EP0348291A1 - Perfectionnements aux procédés d'émaillage sur métaux, notamment sur tôle d'acier, et aux compositions d'émaillage - Google Patents
Perfectionnements aux procédés d'émaillage sur métaux, notamment sur tôle d'acier, et aux compositions d'émaillage Download PDFInfo
- Publication number
- EP0348291A1 EP0348291A1 EP89401726A EP89401726A EP0348291A1 EP 0348291 A1 EP0348291 A1 EP 0348291A1 EP 89401726 A EP89401726 A EP 89401726A EP 89401726 A EP89401726 A EP 89401726A EP 0348291 A1 EP0348291 A1 EP 0348291A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- enamelling
- composition
- article
- layer
- product
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 10
- 239000010959 steel Substances 0.000 title claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 9
- 239000002184 metal Substances 0.000 title claims abstract description 9
- 150000002739 metals Chemical class 0.000 title claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 210000003298 dental enamel Anatomy 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 238000005238 degreasing Methods 0.000 claims abstract description 13
- 238000004017 vitrification Methods 0.000 claims abstract description 3
- 238000004534 enameling Methods 0.000 claims description 18
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 13
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 13
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 10
- 238000010411 cooking Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000007547 defect Effects 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 abstract description 3
- 238000011282 treatment Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000003925 fat Substances 0.000 abstract description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 abstract 2
- 229940035044 sorbitan monolaurate Drugs 0.000 abstract 2
- 238000009991 scouring Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
- C23D5/00—Coating with enamels or vitreous layers
- C23D5/02—Coating with enamels or vitreous layers by wet methods
Definitions
- the present invention relates to enamelling on metals, in particular on sheet steel.
- the enamel is applied either in a single layer, called the mass layer, or, when an excellent surface finish is desired, in two layers, namely a layer of mass applied to the sheet and an outer layer of appearance or finish, which constitutes a covering and which can be white or colored.
- the enameling proper both according to the conventional technique and according to the technique known to the applicant without acid pickling, the enamel is applied: - either dry, by electrostatic powdering; - Either by liquid (or wet) route, the enamel then being ground in water, in the presence of suspending agents, such as clays and / or electrolytes, to form a slip, and the latter applied on the sheet, in particular by means of a gun, by dipping or by sprinkling.
- suspending agents such as clays and / or electrolytes
- a single firing is advantageously carried out after the two layers have been applied successively; in fact, three embodiments of the technique of two layers with a single firing are known, namely: - the two layers are obtained from a determined powder (powder / powder technique), by electrostatic dusting; - the first layer is applied by liquid and the second by dry (liquid / powder technique), the mass layer (first layer) once applied by liquid being dried before application of the white or colored cover (second layer) electrostatic; - the two layers (mass and covered layers) are both applied by liquid (liquid / liquid technique).
- the invention aims to carry out a wet enameling process, at least for the mass layer, without degreasing and without acid pickling.
- the subject of the invention is therefore a method of enamelling on a metallic article, in particular on steel sheet, consisting in applying by liquid means, at least one layer of mass, characterized in that one adds to a composition of enameling by liquid means, at least one hydrophilic surfactant or emulsifier, in that this enameling composition, to which the surfactant has been added, is directly applied to the article, without first carrying out on this degreasing treatment and / or acid pickling, and in that one then proceeds to vitrification, by cooking, of the enamel deposited on the article thus treated, the fats present on the article and the surfactants disappearing during cooking, which prevents enamel defects, after cooking.
- the Applicant has also found that, thanks to this process, the adhesion of the enamel to the metallic article, in particular the steel sheet, is greatly improved due to the combustion of said greases during heating, which promotes oxidation mechanisms.
- the application of the mass layer by the abovementioned process can be followed by the application of an appearance layer, either by the dry route, after drying of the mass, or by the liquid (or wet) route, the cooking having in this case after the application of the appearance layer.
- the surface-active product advantageously consists of the polyoxyethylene sorbitan monolaurate (which is the ester resulting from the saponification of lauric acid by sorbitol), sold in particular under the trade name "Tween 20", this product having a HLB index of 16.7.
