GB1593763A - Treatment of metal surfaces - Google Patents
Treatment of metal surfaces Download PDFInfo
- Publication number
- GB1593763A GB1593763A GB3475/77A GB347577A GB1593763A GB 1593763 A GB1593763 A GB 1593763A GB 3475/77 A GB3475/77 A GB 3475/77A GB 347577 A GB347577 A GB 347577A GB 1593763 A GB1593763 A GB 1593763A
- Authority
- GB
- United Kingdom
- Prior art keywords
- weight
- parts
- stain
- solvent
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 5
- 239000002184 metal Substances 0.000 title claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 25
- 239000000975 dye Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002798 polar solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 8
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 8
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical class C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- -1 glycol ethers Chemical class 0.000 claims description 4
- 150000002462 imidazolines Chemical class 0.000 claims description 4
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 claims description 4
- 108700004121 sarkosyl Proteins 0.000 claims description 4
- 229940016590 sarkosyl Drugs 0.000 claims description 4
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 claims description 4
- 239000011877 solvent mixture Substances 0.000 claims description 4
- POAOYUHQDCAZBD-IDEBNGHGSA-N 2-butoxyethanol Chemical group [13CH3][13CH2][13CH2][13CH2]O[13CH2][13CH2]O POAOYUHQDCAZBD-IDEBNGHGSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 claims description 2
- DIOYAVUHUXAUPX-KHPPLWFESA-N Oleoyl sarcosine Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-KHPPLWFESA-N 0.000 claims description 2
- 108010077895 Sarcosine Proteins 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- YCUVUDODLRLVIC-UHFFFAOYSA-N Sudan black B Chemical group C1=CC(=C23)NC(C)(C)NC2=CC=CC3=C1N=NC(C1=CC=CC=C11)=CC=C1N=NC1=CC=CC=C1 YCUVUDODLRLVIC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229940043230 sarcosine Drugs 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0083—Solutions of dyes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/84—Dyeing
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
(54) TREATMENT OF METAL SURFACES
(71) We, PYRENE CHEMICAL SERVICES
LIMITED, a British Company, of Ridgeway,
Iver, Buckinghamshire, SLO 9JJ, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- There is a major demand in industry for a method of sealing heavy phosphate coatings and applying a uniform black finish. Paint coatings are not satisfactory for the application as they tend to cause too great a dimensional build-up, particularly on close tolerance components such as threaded fasteners. Known alternative methods involve protracted processing sequences.For instance it is known to apply a water black stain in the following sequence ( I ) phosphate; (2) rinse; (3) rinse; (4) aqueous stain (5) dry; (6) oil; and (7) drain.
Water-based black stains in common use are based on mixtures of water-soluble black dyes and chromic acid or chromates. Suitable chromate-containing materials are becoming increasingly unacceptable owing to the health and environmental problems associated with hexavelant chromium.
Instead of using aqueous stains spirit black stains can be applied. However they are usually based on ethanol and/or propanol and thus constitute a significant fire hazard.
Also it is necessary to dry the surface before the application of the stain and so this makes the processing sequence even longer. Attempts to avoid this additional drying step by use of a dewatering composition containing the stain are unsatisfactory since it has not proved practicable to devise such a composition that provides a sufficiently dense colour.
A process is described in French Patent
Specification No. 1,260,026 that is intended to permit the replacement of the previous drying, staining, drying and oiling steps by a single treatment but this process does not seem to have been satisfactory. It comprises the application to the rinsed surface of a composition comprising water immiscible solvents such as petrol ethers, a resin soluble in the solvents, a plasticiser for the resin, pigments such as titanium dioxide, and polar hydrophobic products capable of dewatering the surface.
A dewatering stain according to the invention comprises a solution of a nitrogencontaining dewatering surface active agent, a black dye and an air curable resin all dissolved in a mixture of a volatile hydrocarbon solvent and a volatile water miscible polar organic solvent, the hydrocarbon and polar organic solvents being miscible and each having a flash point above 32"C.
A process according to the invention for treating a metal workpiece comprises contacting the workpiece with a phosphating composition, rinsing the phosphated surface at least once, coating the rinsed surface with a black finish by treating it with a stain of the invention, and drying the stain and curing the resin. The drying and curing can often be achieved in a single step by forced drying, or by leaving the workpiece in air.
Thus the stain of the invention in one step displaces water from the treated surface, applies a uniform black colour and a protective layer. Thus it replaces three steps in the conventional water black stain process and four steps in the conventional spirit black stain process by a single application and also can avoid many of the disadvantages incurred when handling conventional water stains and spirit stains.
The preferred hydrocarbon solvent for use in the invention is white spirit, but any aliphatic hydrocarbon which will volatilise in drying can be used. Aromatic hydrocarbons are less suitable owing to toxicity problems, but a minor proportion of chlorinated hydrocarbons such as 1,1, 1-trichloroethane can be included in the composition.
