JPS631345B2 - - Google Patents
Info
- Publication number
- JPS631345B2 JPS631345B2 JP54104102A JP10410279A JPS631345B2 JP S631345 B2 JPS631345 B2 JP S631345B2 JP 54104102 A JP54104102 A JP 54104102A JP 10410279 A JP10410279 A JP 10410279A JP S631345 B2 JPS631345 B2 JP S631345B2
- Authority
- JP
- Japan
- Prior art keywords
- polyacetal resin
- acid
- weight
- parts
- thermal stability
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229930182556 Polyacetal Natural products 0.000 claims description 43
- 229920006324 polyoxymethylene Polymers 0.000 claims description 43
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 230000000737 periodic effect Effects 0.000 claims description 14
- 229920006305 unsaturated polyester Polymers 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 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 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 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 description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 238000007747 plating Methods 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 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
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000005846 sugar alcohols 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 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
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- JZULKTSSLJNBQJ-UHFFFAOYSA-N chromium;sulfuric acid Chemical compound [Cr].OS(O)(=O)=O JZULKTSSLJNBQJ-UHFFFAOYSA-N 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
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000004898 kneading Methods 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- 150000004702 methyl esters Chemical class 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
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 238000011160 research Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は熱安定性に優れた被表面加工用ポリア
セタール樹脂組成物に関する。
プラスチツクは一般に化学的には極めて安定で
あり、また通常の射出成形等による成形品は表面
が平滑であつて、このため印刷、塗装、蒸着など
の表面加飾や、接着剤による接着など表面の加工
は施しにくい。特にポリアセタール樹脂は表面活
性に乏しく、親和性のある適当な溶剤などもない
ため、このような表面加飾や接着などが難しく、
こうした加工が必要な用途にはほとんど用いられ
ていないのが現状である。逆の見方をすれば、ポ
リアセタール樹脂は機械的性能が優れていること
から、主として機械部品などに使用される例が多
く、表面加飾などを要求されることは従来それほ
どなかつたともいえる。
ところが、最近はプラスチツクの応用が多様、
かつ高度化する傾向が強くなり、機能と外観、あ
るいは機能と接着性といつた従来必ずしも両立を
求められなかつた複数の性能が同時に要求される
場合がしばしば生じてきた。このようにしてポリ
アセタール樹脂の用途においても、良好な表面加
工性が要求される例が多くなつてきている。
ポリアセタール樹脂の表面加工性を向上させる
方法についての研究はこれまで盛んであつたとは
いい難いが、例えば成形品表面を酸性液、または
酸化性液で処理することによつて表面加工性が幾
分か向上することが知られており、酸性液として
はp−トルエンスルホン酸、樟脳スルホン酸、リ
ン酸、酸性硫酸アンモンなどが、また酸化性液と
してクロム硫酸混液が提案されている。
これらの液による処理の目的は、ポリアセター
ル樹脂成形品表面を化学的にしん蝕させることに
よつて粗面をつくり出すとともに、その酸化作用
などによつてポリアセタール分子の一部に活性な
反応基を形成させることにあると考えられるが、
一般にこのような表面処理を行なおうとした場合
表面処理効果を十分に高めようとすると、母材で
あるポリアセタール樹脂成形品の劣化が全体に起
こつたり、亀裂が発生するなどの不都合が生じ
る。一方、母材の劣化を起こさないような処理条
件では表面処理効果が不十分となり良好な表面加
工ができない。このため、実用に供し得る表面加
工性を持つたポリアセタール樹脂成形物は、これ
まで知られていなかつた。
本発明者らは、表面加工性の優れたポリアセタ
ール樹脂成形物を得るべく、ポリマー組成につい
て鋭意検討した結果、ポリアセタール樹脂と周期
