CA1185506A - Method for surface treatment of polyacetal resins - Google Patents
Method for surface treatment of polyacetal resinsInfo
- Publication number
- CA1185506A CA1185506A CA000380772A CA380772A CA1185506A CA 1185506 A CA1185506 A CA 1185506A CA 000380772 A CA000380772 A CA 000380772A CA 380772 A CA380772 A CA 380772A CA 1185506 A CA1185506 A CA 1185506A
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- sulfuric acid
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Abstract
ABSTRACT
A method for the surface treatment of polyacetal resin characterised in that the resin is treated with an acidic solution containing chloride ions and sulfuric acid ions, thus etching the resin surface and enabling it to be plated and attain high adhesion characteristics and superior heat resistance to that of a plated ABS resin. The plated product can be surface-decorated and bonded, for example by coating, vacuum deposition or sputtering.
A method for the surface treatment of polyacetal resin characterised in that the resin is treated with an acidic solution containing chloride ions and sulfuric acid ions, thus etching the resin surface and enabling it to be plated and attain high adhesion characteristics and superior heat resistance to that of a plated ABS resin. The plated product can be surface-decorated and bonded, for example by coating, vacuum deposition or sputtering.
Description
The present in~ention relates to a method for the surface treatment of polyacetal resins. More particularly, the invention relates to a surface treatment method which is preferably adopted as the pre-treatment of polyacetal resins to be carried out prior to plating.
Polyacetal resins have excellent thermal, mechanical and chemical properties. At the present time, however, since they are relatively expensive, they are mainly used as engineering resins for the manufacture of functional parts.
Looking to the uture from the point of view of the raw materials for resins, it is expected that polyacetal resins formed by using methanol as the starting material will become one of the cheapest resins.
Therefore, it is expected that polyacetal resins will be applied even i.n thosefield$ where ABS resins and the like are now applied, such as, eor exanlple, the manufacture of shaped articles decorated by plating and coating.
In this ~ield, however, the surface inactivity which is a merit of a polyacetal resin in the conventional uses becomes a defect. Therefore, the surface trcatrnent Oe polyacetal resins is an important technical problem. By the term 'surface treatment" is meant treatment which renders the surface hydrophilic so that plating or coating becomes possible.
It is said that polyacetal resins can be surface activated by etching w-ith a chromic acid mixture, pho.sphoric acid, sulfonic acid or the like. How-ever, although the surface is roughened by carrying out the etching according to such a conventional method, complete activation is impossible.
We carried out research on the relationship between changes of the surface by etching of a shaped article of a polyacetal resin and the kinds of treating agents, and to our great surprise, it was found that when a polyacetal resin is treated wi~h a liquid mixture of hydrochloric acid and sulfuric acid -- 1 ~ , j~, \\
good activation can be attained although use of each acid singly does not result in good activation, even with a thin depth of etching of less than several ~m.
According to the present invention therefore, there is provided a method for the surface treatment of a polyacetal resin article characterised in that the resin article is treated with an acidic solution containing chloride ions and sulfuric acid ions, neutralized and washed with water, wherein the hydrogen ion content of the solution is about 0.6 to about 1.5 equivalents per 100 grams of the solution and wherein ~he weight ratio of hydrogen chloride to sulfuric acid is about 1:20 to 20:1.
A polyacetal resin shaped article etched according to the method of the present invention can be plated by the same steps as those adopted for the plating of ABS resins. The plated article obtained has a high adhesion compar-able to that of a plated ABS resin article and a heat resistance superior to that of a plated ABS resin article. Furthe~more, the treated article can be surface-decorated and bonded, for example by coating, vacuum deposition or sputtering.
We have also carried out research on the composition of the polyacetal resin to be treated, and have found that a polyacetal resin containing calcium carbonate is especially preferred. By the use of this polyacetal resin, the effccts of the present invention can be further enhanced.
More specifically, in accordance with the present invention, there is provided a method for the surface treatment of a polyacetal resin article, which comprises treating the resin article, preferably a polyacetal resin containing calcium carbonate, with an acidic solution containing chloride ions and sulfuric acid ions, neutralizing and washing with water.
In one embodiment of the present invention, a shaped article is prepared from a polyacetal resin according to a customary procedure, and the treatment of the present invention then carried out, preferably after annealing 6s~j and degreasing. The ~reatment is ordinarily accomplished hy dipping a shaped article of a polyacetal resin for a predetermined time in an acid solution of _ 2a -~.~
::
s~
sulfuric acid containing chlorlde ions. ~or example, in the case of a liquid mixture of 1 part ~y volume of concentra~ed hydrochloric acid, 1 part by volume of concentrated sulfuric acid and 2 parts by volume of water (about 8.6% by weight of HCl plus about 35.3% by ~eight of H2SO4), the treatment is accomplished within 5 to 3Q minutes at 25C. The artlcle treated according to the invention is subjected to neutralization and washing with water. It is then conveniently plated in the same way as in the case of ABS resin, that is by sensitization treatment, activation treatment, catalyst treatment including the sensitization treatment and the acti-vation treatment in combination, non-electrolytic plating treatment or by electric plating.
The polyacetal resin for use in the present invention may be, for example~ a homopolymer, a copolymer or a modified acetal. Especially when a polyacetal resin contains calclu~ carbonate, the treated surface is appropriate-ly roug}l and highl~ active, and therefore, the plating adhesion is remarkably high. The e~ect of improving the plating adhesion by calcium carbonate is highest when the content is 3~ to 5%, and lf the content is higher than this level, a good adhesion can be obtalned $tably. The addition of calcium carbon-ate results not only in stabilizing the plating adhesion but also improves the rigidity and reduces the dimensional change in the shaped article. A
~iller such as, for example, powder glass, silica, talc or pumice exerts similar effects. ~lowever, such filler involves a risk of reducing the surface gloss of the plated article. The calcium carbonate to be used in the present invention can be light calcium carbonate, chalk or heavy calcium carbonate.
Fine particulate products smaller than heavy calcium carbonate have a reduced actiqn of degrading the glossJ but coarser particles are preferred from the viewpaint o~ the plating adhesion. Accordingly, when the surface gloss is important, it is pre~erred that the amount of calcium carbonate added be up to - 3 _ 10%, and when the rigidity and reduction of the dimensional change are important, it is preferred that the amount of the flller added be 10% to 60%.
The treating solution that is used in the present invention is ordinarily prepared from h~drochloric acid and sulfuric acid. However, the method of incorporation of chloride ions and sulfuric acid ions is not limited to mixing of the acids per se. ~or e~ample, salts such as for example calcium chloride, sodium chloride and sodium sulfate may be added to an acidic solution to supply all or part of the necessary ions.
When such salts are used for formation of the acidic treating solu-lQ tion or when the treatment of a polyacetal resin containing calcium carbonate is repeated, it sometimes happens that precipitates are formed in the solution.
In order to smooth the surface of the treated article, it is preferred that these precipitates be removed by filtration.
According to the surface-activating treatment of the present invention, the surface layer is etched preferably to a depth of 0.5 to 50tum, more pre-ferably l to 20 ~ . A similar etching effect can be attained by the treatment using sufuric acid or hydrochloric acid alone, but then the degree of activa-tion is insufficiellt. It is considered that since the shaped article is simultaneously sub~ected to ~oth the action of hydrochloric acid, having a ~0 r~latively low etching activity but a high permeability, and the action of sul-furic acid, having a strong etching activity but a low permeability, the surface layer of the treated article is appropriately decomposed to form an active layer. However, the scope of the present invention is not limited by this conjecture. In general the condltions of treatment according to the invention depend on the composition of the treating liquid, the temperature and time of treatment and on any plating process subsequent to treatment. When the tem-perature and time of treatment are appropriately adjusted, the composition of the ~ ~ _ ~ ~5~
treating solution that is used ~or the treatment of the present invention can be changed within a broad range. ~or example, when the treatment temperature is 0C to 70QC., the treatment time is up ~o 1 hour and the solution is preparedfrom commercially available hydrochloric acid and sulfuric acid, it is pre-ferred that the hydrogen ion concentration in the solution be 0.6 to 1.5 equivalents per 100 g ~0.02 x ll2S0~ (wt.%) * 0.027 HCl (wt.%)~, especially 0.8u to 1.3 equivalents per 100 g, the hydrogen chloride/sulfuric acid weight ratio be ~rom 1/20 to 20/1, especially from 1/10 to l/l and that the concen-tration of hydrogen chloride in the hydrochloric acid used be up to 30% and this hydrochloric acid be mixed with concentrated sulfuric acid ~the especially preferred hydrogen chloride concentration being 7% to 25%). A solution having the intended composition may of course be prepared by mixing concentrated hydrochloric acid and concentrated sulfuric acid with water. The above-mentioned concentration range is not particularly critical, but this concen-tration range may be broadened if the treatment temperature is higher or lower than the above-mentioned temperature or the treatment time is shorter or longer.