The polar solvent should also be such that it will volatilise during drying of the coating.
Thc two solvents should be miscible i.e. the novel stain is of one phase only. The organic polar solvent should also be miscible with water. It may be, for example, a ketone or alcohol miscible with both water and the hydrocarbon solvent, but preferably it is selected from glycol ethers, ketone alcohols and glycols. Particularly suitable polar solvents are 2-butoxyethanol (butyl Cellosolve) and 4-hydroxy-4-methylpentanone (diacetone alcohol). Cellosolve is a trade mark. We find that best results are achieved when both these named solvents are present.
Both types of solvent used in the novel stain should have a flash point exceeding 32"C, for safety and other practical considerations.
The resin used should be one that dissolves in the solvent mixture but which on drying cures in air to form the desired protective film. This curing generally involves polymerisation and preferably the polymerisation occurs at ambient temperatures or only slightly elevated temperatures, e.g. below 150"C. Preferred resins are urethane resins.
The dyes must also dissolve into the solvent mixture and preferably are diazo dyes since we have found that many diazos are capable of giving a denser colour than other dyes.
The nitrogen containing surface active agent must be one that will replace water on the treated surface and suitable surfactants for this purpose are known. It should also leave an adsorbed corrosion inhibiting film.
Preferred surfactants are selected from ethoxylateda amines, ethoxylated diamines, imidazoline derivatives and sarcosine derivatives. The resin, surfactant and dye components should all be soluble in the hydrocarbon solvent.
In the stain of the invention, the preferred amounts of the various constituents are as follows: 670 to 884, preferably 700 to 813, parts by weight of hydrocarbon solvent; 10 to
100, preferably 32 to 78, parts by weight of polar solvent; 100 to 200, preferably 130 to
175, parts by weight of resin: I to 20, preferably 4 to 16, parts by weight of surface active agent; and 5 to 40, preferably 20 to 25, parts by weight of black dye, all per 1000 parts by weight of stain.
The following Example illustrates the invention.
Example
A composition was made up from 4 parts by weight of an oleyl sarcosine surfactant, 2 parts by weight of an ethoxylated diamine surfactant, 300 parts by weight of a 50% solution of a urethane resin in white spirit, 30 parts by weight of ablack diazo dye, 50 parts by weight of 4-hydroxy-4-methylpentanone, 4 parts by weight of 2-butoxy ethanol and 610 parts by weight of white spirit with a flash point of 47"C. The sarcosine surfactant is 'Sarkosyl" 0 supplied by Ciba Geigy
Limited. The diamine surfactant is "Ethoduomeen" T/13 supplied by Akzo Chemie. The urethane resin solution is "Unithane" 640w supplied by Cray Valley Products and the dye is Ceres Black BN supplied by Bayer.
"Sarkosyl", "Ethoduomeen" and "Unithane" are trade marks.
Steel panels were phosphated to give a heavy zinc phosphate coating in accordance with British Standard 3189 1973 Type 1B.
After phosphating the panels were rinsed with water and dipped without immediate drying in the above composition. On draining and drying at 120"C for 10 minutes a uniform black finish was obtained which withstood 48 hours exposure to the ASTM
B117 salt spray test.
WHAT WE CLAIM IS: 1. A stain comprising a nitrogen-containing dewatering surface active agent, a black dye and an air curable resin all dissolved in a mixture of a volatile hydrocarbon solvent and a volatile water miscible polar organic solvent and in which the volatile hydrocarbon solvent and the volatile polar organic solvent are miscible and each has a flash point above 32"C.
2. A stain according to claim 1 in which the dye is a diazo dye.
3. A stain according to claim 1 or claim 2 in which the resin is a urethane resin.
4. A stain according to any preceding claim in which the polar solvent is selected from 2-butoxyethanol and 4-hydroxy-4-methylpentanone.
5. A stain according to any preceding claim in which the hydrocarbon solvent comprises white spirit.
6. A stain according to any preceding claim in which the surfactant is selected from ethoxylated amines, ethoxylated diamines, imidazoline derivatives and sarcosine derivatives.
7. A stain according to any preceding claim comprising, per 1000 parts by weight, from 670 to 884 part by weight of hydrocarbon solvent, 10 to 100 parts by weight of polar solvent, 100 to 200 parts by weight of resin, I to 20 parts by weight of surface active agent and 5 to 40 parts by weight of dye.