律表第族の金属塩とある種の重合物とからなる
組成物が、熱安定性および被メツキ性に優れた性
能を示すことを見い出した。
すなわち、本発明は、(a)ポリアセタール樹脂
100重量部、(b)周期律表第族金属の炭酸塩、り
ん酸塩、酢酸塩またはそれらの混合物の平均粒径
が0.1〜4.0ミクロンの範囲にある粉末2〜35重量
部、および(c)不飽和ポリエステル、アクリル酸あ
るいはメタクリル酸のアルキルエステル、アクリ
ル酸あるいはメタクリル酸のアミド、シアヌル酸
トリアリル、ジアリルフタレート、酢酸ビニルお
よびジビニルベンゼンの群から選ばれた化合物の
重合物、共重合物あるいはそれらの混合物0.01〜
20重量部とからなる熱安定性に優れた被表面加工
用ポリアセタール樹脂組成物に関するものであ
る。
本発明において、ポリアセタール樹脂に周期律
表第族金属の各種塩を含有せしめる目的は、表
面加工に適した粗化表面を容易に形成させるため
である。つまりポリアセタール連続相中に、周期
律表第族金属の各種塩を分散点在せしめると、
それらが適当な酸により容易に分解除去され、そ
の跡が粗化表面として残るのである。本発明に用
いられる周期律表第族金属の各種塩中、好まし
い炭酸塩の例としては、炭酸カルシウム、炭酸マ
グネシウム、炭酸亜沿、炭酸バリウムなどが挙げ
られるが、特に炭酸カルシウムが最も好ましい。
また、表面加工、例えばメツキにおいてはしば
しば表面の鏡面性およびメツキ金属と樹脂間の密
着力が基本的に重要な特性となる。また成形時の
熱安定性が良いことが厳しく要求されることもあ
る。本発明者らは、これらの特性と周期律表第
族金属の各種塩の平均粒径との関係を検討した結
果、平均粒径4.0ミクロンを越える前記金属塩は
鏡面性および密着力を悪化せしめ、一方平均粒径
0.1ミクロン未満の金属塩は密着力および熱安定
性を低下せしめることがわかつた。従つて鏡面
性、密着力、熱安定性を考慮した場合、周期律表
第族金属の各種塩の平均粒径は0.1〜4.0ミクロ
ン、特に0.5〜2.0ミクロンの範囲にあることが好
ましい。また含有せしめる周期律表第族金属の
各種塩の重量は、少量では表面加工性改良の効果
が現われず多すぎるとポリアセタール樹脂として
の機械的特性が低下するのみならず、表面加工性
改良効果も逆に低下し、更に成形時の熱安定性も
悪くなるので、それらのバランスを考慮すると、
ポリアセタール樹脂100重量部に対して2〜35重
量部であるのが好ましい。
一方、本発明者らはこのポリアセタール樹脂組
成物、すなわちポリアセタール樹脂に前記した範
囲の平均粒径および量の周期律表第族金属の各
種塩を加えた組成物について種々検討したとこ
ろ、成形物を適当な酸、すなわち酸性液または酸
化性液でエツチングする場合、特に強い酸性液、
強い酸化性液において成形物自体に亀裂が入り、
メツキ物の鏡面性および機械的性能が著しく低下
すること、および組成物によつては成形時成形条
件を十分管理しなければ成形物が変色したり、成
形物にポリアセタール樹脂が熱分解して生じた分
解ガスの条痕が残つてしまつたりすることなどが
明らかとなつた。
そこで、本発明者らはこれらの問題を解決すべ
く、さらに鋭意検討した結果、上記ポリアセター
ル樹脂組成物に、さらに不飽和ポリエステル、ア
クリル酸あるいはメタクリル酸のアルキルエステ
ル、アクリル酸あるいはメタクリル酸のアミド、
シアヌル酸トリアリル、ジアリルフタレート、酢
酸ビニルおよびジビニルベンゼンから選ばれた化
合物の重合物、共重合物あるいはそれらの混合物
である(c)成分を含有させることによつて、上記問
題がなくなることを見い出したものである。(c)成
分を含有せしめた理由は上記による。
不飽和ポリエステルは不飽和ポリエステルプレ
ポリマー単独またはこれとビニル単量体あるいは
その不飽和残基をもつプレポリマーからなる架橋
剤との混合の形で提供される。
不飽和ポリエステルプレポリマーとしては不飽
和ジカルボン酸、またはこれに飽和ジカルボン酸
や飽和不飽和モノカルボン酸を併用したものと、
多価アルコールまたはこれと一価アルコールとを
併用したものとをエステル化反応させることによ
つて得られる生成物が用いられる。
不飽和ポリエステルプレポリマーの製造に用い
られる酸類としては、不飽和ジカルボン酸として
例えばマレイン酸、無水マレイン酸、フマル酸、
イタコン酸、シトラコン酸、エンドメチレンテト
ラヒドロフタル酸など、また飽和ジカルボン酸と
してオルソフタル酸、無水フタル酸、イソフタル
酸、テレフタル酸、アジピン酸などが挙げられ
る。これらの2種またはそれ以上の混合物も使用
可能である。モノカルボン酸としては、酢塩、プ
ロピオン酸、酪酸、安息香酸、アクリル酸、メタ
クリル酸などが挙げられ、この2種またはそれ以
上の混合物もまた用いられる。以上のカルボン酸
類はまたメチルエステル、ジメチルエステルなど
のアルキルエステルの形で提供されてもよい。
多価アルコールとしては、エチレングリコー
ル、プロピレングリコール、ブタンジオール、ジ
エチレングリコール、ジプロピレングリコール、
グリセリン、トリメチロールプロパンなど、また
一価アルコールとしてはメタノール、エタノー
ル、アリルアルコールなどが使用される。
架橋剤としては、本願発明の(c)成分とした化合
物が用いられるが、それ以外にもスチレン、α−
メチルスチレン、ビニルピリジン、ビニルピロリ
ドン、プロピオン酸ビニルなどがある。
上記した(c)成分以外の架橋剤の添加量は、不飽
和ポリエステルプレポリマーの重量に対し0.2な
いし1.0倍の範囲が好ましく、さらに好ましい結
果をもたらすためには、ポリアセタール樹脂100
重量部に対して5重量部以下である。
本発明において、ポリアセタール樹脂に周期律
表第族金属の各種塩とともに含有させる上記重
合物は、本発明の必須構成要件である。その目的
をもう一度要約すると、前述のごとく、特に強い
酸性液、強い酸化性液によるエツチングにおいて
も成形物に亀裂が入らないようにするとともに、
ポリアセタール樹脂に周期律表第族金属の各種
塩を含有させたときの成形時の熱安定性の低下を
防ぐためである。
エツチング時の亀裂防止の理由については明ら
かではないが、ポリアセタール樹脂に周期律表第
族金属の各種塩を含有せしめると、その組成物
はかたくなり、内部歪が増大するが、これに上記
重合物をさらに存在せしめると、その可塑剤的な
働きにより、内部歪が小さくなり、またはなくな
り、亀裂が防止されるものと思われる。
また、本発明に用いられる重合物の量は、それ
らの種類によつて異なり、ポリアセタール樹脂
100重量部に対して0.01〜20重量部であることが
好ましい。0.01重量部未満では上記効果が得られ
ず、20重量部を超える場合には、組成物全体とし
ての強度、その他の特性を低下せしめる。