Phosphori.c acid ions, sulfonic acid ions, boric acid ions, other halogen ions, halogenic acid ions, nitric acid ions, silicofluoric acid, borofluoric acid, organic acids such as ~or example ~ormic acid, and organic materials such as tor e~ample surface active agents may be incorporated, so far as the ef~ects o~ the present invention are no~ reduced.
The present invention will now ~e described with re~erence to the following ~xamples and Comparative Examples.
A plate having a side o 5 cm and a thickness of 3 mm was prepared ~rom a polyacetal resin ~Duracon* ~0 manufactured by ~olyplastics Kabushiki ~aisha) by injection moulding. The shaped article ~as annealed at 1~0C. for *Trade Mark - 5 ~
1 hour and degreased ~ith methylene chloride.
The degreased shaped article was treated at room temperature ~25C) for 2Q minutes with a liquid mixture comprising 1 part by volume of concentrated s,ulfuric acid and 1 part by volume of water, and was neutralized with a solution of sodium hydroxide, washed with water and treated at 25C. for 3 minutes with catalyst manufactured by Kizai Kabushiki Kaisha ~1 part by volume of a catalyst~
1 part by volume of concentrated hydrochloric acid and 5 parts by volume of water~ and at 25C ~or 2 minutes with a solution comprising 1 part by volume of concentrated hydrochloric acid and 3 parts by ~olume of water. Then, the article was non-electricall~ plated with a solution manufactured by Kizai Kabushiki Kaisha (1 part by volume of chemical nickelplating solution A, 1 part by volume o chemical nickel plating solution ~ and 2 parts by volume of water) and electrically plated with copper (a solution comprising 220 g/Q of copper sulfate and 55 g/~ of concentrated sulfuric acid). The plated article was dried at 80~C or 1 hour and the adhesion force was measured. It was found that the adhesion force was lower than 100 g/cm. The adhesion force was deter-mLncd by forming a scar ha~ing a width of 1 cm with a knife so that the scar was extended to the resin layer from the plating surface and measuring the load neccssary to pee~l the plated layer from the polyacetal.
Conlparative Bxample 2 The plating treat~ent ~as, carried out in the same manner as in Comparative Example 1 except that a treating solution comprising 1 part by volume of water was used. The adhesion force of the plated article was substan-t;ally ~ero.
Bxample 1 The plating tre,atnlent was carried out in the same manner as in Comparative ~xalnple 1 except that a treating solution comprising 1 part by ~ 6 -Yolume of concentrated sul~uric acid, 1 part by ~olume of 35~ hydrochloric acid and 2 parts by Yolume of water was used. The adhesion force of the plated article was 700 g/cm.
Examples 2 to 16 Polyacetal resins shown in Table 1 and treated under conditions shown in Table 1 were plated in the same manner as in E~ample 1. The results obtained arc shown in Table 1.
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Polyacetal resins have excellent thermal, mechanical and chemical properties. At the present time, however, since they are relatively expensive, they are mainly used as engineering resins for the manufacture of functional parts.
Looking to the uture from the point of view of the raw materials for resins, it is expected that polyacetal resins formed by using methanol as the starting material will become one of the cheapest resins.
Therefore, it is expected that polyacetal resins will be applied even i.n thosefield$ where ABS resins and the like are now applied, such as, eor exanlple, the manufacture of shaped articles decorated by plating and coating.
In this ~ield, however, the surface inactivity which is a merit of a polyacetal resin in the conventional uses becomes a defect. Therefore, the surface trcatrnent Oe polyacetal resins is an important technical problem. By the term 'surface treatment" is meant treatment which renders the surface hydrophilic so that plating or coating becomes possible.
It is said that polyacetal resins can be surface activated by etching w-ith a chromic acid mixture, pho.sphoric acid, sulfonic acid or the like. How-ever, although the surface is roughened by carrying out the etching according to such a conventional method, complete activation is impossible.