- the content of added surfactant or emulsifier is generally on the order of 0.2 to 5%, in particular on the order of 0.5% in the case of polyoxyethylene sorbitan monolaurate.
- the subject of the invention is also, as a new industrial product, an enameling composition, allowing enamelling, in particular on a steel sheet, without degreasing or acid pickling before the application of the enameling composition , characterized in that it comprises at least one hydrophilic surfactant or emulsifier product.
- the enameling composition comprises of the order of 0.2 to 5% of at least one surfactant compound having an HLB index (average, in the case of several compounds) greater than 10 (value which corresponds to the solubilization of oil in water).
- composition comprising of the order of 0.5% of polyoxyethylene sorbitan monolaurate.
- EXAMPLE 1 Production by liquid (or wet) of a layer of mass, of colored or white appearance, without deposit of a cover layer (monolayer technique).
- This mass is then dry milled, in a ball mill, to a fineness of 16% using a 325 mesh sieve (45 ⁇ m opening, wire diameter of 0.035 mm) this mass with the following additives: Fritte 100% Inert product (feldspar) 10% K 26 (lithium salt as deflocculant) 0.15% Ethylene glycol (grinding accelerator) 0.1% Sodium nitrite (metal antioxidant) 0.08% Clay (suspensive) 6% Tween 20 (emulsifier) 0.5%
- the powder thus obtained is disintegrated in an aqueous medium, and a slip having a density of approximately 1.68 is obtained.
- the slip thus obtained is applied in an amount of between 300 and 450 g / m2 of sheet metal, on one face of the latter.
- the powder thus obtained is disintegrated in an aqueous medium and a slip having a density between 1.53 and 1.60 is obtained.
- This slip is applied by means of a gun, electrostatically for example, on a sheet not degreased, but freshly stamped, and this in an amount of 50 to 150 g of dry enamel per m2 of sheet.
- a second layer of enamel is applied electrostatically to the layer of dry mass.
- the white powder enamel can have the following composition: WHERE 17.1% R2O 16.4% WHERE 1.2% If 44.3% TiO2 19.1% ZrO2 1.2% F 1.3% which is prepared as indicated in US Patent 3,928,668.
- Cooking is carried out in a continuous oven, the heating zones of which are maintained at temperatures between 800 ° and 850 ° C for 4 to 8 minutes.
- EXAMPLE 3 Application of two layers (mass layer and finishing layer) by the liquid / liquid technique.
- a white enamel of the following composition is prepared: WHERE 17.1% R2O 16.4% WHERE 1.2% If 44.3% TiO2 19.1% ZrO2 1.2% F 1.3%
- This white enamel is dry milled in a ball mill to a fineness of 10% using the aforementioned 325 mesh sieve with the following products: Fritte 100% K 26 (lithium salt as deflocculant) 0.15% Ethylene glycol (grinding accelerator) 0.1% Clay (suspensive) 6% Tween 20 (emulsifier) 0.5% CPT 1131 (dye) 3%
- the above composition is applied to the still wet mass layer, by means of a gun, for example electrostatic, to form the finishing layer, and the baking is carried out in a continuous oven whose heating zones are maintained at a temperature between 800 ° and 850 ° C for 4 to 8 minutes.