本発明に使用されるポリアセタール樹脂は、ホ
モ重合体、すなわちホルムアルデヒドまたはトリ
オキサンを重合して得られる重合物(末端を安定
化処理したものを含む)であつてもよく、またト
リオキサンと環状エーテル、環状アセタールのよ
うな共単量体を共重合させた、二元あるいは三元
以上の共重合物であつてもよい。
本発明の組成物には、通常ポリアセタール樹脂
に添加される各種添加剤、例えば熱安定剤、酸化
防止剤、紫外線吸収剤、帯電防止剤、結晶核剤、
顔料などが加えられても差し支えない。
本発明の組成物を得るためには、ニーダー、ロ
ールミル、押出機などの、通常樹脂溶融体の混練
に用いられる装置を用いて構成各成分を混合する
ことが好ましい。酸素の遮断や作業環境の点など
からは、押出機が最も好ましい。
混合の温度は、使用するポリアセタール樹脂の
融点以上である。これは、ポリアセタール樹脂の
溶融状態で混合を均一に行なう必要から決定され
る。温度の上限は一般に使用するポリアセタール
樹脂の熱分解に対する安定性によつて制限され、
通常250℃以下、好ましくは230℃以下で混合が行
なわれる。
熱安定性および亀裂防止のための不飽和ポリエ
ステル等重合物は、重合物としてそのまま混合し
ても良いし、単量体あるいはプレポリマーの状態
で添加し、押出機中で重合せしめても良い。熱硬
化型の重合物の場合は、後者のほうが好ましい。
また、構成各成分をあらかじめタンブラーある
いはヘンシエルミキサーなどを用いて予備混合し
ておくことが、均質な組成物を作る上で好ましく
ポリアセタール樹脂は粉末状態で用いることが押
出機への安定供給上さらに好ましいが、これらは
必須条件ではない。
なお、上記単量体またはプレポリマーを添加す
る方法の場合には、予備混合中に重合反応が起こ
らない程度の温度を保つことが好ましい。
上記単量体またはプレポリマーを添加する方法
の場合、それらを重合に到らしめる加熱条件とし
ては、単量体またはプレポリマーの種類にもよる
が、例えば190℃×1〜10分程度が必要である。
この条件は、通常の押出機を用いてポリアセター
ル樹脂組成物を混合する際用いられる一般的な温
度と時間(押出速度により決まる)の組み合わせ
により、ほとんどの場合達成でき、それ以外の補
助的加熱手段を必要としないが、本発明において
は加熱方法自体について何らかの限定をするもの
ではない。
また、組成物に重合開始剤を添加せしめても差
し支えない。
上記加熱により、添加した単量体またはプレポ
リマーの重合が完結して未反応物が残つていない
ことを確認する方法には種々あるが、簡単な方法
は加熱混合直後(通常ペレツト状)の臭いによる
確認法、さらにはペレツトを溶媒に浸漬し、未反
応物が抽出されるかどうかの赤外線分光光度法な
どによる確認法がある。
以上の方法で製造された本発明のポリアセター
ル樹脂組成物は通常、射出成形機により成形品と
され(成形品形状によつては押出機その他も使用
され得る)、さらにそれが適当な酸によつてエツ
チングされる。これによつて所望の表面加工性の
優れたポリアセタール樹脂成形物が得られる。
本発明のポリアセタール樹脂組成物のエツチン
グに用いられる適当な酸は、前記したように配合
された周期律表第族金属の各種塩を分解させる
酸性液または酸化性液であれば、どのようなもの
でも使用できるが、好ましくは揮発性の少ない酸
性液または酸化性液、例えば硫酸水溶液、硫酸−
リン酸の混合水溶液、硫酸−クロム酸の混合水溶
液、リン酸水溶液などが作業性の点から好まし
い。
このようにしてエツチングされた、表面加工性
の優れたポリアセタール樹脂成形物は、金属メツ
キした際のメツキ層の剥離強度(Kg/cm)が1
Kg/cm以上、通常1.5〜2.5Kg/cmの密着力を有
し、また金属メツキ以外の塗装や接着剤による接
着においても驚くべき効果を示し、本発明のポリ
アセタール樹脂組成物がいかに有用であるかがう
かがえる。
以下実施例により、本発明をさらに具体的に説
明する。
実施例1〜13および比較例1〜2
ポリアセタール樹脂として「テナツク5010」
(旭化成工業株式会社製、アセタールホモ重合体、
一般用グレード)100重量部に、微粉状の炭酸カ
ルシウム(白石カルシウム株式会社製、ホワイト
ンSSB赤、平均粒径1.25ミクロン)8.7重量部
および第1表に示す量の化合物をタンブラーで混
合した後190℃に設定した押出機で混練してペレ
ツト化した。このペレツトを用いて、熱安定性を
測るとともに、射出成形による3mm厚平板を作製
し、供試材料とした。
この平板を1,1,1−トリクロルエタンによ
り脱脂し、96%硫酸/85%リン酸/水=40/25/
35(重量比)からなる溶液に40℃、8分間浸漬し
てエツチングを行なつた。
次に、上記エツチング処理した平板を常法によ
りメツキした。まずプラスチツクメツキ用前処理
液(奥野製薬工業株式会社製、キヤタリスト)お
よびアクセレーター(10%塩酸水溶液)に所定時
間浸漬した後、化学メツキ液(奥野製薬工業株式
会社製、TMP化学ニツケルメツキ液)により所
定の方法で化学メツキし、速やかに電気メツキに
供した。平均メツキ膜厚は銅40μ、ニツケル10μ、
クローム0.1μとした。このようにしてメツキを施
したメツキ物の性能は第1表の通りであつた。な
お、メツキ性能の測定は次の方法で行なつた。
(1) メツキ品の剥離強度;メツキ面に10mm幅の平
行な切れ目を入れ、切れ目の間の部分のメツキ
膜を平板面に直角方向に引張り、剥離に要した
応力を求める。
(2) メツキ品の外観;300ルツクス以上の光源下
で、試験面から60cmの距離をへだてて目視によ
り行なう。評価基準は第1表の(注)に示す通りで
ある。
第1表から、本発明のポリアセタール樹脂組成
物は熱安定性が向上し、しかもメツキ品性能に優
れていることがわかる。
The present invention relates to a polyacetal resin composition for surface processing which has excellent thermal stability. Plastics are generally extremely stable chemically, and molded products made by ordinary injection molding have smooth surfaces. Difficult to process. In particular, polyacetal resin has poor surface activity and there are no suitable solvents that have affinity for it, so surface decoration and adhesion are difficult.