8. A stain according to any preceding claim substantially as herein described with reference to the Example.
9. A process for treating a metal workpiece comprising contacting the workpiece with a phosphating composition, rinsing the phosphated surface at least once, coating the rinsed surface with a stain according to any preceding claim, and drying the stain and curing the resin.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (10)
1. A stain comprising a nitrogen-containing dewatering surface active agent, a black dye and an air curable resin all dissolved in a mixture of a volatile hydrocarbon solvent and a volatile water miscible polar organic solvent and in which the volatile hydrocarbon solvent and the volatile polar organic solvent are miscible and each has a flash point above 32"C.
2. A stain according to claim 1 in which the dye is a diazo dye.
3. A stain according to claim 1 or claim 2 in which the resin is a urethane resin.
4. A stain according to any preceding claim in which the polar solvent is selected from 2-butoxyethanol and 4-hydroxy-4-methylpentanone.
5. A stain according to any preceding claim in which the hydrocarbon solvent comprises white spirit.
6. A stain according to any preceding claim in which the surfactant is selected from ethoxylated amines, ethoxylated diamines, imidazoline derivatives and sarcosine derivatives.
7. A stain according to any preceding claim comprising, per 1000 parts by weight, from 670 to 884 part by weight of hydrocarbon solvent, 10 to 100 parts by weight of polar solvent, 100 to 200 parts by weight of resin, I to 20 parts by weight of surface active agent and 5 to 40 parts by weight of dye.
8. A stain according to any preceding claim substantially as herein described with reference to the Example.
9. A process for treating a metal workpiece comprising contacting the workpiece with a phosphating composition, rinsing the phosphated surface at least once, coating the rinsed surface with a stain according to any preceding claim, and drying the stain and curing the resin.
10. A metal workpiece stained by a
process according to claim 9.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3475/77A GB1593763A (en) | 1977-01-28 | 1977-01-28 | Treatment of metal surfaces |
| FR7800648A FR2378828A1 (en) | 1977-01-28 | 1978-01-11 | BLACK COLORING COMPOSITION AND ITS APPLICATION TO THE TREATMENT OF METAL PARTS |
| DE19782801589 DE2801589A1 (en) | 1977-01-28 | 1978-01-14 | METHOD AND MEANS FOR SEALING AND COLORING PHOSPHATE LAYERS |
| JP53008178A JPS6043918B2 (en) | 1977-01-28 | 1978-01-27 | Black finishing composition for chemically treated metal surfaces |
| SE7801051A SE7801051L (en) | 1977-01-28 | 1978-01-27 | PROCEDURE AND MEASURES FOR SEALING AND FARMING OF PHOSPHATE LAYERS |
| IT19695/78A IT1092365B (en) | 1977-01-28 | 1978-01-27 | METAL SURFACE TREATMENT |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3475/77A GB1593763A (en) | 1977-01-28 | 1977-01-28 | Treatment of metal surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1593763A true GB1593763A (en) | 1981-07-22 |
Family
ID=9759043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB3475/77A Expired GB1593763A (en) | 1977-01-28 | 1977-01-28 | Treatment of metal surfaces |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS6043918B2 (en) |
| DE (1) | DE2801589A1 (en) |
| FR (1) | FR2378828A1 (en) |
| GB (1) | GB1593763A (en) |
| IT (1) | IT1092365B (en) |
| SE (1) | SE7801051L (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487869A (en) * | 1983-09-23 | 1984-12-11 | Inmont Corporation | Super jet black coatings |
| FR2615870B1 (en) * | 1987-05-25 | 1992-12-31 | Dbb Ste Civile Rech | PROCESS FOR THE COLORING OF ZINC-PLATED, ZINC-PLATED AND ALLOYED SURFACES THEREOF |
| JPH046327A (en) * | 1990-04-24 | 1992-01-10 | Matsushita Electric Works Ltd | Floor heating controller |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE729723C (en) * | 1939-06-06 | 1942-12-22 | Metallgesellschaft Ag | Black for post-treatment of phosphate surface layers |
-
1977
- 1977-01-28 GB GB3475/77A patent/GB1593763A/en not_active Expired
-
1978
- 1978-01-11 FR FR7800648A patent/FR2378828A1/en active Granted
- 1978-01-14 DE DE19782801589 patent/DE2801589A1/en not_active Withdrawn
- 1978-01-27 JP JP53008178A patent/JPS6043918B2/en not_active Expired
- 1978-01-27 IT IT19695/78A patent/IT1092365B/en active
- 1978-01-27 SE SE7801051A patent/SE7801051L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IT7819695A0 (en) | 1978-01-27 |
| JPS6043918B2 (en) | 1985-10-01 |
| IT1092365B (en) | 1985-07-12 |
| FR2378828A1 (en) | 1978-08-25 |
| SE7801051L (en) | 1978-07-29 |
| FR2378828B1 (en) | 1981-01-23 |
| JPS5395840A (en) | 1978-08-22 |
| DE2801589A1 (en) | 1978-08-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |