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INVENTION
Patent of the Russian Federation RU2152971
GOLD-CONTAINING CERAMIC PAINT FOR DECORATION OF PORCELAIN,
CERAMICS AND CRYSTAL
Name of the applicant: Griazev Vladimir Fedotovich; Anatoly Lebedev; Lebedeva Olga Mikhailovna; Albrecht Vladimir Genrikhovich; Timofeev Nikolay Ivanovich
The name of the inventor: Gryazev VF; Lebedev AN; Lebedeva OM; Albrekht V.G .; Timofeev N.I.
The name of the patent holder: Griazev Vladimir Fedotovich; Anatoly Lebedev; Lebedeva Olga Mikhailovna; Albrecht Vladimir Genrikhovich; Timofeev Nikolay Ivanovich
Address for correspondence: 620219, Yekaterinburg, ul. Bardeen 28, House of Engineering, k.232, Ekaterinburg Union of Scientific and Engineering Organizations, President of the Union Lebedev A.N.
Date of commencement of the patent: 1998.11.30
A gold-containing ceramic paint for decorating porcelain, ceramics and crystal containing gold, bismuth, chromium and rhodium rubbers, rosin and nitrobenzene is described, characterized in that it additionally contains chlorobenzene at the following component ratio, by weight : gold powder (organic gold compound , Containing 50% of metallic gold ) - 16-32, 6% solution of bismuth resinate - 6-12, 3.3% solution of chromium resinate - 1.7-3.5, 5% solution of rhodium rubber - 0,35-0,70 , rosin - 5-30 , nitrobenzene - 28-32 , chlorobenzene - 15-20 . The technical result is the prevention of the deposition of metallic gold from the paint and the elimination of its thickening during use and storage.
DESCRIPTION OF THE INVENTION
The invention relates to the field of ceramic paints intended for the decoration of glazed porcelain, earthenware, glass and crystal products. Decoration serves to decorate items to revive their surface with a well-chosen range of colors, to emphasize or complement the characteristics and features.
Ceramic paints are subject to certain requirements. They should not form a deposit during long-term storage, spread out when applying the pattern to glazed and glassware, should be sufficiently viscous and at the same time freely descend from the brush or pen, forming a flat surface.
The paint applied to the products should dry quickly enough, and the film formed during firing should be stable in the oxidizing atmosphere of the furnace, and the gloss corresponding to the standard should not be erased during operation. In addition, the paint must comply with the approved sanitary and hygienic standards.
The composition is known ( see the author's certificate of the USSR No. 15778094, MKI S 03 C 17/44, C 09 D 121/00, 5/28, public 15.07.90, BI N 26 ) of ceramic paint for decorative finishing of porcelain and Ceramics, including bismuth resinate, titanium resinate and cobalt resinate, chromite resinate, nitrobenzene, turpentine and chloroform at the following component ratio, wt. Hours :
- Bismuth Resin - 5.5-8.3
- Titanium rubber - 3,1-6,3
- Cobalt rubber - 8,8-11,4
- Chromium Resin - 14,8-20,8
- Turpentine - 27,3-50,1
- Nitrobenzene 16.9-24.1
- Chloroform - 0,8-1,8
This paint composition allows the firing of decorative products at 1020-1050 ° C , the paint is stable during storage, provides rapid drying of products and the production of turquoise coatings.
However, this composition after firing the decorated items does not give a mirror-like golden surface, which greatly improves the artistic perception of the product and is appreciated by the buyer.
Such a surface is provided with ceramic dyes containing gold in the form of a chemical compound. Known is the gold-containing composition of the ceramic paint, which is closest to the claimed invention and is chosen as a prototype.
This paint composition was developed at the Dulevsky paint factory and is now widely used in the domestic porcelain industry ( TU 17 RSFSR 0303830-014-91 ). The composition of the paint is described in detail in the literature ( see Martynov, MA, Vizir, VA, "Technology of the production of ceramic paints." Moscow, Gostekhizdat, 1966. p. 126-133, or Vizir, VA, Martynov, MA "Ceramic Paint", Kiev, publishing house "Engineering", 1964, p. 128, or Tumanov SG "Liquid gold preparation for glass and porcelain", "Glass and ceramics" No. 6, 1961 ).