We carried out research on the relationship between changes of the surface by etching of a shaped article of a polyacetal resin and the kinds of treating agents, and to our great surprise, it was found that when a polyacetal resin is treated wi~h a liquid mixture of hydrochloric acid and sulfuric acid -- 1 ~ , j~, \\
good activation can be attained although use of each acid singly does not result in good activation, even with a thin depth of etching of less than several ~m.
According to the present invention therefore, there is provided a method for the surface treatment of a polyacetal resin article characterised in that the resin article is treated with an acidic solution containing chloride ions and sulfuric acid ions, neutralized and washed with water, wherein the hydrogen ion content of the solution is about 0.6 to about 1.5 equivalents per 100 grams of the solution and wherein ~he weight ratio of hydrogen chloride to sulfuric acid is about 1:20 to 20:1.
A polyacetal resin shaped article etched according to the method of the present invention can be plated by the same steps as those adopted for the plating of ABS resins. The plated article obtained has a high adhesion compar-able to that of a plated ABS resin article and a heat resistance superior to that of a plated ABS resin article. Furthe~more, the treated article can be surface-decorated and bonded, for example by coating, vacuum deposition or sputtering.
We have also carried out research on the composition of the polyacetal resin to be treated, and have found that a polyacetal resin containing calcium carbonate is especially preferred. By the use of this polyacetal resin, the effccts of the present invention can be further enhanced.
More specifically, in accordance with the present invention, there is provided a method for the surface treatment of a polyacetal resin article, which comprises treating the resin article, preferably a polyacetal resin containing calcium carbonate, with an acidic solution containing chloride ions and sulfuric acid ions, neutralizing and washing with water.
In one embodiment of the present invention, a shaped article is prepared from a polyacetal resin according to a customary procedure, and the treatment of the present invention then carried out, preferably after annealing 6s~j and degreasing. The ~reatment is ordinarily accomplished hy dipping a shaped article of a polyacetal resin for a predetermined time in an acid solution of _ 2a -~.~
::
s~
sulfuric acid containing chlorlde ions. ~or example, in the case of a liquid mixture of 1 part ~y volume of concentra~ed hydrochloric acid, 1 part by volume of concentrated sulfuric acid and 2 parts by volume of water (about 8.6% by weight of HCl plus about 35.3% by ~eight of H2SO4), the treatment is accomplished within 5 to 3Q minutes at 25C. The artlcle treated according to the invention is subjected to neutralization and washing with water. It is then conveniently plated in the same way as in the case of ABS resin, that is by sensitization treatment, activation treatment, catalyst treatment including the sensitization treatment and the acti-vation treatment in combination, non-electrolytic plating treatment or by electric plating.
The polyacetal resin for use in the present invention may be, for example~ a homopolymer, a copolymer or a modified acetal. Especially when a polyacetal resin contains calclu~ carbonate, the treated surface is appropriate-ly roug}l and highl~ active, and therefore, the plating adhesion is remarkably high. The e~ect of improving the plating adhesion by calcium carbonate is highest when the content is 3~ to 5%, and lf the content is higher than this level, a good adhesion can be obtalned $tably. The addition of calcium carbon-ate results not only in stabilizing the plating adhesion but also improves the rigidity and reduces the dimensional change in the shaped article. A
~iller such as, for example, powder glass, silica, talc or pumice exerts similar effects. ~lowever, such filler involves a risk of reducing the surface gloss of the plated article. The calcium carbonate to be used in the present invention can be light calcium carbonate, chalk or heavy calcium carbonate.
Fine particulate products smaller than heavy calcium carbonate have a reduced actiqn of degrading the glossJ but coarser particles are preferred from the viewpaint o~ the plating adhesion. Accordingly, when the surface gloss is important, it is pre~erred that the amount of calcium carbonate added be up to - 3 _ 10%, and when the rigidity and reduction of the dimensional change are important, it is preferred that the amount of the flller added be 10% to 60%.
The treating solution that is used in the present invention is ordinarily prepared from h~drochloric acid and sulfuric acid. However, the method of incorporation of chloride ions and sulfuric acid ions is not limited to mixing of the acids per se. ~or e~ample, salts such as for example calcium chloride, sodium chloride and sodium sulfate may be added to an acidic solution to supply all or part of the necessary ions.