Currently, it is hardly used in applications that require such processing. Looking at it from the other side, polyacetal resins have excellent mechanical properties, so they are often used mainly for mechanical parts, and it can be said that there has not been much demand for surface decoration etc. in the past. However, recently the applications of plastics are diverse.
In addition, there has been a strong tendency for products to become more sophisticated, and there are often cases where multiple performances, such as functionality and appearance, or functionality and adhesiveness, which were not always required to be compatible in the past, are required at the same time. In this way, polyacetal resins are increasingly being used in many cases where good surface workability is required. Although it cannot be said that there has been much research into ways to improve the surface workability of polyacetal resins, for example, it is possible to improve the surface workability to some extent by treating the surface of a molded product with an acidic or oxidizing liquid. p-toluenesulfonic acid, camphor sulfonic acid, phosphoric acid, acidic ammonium sulfate, etc. have been proposed as acidic liquids, and a chromium sulfuric acid mixture has been proposed as oxidizing liquids. The purpose of treatment with these liquids is to chemically erode the surface of the polyacetal resin molded product to create a rough surface, and also to form active reactive groups in some polyacetal molecules through its oxidizing action. It is thought that the purpose is to make
Generally, when such surface treatment is attempted to sufficiently enhance the surface treatment effect, problems such as overall deterioration of the polyacetal resin molded product, which is the base material, or the occurrence of cracks occur. On the other hand, if the treatment conditions do not cause deterioration of the base material, the surface treatment effect will be insufficient and good surface treatment will not be possible. For this reason, polyacetal resin molded products with surface workability suitable for practical use have not been known until now. In order to obtain a polyacetal resin molded product with excellent surface workability, the present inventors conducted extensive studies on polymer compositions, and as a result, they developed a composition consisting of a polyacetal resin, a metal salt from group 3 of the periodic table, and a certain type of polymer. It has been found that this material exhibits excellent thermal stability and plating resistance. That is, the present invention provides (a) polyacetal resin
100 parts by weight, (b) 2 to 35 parts by weight of a powder having an average particle size in the range of 0.1 to 4.0 microns of a carbonate, phosphate, acetate or a mixture thereof of a group metal of the periodic table, and (c ) Unsaturated polyesters, alkyl esters of acrylic acid or methacrylic acid, amides of acrylic acid or methacrylic acid, triallyl cyanurate, diallyl phthalate, polymers or copolymers of compounds selected from the group of vinyl acetate and divinylbenzene, or the like. mixture of 0.01~
The present invention relates to a polyacetal resin composition for surface treatment, which is composed of 20 parts by weight and has excellent thermal stability. In the present invention, the purpose of incorporating various salts of Group Group metals in the periodic table into the polyacetal resin is to easily form a roughened surface suitable for surface processing. In other words, when various salts of group metals of the periodic table are dispersed in the polyacetal continuous phase,
They are easily decomposed and removed by a suitable acid, leaving traces as a roughened surface. Among the various salts of Group Group metals of the periodic table used in the present invention, examples of preferable carbonates include calcium carbonate, magnesium carbonate, carbonate, and barium carbonate, with calcium carbonate being the most preferable. Furthermore, in surface treatments such as plating, the specularity of the surface and the adhesion between the plating metal and the resin are often fundamentally important characteristics. In addition, good thermal stability during molding is sometimes strictly required. The present inventors investigated the relationship between these characteristics and the average particle size of various salts of group metals of the periodic table, and found that metal salts with an average particle size exceeding 4.0 microns deteriorate specularity and adhesion. , while the average particle size
Metal salts smaller than 0.1 micron were found to reduce adhesion and thermal stability. Therefore, when specularity, adhesion, and thermal stability are taken into account, the average particle diameter of the various salts of Group Group metals of the periodic table is preferably in the range of 0.1 to 4.0 microns, particularly 0.5 to 2.0 microns. In addition, if the weight of the various salts of group metals of the periodic table contained is small, the effect of improving surface workability will not appear, and if it is too large, not only will the mechanical properties of the polyacetal resin deteriorate, but also the effect of improving surface workability will not appear. On the contrary, it will decrease, and the thermal stability during molding will also worsen, so if you consider the balance of these,
The amount is preferably 2 to 35 parts by weight based on 100 parts by weight of the polyacetal resin. On the other hand, the present inventors conducted various studies on this polyacetal resin composition, that is, a composition in which various salts of metals of Group Group of the Periodic Table were added to the polyacetal resin in the above-mentioned average particle diameter and amount. When etching with suitable acids, i.e. acidic or oxidizing liquids, particularly strong acidic liquids,
In strong oxidizing liquids, the molded product itself cracks,
The specularity and mechanical performance of the plated product may deteriorate significantly, and depending on the composition, if the molding conditions during molding are not carefully controlled, the molded product may discolor or the polyacetal resin may thermally decompose in the molded product. It has become clear that decomposition gas can leave traces of decomposition gas. In order to solve these problems, the present inventors further investigated and found that the above-mentioned polyacetal resin composition further contains unsaturated polyester, an alkyl ester of acrylic acid or methacrylic acid, an amide of acrylic acid or methacrylic acid,
It has been found that the above problem can be eliminated by containing component (c) which is a polymer, copolymer or a mixture thereof of a compound selected from triallyl cyanurate, diallyl phthalate, vinyl acetate and divinylbenzene. It is something. The reason for including component (c) is as described above. The unsaturated polyester is provided in the form of an unsaturated polyester prepolymer alone or in the form of a mixture thereof with a crosslinking agent consisting of a vinyl monomer or a prepolymer having an unsaturated residue thereof. Unsaturated polyester prepolymers include unsaturated dicarboxylic acids, or combinations of saturated dicarboxylic acids and saturated unsaturated monocarboxylic acids;
A product obtained by esterifying a polyhydric alcohol or a combination thereof with a monohydric alcohol is used. Examples of acids used in the production of unsaturated polyester prepolymers include unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid,
Examples include itaconic acid, citraconic acid, endomethylenetetrahydrophthalic acid, and saturated dicarboxylic acids such as orthophthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and adipic acid. Mixtures of two or more of these can also be used. Examples of monocarboxylic acids include acetate, propionic acid, butyric acid, benzoic acid, acrylic acid, methacrylic acid, and mixtures of two or more of these acids may also be used. The above carboxylic acids may also be provided in the form of alkyl esters such as methyl esters and dimethyl esters. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol,
Glycerin, trimethylolpropane, etc., and monohydric alcohols such as methanol, ethanol, allyl alcohol, etc. are used. As the crosslinking agent, the compound used as the component (c) of the present invention is used, but in addition to that, styrene, α-
Examples include methylstyrene, vinylpyridine, vinylpyrrolidone, and vinyl propionate. The amount of the crosslinking agent other than component (c) mentioned above is preferably in the range of 0.2 to 1.0 times the weight of the unsaturated polyester prepolymer.
It is not more than 5 parts by weight. In the present invention, the above polymer contained in the polyacetal resin together with various salts of group metals of the periodic table is an essential component of the present invention. To summarize the purpose again, as mentioned above, it prevents cracks from forming in the molded product even when etching with particularly strong acidic liquids and strong oxidizing liquids, and
This is to prevent a decrease in thermal stability during molding when the polyacetal resin contains various salts of Group Group metals of the periodic table. The reason for preventing cracking during etching is not clear, but when polyacetal resin contains various salts of group metals of the periodic table, the composition becomes hard and internal strain increases. It is thought that the further presence of , due to its plasticizing action, reduces or eliminates internal strain and prevents cracks. In addition, the amount of polymers used in the present invention varies depending on the type of polymer, and
The amount is preferably 0.01 to 20 parts by weight per 100 parts by weight. If it is less than 0.01 part by weight, the above effects cannot be obtained, and if it exceeds 20 parts by weight, the strength and other properties of the composition as a whole will be reduced. The polyacetal resin used in the present invention may be a homopolymer, that is, a polymer obtained by polymerizing formaldehyde or trioxane (including those whose terminals have been stabilized), or a polymer obtained by polymerizing formaldehyde or trioxane, or a polymer obtained by polymerizing trioxane and a cyclic ether, a cyclic It may be a binary, ternary or more copolymer obtained by copolymerizing comonomers such as acetal. The composition of the present invention includes various additives normally added to polyacetal resins, such as heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, crystal nucleating agents,
There is no problem even if pigments are added. In order to obtain the composition of the present invention, it is preferable to mix the constituent components using equipment, such as a kneader, roll mill, or extruder, which is normally used for kneading resin melts. An extruder is most preferable from the viewpoint of blocking oxygen and working environment. The mixing temperature is above the melting point of the polyacetal resin used. This is determined by the need to uniformly mix the polyacetal resin in its molten state. The upper temperature limit is generally limited by the thermal decomposition stability of the polyacetal resin used;
Mixing is usually carried out at a temperature below 250°C, preferably below 230°C. Polymers such as unsaturated polyesters for thermal stability and crack prevention may be mixed directly as polymers, or may be added in the form of monomers or prepolymers and polymerized in an extruder. In the case of thermosetting polymers, the latter is preferred. In addition, it is preferable to premix the constituent components in advance using a tumbler or Henschel mixer, etc. in order to make a homogeneous composition, and it is preferable to use the polyacetal resin in a powdered state for stable supply to the extruder. Although preferred, these are not required. In addition, in the case of the method of adding the above-mentioned monomer or prepolymer, it is preferable to maintain a temperature at which a polymerization reaction does not occur during premixing. In the case of the above method of adding monomers or prepolymers, the heating conditions for polymerizing them are, for example, 190°C x 1 to 10 minutes, depending on the type of monomer or prepolymer. It is.
This condition can be achieved in most cases by the typical temperature and time combinations (determined by the extrusion speed) used when mixing polyacetal resin compositions using conventional extruders, or by other auxiliary heating means. However, the present invention does not impose any limitations on the heating method itself. Further, a polymerization initiator may be added to the composition. There are various ways to confirm that the polymerization of the added monomer or prepolymer is completed by the above heating and that no unreacted materials remain. There are methods for checking by odor, and further checking by immersing pellets in a solvent and checking whether unreacted substances are extracted using infrared spectrophotometry. The polyacetal resin composition of the present invention produced by the above method is usually made into a molded product using an injection molding machine (an extruder or other machine may be used depending on the shape of the molded product), and then the molded product is further molded with an appropriate acid. and is etched. As a result, a polyacetal resin molded product having the desired excellent surface workability can be obtained. Suitable acids for use in etching the polyacetal resin composition of the present invention include any acidic or oxidizing liquid that can decompose the various salts of Group Group metals of the periodic table blended as described above. However, it is preferable to use less volatile acidic or oxidizing liquids, such as aqueous sulfuric acid solution, sulfuric acid-
A mixed aqueous solution of phosphoric acid, a mixed aqueous solution of sulfuric acid and chromic acid, a phosphoric acid aqueous solution, and the like are preferred from the viewpoint of workability. The thus etched polyacetal resin molded product with excellent surface workability has a peel strength (Kg/cm) of the plating layer of 1 when plated with metal.
The polyacetal resin composition of the present invention is extremely useful as it has an adhesion strength of Kg/cm or more, usually 1.5 to 2.5 Kg/cm, and also shows surprising effects in coatings other than metal plating and bonding with adhesives. I can see the light. The present invention will be explained in more detail below with reference to Examples. Examples 1 to 13 and Comparative Examples 1 to 2 "Tenatsuku 5010" as polyacetal resin
(Manufactured by Asahi Kasei Corporation, acetal homopolymer,
After mixing 100 parts by weight of general grade) with 8.7 parts by weight of finely powdered calcium carbonate (Whiten SSB Red, manufactured by Shiraishi Calcium Co., Ltd., average particle size 1.25 microns) and the amount of the compound shown in Table 1 in a tumbler. The mixture was kneaded and pelletized using an extruder set at 190°C. Using this pellet, thermal stability was measured, and a 3 mm thick flat plate was produced by injection molding and used as a test material. This flat plate was degreased with 1,1,1-trichloroethane, and 96% sulfuric acid/85% phosphoric acid/water = 40/25/
Etching was carried out by immersing it in a solution consisting of 35 (weight ratio) at 40°C for 8 minutes. Next, the etched flat plate was plated using a conventional method. First, it is immersed in a pre-treatment liquid for plastic plating (manufactured by Okuno Pharmaceutical Co., Ltd., Catalyst) and an accelerator (10% aqueous hydrochloric acid solution) for a predetermined time, and then treated with a chemical plating liquid (manufactured by Okuno Pharmaceutical Co., Ltd., TMP chemical nickel plating liquid). It was chemically plated using a prescribed method and immediately subjected to electroplating. Average plating film thickness is copper 40μ, nickel 10μ,
Chrome was set to 0.1μ. The performance of the plated products plated in this manner was as shown in Table 1. The plating performance was measured using the following method. (1) Peeling strength of plated products: Make parallel cuts of 10 mm width on the plated surface, pull the plated film between the cuts in a direction perpendicular to the flat plate surface, and calculate the stress required for peeling. (2) Appearance of plated products: Visually inspect from a distance of 60 cm from the test surface under a light source of 300 lux or more. The evaluation criteria are as shown in (note) in Table 1. Table 1 shows that the polyacetal resin composition of the present invention has improved thermal stability and excellent plating performance.
【表】【table】
【表】
実施例14〜17および比較例3,4
ポリアセタール樹脂「テナツク5010」(旭化
成工業株式会社製、アセタールホモ重合体、一般
グレード)100重量部に、炭酸カルシウムの代り
に、炭酸マグネシウム(平均粒径2〜3μ)、炭酸
バリウム(平均粒径2μ)、酢酸バリウム(平均粒
径3μ)またはリン酸水素カルシウム(平均粒径
2〜3μ)8.7重量部および反応性化合物として不
飽和ポリエステル(東洋紡績株式会社製、ユピカ
CLC−834)の所定量部を、タンブラーで混合
した後同様に押出機で混練してペレツト化した。
このペレツトを用いて熱安定性を測るとともに
平板を成形し、実施例1と同じ方法でメツキして
メツキ物の性能を調べた。
これらのポリアセタール樹脂組成物の熱安定性
およびメツキ物の性能は第2表の通りであつた
(上記金属塩はいずれも試薬一級品で、酢酸バリ
ウムについては、乳鉢で砕いて使用、その他のも
のはそのまま使用した。)。[Table] Examples 14 to 17 and Comparative Examples 3 and 4 Magnesium carbonate (average 8.7 parts by weight of barium carbonate (average particle size 2μ), barium acetate (average particle size 3μ) or calcium hydrogen phosphate (average particle size 2~3μ) and as a reactive compound unsaturated polyester (Toyo Manufactured by Boseki Co., Ltd., U-Pika
A predetermined amount of CLC-834) was mixed in a tumbler and kneaded in the same manner using an extruder to form pellets. The thermal stability was measured using this pellet, and a flat plate was formed and plated in the same manner as in Example 1 to examine the performance of the plated product. The thermal stability and performance of the plated materials of these polyacetal resin compositions are shown in Table 2 (all of the metal salts mentioned above are first-grade reagents, barium acetate is used by crushing it in a mortar, and other was used as is.)
