GB2091274A - A process for the treatment of polyacetal articles - Google Patents
A process for the treatment of polyacetal articles Download PDFInfo
- Publication number
- GB2091274A GB2091274A GB8136306A GB8136306A GB2091274A GB 2091274 A GB2091274 A GB 2091274A GB 8136306 A GB8136306 A GB 8136306A GB 8136306 A GB8136306 A GB 8136306A GB 2091274 A GB2091274 A GB 2091274A
- Authority
- GB
- United Kingdom
- Prior art keywords
- article
- solution
- polyacetal
- acid
- treatment
- 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.)
- Granted
Links
- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 21
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004544 sputter deposition Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000003929 acidic solution Substances 0.000 claims abstract description 8
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000001465 metallisation Methods 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 235000005985 organic acids Nutrition 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 235000011149 sulphuric acid Nutrition 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229920005177 Duracon® POM Polymers 0.000 description 2
- -1 acrylic ester Chemical class 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
- C08J2359/02—Copolyoxymethylenes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Physical Vapour Deposition (AREA)
- Chemically Coating (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
To improve the adhesion of a metallized coating applied to a polyacetal article by a sputtering technique, the article is surface treated, prior to metallization, by an acidic solution. The acidic solution may be composed of an aqueous solution of one or more inorganic acids and/or one or more organic acids and/or one or more acidic oxidizing mixtures. After surface treatment and before metallizing, the article may be treated with an agent for neutralizing the acidic solution.
Description
SPECIFICATION
A process for the treatment of polyacetal articles
This invention relates to a process for the treatment of polyacetal articles prior to metallization thereof by a cathode sputtering technique, and also relates to a process of metallizing polyacetal articles.
Generally, the metallization by means of sputtering, which is applied to plastics (e.g. ABS articles is effected in order to impart a metallic lustre thereto. One such conventional process comprises degreasing the article with the appropriate solvent, coating and the article with an undercoat of a paint (such as a urethane, an acrylic urethane or an acrylic ester), drying the undercoat, sputtering chromium (SUS-304), a chromium alloy, of aluminium in an argon atmosphere at a pressure of 5 x 10-3 to 2 X 10-4 Torr so as to form a metal layer with a thickness of 300 to 1,000 A, and then applying a top coat (such as an acrylic ester or acrylic urethane) to the metallized article.
However, in the case of polyacetal articles, there is currently no material for the undercoat which has good enough adhesion to the object to be of practical use, because polyacetal is highly crystalline and chemically stable. Thus, the above-described conventional process cannot be used for metallizing polyacetal articles. It has now been found that the surface treatment of polyacetal articles using an acidic solution is very effective promoting strong adhesion of an undercoat to the articles. Additionally such a surface modification does not deleteriously affect the surface smoothness, further provides a good surface suitable for sputtering metals. Suitable inorganic acids include hydrochloric acid, sulphuric acid, phosphoric acid and mixtures thereof, and an oxidizing mixture consisting of potassium dichromate and sulphuric acid.Suitable organic acids include acetic acid and p-toluene sulphonic acid. A mixed acid consisting of an inorganic acid and an organic acid may be used in this invention. Although the treatment condition varies with the type of acid being used, favourable effects can be expected particularly when one or a mixture of inorganic acids are employed with high concentration.
In the case of organic acid solutions, the treatment temperature may be O to 1 00 C, whilst the treatment time is preferably not more than 360 minutes.
In the case of inorganic acid solutions and oxidizing mixtures, the treatment temperature may be O to 80"C whilst the treatment time is preferably not more than 30 minutes.
More specifically, in the case of acid mixtures, for example, when the acid solution is composed of 30-60 percent by weight of sulphuric acid, 5-30 percent by weight of hydrochloric acid, and 65-10 percent by weight of water, the preferred temperature is between
O and 30'C and the preferred time is not greater than 1 5 minutes. In one preferred embodiment, the acid solution consists of 20-50 percent by weight of sulphuric acid, 30-50 percent by weight of phosphoric acid, and 50-0 percent by weight of water. In the case of an oxidizing mixture, one preferred mixture consists of 1-5 percent by weight of potassium dichromate, 50-95 percent by weight of sulphuric acid, and 49-0 percent by weight of water.
After surface modification of the polyacetal article, the article is dipped into a neutralizing solution to neutralize any acidic material on the surface of the article and then an undercoat is applied. Subsequently, drying of the undercoat is carried out (for example at 1 20 C for 30 minutes) and then the metallization by sputtering is performed. Thus, a metal layer with uniform thickness is formed on the undercoat without giving any micro-cracks.
The term "polyacetal" as used herein includes any grade of polyacetal homopolymers, polyacetal copolymers having different compositions, and polyacetal homopolymers or copolymers modified with various kinds of compounds.