The technology of preparation and the composition of the ceramic paint are described in detail in the above-mentioned article by SG Tumanov. In the journal "Glass and Ceramics", on the basis of which we give below the description of the PROTOTYPE. Gold-containing ceramic paint in the porcelain industry is usually called a liquid gold preparation, and then we accept this terminology.
The content of metallic gold in the Dulevese preparation usually ranges from 10-12% to 15% . The preparation of the preparation is rather complicated.
The composition of the components of the dual preparation is the following, g :
- Gold resinate powder (organic gold compound containing 50% metallic Au ) - 240
- 6% solution of bismuth resinate - 90%
- 3.3% chromium resinate solution - 25.25
- 5% Rhodium Resinate solution - 5.25
"Ether" is added in the amount necessary to prepare 1000 g of a 12% gold preparation. At the same time, the composition of "Ether" is the following, mass% :
- Rosin - 25,73
- Nitrobenzene 2.57
- Turpentine - 27,44
- 2% bismuth resinate solution - 3.09
- Chloroform - 41.17
Rubber gold is a complex organic compound of gold . To obtain it, the required amount of ammonium chloride-ammonium salt is dissolved in ethyl alcohol, and then the calculated amount of sulfur balsam is poured, followed by the precipitation of a hardly soluble precipitate of the organic compound of gold of the type C 10 H 16 S · AuCl 3 .
6% solution of bismuth resinate is prepared as follows. The calculated amount of basic Bi 3 (OH) 6 (NO 3 ) 3 bismuth nitrate is added to the molten rosin. Further, the required amount of nitrobenzene and turpentine are added to the melt of rosin. The solution is allowed to settle, after which it is filtered through a silk sieve, and after 10-15 days, it is decanted into a special container.
A 3.3% chromium resinate solution is prepared as follows. The calculated amount of chromium chloride is introduced into molten rosin, then the required amount of turpentine and nitrobenzene are added. Then the solution is cooled, filtered, left to stand for 10-15 days and decanted into a special container.
A 5% solution of rhodium rhodium is prepared as follows. The calculated amount of rhodium trichloride ( RhCl 3 4H 2 O ) is dissolved in ethyl alcohol and then, after aging, the necessary amount of sulfur balsam is added. The resulting precipitate of the organic rhodium compound is washed with ethyl alcohol and dried at a temperature of 35-40 ° C. Further, the dried precipitate of resinate is dissolved in nitrobenzene and the desired solution is obtained.
The known (Doulevsky) preparation of liquid gold has uniform spreadability, well "holds" the outline of the pattern and easily drains from the brush onto the glazed surface of the product. After firing products with a gold preparation applied on them, an even mirror-shiny gold film is obtained, which has sufficient wear resistance during operation.
The shades and strength of the gold film depend on the gold content of the preparation and on the additives in minor amounts of other metals-bismuth, chromium and rhodium, which play the role of fluxes and brighteners.
However, a significant drawback of the known liquid gold preparation is its tendency to thicken and precipitate metallic gold , progressing over time and seriously complicating its use on porcelain conveyors. This is due to the following reasons.
The presence of chloroform in the formulation causes the reduction of metallic gold from its organic compound and the gradual precipitation from the solution in the form of a heavy fine precipitate. Redox deposition of gold is somewhat slowed by the presence of nitrobenzene in the preparation, which acts as a soft oxidizing agent.
The presence of turpentine in a certain proportion with chloroform determines the viscosity of the preparation, which is important when applying the pattern to the surface of the product.
Chloroform also causes rapid drying of the pattern applied to the product, but during storage of the preparation or when using porcelain plant on the conveyor, chloroform gradually evaporates, and this leads to excessive thickening of the preparation and the impossibility of its further use. Thickening of the drug is further aggravated by the fact that the turpentine, remaining during the evaporation of chloroform, is not able to retain any significant amount of gold resinate in the solution and, thus, the gold from the homogeneous solution turns into a precipitate.
All this requires frequent and thorough mixing of the drug during its use or dilution in order to maintain in a sufficiently fluid state, which creates significant technological difficulties in porcelain factories when painting products.
In addition, the Dulev liquid gold preparation has a strong, stable odor due to its specific composition.
Thus, in the composition of the known (Dulyovo) liquid gold preparation, a technical contradiction is revealed between its features and the effect achieved. In this case, you can not be sure of obtaining a drug that meets all the requirements presented to it. Moreover, with the monopoly existing in our country for the production of a liquid gold preparation at the Dulevsky paint and varnish factory, the preparation must be ordered in advance, transported by the special communication service to porcelain factories scattered throughout the country, and stored before use.
