: 1. Non-volatile constituents a) Film Former> b) Resin Binder c) Softener ^ d) Pigments e) Excipients 2. Volatile constituents a) Solvent b) Precipitating solvent

For further description of the term varnish, see Ullmann's Encyclopedia of the Technique Chemie, Volume 11, page 279 et seq., 3rd edition. .

The present pigment composition may also be used as a pigmentation agent for inks such as e.g. newspaper printing ink, letter printing and excitation ink, illustration and autotype ink, embellished ink, heat-curing ink, or moisture and steam-curing ink used in the various printing methods, such as high pressure, rubber pressure, surface pressure, gravure pressure and the like.

6 147107

Newspaper inks generally consist of soot (flame soda and gas soda) and a resin, bitumen and binders containing turpentine oil and mineral oil (compositional varnish, resin varnish). As a result of the rapid printing process, they are very thin-flowing and they are anchored to the suction-proof newsprint by absorption and curing.

Letterpress and accent colors are used for printing books, posters, business papers, etc. They contain better soot and binders based on linseed oil and resin varnish, and they are dried oxidatively and by penetration into the printed material (the paper).

Among the best inks include illustration and autotypy inks made using gas ood and with linseed oil varnish or other drying oil as a binder.

Since black inks, depending on the quality of the soot or binder, often have a brownish tone, "beautify" them by adding solutions of blue and violet color bases or of Milo-rib blue and Reflective blue.

For heat curing inks used as binder e.g. nitrocellulose (at relatively low viscosity) or cyclized rubber in diethylene glycol monobutyl ether, dibutyl phthalate and blown castor oil. The binder is of such a character that it does not dry on the rollers of the printing machine, but immediately becomes solid at 150 ° C during evaporation and polymerization as the printed material passes at high speed the drying zone connected to the printing machine.

Moisture and vapor-curing inks are characterized in that, as a binder, e.g. contains rosin or a substance dissolved in dibutylene glycol or diethylene glycol or the like, i.e. in a water-miscible solvent. The binder does not dry at normal temperature and it is rubbed off with color pigments such as soot or the like on a three-roll chair. An ink thus produced produces pressures which, upon exposure to moisture, steam or the like, immediately secrete the binder in a dry state on the paper.

The high-pressure methods also include rubber printing that has been obtained. great importance for printing packaging for food and beverages. In addition to paper, non-absorbent supports such as cellophane, metal foil and the like are printed.

For further description of the concept of inks, see Ullmann's Encyclopedia of Technology Chemie, Volume 8, 3rd Edition, page 316 et seq. (graphic colors).

7 147107

The invention is further illustrated by the following examples.

Example 1

A soot pigment composition was prepared having the following dry matter content composition:

R

Basic recipe: 14.0 wt.% Soot FW2 14.0 wt.% Dibutyl phthalate 16.0 wt.% Nitrocellulose compatible alkyd resin 55.25 wt.% Nitrocellulose wool E 620 (solid) 0.75 wt.% Dispersant.

The soot FW 2 used is a finely divided gas sod having a particle size (determined electron microscopically) of 13 πιμ, a BET surface of 460 m / g, a volatiles content (determined at 940 ° C) of 15% and a pH of 3.

The nitrocellulose is used moistened with alcohol (isopropanol).

To prepare the soot pigment preparation, the ingredients are mixed with nitrocellulose (moistened with isopropanol), dibutyl phthalate, alkyd resin and an addition of approx. 10% ethyl acetate as the solvent and the dispersant in a kneader for a plastic mass.

In this pre-mixed mass, the soot was inhaled. Then, the product thus produced is taken from the kneader as chunks and rolled between two rollers to further disperse the soot and to evaporate the solvent to form a thin layer which breaks into so-called chips.

The tested product was tested in a nitrocellulose lacquer's 10 parts by weight of soot pigment preparation 90 parts by weight of nitrocellulose paint.

The nitrocellulose lacquer was constructed as follows: 8 147107

Nitrocellulose varnish: 18.0 parts by weight of nitrocellulose wool E-330 (wetted with isopropanol) 13.0 parts by weight of castor alkyd resin "Alphthalate" 143/5 60%

4.0 parts by weight of malinate resin "Alresat" 313 / C

2.5 parts by weight dioctyl phthalate 5.0 parts by weight carbamic acid resin "Uresin-B" 5.0 parts by weight melamine resin "Maprenal" NP / 55% 8.0 parts by weight xylene 8.0 parts by weight butano1 5.0 parts by weight ethylglycol acetate 14.0 parts by weight butyl acetate 16.5 parts by weight methylisobutyl ketone 1.0% by weight silicone oil 100% by weight

The varnish is made by spraying layers with a thickness of approx. 60 μ and the intensity of the black color were assessed with a den-cytometer, the gloss was assessed with a measuring device for this purpose, and the surface purity (spots) was assessed visually. A large densitometer value denotes a lacquer with a high and a lower densitometer value than lacquer with a lesser degree of blackness. A high gloss number denotes a high gloss for the surface of the varnish. In the visual surface assessment, the surface with the fewest dots is assigned the value 1 and surfaces with several dots are assigned higher numerical values.

Degree of blackness

Dispersant (Densitometer - Gloss Number Surface _ Index) _% _ (dots)

Benzidine 2.82 100 4 p-Phenylenediamine 2.81 103 4

Copper Naphthenate 2.81 105 3

Copper oleate 2.80 105 2

Copper octate 2.81 110 2

Barium octate 2.84 115 1

Taking all test results into consideration, barium octate proves to be particularly advantageous.

Processing of the soot pigment compositions in question is easier than when diamines are present as dispersants. Furthermore, the soot concentrates in question dissolve significantly faster.

9 147107

Example 2

Soot concentration Weight% 22 25 28 32 36

Parvesod FW 2 Weight% 22.0 25.0 28.0 32.0 36.0

Dibutyl Phthalate Weight% 10.0 9.0 9.0 8.0 6.0

Alkyd Resin Weight% 13.0 12.0 12.0 11.0 11.0

Nitrocellulose E 620% by weight 53.9 52.7 49.5 47.2 45.0

Barium octate Weight% 1.2 1.3 1.5 1.8 2.0

The final product is prepared as described in Example 1 and broken into chips. These chips, which are in the form of small plates, are incorporated into the nitrocellulose varnish described in Example 1.

With this varnish, coatings are produced both by spraying of tinplate and by immersion. The degree of blackness is measured with a densitometer.

Black Beauty Grad

Densitometer value 22% soot FW 2 2.81 2.79 25% soot FW 2 2.78 2.76 28% soot FW 2 2.77 2.76 32% soot FW 2 2.74 2.75 36% soot FW 2 2.71 2.71

The results show that even at high concentrations of the extremely finely divided soot FW 2, which has a large surface, easily dispersible soot-binder compositions appear, which give deep black lacquer surfaces. Even in these highly concentrated mixtures, barium octate is a suitable dispersant.

Soot concentrates with a high soot content do not have the insignificant advantage that they enable a significantly more economical transport.