GB2035335A - Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same - Google Patents
Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same Download PDFInfo
- Publication number
- GB2035335A GB2035335A GB7936174A GB7936174A GB2035335A GB 2035335 A GB2035335 A GB 2035335A GB 7936174 A GB7936174 A GB 7936174A GB 7936174 A GB7936174 A GB 7936174A GB 2035335 A GB2035335 A GB 2035335A
- Authority
- GB
- United Kingdom
- Prior art keywords
- weight
- polyacetal resin
- acid
- parts
- sulfuric acid
- 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 69
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 69
- 239000011342 resin composition Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 35
- 230000008569 process Effects 0.000 title claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 230000000737 periodic effect Effects 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000009713 electroplating Methods 0.000 claims abstract description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000004641 Diallyl-phthalate Substances 0.000 claims abstract description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 5
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 47
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 14
- 238000007788 roughening Methods 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000010586 diagram Methods 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 239000003484 crystal nucleating agent Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- ICHDQVUPSYOJMO-UHFFFAOYSA-N phosphoric acid sulfuric acid hydrate Chemical compound O.P(O)(O)(O)=O.S(O)(O)(=O)=O ICHDQVUPSYOJMO-UHFFFAOYSA-N 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 238000005530 etching Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003929 acidic solution Substances 0.000 description 5
- -1 cyclic acetal Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910008066 SnC12 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229920005177 Duracon® POM Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BYNPVFHVZRNRQD-UHFFFAOYSA-N acetic acid;benzene Chemical compound CC(O)=O.C1=CC=CC=C1 BYNPVFHVZRNRQD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
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- 238000000748 compression moulding Methods 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/02—Polyacetals containing polyoxymethylene sequences only
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
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- Mechanical Engineering (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Chemically Coating (AREA)
Abstract
A polyacetal resin composition comprises (a) about 100 parts by weight of polyacetal resin (b) about 2 to about 35 parts by weight of carbonate, phosphate, acetate or their mixture of a metal belonging to Group II of the periodic table and (c) about 0.01 to about 20 parts by weight of polymer, copolymer or their mixture of a compound selected from unsaturated polyester, alkyl ester of (meth)acrylic acid, (meth)acrylamide, triallyl cyanurate, diallyl phthalate, vinyl acetate and divinylbenzene. Articles molded from this composition are surface- ` roughened by dipping the molded article into an aqueous solution containing sulfuric acid. After this treatment the surface of the molded article is receptive to a surface coating, such as electroplating.
Description
SPECIFICATION
Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same
This invention relates to a polyacetal resin composition excellent in heat stability and surface processability.
Generally speaking, plastics are quite stable chemically and their molded products by injection molding or the like have a smooth surface, so that their surface is difficult to be decorated by means of printing, coating, deposition or the like or to subject to a surface processing such as adhesion by means of adhesive. Since polyacetal resin is particularly poor in surface activity and there is known no appropriate solvent having an affinity to polyacetal, its surface decoration and adhesion are difficultto practice and it is scarcely put to uses requiring such treatments at the present stage. Conversely speaking, since polyacetal resin is excellent in mechanical properties, it is mainly used as mechanical parts or the like in many cases and its surface decoration has not been required hitherto so frequently.
However, the application of plastics has intensely inclined to diversification and higher class usage in the recent time and it is frequently required to simultaneously satisfy plural performances, such as function and appearance or function and adhesion property, of which compatability has not necessarily been required hitherto. Thus, it is the current trend to require good surface processability even in the application of polyacetal.
Though it is difficult to say that the process for improving surface processability of polyacetal has actively been studied hitherto, we are informed of the fact that the surface processability can be improved to some extent by treating the surface of molded product with an acidic solution of an oxidant solution. As said acidic solution, p-toluenesulfonic acid, comphorsulfonic acid, phosphoric acid, acid ammonium sulfate and the like were proposed, while as said oxidant solution chromic acid-sulfuric acid mixture was proposed.
The object of the treatment with these solutions is considered to consist in producing a rough surface by chemically etching the surface of molded product of polyacetal resin and simultaneously forming reactive groups on a part of polyacetal molecule by the oxidizing action of the solutions. In general, if it is attempted to enhance the effect of surface treatment in such a treatment, there rise troubles such as deterioration of parent material, i.e. polyacetal resin, throughout whole the body of molded article, a formation of crack, etc.
On the other hand, if the treatment is carried out under a condition causing no deterioration of parent material, the effect of surface treatment is insufficient and a good surface processing cannot be practised.
For these reasons, there has hitherto been known no molded product of polyacetal resin having an enough surface processability for practical use.
The present inventors earnestly studied the composition of polymer with the aim of obtaining a molded product of polyacetal resin excellent in surface processability. As the result, it was found that a composition comprising polyacetal resin, a salt of a metal belonging to Group II of the periodic table and a certain kìnd of polymer exhibits excellent performances in heat stability and surface processability.
Thus, this invention relates to a polyacetal resin composition excellent in heat stability and surface processability which comprises (a) about 100 parts by weight of polyacetal resin, (b) about 2 to about 35 parts by weight of carbonate, phosphate, acetate or their mixture of a metal belonging to Group II of the periodic table, and (c) about 0.01 to about 20 parts by weight of a polymer, copolymer or their mixture of a compound selected from unsaturated polyester, alkyl ester of acrylic or methacrylic acid, amide of acrylic or methacrylic acid, triallyl cyanurate, diallyl phthalate, vinyl acetate and divinylbenzene.
In this invention, the object of adding a salt of a metal belonging to Group II of the periodic table to polyacetal resin consists in facilitating the formation of roughened surface suitable for surface processing.
That is to say, if a salt of a metal belonging to Group II of the periodic table is dispersed in the continuous phase of polyacetal, it can easily be decomposed and removed with an acid and the mark remains as a roughened surface.
Examples of the metal belonging to Group II of the periodic table used in this invention include calcium, magnesium, barium, zinc and the like, and examples of said salt include carbonate, phosphate, acetate and the like. Among the salts, the salts of calcium, magnesium and barium are preferable and carbonates of these metals are particularly preferable. Particularly, calcium carbonate is most preferable. Among the phosphates, hydrogen phosphates are most preferable.
In the surface treatment, for example plating, of a resin, the specular character of surface and the adhesion between the plated metal layer and the surface of a resin are frequently fundamentally important characteristics. Further, good heat stability at the time of molding is severely required sometimes. The inventors studied the relation between these characteristics and average particle size of various salts of metals belonging to Group II of the periodic table to reveal that the metallic salt deteriorates specular character and adhesion if the average particle size exceeds about 4.0 microns and it deteriorates adhesion and heat stability if the average particle size is smaller than about 0.1 micron.Accordingly, if specular character, adhesion and heat stability are all taken into consideration, the average particle size of the salt of metal belonging to Group II of the periodic table is preferably in the range of about 0.1 to about 4.0 microns and particularly in the range of about 0.5 to about 2.0 microns.
If the amount of salt of metal belonging to Group II of the periodic table is too small, the effect of improving the surface processability cannot be exhibted. If it is too large, the mechanical characteristic properties of polyacetal resin are deteriorated and, simultaneously, the effect of improving surface processability rather drops and heat stability at the time of molding is also deteriorated. Considering these balance, therefore, the amount of the salt is preferably in the range of about 2 to about 35 parts by weight and more preferably in the range of about 2 to about 25 parts by weight per about 100 parts by weight of polyacetal resin.
On the other hand, the inventors conducted extensive studies about this polyacetal resin composition, i.e.
various compositions comprising a polyacetal resin and various salts of metals belonging to Group II of the periodic table of which average particle size and amount are in the ranges defined above, to reveal that, in etching a molded product with an appropriate acid, i.e. an acidic solution or an oxidant solution, the molded product itself is cracked and specular character and mechanical performances of plated product are markedly deteriorated if the acidic or oxidant solution is particularly strong and that, if the condition of molding are not controlled sufficiently at the time of molding, the molded product can sometimes be discoloured and streaks of decomposition gas formed by the thermal decomposition of polyacetal resin at the time of molding can sometimes remain in the surface of the molded product.
The inventors conducted further studies with the aim of solving these problems. As the result, it was found that the above-mentioned problems can be overcome by additional incorporating, into the above-mentioned polyacetal resin composition, a polymer, a copolymer or their mixture of a compound selected from unsaturated polyester, alkyl ester of acrylic acid or methyacrylic acid, amide of acrylic acid or methacrylic acid, triallyl cyanurate, diallyl phthalate, vinyl acetate and divinylbenzene. Based on this finding, the present invention was accomplished.
As said unsaturated polyester, a product obtainable by esterifying an unsaturated dicarboxylic acid or its mixture with a saturated dicarboxylic acid or a saturated or unsaturated monocarboxylic acid with a polyhydric alcohol or its mixture with a monohydric alcohol can be used.
As the acid used for the production of said unsaturated polyester, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, endomethylenetetrahydrophthalic acid and the like can be used as said unsaturated dicarboxylic acid, and o-phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid and the like can be used as the saturated dicarboxylic acid. Mixtures of two or more members of them can also be used. As said monocarboxylic acid, acetic acid, propionic acid, butyric acid, benzoic acid, acrylic acid, methacrylic acid and the like can be used, and mixtures of two or more members of them can be used. The above-mentioned carboxylic acids may also be supplied in the form of alkyl ester such as methyl ester, dimethyl ester or the like.
As said polyhydric alcohol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like can be used. As said monohydric alcohol, methanol, ethanol, allyl alcohol and the like can be used.
An example of preferable unsaturated polyesters is an ester comprising isophthalic acid, maleic anhydride and diethylene glycol.
Said unsaturated polyester, in order to facilitate its thermosetting, is frequently provided in the form of a mixture with a crosslinking agent having reactive unsaturated bond, such as, a vinyl monomer or a prepoiymer having an unsaturated residue of vinyl group. As said crosslinking agent, styrene, amethylstyrene, vinylpyridine, vinylpyrrolidone, vinyl propionate and the like can be used.
When styrene, a-methylstyrene, vinylpyridine, vinylpyrrolidone, vinyl propionate or the like is added as a crosslinking agent, its amount is preferably in the range of about 0.2 time to about 1.0 time the weight of unsaturated polyester or the total weight of unsaturated polyester and other compounds (as has been mentioned above, it is such a range that the weight of unsaturated polyester or the total weight of unsaturated polyester and other compounds becomes about 20 parts by weight or less per about 100 parts by weight of polyacetal resin). In case of using together with crosslinking agent, said amount of the unsaturated polyester means the amount including that of the crosslinking agent used.
In the component (c) of this invention, when said unsaturated polyester is copolymerized or mixed with other compounds, their proportion may be selected arbitrarily.
As said alkyl ester of acrylic acid or methacrylic acid, those of which alkyl group has 1-5 carbon atoms and preferably 1-2 carbon atoms can be used recommendably.
In this invention, accordingly, the abovementioned component (c) to be incorporated into polyacetal resin (a) together with the salt of metal belonging to Group II of the periodic table (b) constitutes an indispensable constructional condition of the invention. The object of adding component (c) will be again summarized hereunder. It is added for the purpose of preventing a molded product from crack formation even when the etching is carried out with a particularly strong acidic solution or oxidant solution and, at the same time, for the purpose of preventing the deterioration of heat stability at the time of molding which may occur when a salt of metal belonging to Group II of the periodic table is added to polyacetal resin.
Though the reason why the cracking at the time of etching can be prevented is not known clearly, it seems to be as follows. When a salt of a metal belonging to Group II of the periodic table is added to polyacetal resin, the composition obtained is rigid and has an increased internal strain. When the above-mentioned component (c) is added thereto, the internal strain becomes smaller or disappears owing to a plasticizer-like action of component (c), so that the formation of crack can be prevented.
Though the amount of component (c) used in this invention varies depending on its kind, it is preferably used in an amount of about 0.01 to about 20 parts by weight and more preferably in an amount of about 0.01 to about 15 parts by weight per about 100 parts by weight of polyacetal resin. If its amount is less than about 0.01 part by weight, the abovementioned effect is not achievable. If its amount exceeds about 20 parts by weight, the overall strength and other characteristic properties of the compositon are deteriorated.
The polyacetal resin used in this invention may be a homopolymer, i.e. a polymer obtainable by polymerizing formaldehyde ortrioxan (including those subjected to the end group stabilization treatment) or binary, ternary or higher order copolymers obtained by copolymerizing trioxan with comonomers such as cyclic ether, cyclic acetal or the like.
It is allowable to add, to the composition of this invention, various additives usually added to polyacetal resin such as heat stabilizer, antioxidant, ultraviolet absorber, antistatic agent, crystalnucleating agent, pigment and the like.
In obtaining the composition of this invention, it is preferable to blend together the constitutional components by the use of an apparatus conventionally employed for kneading resin melts, such as kneader, roll mill, extruder and the like. From the viewpoint of interception of oxygen and work environment, the use of exbruder is most recommendable.
The temperature of blending is not lower than the melting point of polyacetal resin used. This is determined from the necessity to effect the blending of polyacetal resin uniformly in a molten state. Upper limit of the temperature is usually carried out at about 250"C or below, preferably at about 230"C or below.
Component (c) used for the sake of heat stabilization and prevention of crack, such as unsaturated polyester, may be directly blended as a polymer or a copolymer, or it may be added in the state of a monomer or a prepolymer and then polymerized in an extruder. In the case of thermosetting type of polymers, the latter method is more preferable.
From the viewpoint of producing a composition of uniform quality, it is preferable to beforehand subject the individual constitutional components to a preliminary blending by means of tumbler or Henschel mixer.
Further, from the viewpoint of stabilizing the feed into an extruder, it is more preferable to use the polyacetal resin in a powdered state. However, these are not indispensable conditions.
In the above-mentioned method in which a monomer or a prepolymer is added, it is preferable to keep the temperature of preliminary blending at a value causing no polymerization.
In the above-mentioned method in which a monomer or a prepolymer is added, a temperature of about 1 90 C and a duration of about 1 to about 10 minutes are necessary as an example of the conditions of heating enough to polymerize them, though the conditions may vary depending on the kind of monomer or prepolymer. Such conditions are attainable in most cases by combining the temperature and duration conventionally employed for blending a polyacetal resin composition by means of a conventional extruder (they are dependent on the speed of extrusion), and no auxiliary heating means is necessary. In this invention, the heating means itself is not limited.
It is also allowable to incorporate a polymerization initiator into the composition.
By the above-mentioned heating, the monomer or prepolymer added is brought into polymerization. At this time, there are many methods for ascertaining that nothing is left unreacted. Among them, a simple method is to judge it from the odor of the mixture just after being heated and extruded (usually pelletformed). Another method adoptable is to dip the pellet in a solvent and to check the extraction of unreacted matter by means of infrared spectroscopy.
The pellet of polyacetal resin composition of this invention, produced by the above-mentioned process, is then molded into any desired shape by the conventional molding means such as injection molding, extrusion molding, compression molding or the like. Said molded product has an excellent surface processability. It is subjected to a surface roughening treatment with an appropriate solution mentioned later, after which it is put to use of electro-plating, coating or the like to display its excellent characteristic properties;
As the appropriate solution used for the surface roughening treatment of the molded product obtained from the polyacetal resin composition of this invention, any solution may be used so far as it is an acidic solution or an oxidant solution capable of decomposing the metallic salt present in the composition.From the viewpoint of workability, less volatile solutions such as aqueous solution of sulfuric acid, mixed aqueous solution of sulfuric acid and phosphoric acid, mixed aqueous solution of sulfuric acid and potassium bichromate and the like are used.
When the polyacetal resin is constituted of a copolymer, the surface roughening can sufficiently be carried out with aqueous solution of sulfuric acid, mixed aqueous solution of sulfuric acid and potassium bichromate, or the like. When the polyacetal resin is constituted of a homopolymer, there is an intense tendency that the roughening of surface progresses in an ideal manner. When a mixed aqueous solution of sulfuric acid and phosphoric acid is used, the roughening of surface progresses satisfactorily whether the polyacetal is a copolymer or a homopolymer, though the progress is particularly satisfactory in the case of homopolymer. When a mixed aqueous solution of sulfuric acid and phosphoric acid is used, the proportion defined by the range shown in the attached drawing is preferable. Hereunder, using 96% sulfuric acid and 85% phosphoric acid, this will be explained with reference to a sulfuric acid-phosphoric acid concentration diagram.
The drawing attached is a diagram representing the concentrations of sulfuric acid and phosphoric acid in the etching acid solution, wherein abscissa is the content (%) of 96% by weight sulfuric acid based on water and ordinate is the content (%} of 85% by weight phosphoric acid based on water, for convenience.
The scope of concentration of the aqueous etching solution used in this invention will be explained with reference to the drawing showing the area surrounded by the straight line connecting the 100% point of 96% sulfuric acid on abscissa and the 100% point of 85% phosphoric acid on ordinate and the two axes. This area can be divided into the following parts:
(1) The left-side part of line a: Adhesion force, i.e. the peeling strength (kg/cm) of plated metal layer formed after etching and by subsequent plating process, is so low as less than 1 kg/cm. In the figure, this corresponds to the low sulfuric acid concentration region residing in the left side of the line a denoting 15% by weight of 96% sulfuric acid.
(2) The under side of line b: The etching time for giving maximum adhesion is too long (more than 150 minutes is necessary at 40"C) so that productivity is poor. In the figure, this corresponds to the region residing in the left-down side of the straight line b connecting 35% by weight point of 96% sulfuric acid and 45% by weight point of 85% phosphoric acid.
(3) The upper side of line c: The etching time for giving maximum adhesion is too short (1 minute or less at 40"C) so that stability is poor. In the figure, this corresponds to the region residing in the right-upper side of the straight line c connecting the 75% by weight point of 96% sulfuric acid and the 90% by weight point of 85% phosphoric acid.
All the above-mentioned regions (1), (2) and (3) are unemployable industrially, and the region other than (1), (2) and (3), i.e. the shadowed region which is surrounded by lines a, b and c in the figure, is the industrially employable region of this invention. When expressing the contents of said 96% sulfuric acid and 85% phosphoric acid by "x" and "y", respectively, the shadowed region is the range limited by the formulae, x 15,y --79x + 45 and - 6 ~Fr.x + 90.
Further, an aqueous solution having the total content of said 96% sulfuric acid and 85% phosphoric acid being 45 to75% by weight and the content of said 96% sulfuric acid being 15% by weight is preferable, and furthermore, in the shadowed region, the upper side
of the straight line d connecting the point of 20% by weight of 96% sulfuric acid and the point of 90% by weight ot 96% sulfuric acid and 10% by weight ot 85% phosphoric acid is particularly preferable.
The sulfuric acid and the phosphoric acid used in this invention may be usually commercialized ones. As to sulfuric acid, that having a concentration of 96% is usually available, while as to phosphoric acid that having a concentration of 85% is usually available. The concentration area of this invention has been determined on these bases. When sulfuric acid and/or phosphoric acid having a different concentration is to be used, it is necessary to use the acid or acids after re-calculation on the basis of its actual concentration.
Next, as examples of use of the molded product obtained from the composition of this invention, electroplating process and coating process will be illustrated.
The electroplating of molded plastic articles has extensively been known hitherto and is industrially employed in the case of ABS or the like. These disclosed processes may also be applied to the electroplating of the polyacetal resin composition of this invention. For example, each process is carried out in the following manner according to the description of Modern Plastics Encyclopedia, pp. 1019-1021(1967): (1) Defatting of molded article: The object of this process is to remove the fat of human hand or the mechanical oil adhering on the surface of molded article. This is carried out by dipping or vapor defatting with 1,1,1 -trichloroethane. Defatting with converitional detergent is also possible.
(2) Surface roughening: A molded article is immersed in the above-mentioned acid. Though the conditions of immersion vary with kind of molded article and composition of acid, the combination of temperature and time is selected so that the final plated product can have an excellent appearance (specular character) and around maximum and stable peeling strength. Some examples are shown in the Examples.
(3) Endowment of electrical conductivity (sensitizing, activation and electroless plating): The roughened surface thus obtained is dipped in an aqueous HC1 solution containing SnC12 and then in an aqueous HC1 solution containing SnC12 and then in an aqueous HC1 solution containing PdCl2. According to a more preferable process adoptable, it is dipped in a mixed aqueous HC1 solution containing SnC12 and PdCI2 in one step. Thus, nuclea of Pd are deposited on the roughened surface, around which a thin layer of nickel is formed chemically at the next process. Thus, an electrical conductivity is given to the surface of molded article.
(4) Electroplating: Electroplating is carried out to a thickness fit for the use according to the usual method in the order of, for example, Cu/Ni/Cr.
When the polyacetal resin molded product having an excellent surface processability is etched and electro-plated in the above-mentioned manner, the adhesion or peeling strength of the plated layer is about 1 kg/cm or more and usually about 1.5 to about 2.5 kg/cm. The etched article also shows a surprising effect in the case of other than metal plating, namely in the case of coating or adhesion with adhesive, which demonstrates the usefulness of the polyacetal resin composition of this invention.
Next, the coating process will be illustrated. The molded article is defatted and surface-roughened by the same or similar process as in electroplating, after which the surface is thoroughly dried. Then general coating materials are applied and baked for an appointed period of time.
This invention will be illustrated more concretely bythefollowing examples.
Examples 1-13 and Comparative Examples 1-2
100 parts by weight of polyacetal resin 'TenacCR5010 (manufactured by Asahi Kasei Kogyo Co., acetal homopolymer, general grade) was mixed with 8.7 parts by weight of finely powdered calcium carbonate (manufactured by Shiraishi Calcium Co., average particle size 1.25 microns) and a quantity shown in Table 1 of component (c) compound by means of tumbler, after which the mixture was kneaded and pelletized by means of an extruder set at 190"C. By using the pellet, its heat stability was measured and, at the same time, a plaque of " thick was prepared by injection molding as a sample material.
The plaque was defatted with 1,1,1 -trichloroethane and then etched by dipping it in a solution comprising 96% sulfuric acid/85% phosphoric acid/water = 40/25/35 (wt %) at 40"C for 8 minutes.
Then, the etched plaque was plated in the usual manner. Namely, it was dipped for an appointed period of time in a pretreatment solution for plastic plating (manufactured by Okuno Seiyaku Kogyo Co., "Catalyst") and then an accelerator (10% aqueous solution of hydrochloric acid), after which it was chemically plated with a chemical plating solution (manufactured by Okuno Seiyaku Kogyo Co., TMP chemical nickel plating solution) according to the appointed method and then immediately subjected to electroplating. The average thicknesses of the plated metal layers were copper 40 microns, nickel 10 microns and chromium 0.1 micron.
Performances of the plated product thus obtained were as shown in Table 1. The performances were measured by the following methods:
(1) Peeling strength of plated product: Two parallel breaking lines, 10 mm apart, were drawn on the plated surface, and the plated metal layer between the breaking lines was stretched to the right angle direction of the flat plate to measure the stress necessary for peeling.
(2) Appearance of plated product: Under a light source of 300 luxes or more, the appearance was examined by the naked eye at a distance of 60 cm from the test surface. The criterion of the evaluation was as shown in the foot note of Table 1.
As is understandable from Table 1, the polyacetal resin composition of th is invention is improved in heat stability and excellent in plating characteristics.
TABLE 1
Comparative Example Example 1 2 1 2 3 4 5 6 7
Polyacetal resin (TenacR5010) 100 100 100 100 100 100 100 100 100 (parts by wt.)
Calcium carbonate (av. particle size 1.25 ) 0 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 (parts by wt.)
Unsatu- Methyl Ethyl Meth
Compound rated Methyl Ethyl meth- meth- Acryl- acrylpolyester acrylate acrylate acrylate acrylate amide amide (Note 5) (parts by wt.) 0 0 0.87 0.01 0.76 0.87 0.01 0.87 0.87
Heat stability (Note 1) Residual unreacted compound None None None None None None None
Method of detection (Methanol (Meth- (Meth- (Meth- (Meth (odor) (odor) (solvent extraction toluene) anol) anol) anol) anol) or odor)
Appearance of plated product (Note 2) Peeling strength of plated 0.2 2.2 2.3 1.6 1.8 1.7 1.6 2.0 2.1 product (kg/cm) TABLE I cont
Example 8 9 10 11 12 13 100 100 100 100 100 100 8.7 8.7 8.7 8.7 8.7 8.7
Triallyl Diallyl Polyvinyl Unsatucyanurate phthalate Vinyl Divinyl- acetate rated Acryl (Note 3) (Note 3) acetate benzene (Note 4) polyester amide 6.10 0.87 0.87 0.87 0.87 0.50 0.40
None None None None None (odor) (odor) (odor) (odor) - (odor)
1.8 1.6 1.7 2.1 2.2 2.1 (Note 1)
Injection molding can be carried out quite satisfactorily under usual conditions.
Injection molding is possible without practical problems though the range of suitable
conditions are somewhat narrow.
At the time of injection molding, streaks are formed due to decomposition of resin.
x Extrusion is impossible
Note 2) Appearance was evaluated by the naked eye according to the following criterion: o The so-called mirror surface having no crack.
A Obscure image though the face is reflected; no crack.
x No reflected image of face; crack formed.
(In the following Tables, same symbols as above have the same meanings as above.)
Note 3) 0.20 part by weight (Example 8) and 0.04 part by weight (Example 9) of 2,5-dimethyl-2,5-di(t
butylperoxy)-hexane was added as polymerization initiator.
[Note 4) Degree of polymerization 200 (Nihon Gosei Kaguku Kogyo Co.); the other compounds were of
chemically pure grade.
(Note 5) Upica CLC-834 (manufactured by Toyo Boseki Co.)
Examples 1417 and Comparative Examples 3-4
100 Parts by weight of polyacetal resin "Tenac5010" (manufactured by Asahi Kasei Kogyo Co., acetal homopolymer, general grade) was mixed with 8.7 parts by weight of magnesium carbonate (average particle size 2-3 microns), barium carbonate (average particle size 2 microns), barium acetate (average particle size 3 microns) or calcium hydrogen phosphate (average particle size 2-3 microns) in place of the calcium carbonate, and as a reactive compound, an appointed quantity of unsaturated polyester [a mixture comprising 70 parts by weight of a polyester prepolymer, which was produced from isophthalic acid/maleic anhydride/diethylene glycol (= 1 mole/1 mole/2 moles) and has an average polymerization degree of 10, and 30 parts by weight of styrene as cross-linking agent] by means of a tumbler, after which the mixture was
kneaded and pelletized by means of an extruder in the same manner as above.
The heat stability of this pellet was measured and, at the same time, a plaque was made therefrom and
plated by the same process as in Example 1 to investigate the performances of plated product.
Heat stabilities of these polyacetal resind compositions and the performances of the plated products were as shown in Table 2.
(All the above-mentioned metallic salts were of chemically pure grade. Barium acetate was used after pulverization in a mortar, while the other were used as they are.) TABLE 2
Comparative Example Comparative Example Example Example
Example 3 14 Example 4 15 16 17
Polyacetal resin 100 100 100 100 100 100 (Tenac R5010) (parts by wt.)
Magnesium caronate (Av. particle size 2-3 l) 8.7 8.7 - - - (parts by wt.)
Barium carbonate (Av. particle sise 2 ) - - 8.7 8.7 - (parts by wt.)
Barium acetate (Av. particle sise 3 ) - - - - 8.7 (pats by wt.)
Calcium hydrogen phosphate (Av. particle size 2-3 ) - - - - - 8.7 (parts by wt.)
Unsaturated polyester - 8.7 - 10.0 0.15 0.87 (parts by wt.)
Violent Violent
Extrudability Good Good Good Good foaming foaming Heat stability
Appearance of plated product
Peeling strength of plated - 1.8 - 1.7 1.6 1.7 metal layer (kg/cm) Examples 18-20 and Comparative Examples 5-6
100 Parts by weight of polyacetal resin "Tenac z 5010" (manufactured by Asahi Kasei Kogyo Co.) was mixed with 11.1 parts by weight of calcium carbonate (manufactured by Shiraishi Calcium Co.) having the various average particle size shown in Table 3 and 1.1 parts by weight of unsaturated polyester (manufactured by Toyo Boseki Co.).The resin composition obtained was plated by the same method as in
Example land performances of the plated products were investigated.
Performances of these plated products were as shown in Table 3.
TABLE 3 Comparative Example Example Example Comparative
No. Example 5* 18 19 20** Example 6
Average particle size of calcium carbonate 0.08 1.0 1.25 3.6 5.0 (micron) Heat stability x O Appearance - 0 0 A x Peeling strength - 2.0 2.0 1.5 1.0 (kg/cm) * Extrution was impossible.
** It is applicable to uses for which good appearance is not necessarily required.
Examples 21-23 and Comparative Example 7
The same etched plaque as in Table 3 was used. After being etched, it was thoroughly washed with water, air-dried, coated with an acrylic coating material (manufactured by Tokyo Paint Co.) and then baked at 150"C for 30 minutes. Adherence of coated film was tested by pressing a strip of pressure sensitive transparent adhesive tape over an area of the surface which was cross hatched with " sqares and then stripping the tape away. The results are shown in Table 4.
TABLE 4 Comparative No. Example 21 Example 22 Example 23 Example7 Average particle size of calcium carbonate 1.0 1.25 3.6 5.0 (micron)
Adherence of coating film ({ ) 0 x
Gloss Glossy Glossy Glossy Not glossy
Criterion for the evaluation of adherence test: z No change occurs at all.
O Partial peeling occurs at corner parts.
x Percentage of peeled squares is 20% or less
xx Almost all the squares are peeled.
Examples 24-27 and Comparative Examples 8-10
Using the same calcium carbonate as in Example 1 (average particle size 1.25 microns), plating was carried out by the same method as in Example 1, provided that the amount of calcium carbonate was varied as shown in Table 5 and unsaturated polyester was added in an amount corresponding to 10% of the amount of calcium carbonate (parts by weight). The results are shown in Table 5.
TABLE 5
No. Compa- Compa- Comparative rative Example Example Example Example rative
Example Example 24 25 26 27 Example 8 9 10
Polyacetal resin (TenacR5010) (parts by wt.) 100
Calcium carbonate (Av. particle size 1.25 ) 0 1 3.1 8.7 17.6 25.0 42.9 (parts by wt.)
Unsaturated polyester (parts by wt.) 0 0.1 0.31 0.87 1.76 2.5 4.3
Heat stability o o o o o 0 x
Tensile strength 700 700 690 650 600 580 (kg/cm)
Perfor- Tensile elongation 18 17 16 12 9 8 mances (between chucks, %) before plating Flexural strength 1,050 1,050 1,040 1,040 1,030 1,020 (kg/cm)
Izod impact strength (notched,) 6 6 5 5 4 4 kg.cm/cm)
Appearance of plated product x x O O O O
Peeling strength of plated 0.7 0.9 1.5 2.3 2.3 2.0 metal layer (kg/cm) (Note) In Comparative Example 10, the resin decomposed when extruded.
Examples 28-31 and Comparative Examples 11-12
The experiment of Examples 25-27 and Comparative Example 8 was repeated, except that "Duracon 23 M90-02" (manufactured by Polyplastics Co., acetal copolymer, general grade) was used as polyacetal resin.
The results are shown in Table 6.
TABLE 6
Comparative Example Example Example Example Comparative
Example 11 28 29 30 31 Example 12
Polyacetal resin (Duracon RM90-02) 100 100 100 100 100 100 (parts by wt.)
Calcium carbonate (Av. particle size 1.25 ) 0 8.7 17.6 25.0 33.3 42.9 (parts by wt.)
Unsuturated polyester 0 0.87 1.76 2.50 3.33 4.29 (parts by wt.)
Heat stability o o o o 0 #
Appearance of plated product O O O O # x
Peeling strength of plated 0.2 1.3 2.1 1.8 1.5 1.0 metal layer (kg/cm) Examples 32-34 and Comparative Example 13
The experiment of Example 25 was repeated, except that the amount of unsaturated polyester was varied.
The results are shown in Table 7.
TABLE 7
Comparative
Example 13
Example 32 Example 33 Example 34
Polyacetal resin (TenacR5010) 100 100 100 100 (parts by wt.)
Calcium carbonate (Av. particle size 8.7 8.7 8.7 8.7 1.25 ) (parts by wt.)
Unsaturated polyester (parts by wt.) 0.87 10 15 25
Heat stability # O O x
Tensile strength (kg/cm) 650 600 570 520
Tensile elongation 12 13 13 14 (between chucks, %)
Flexural strength (kg/cm) 1,040 900 850 740
Izod impact strength 5 4 3 2 (notched, kg-cm/cm) Examples 35-40 and Comparative Examples 14-18
The same plaque having a thickness of 3 mm as in Example 1 was plated in the same manner as in
Example 1, provided that the composition of etching solution was varied as shown in Table 8. Peeling strengths of the plated metal layers obtained were as shown in Table 8.
TABLE 8
Example Comparative Example 35 36 37 38 39 40 14 15 16 17 18 96% sulfuric acid/ 85% phosphoric acid 40/25 30/35 32/10 25/55 45/0 60/0 20/0 10/15 20/15 76/24 80/0 (parts by wt.)*
Optimum etching time 8 8 70 3 50 4 800 1,000 600 1 1 (40 C x min.)
Peeling strength 2.2 2.0 1.6 2.0 1.5 1.6 1.0 0.4 1.1 1.9 1.4 (kg/cm) * When the sum of parts by weight was less than 100, water was added till the total weight reached 100 parts by weight.
Example 41
The same plaque having a thickness of 3 mm as in Example 29 was dipped in an etching solution having the following composition at 400C for 12 minutes and then subjected to electroplating by repeating the steps mentioned in Example 29. Peeling strength of the plated metal layer obtained was 1.3 kg/cm.
Composition of etching solution:
96% sulfuric acid 55 parts by weight
potassium bichromate 4 parts by weight
water 45 parts by weight
As is understandable from the examples mentioned above, the polyacetal composition of this invention is excellent in heat stability and, when its molded product is etched with an appropriate acid, it gives a molded product excellent in surface processability, so that the application field of the resin is further expanded. For example, it is substitutive for metals in the parts of which both functional and decorative characters are required. Thus, its effect of weight reduction and cost saving is very great.
Claims (18)
1. A polyacetal resin composition excellent in heat stability and surface processability which comprises
(a) about 100 parts by weight of polyacetal resin, (b) about 2 to about 35 parts by weight of carbonate,
phosphate, acetate or their mixture of a metal belonging to Group II of the periodic table and (c) about 0.01 to
about 20 parts by weight of polymer, copolymer or their mixture of a compound selected from unsaturated
polyester, alkyl ester of acrylic acid or methacrylic acid, amide of acrylic acid or methacrylic acid, triallyl
cyanurate, diallyl phthalate, vinyl acetate and divinylbenzene.
2. A polyacetal resin composition according to Claim 1, wherein said metal belonging to Group II of the
periodic table is calcium, magnesium or barium.
3. A polyacetal resin composition according to Claim 1, wherein said salt of metal belonging to Group II
of the periodic table has an average particle size of about 0.1 to about 4.0 microns.
4. A polyacetal resin composition according to Claim 1, wherein said salt of metal belonging to Group II
of the periodic table is calcium carbonate having an average particle size of about 1.25 microns.
5. A polyacetal resin composition according to Claim 1, wherein said alkyl ester of acrylic acid or
methacrylic acid is methyl ester or ethyl ester.
6. A composition according to Claim 1, wherein said polyacetal resin contains a heat stabilizer, an
antioxidant, an ultraviolet absorber, an antistatic agent, a crystal-nucleating agent or a pigment.
7. A process for roughening the surface of a molded product constituted of a polyacetal resin
composition excellent in heat stability and surface processability and comprising (a) about 100 parts by
weight of polyacetal resin, (b) about 2 to about 35 parts by weight of carbonate, phosphate, acetate or their
mixture of a metal belonging to Group II of the periodic table and (c) about 0.01 to about 20 parts by weight
of polymer, copolymer or their mixture of a compound selected from unsaturated polyester, alkyl ester of
acrylic acid or methacrylic acid, amide of acrylic acid or methacrylic acid, triallyl cyanurate, diallyl phthalate,
vinyl acetate and divinylbenzene, which comprises dipping said molded product in an aqueous solution
containing sulfuric acid.
8. A process for roughening the surface according to Claim 7, wherein said aqueous solution containing
sulfuric acid has a sulfuric acid concentration of 35% by weight to 75% by weight.
9. A process for roughening the surface according to Claim 7, wherein said aqueous solution containing
sulfuric acid additionally contains phosphoric acid.
10. A process for roughening the surface of a molded product of polyacetal resin according to Claim 9,
wherein the composition of sulfuric acid, phosphoric acid and water is represented, in a sulfuric
acid-phosphoric acid-water concentration diagram, by the region which is in the right side of line a
expressing 15% by weight of 96% sulfuric acid, in the upper side of straight line b connecting the point of
35% by weight aqueous solution of 96% sulfuric acid and the point of 45% by weight aqueous solution of
85% phosphoric acid, and in the down side of straight line c connecting the point 75% by weight aqueous
solution of 96% sulfuric acid and the point of 90% by weight aqueous solution of 85% phosphoric acid.
11. A process for roughening the surface according to Claim 7, wherein said aqueous solution containing
sulfuric acid additionally contains potassium bichromate.
12. A process for roughening the surface according to Claim 9, wherein the roughening is carried out
with a solution having a composition of sulfuric acid/phosphoric acid/water = about 40/about 25/about 35, as
expressed by parts by weight.
13. A process for roughening the surface according to Claim 7 substantially as described in any one of
the Examples.
14. A molded product having a roughened surface obtained by a process according to any one of Claims
7 to 13.
15. A process according to anyone of Claims 7 to 13 further comprising electroplating or coating the
roughened surface of the molded product.