These negative features of the known preparation forced the authors of the invention to critically approach the formulation and technology of its manufacture, to search for the causes of the deterioration of the quality of the known preparation.
The object of the invention is to eliminate the deposition of metallic gold from the preparation, thicken it and improve the organoleptic properties.
This technical result is achieved by introducing chlorobenzene into the liquid gold preparation containing rubites of gold , rhodium, bismuth and chromium, rosin and nitrobenzene at the following component ratio, by weight :
Powder of gold resinate (organic gold compound, containing 50% of metallic gold ) - 16-32
6% solution of bismuth resinate - 6-12
3,3% solution of chromium resinate - 1,7-3,5
5% rhodium resinate solution - 0,35-0,7
Rosin - 5-30
Nitrobenzene 28-32
Chlorobenzene 15-20
In addition, aromatizing additives, for example vanillin, are added to the finished liquid gold preparation to improve its organoleptic properties.
Characteristics and methods of preparation of gold resinate, 6% bismuth resinate solution, 3.3% chromium resinate solution, 5% rhodium rhodium rubber are given above.
Comparison of the compositions of the prototype preparation and the claimed liquid gold preparation revealed that the latter has the following differences:
- There is no so-called "ether", although such ether components as rosin and nitrobenzene occur, but in other quantities;
- There is no turpentine and chloroform, but chlorobenzene is used instead, but its quantity does not correspond to the total amount of chloroform and turpentine.
Thus, the claimed technical solution corresponds to the criterion of the invention "novelty". It also corresponds to the criterion of "inventive level".
From the state of the art (see the above analysis of known technical solutions), it follows that none of them provide a technical result: to prevent the deposition of metallic gold from the solution and to eliminate thickening of the preparation during its use and storage. Thanks to the composition of the preparation proposed by the inventors, such a result is achieved.
Chlorobenzene dissolves gold resinate well and does not cause side-effects of oxidation-reduction transformations of the elements of the preparation. The use of chlorobenzene in the claimed percentage allows us to exclude from the process the so-called "Ether", which is a multicomponent mixture (rosin solution in a mixture of nitrobenzene, chloroform and turpentine) and simplify the procedure for dissolving gold resinate. This eliminates the need to prioritize the addition of various solvents to gold and monitor the redox balance of the system.
In addition, the less volatility and high solubility of chlorobenzene, and the lack of turpentine, significantly reduce the risk of thickening of the drug. The presence of chlorobenzene in the preparation preserves its homogeneity in time, and a change in its content from maximum to minimum leads only to a corresponding change in the spreadability and drying time on the surface of the product.
To improve the organoleptic properties of the drug, the inventors introduced into its composition an insignificant amount of vanillin. Testing of the drug at one of the porcelain factories showed that the introduction of vanillin brought the odor of the drug to the smell of bird cherry unexpectedly, as the artists working on the conveyer positively responded.
It follows from the above that between the essential features of the invention and the result achieved, there is a new cause-and-effect relationship.
The claimed invention is industrially applicable. At present, the site has been designed, the necessary equipment for the industrial production of the preparation described in the proposed invention has been assembled. It should be noted that chlorobenzene, which is offered by the inventors as a solvent, is an available raw material for the production of the preparation.
An example of preparation of a liquid gold preparation according to the invention. A preparation with a metallic gold content of 12% was prepared.
In the beginning, the necessary components for the preparation of the preparation were made: sulfur balsam, chlorine-ammonium salt of gold , resinates of gold , bismuth, chromium and rhodium.
Sulfur balm. In a glass flask with a capacity of 15 liters, 10-12 liters of freshly dispensed turpentine were poured and 1-1.2 kg of ground sulfur cuttings were poured there. The solution was warmed to 160 ° C and held for 4 hours . The liquid boiled and the distillation process proceeded. The distillation process was terminated when 22.9% by weight of distillate was collected. The yield of the product was about 75%.
Chlor-ammonium salt of gold . 120 g of metallic gold was loaded into the flask with "royal vodka". The flask was heated to complete dissolution of gold , and then nitric acid was distilled off by adding hydrochloric acid in small portions. The solution was allowed to cool and a stoichiometric amount of ammonium chloride was added. The resulting solution was evaporated to dryness in a water bath to give a white powder of the chloroammonium salt.
Rubber gold . The obtained ammonium chloride-ammonium salt was loaded into a container with ethyl alcohol at the rate of 5 g of alcohol per 1 g of gold . After dissolving the salt in alcohol impregnated sulphide balsam (at the rate of 3.5 g of balsam per 1 g of gold ). The process of formation of an insoluble precipitate, gold resinate, proceeded with heating for 1.5 hours . After the formation of resinate, 3-4 liters of alcohol were additionally introduced and mixed well. The mixtures were allowed to stand and the solution was decanted and the remaining gold precipitate cake was washed on the filter with hot water and alcohol and then dried. The content of metallic gold in rubber was 50% .
Bismuth resinate. Rosin ( 1 kg ) was melted and heated to 210-220 ° C. Then 220 g of basic bismuth nitrate were added in portions to the melt of rosin. After that, the heating was stopped and the required amount of nitrobenzene was introduced into the molten rosin with stirring. The solution was allowed to settle, after which it was filtered through a silk sieve. The solution was again allowed to settle and decanted into a special container. Thus, a 6% bismuth resinate solution was obtained.
Rubber chromium. Rosin ( 1 kg ) was melted at 170 -180 ° C. 300 g of chromium chloride were introduced into the melt and the temperature was raised to 210-220 ° C. The heating was then stopped and, with stirring, the necessary amount of nitrobenzene was poured in small portions. After cooling, the solution was filtered, decanted and decanted into a special container. Thus, a 3.3% strength solution of chromium resinate was obtained.
Rubber rhodium. 200 g of rhodium trichloride were added with 2-3 liters of ethyl alcohol, after a day the solution was decanted and 1100 g of sulphurous balsam were added to it. Rhodium resinate precipitation was carried out in an oven at 55-60 ° C for 3-4 days . The rhodium rubid precipitate was washed on the filter with ethyl alcohol and then dried at a temperature of 35-40 ° C. After that, the dried Rhodium Resinate was dissolved in a double (by weight) amount of nitrobenzene. From the indicated sample of rhodium trichloride, about 1200 g of a 5% rhodium rhodium solution were obtained.
PREPARATION OF THE PREPARATION . To prepare 1 kg of a 12% gold preparation, 240 g of a 50% gold powder was taken and, with stirring, it was dissolved in 3000 ml of distilled chlorobenzene. The resulting solution was allowed to settle for 5-6 days, and then gently decanted it from a gel-like precipitate. Then, the gold content of the solution was determined and 300 g of nitrobenzene ( 30% by weight of the preparation) were charged, then excess chlorobenzene was distilled off in vacuo to about 17% of the weight of the preparation.
90 g of a 6% bismuth resinate solution ( 9% by weight of the preparation) were added successively to the resulting concentrate, 26.3 g of a 3.3% solution of resinate chromium ( 2.63% by weight of the preparation) 5.2 g of 5% ( 0.52% by weight of the preparation) and 170 g ( 17% by weight of the formulation) of rosin, after which the mixture was mixed until a homogeneous solution was obtained.
The resulting solution was allowed to stand for 24 hours and filtered through a silk or kapron filter until complete absence of suspended particles. In the finished product, the gold content was determined, an aromatic vanillin additive was added to it, and the preparation was then poured into glass sealed cans of orange glass.
The preparation thus obtained does not thicken during storage and use, does not form a deposit of metallic gold , has a pleasant smell and corresponds to all technical requirements for ceramics and approved sanitary and hygienic standards.
CLAIM
- Gold-containing ceramic paint for the decoration of porcelain, ceramics and crystal, containing resinates of gold , bismuth, chromium and rhodium, rosin and nitrobenzene, characterized in that it additionally contains chlorobenzene at the following ratio of components, mass% :
Powder of gold resinate (organic gold compound, containing 50% of metallic gold ) - 16 - 32
6% solution of bismuth resinate - 6 - 12
3,3% solution of chromium resinate - 1,7 - 3,5
5% Rhodium Resinate solution - 0.35-0.70
Rosin - 5 - 30
Nitrobenzene - 28 - 32
Chlorobenzene 15-20
- The gold-containing ceramic paint according to claim 1 , characterized in that it further comprises synthetic flavoring additives.
print version
Date of publication 16.11.2006гг
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