【表】
実施例18〜20および比較例5,6
ポリアセタール樹脂「テナツク5010」(旭化
成工業株式会社製)100重量部に、第3表に示す
各種平均粒径の炭酸カルシウム(白石カルシウム
株式会社製)11.1重量部および不飽和ポリエステ
ル(東洋紡績株式会社製)1.1重量部を混合し、
その樹脂組成物について実施例1と同じ方法でメ
ツキして、メツキ物の性能を調べた。
これらのメツキ物の性能は第3表の通りであつ
た。[Table] Examples 18 to 20 and Comparative Examples 5 and 6 Calcium carbonate (manufactured by Shiroishi Calcium Co., Ltd.) with various average particle sizes shown in Table 3 was added to 100 parts by weight of polyacetal resin "Tenatsuku 5010" (manufactured by Asahi Kasei Corporation). ) and 1.1 parts by weight of unsaturated polyester (manufactured by Toyobo Co., Ltd.),
The resin composition was plated in the same manner as in Example 1, and the performance of the plated product was examined. The performance of these plated products was as shown in Table 3.
【表】【table】
【表】
※ 押出し不可能であつた。
※※ 外観をあまり厳しく要求されない用途
には適用可。
実施例21〜23および比較例7
第3表で用いた、エツチング平板と同じものを
用い、エツチング後十分水洗、風乾し、アクリル
系塗料(東京ペイント株式会社製、アクリスタ
ー、青)を塗布し、150℃で30分間焼付処理を行
なつた。塗膜に碁盤目状の切目を入れ、スコツチ
テープによる剥離試験を行なつた。結果を第4表
に示す。[Table] * It was impossible to extrude.
※※ Applicable for applications that do not require very strict appearance.
Examples 21 to 23 and Comparative Example 7 The same etching plates used in Table 3 were used, and after etching, they were thoroughly washed with water, air-dried, and coated with acrylic paint (manufactured by Tokyo Paint Co., Ltd., Acrystar, blue). , baking treatment was performed at 150°C for 30 minutes. Cuts in a grid pattern were made in the coating film, and a peel test using Scotch tape was performed. The results are shown in Table 4.
【表】【table】
【表】
実施例24〜27および比較例8〜10
実施例1と同じ炭酸カルシウム(平均粒径1.25
ミクロン)を用い、実施例1と同じ方法でメツキ
を施した。但し炭酸カルシウムの量を第5表の通
り変え、不飽和ポリエステル量は炭酸カルシウム
重量部の10%相当量を加えた。結果を第5表に示
す。[Table] Examples 24 to 27 and Comparative Examples 8 to 10 Same calcium carbonate as Example 1 (average particle size 1.25
Plating was carried out in the same manner as in Example 1 using a micron). However, the amount of calcium carbonate was changed as shown in Table 5, and the amount of unsaturated polyester was added in an amount equivalent to 10% of the weight of calcium carbonate. The results are shown in Table 5.
【表】【table】
【表】
実施例28〜31および比較例11〜12
実施例25〜27および比較例8、10と同じ実験
を、さらに実施例31では炭酸カルシウムおよび不
飽和ポリエステルの添加量を増す実験を、ポリア
セタール樹脂として「ジユラコンM90−02」
(ポリプラスチツクス株式会社製、アセタール共
重合体、一般グレード)を用いて実施した。結果
を第6表に示す。[Table] Examples 28 to 31 and Comparative Examples 11 to 12 The same experiments as Examples 25 to 27 and Comparative Examples 8 and 10 were carried out, and in Example 31, an experiment was carried out in which the amounts of calcium carbonate and unsaturated polyester were increased. "Jyuracon M90-02" as a resin
(manufactured by Polyplastics Co., Ltd., acetal copolymer, general grade). The results are shown in Table 6.
【表】
実施例32〜34および比較例13
実施例25と同じ実験を、不飽和ポリエステルの
添加量を変えて実施した。結果を第7表に示す。[Table] Examples 32 to 34 and Comparative Example 13 The same experiment as in Example 25 was carried out by changing the amount of unsaturated polyester added. The results are shown in Table 7.
【表】【table】
【表】
以上の実施例から判るように、本発明のポリア
セタール樹脂組成物は、熱安定性に優れ、かつそ
の成形物を適当な酸でエツチングすることにより
優れた表面処理成形物となるため、該樹脂の応用
分野を一層拡大し、例えば機能性、装飾性共に要
求される部品などで金属に代替することができ、
軽量化、コストダウンに寄与する効果は極めて大
きい。[Table] As can be seen from the above examples, the polyacetal resin composition of the present invention has excellent thermal stability, and when the molded product is etched with an appropriate acid, an excellent surface-treated molded product can be obtained. The field of application of this resin can be further expanded, for example, it can be used as a substitute for metal in parts that require both functionality and decoration.
The effect of contributing to weight reduction and cost reduction is extremely large.