- Example 4 is identical to Example 3, apart from the fact that the grinding of the mass and of the cover enamel takes place in the liquid phase.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Detergent Compositions (AREA)
- Laminated Bodies (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8808385A FR2633312B1 (fr) | 1988-06-22 | 1988-06-22 | Perfectionnements aux procedes d'emaillage sur metaux, notamment sur tole d'acier, et aux compositions d'emaillage |
| FR8808385 | 1988-06-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0348291A1 true EP0348291A1 (fr) | 1989-12-27 |
Family
ID=9367587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89401726A Withdrawn EP0348291A1 (fr) | 1988-06-22 | 1989-06-19 | Perfectionnements aux procédés d'émaillage sur métaux, notamment sur tôle d'acier, et aux compositions d'émaillage |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0348291A1 (es) |
| DE (1) | DE348291T1 (es) |
| DK (1) | DK310789A (es) |
| ES (1) | ES2013227A4 (es) |
| FR (1) | FR2633312B1 (es) |
| GR (1) | GR900300039T1 (es) |
| MA (1) | MA21580A1 (es) |
| TN (1) | TNSN89066A1 (es) |
| TR (1) | TR23946A (es) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0447323A1 (fr) * | 1990-03-15 | 1991-09-18 | Ferro Corporation | Procédé d'émaillage sans dégraissage sur métaux, notamment sur tôle d'acier et composition d'émaillage sans dégraissage |
| FR2680986A1 (fr) * | 1991-09-05 | 1993-03-12 | Rhone Poulenc Chimie | Preparation d'un revetement a partir d'une barbotine comprenant un polymere precurseur de ceramique. |
| ES2063696A1 (es) * | 1993-04-16 | 1995-01-01 | Consejo Superior Investigacion | Recubrimientos protectores sobre acero inoxidable producidos por sol-gel. |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0064649A2 (de) * | 1981-05-05 | 1982-11-17 | Bayer Ag | Emailschlicker und Verfahren zur Zwei- und Mehrschichtemaillierung in einem Brand |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5847801A (ja) * | 1981-09-16 | 1983-03-19 | 日本国有鉄道 | 融雪除氷装置 |
-
1988
- 1988-06-22 FR FR8808385A patent/FR2633312B1/fr not_active Expired - Lifetime
-
1989
- 1989-06-19 ES ES89401726T patent/ES2013227A4/es active Pending
- 1989-06-19 EP EP89401726A patent/EP0348291A1/fr not_active Withdrawn
- 1989-06-19 DE DE1989401726 patent/DE348291T1/de active Pending
- 1989-06-22 MA MA21833A patent/MA21580A1/fr unknown
- 1989-06-22 TN TNSN89066 patent/TNSN89066A1/fr unknown
- 1989-06-22 DK DK310789A patent/DK310789A/da not_active Application Discontinuation
- 1989-06-22 TR TR64689A patent/TR23946A/xx unknown
-
1991
- 1991-07-31 GR GR90300039T patent/GR900300039T1/el unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0064649A2 (de) * | 1981-05-05 | 1982-11-17 | Bayer Ag | Emailschlicker und Verfahren zur Zwei- und Mehrschichtemaillierung in einem Brand |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 100, no. 16, 16 avril 1984, page 633, résumé no. 130902q, Columbus, Ohio, US; & JP-A-58 47 801 (FURUKAWA ELECTRIC CO. LTD) 25-10-1983 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0447323A1 (fr) * | 1990-03-15 | 1991-09-18 | Ferro Corporation | Procédé d'émaillage sans dégraissage sur métaux, notamment sur tôle d'acier et composition d'émaillage sans dégraissage |
| FR2680986A1 (fr) * | 1991-09-05 | 1993-03-12 | Rhone Poulenc Chimie | Preparation d'un revetement a partir d'une barbotine comprenant un polymere precurseur de ceramique. |
| ES2063696A1 (es) * | 1993-04-16 | 1995-01-01 | Consejo Superior Investigacion | Recubrimientos protectores sobre acero inoxidable producidos por sol-gel. |
Also Published As
| Publication number | Publication date |
|---|---|
| GR900300039T1 (en) | 1991-07-31 |
| TR23946A (tr) | 1990-12-21 |
| TNSN89066A1 (fr) | 1991-02-04 |
| DK310789D0 (da) | 1989-06-22 |
| DE348291T1 (de) | 1990-06-13 |
| MA21580A1 (fr) | 1989-12-31 |
| FR2633312A1 (fr) | 1989-12-29 |
| FR2633312B1 (fr) | 1990-10-05 |
| DK310789A (da) | 1989-12-23 |
| ES2013227A4 (es) | 1990-05-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES GB GR IT LI LU NL SE |
|
| ITCL | It: translation for ep claims filed |
Representative=s name: STUDIO DR. CAVATTONI ING. A. RAIMON |
|
| TCNL | Nl: translation of patent claims filed | ||
| TCAT | At: translation of patent claims filed | ||
| GBC | Gb: translation of claims filed (gb section 78(7)/1977) | ||
| DET | De: translation of patent claims | ||
| 17P | Request for examination filed |
Effective date: 19900512 |
|
| 17Q | First examination report despatched |
Effective date: 19920519 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 19930720 |