Examples of the modifiers include fillers (e.g. CaCO3 or talc), inorganic reinforcing agents (e.g.
glass fibres, beads, glass flakes or mica), organic reinforcing agents, organic modifiers, and stabilizers of any kind.
The present invention will be explained more in detail according to the following examples.
Plates of DURACON M90 (a polyacetal resin produced by Polyplastics Co., Ltd.) having a lenght of 70mm, a width of 50mm, and a thickness of 3mm, were solvent degreased using an organic solvent (e.g. isopropylalcohol or acetone) and were then surface treated under a variety of conditions as shown in the Table. Any adherent acid coating on the plates was then neutralizsd by immersing the plates in a neutralizer (e.g. a 50 % by weight sodium hydroxide aqueous solution). After that, EXP 1 245 (an urethane paint, a sputtering undercoat for ABS resin manufactured by Fujikura Kasei Co., Ltd.) was applied to the surface-treated plates and dried at 1 20 C for 30 minutes.
These undercoated plates were placed in a sputtering apparatus sold as CFS-8ES manufactured by Tokuda Manufacturing Co. Ltd., and then a chromoium alloy was sputtered on it so as to produce a 300-400 A thick chromium surface layer.
EXP 1 380 (an acrylic urethane paint, a topcoat made by Fujikura Kasei Co., Ltd.) was painted onto the metallized plates which were then dried at 80"C for 30 minutes to complete curing of the topcoat.
If desired or necessary, before acid treatment, the polyacetal articles may be subjected to an annealing step by heat treatment, for example, at 1 40'C for 1 hour, for stress relieving purposes.
in order to compare the degree of the adhesion of each deposit (undercoat + sputtered metal layer + topcoat) to the substrate of Duracon, a cellophane adhesive tape, which was applied to the deposit in which 1 mm x 1 mm checkers had been produced by two mutually perpendicular sets of parallel cuts through the deposit, was peeled off at an angle of 180 to the surface to which the adhesive tape was adhered. The number of checkers left behind on the substrate was counted. The lustre of the sputtered metal layers on the sample were visually compared. The results are shown in the Table.
N.B. *1) H2SO4/H3PO4/H2O = 40/40/20 (wt %) *2) K2Cr2O7/H2SO4/H2O = 5/80/15 (wt %)
Table 1 *3) H2SO4/HCl/H2O = 35/8/57 (e#wt %)
Peling-off resistance Treatement (left-behind checkers/ Example Agents used for treatement condition total checkers) Example 1 88% H2SO4 24 C X 30 sec.
2 98% H2SO4 25 CX 180 sec.
3 50% H2SO4 solution 25 C X 5 min.
4 50% H2SO4 solution 25 C X 30 min.
5 85% H3PO4 solution 25 C X 10 min.
6 85% H3PO4 solution 25 C X 30 min.
7 20% HCl solution 25 C X 10 min.
8 20% HCl solution 25 C X 30 min.
*1) 9 H2SO4/H3PO4/H2O 25 C X 5 min.
*1)10 H2SO4/H3PO4/H2O 25 C X 30 min.
*2)11 K2Cr2O7/H2SO4/H2O 25 C X 20 sec.
*2)12 K2Cr2O7/H2SO4/H2O 25 C X 180 sec. # 100/100 # Good *3)13 H2SO4/HCl/H2O 25 C X 3 min.
*3) 14 H2SO4/HCl/H2O 25 C X 15 min.
15 10% p-toluene sulphonic acid solution 80 C X 10 min.
16 10% p-toluene sulphonic acid solution 80 C X 30 min.
17 80% glacial acetic acid solution 25 C X 60 min.
18 80% glacial acetic acid solution 25 C X 180 min.
1910 % H2SO4 solution 80 C X 5 min.
20 10%H2SO4 solution 80 C X 20 min.
21 (30% H2SO4 + 5% p-toluene sulphonic acid) solution 30 C X 20 min.
22 (30% H2SO4 + 5% p-toluene sulphonic acid) solution 30 C X 40 min.
Comp. Example 1 Untreated - 0/100 Good 2 Sandpapered - 100/100 Bad
Claims (9)
1. A pocess for the treatment of a polyacetal article prior to metallizing by sputtering, which process comprises surface treating the article with an acid solution.
2. A process as claimed in claim- 1, in which the acidic solution is an aqueous solution of one or more inorganic acids.
3. A process as claimed in claim 1, in which the acidic solution is an aqueous solution of one or more organic acids.
4. A process as claimed in claim 1, in which the acidic solution is an aqueous solution of one or more inorganic acids, and one or more organic acids.
5. A process as claimed in claim 1, in which the acid solution is an oxidizing mixture of one or-more salts, one or more inorganic- acids,- and water.
6. A process as claimed in claim 1, substantially as hereinbefore described in any one of
Examples 1 to 22.
7. A polyacetal article whose surface has been treated, prior to metallizing by sputtering, by a process as claimed in any preceding claim.