Claims (1)
表第族金属の炭酸塩、りん酸塩、酢酸塩または
それらの混合物の平均粒径が0.1〜4.0ミクロンの
範囲にある粉末2〜35重量部、および(c)不飽和ポ
リエステル、アクリル酸あるいはメタクリル酸の
アルキルエステル、アクリル酸あるいはメタクリ
ル酸のアミド、シアヌル酸トリアリル、ジアリル
フタレート、酢酸ビニルおよびジビニルベンゼン
の群から選ばれた化合物の重合物、共重合物ある
いはそれらの混合物0.01〜20重量部とからなる熱
安定性に優れた被表面加工用ポリアセタール樹脂
組成物。1. (a) 100 parts by weight of polyacetal resin; (b) powder of carbonate, phosphate, acetate or a mixture thereof of a group metal of the periodic table, with an average particle size in the range of 0.1 to 4.0 microns 2 to 35 parts by weight, and (c) a polymer of a compound selected from the group of unsaturated polyesters, alkyl esters of acrylic or methacrylic acid, amides of acrylic or methacrylic acid, triallyl cyanurate, diallyl phthalate, vinyl acetate and divinylbenzene. , a copolymer or a mixture thereof. A polyacetal resin composition for surface treatment with excellent thermal stability.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10410279A JPS5628236A (en) | 1979-08-17 | 1979-08-17 | Polyacetal resin composition for molded article to be surface treated and having excellent thermal stability |
GB7936174A GB2035335B (en) | 1978-10-25 | 1979-10-18 | Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same |
DE2953528A DE2953528C2 (en) | 1978-10-25 | 1979-10-23 | Process for roughening the surface of molded parts made from a polyacetal resin composition |
IT50647/79A IT1164132B (en) | 1978-10-25 | 1979-10-23 | COMPOSITION OF POLYACETAL RESIN AND PROCEDURE TO TREAT THE SURFACE OF A PRODUCT PRINTED BY IT |
DE2942744A DE2942744C2 (en) | 1978-10-25 | 1979-10-23 | Polyacetal resin composition excellent in heat resistance and surface machinability |
FR7926404A FR2439803A1 (en) | 1978-10-25 | 1979-10-24 | POLYACETAL RESIN COMPOSITION EXCELLENT IN ITS HEAT STABILITY AND EASY PROCESSING, PROCESS FOR MAKING ITS SURFACE ROUGH AND PRODUCT OBTAINED |
US06/251,936 US4464435A (en) | 1978-10-25 | 1981-04-07 | Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same |
US06/571,677 US4521488A (en) | 1978-10-25 | 1984-01-17 | Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
---|---|
JPS5628236A JPS5628236A (en) | 1981-03-19 |
JPS631345B2 true JPS631345B2 (en) | 1988-01-12 |
Family
ID=14371748
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10410279A Granted JPS5628236A (en) | 1978-10-25 | 1979-08-17 | Polyacetal resin composition for molded article to be surface treated and having excellent thermal stability |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5628236A (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4766168A (en) * | 1986-04-15 | 1988-08-23 | E. I. Du Pont De Nemours And Company | Stabilized polyacetal compositions |
US4814397A (en) * | 1986-04-15 | 1989-03-21 | E. I. Du Pont De Nemours And Company | Stabilized polyacetal compositions |
JPH01138258A (en) * | 1987-07-15 | 1989-05-31 | Asahi Chem Ind Co Ltd | Weather-resistant polyoxymethylene composition and its molding |
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 |
US20040228971A1 (en) * | 2003-05-13 | 2004-11-18 | Pascal Scaramuzzino | Modified polyacetals for decorative applications |
US20040258906A1 (en) * | 2003-06-20 | 2004-12-23 | Pascal Scaramuzzino | Modified polyacetals for plating |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51128349A (en) * | 1975-04-30 | 1976-11-09 | Asahi Chem Ind Co Ltd | Reinforled polyacetal resin composition and method of preparing the sa me |
-
1979
- 1979-08-17 JP JP10410279A patent/JPS5628236A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51128349A (en) * | 1975-04-30 | 1976-11-09 | Asahi Chem Ind Co Ltd | Reinforled polyacetal resin composition and method of preparing the sa me |
Also Published As
Publication number | Publication date |
---|---|
JPS5628236A (en) | 1981-03-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4464435A (en) | Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same | |
JPS5842631A (en) | Strengthening accelerator for filler-containing thermoplastic polymer | |
JPS631345B2 (en) | ||
JPH08106806A (en) | Molded article that consists of bmc molding compounds with improved surface | |
GB2035335A (en) | Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same | |
US4521488A (en) | Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same | |
JPS60144360A (en) | Method of reforming thermoplastic polymer surface | |
JPS58134137A (en) | Thermoplastic resin composition | |
JPH0224346A (en) | Fiber-reinforced thermoplastic resin composition | |
JPS584936B2 (en) | Surface treatment method for polyacetal resin composition | |
JPH03202477A (en) | Plated article | |
JPS631346B2 (en) | ||
JPS6364468B2 (en) | ||
JPH0142295B2 (en) | ||
JP2794753B2 (en) | Polyester molding material | |
JPS5883043A (en) | Reinforced polyolefin | |
JPS606969B2 (en) | Reinforced polyacetal resin composition and method for producing the same | |
JPH0128772B2 (en) | ||
JP2540338B2 (en) | Powder paint | |
JPS6059255B2 (en) | Surface treatment method for polyacetal resin molded products | |
JP2002529561A (en) | Use of aromatic carboxamides to permanently improve the adhesion and / or coating compatibility of molded articles, fibers and films based on polyolefins | |
JPS5950171B2 (en) | Method for manufacturing surface-modified polyolefin molded products | |
JP3135321B2 (en) | Colored styrenic resin composition | |
JPS5936667B2 (en) | Hifukuyoujiyushisoseibutsu | |
JP2000511215A (en) | Polyolefin materials with improved adhesion |