When such salts are used for formation of the acidic treating solu-lQ tion or when the treatment of a polyacetal resin containing calcium carbonate is repeated, it sometimes happens that precipitates are formed in the solution.
In order to smooth the surface of the treated article, it is preferred that these precipitates be removed by filtration.
According to the surface-activating treatment of the present invention, the surface layer is etched preferably to a depth of 0.5 to 50tum, more pre-ferably l to 20 ~ . A similar etching effect can be attained by the treatment using sufuric acid or hydrochloric acid alone, but then the degree of activa-tion is insufficiellt. It is considered that since the shaped article is simultaneously sub~ected to ~oth the action of hydrochloric acid, having a ~0 r~latively low etching activity but a high permeability, and the action of sul-furic acid, having a strong etching activity but a low permeability, the surface layer of the treated article is appropriately decomposed to form an active layer. However, the scope of the present invention is not limited by this conjecture. In general the condltions of treatment according to the invention depend on the composition of the treating liquid, the temperature and time of treatment and on any plating process subsequent to treatment. When the tem-perature and time of treatment are appropriately adjusted, the composition of the ~ ~ _ ~ ~5~
treating solution that is used ~or the treatment of the present invention can be changed within a broad range. ~or example, when the treatment temperature is 0C to 70QC., the treatment time is up ~o 1 hour and the solution is preparedfrom commercially available hydrochloric acid and sulfuric acid, it is pre-ferred that the hydrogen ion concentration in the solution be 0.6 to 1.5 equivalents per 100 g ~0.02 x ll2S0~ (wt.%) * 0.027 HCl (wt.%)~, especially 0.8u to 1.3 equivalents per 100 g, the hydrogen chloride/sulfuric acid weight ratio be ~rom 1/20 to 20/1, especially from 1/10 to l/l and that the concen-tration of hydrogen chloride in the hydrochloric acid used be up to 30% and this hydrochloric acid be mixed with concentrated sulfuric acid ~the especially preferred hydrogen chloride concentration being 7% to 25%). A solution having the intended composition may of course be prepared by mixing concentrated hydrochloric acid and concentrated sulfuric acid with water. The above-mentioned concentration range is not particularly critical, but this concen-tration range may be broadened if the treatment temperature is higher or lower than the above-mentioned temperature or the treatment time is shorter or longer.
Phosphori.c acid ions, sulfonic acid ions, boric acid ions, other halogen ions, halogenic acid ions, nitric acid ions, silicofluoric acid, borofluoric acid, organic acids such as ~or example ~ormic acid, and organic materials such as tor e~ample surface active agents may be incorporated, so far as the ef~ects o~ the present invention are no~ reduced.
The present invention will now ~e described with re~erence to the following ~xamples and Comparative Examples.
A plate having a side o 5 cm and a thickness of 3 mm was prepared ~rom a polyacetal resin ~Duracon* ~0 manufactured by ~olyplastics Kabushiki ~aisha) by injection moulding. The shaped article ~as annealed at 1~0C. for *Trade Mark - 5 ~
1 hour and degreased ~ith methylene chloride.
The degreased shaped article was treated at room temperature ~25C) for 2Q minutes with a liquid mixture comprising 1 part by volume of concentrated s,ulfuric acid and 1 part by volume of water, and was neutralized with a solution of sodium hydroxide, washed with water and treated at 25C. for 3 minutes with catalyst manufactured by Kizai Kabushiki Kaisha ~1 part by volume of a catalyst~
1 part by volume of concentrated hydrochloric acid and 5 parts by volume of water~ and at 25C ~or 2 minutes with a solution comprising 1 part by volume of concentrated hydrochloric acid and 3 parts by ~olume of water. Then, the article was non-electricall~ plated with a solution manufactured by Kizai Kabushiki Kaisha (1 part by volume of chemical nickelplating solution A, 1 part by volume o chemical nickel plating solution ~ and 2 parts by volume of water) and electrically plated with copper (a solution comprising 220 g/Q of copper sulfate and 55 g/~ of concentrated sulfuric acid). The plated article was dried at 80~C or 1 hour and the adhesion force was measured. It was found that the adhesion force was lower than 100 g/cm. The adhesion force was deter-mLncd by forming a scar ha~ing a width of 1 cm with a knife so that the scar was extended to the resin layer from the plating surface and measuring the load neccssary to pee~l the plated layer from the polyacetal.