8. A process of producing a metallized polyacetal article comprising surface treating a polyacetal article by a process as claimed in any one of claims 1 ta 6 and subsequently metallizing said treated article by a sputtering technique.
9. A process-as claimed in claim 8, wherein after surface treatement and before metalliza tion, the article is treated with an agent for neutralizing the acidic solution.
1Q. A polyacetal article when metallized by a process as claimed in claim 8 or 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55172499A JPS5796026A (en) | 1980-12-05 | 1980-12-05 | Surface treatment for sputtering |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2091274A true GB2091274A (en) | 1982-07-28 |
| GB2091274B GB2091274B (en) | 1985-08-21 |
Family
ID=15943101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8136306A Expired GB2091274B (en) | 1980-12-05 | 1981-12-02 | A process for the treatment of polyacetal articles |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5796026A (en) |
| KR (1) | KR870001091B1 (en) |
| GB (1) | GB2091274B (en) |
| HK (1) | HK16386A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0259064A1 (en) * | 1986-09-01 | 1988-03-09 | Polyplastics Co. Ltd. | Painted moulded polyacetal resin product |
| EP0259011A3 (en) * | 1986-08-06 | 1988-08-24 | Polyplastics Co. Ltd. | Method of surface treating a moulded polyacetal resin product |
| EP0214827A3 (en) * | 1985-09-02 | 1988-11-09 | Polyplastics Co. Ltd. | Surface-metallized, moulded resin article |
| EP0329417A3 (en) * | 1988-02-16 | 1990-03-21 | Hoechst Celanese Corporation | Process for improving the adhesion to polyacetal articles |
| FR2703074A1 (en) * | 1990-11-27 | 1994-09-30 | Eumail | Process for the treatment of chromable polyacetals with a mixture of acids |
| WO2004058863A3 (en) * | 2002-12-20 | 2004-08-19 | Du Pont | Surface treatment of polyacetal articles |
| ES2288426A1 (en) * | 2006-06-26 | 2008-01-01 | Albert Sanahuja Julibert | Pretreatment method for piece or surface of plastic material, involves opening of pores of three dimensional substrate of material, in individual pieces or surfaces |
| CN103757677A (en) * | 2013-11-29 | 2014-04-30 | 云南云天化股份有限公司 | Polyformaldehyde product surface processing method |
-
1980
- 1980-12-05 JP JP55172499A patent/JPS5796026A/en active Granted
-
1981
- 1981-12-02 GB GB8136306A patent/GB2091274B/en not_active Expired
- 1981-12-04 KR KR1019810004736A patent/KR870001091B1/en not_active Expired
-
1986
- 1986-03-06 HK HK163/86A patent/HK16386A/en not_active IP Right Cessation
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0214827A3 (en) * | 1985-09-02 | 1988-11-09 | Polyplastics Co. Ltd. | Surface-metallized, moulded resin article |
| EP0259011A3 (en) * | 1986-08-06 | 1988-08-24 | Polyplastics Co. Ltd. | Method of surface treating a moulded polyacetal resin product |
| EP0259064A1 (en) * | 1986-09-01 | 1988-03-09 | Polyplastics Co. Ltd. | Painted moulded polyacetal resin product |
| EP0329417A3 (en) * | 1988-02-16 | 1990-03-21 | Hoechst Celanese Corporation | Process for improving the adhesion to polyacetal articles |
| FR2703074A1 (en) * | 1990-11-27 | 1994-09-30 | Eumail | Process for the treatment of chromable polyacetals with a mixture of acids |
| WO2004058863A3 (en) * | 2002-12-20 | 2004-08-19 | Du Pont | Surface treatment of polyacetal articles |
| ES2288426A1 (en) * | 2006-06-26 | 2008-01-01 | Albert Sanahuja Julibert | Pretreatment method for piece or surface of plastic material, involves opening of pores of three dimensional substrate of material, in individual pieces or surfaces |
| ES2288426B1 (en) * | 2006-06-26 | 2008-12-16 | Albert Sanahuja Julibert | PRE-TREATMENT PROCEDURE FOR A PART OR SURFACE OF PLASTIC MATERIAL, IN PARTICULAR OF METHYLENE POLYOXIDE. |
| CN103757677A (en) * | 2013-11-29 | 2014-04-30 | 云南云天化股份有限公司 | Polyformaldehyde product surface processing method |
| CN103757677B (en) * | 2013-11-29 | 2017-01-25 | 云南云天化股份有限公司 | Polyformaldehyde product surface processing method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR870001091B1 (en) | 1987-06-04 |
| JPS5796026A (en) | 1982-06-15 |
| HK16386A (en) | 1986-03-14 |
| JPH0158266B2 (en) | 1989-12-11 |
| GB2091274B (en) | 1985-08-21 |
| KR830007879A (en) | 1983-11-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19991202 |