16. A molded product which has been electroplated or coated by a process according to Claim 15.
17. A polyacetal resin composition according to Claim 1 substantially as described in any one of the
Examples.
18. A molded product obtained by molding a polyacetal resin composition according to any one of Claims 1 to 6 or Claim 17
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53130479A JPS584936B2 (en) | 1978-10-25 | 1978-10-25 | Surface treatment method for polyacetal resin composition |
| JP10410279A JPS5628236A (en) | 1979-08-17 | 1979-08-17 | Polyacetal resin composition for molded article to be surface treated and having excellent thermal stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2035335A true GB2035335A (en) | 1980-06-18 |
| GB2035335B GB2035335B (en) | 1983-01-19 |
Family
ID=26444647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7936174A Expired GB2035335B (en) | 1978-10-25 | 1979-10-18 | Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same |
Country Status (4)
| Country | Link |
|---|---|
| DE (2) | DE2953528C2 (en) |
| FR (1) | FR2439803A1 (en) |
| GB (1) | GB2035335B (en) |
| IT (1) | IT1164132B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4587033A (en) * | 1984-07-02 | 1986-05-06 | Monsanto Company | Polymeric acetal carboxylate compositions |
| USRE34141E (en) * | 1988-08-22 | 1992-12-08 | Polyplastics Co., Ltd. | Weather-resistant polyacetal resin composition and molded articles therefrom |
| WO2004104096A1 (en) * | 2003-05-13 | 2004-12-02 | E.I. Dupont De Nemours And Company | Modified polyacetals for decorative applications |
| WO2005000950A1 (en) * | 2003-06-20 | 2005-01-06 | E.I. Dupont De Nemours And Company | Modified polyacetals for plating |
| WO2009050176A1 (en) * | 2007-10-16 | 2009-04-23 | Basf Se | Method for producing impact-resistant modified pom |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665704B2 (en) * | 1985-02-04 | 1994-08-24 | ポリプラスチックス株式会社 | Polyacetal resin composition for plating |
| JPH07110917B2 (en) * | 1988-07-14 | 1995-11-29 | ポリプラスチックス株式会社 | Weather resistant polyacetal resin composition |
| SG49180A1 (en) * | 1989-03-17 | 1998-05-18 | Du Pont | Polyacetal resins containing non-meltable polymer stabilizers or cellulose stabilizers |
| AU718841B2 (en) * | 1995-10-31 | 2000-04-20 | Indigo Medical, Incorporated | Light-diffusing device for an optical fiber, methods of producing and using same, and apparatus for diffusing light from an optical fiber |
| DE19725054A1 (en) * | 1997-06-13 | 1998-12-17 | Basf Ag | Molding compounds resistant to sliding friction |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1026017A (en) * | 1962-04-19 | 1966-04-14 | Celanese Corp | Oxymethylene polymer compositions |
| GB1048115A (en) * | 1963-09-09 | 1966-11-09 | Toyo Rayon Co Ltd | Process for melt-shaping polyacetal |
| DE2233143C3 (en) * | 1972-07-06 | 1980-09-18 | Hoechst Ag, 6000 Frankfurt | Thermoplastic molding compounds based on poly (oxymethylene) |
| DE2108475A1 (en) * | 1971-02-23 | 1972-09-07 | Thoener R | Eching polyoxy methylene (co) olymer articles - with phosphoric acid and alcohol mixt before metal plating |
| JPS5936644B2 (en) * | 1975-04-30 | 1984-09-05 | 旭化成株式会社 | Polyoxymethylene resin composition |
| JPS606969B2 (en) * | 1975-04-30 | 1985-02-21 | 旭化成株式会社 | Reinforced polyacetal resin composition and method for producing the same |
| JPS599580B2 (en) * | 1975-05-12 | 1984-03-03 | 旭化成株式会社 | Highly lubricating resin composition |
| JPS53102358A (en) * | 1977-02-19 | 1978-09-06 | Fuji Electric Co Ltd | Arc extinguishing thermosetting resin composition |
-
1979
- 1979-10-18 GB GB7936174A patent/GB2035335B/en not_active Expired
- 1979-10-23 DE DE2953528A patent/DE2953528C2/en not_active Expired
- 1979-10-23 DE DE2942744A patent/DE2942744C2/en not_active Expired
- 1979-10-23 IT IT50647/79A patent/IT1164132B/en active
- 1979-10-24 FR FR7926404A patent/FR2439803A1/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4587033A (en) * | 1984-07-02 | 1986-05-06 | Monsanto Company | Polymeric acetal carboxylate compositions |
| USRE34141E (en) * | 1988-08-22 | 1992-12-08 | Polyplastics Co., Ltd. | Weather-resistant polyacetal resin composition and molded articles therefrom |
| WO2004104096A1 (en) * | 2003-05-13 | 2004-12-02 | E.I. Dupont De Nemours And Company | Modified polyacetals for decorative applications |
| WO2005000950A1 (en) * | 2003-06-20 | 2005-01-06 | E.I. Dupont De Nemours And Company | Modified polyacetals for plating |
| WO2009050176A1 (en) * | 2007-10-16 | 2009-04-23 | Basf Se | Method for producing impact-resistant modified pom |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1164132B (en) | 1987-04-08 |
| IT7950647A0 (en) | 1979-10-23 |
| DE2953528C2 (en) | 1982-03-18 |
| DE2942744C2 (en) | 1982-05-06 |
| FR2439803B1 (en) | 1985-03-08 |
| DE2942744A1 (en) | 1980-04-30 |
| FR2439803A1 (en) | 1980-05-23 |
| GB2035335B (en) | 1983-01-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19971018 |