Conlparative Bxample 2 The plating treat~ent ~as, carried out in the same manner as in Comparative Example 1 except that a treating solution comprising 1 part by volume of water was used. The adhesion force of the plated article was substan-t;ally ~ero.
Bxample 1 The plating tre,atnlent was carried out in the same manner as in Comparative ~xalnple 1 except that a treating solution comprising 1 part by ~ 6 -Yolume of concentrated sul~uric acid, 1 part by ~olume of 35~ hydrochloric acid and 2 parts by Yolume of water was used. The adhesion force of the plated article was 700 g/cm.
Examples 2 to 16 Polyacetal resins shown in Table 1 and treated under conditions shown in Table 1 were plated in the same manner as in E~ample 1. The results obtained arc shown in Table 1.
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Claims (17)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for the surface treatment of a polyacetal resin article character-ised in that the resin article is treated with an acidic solution containing chloride ions and sulfuric acid ions, neutralized and washed with water, wherein the hydrogen ion content of the solution is about 0.6 to about 1.5 equivalents per 100 grams of the solution and wherein the weight ratio of hydrogen chloride to sulfuric acid is about 1:20 to 20:1.
2. A method according to claim 1 characterised in that the polyacetal resin contains a filler.
3. A method according to claim 2 characterised in that the filler is calcium carbonate.
4. A method according to claim 3 characterised in that the resin contains 3% to 5% of the calcium carbonate.
5. A method according to claim 1 characterised in that the surface of the resin is etched by the treatment to a depth of 0.05 to 50 µm.
6. A method according to claim 5 characterised in that the surface of the resin is etched to a depth of 1 to 20 µm.
7. A method according to claim 1 characterised in that the acidic solution is a mixed solution of hydrochloric acid and sulfuric acid.
8. A method according to claim 1 wherein the hydrogen ion content is about 0.8 to about 1.3 equivalents per 100 grams of solution.
9. A method according to claim 1 wherein the weight ratio of hydrogen chloride to sulfuric acid is about 1:10 to about 1:1.
10. A method according to claim 1 wherein the acidic solution contains 1 part by volume of concentrated sulfuric acid, 1 part by volume of hydro-chloric acid and 2 parts by volume of water.
11. A method according to claim 1 wherein the resin article is treated at a temperature of 0°-70°C. for about 1 minute to 1 hour.
12. A method according to claim 1 wherein the resin article is treated at a temperature of 25°C. for about 5 to 30 minutes.
13. A method according to claim 1 characterised in that the treatment temperature is 0°C to 70°C, the treatment time is up to one hour and the acidic solution is prepared from commercial hydrochloric and sulfuric acids, the hydrogen ion concentration in the solution being 0.6 to 1.5 equivalents per 100 g., the hydrochloric acid/sulfuric acid weight ratio being from 1/20 to 20/1 and the concentration of hydrogen chloride in the hydrochloric acid being up to 30%.
14. A method according to claim 13 characterised in that the hydrogen ion concentration is 0.8 to 1.3 equivalents per 100 g., the hydrochloric acid/
sulfurlc acid weight ratio is from 1/10 to 1/1 and the hydrogen chloride concentration in the hydrochloric acid is 7% to 25%.
sulfurlc acid weight ratio is from 1/10 to 1/1 and the hydrogen chloride concentration in the hydrochloric acid is 7% to 25%.
15. a method according to claim 1 characterised in that the treatment is carried out after annealing and decreasing of the resin surface.
16. A method according to claim 1 characterised in that the resin article is in the form of a shaped article.
17. A method according to claim 16 characterised in that the shaped article is dipped in the acidic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000380772A CA1185506A (en) | 1981-06-26 | 1981-06-26 | Method for surface treatment of polyacetal resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000380772A CA1185506A (en) | 1981-06-26 | 1981-06-26 | Method for surface treatment of polyacetal resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1185506A true CA1185506A (en) | 1985-04-16 |
Family
ID=4120329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000380772A Expired CA1185506A (en) | 1981-06-26 | 1981-06-26 | Method for surface treatment of polyacetal resins |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1185506A (en) |
-
1981
- 1981-06-26 CA CA000380772A patent/CA1185506A/en not_active Expired
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