JPH0192241A - Surface treatment of molded article of liquid crystal polyester resin - Google Patents
Surface treatment of molded article of liquid crystal polyester resinInfo
- Publication number
- JPH0192241A JPH0192241A JP62249196A JP24919687A JPH0192241A JP H0192241 A JPH0192241 A JP H0192241A JP 62249196 A JP62249196 A JP 62249196A JP 24919687 A JP24919687 A JP 24919687A JP H0192241 A JPH0192241 A JP H0192241A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystalline
- inorganic filler
- polyester resin
- molded article
- crystalline polyester
- 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
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 14
- 239000004645 polyester resin Substances 0.000 title claims abstract description 14
- 238000004381 surface treatment Methods 0.000 title claims description 12
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 5
- 229920000728 polyester Polymers 0.000 claims abstract description 37
- 239000011256 inorganic filler Substances 0.000 claims abstract description 22
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 230000000737 periodic effect Effects 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 150000004760 silicates Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 16
- 238000007747 plating Methods 0.000 abstract description 10
- 125000003118 aryl group Chemical group 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000010128 melt processing Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000005034 decoration Methods 0.000 abstract description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract 2
- 150000004692 metal hydroxides Chemical class 0.000 abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 238000005530 etching Methods 0.000 description 17
- -1 polybutylene terephthalate Polymers 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000002344 surface layer Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000835 fiber Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 229920006295 polythiol Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004615 ingredient Substances 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
- 239000000314 lubricant Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- LMXZDVUCXQJEHS-UHFFFAOYSA-N 2-(1-phenylethyl)benzene-1,4-diol Chemical compound C=1C(O)=CC=C(O)C=1C(C)C1=CC=CC=C1 LMXZDVUCXQJEHS-UHFFFAOYSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000343 polyazomethine Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は異方性溶融相を形成しうる溶融加工性ポリエス
テル（以後単に「液晶性ポリエステル」と略す）樹脂成
形品の表面処理法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for surface treatment of a melt-processable polyester (hereinafter simply referred to as "liquid crystalline polyester") resin molded product capable of forming an anisotropic melt phase.
更に詳しくは印刷、塗装、蒸着、メツキ等による表面装
飾や接着剤による接着などに適した表面特性を有する耐
熱性、成形加工性に優れた液晶性ポリエステル樹脂成形
品を効率よく得るための表面処理法に関する。More specifically, surface treatment to efficiently obtain liquid crystalline polyester resin molded products with excellent heat resistance and moldability that have surface characteristics suitable for surface decoration by printing, painting, vapor deposition, plating, etc. and adhesion with adhesives. Regarding the law.
液晶性ポリエステルは、一般に知られている熱可塑住ポ
リエステル、例えばポリブチレンテレフタレート、ポリ
エチレンテレフタレートと異なり、剛直な高分子よりな
り、溶融状態でも分子鎖は折れ曲がり難く棒状を保って
いるため、溶融時に分子の絡み合いが少なく、僅かな剪
断応力を受けるだけで一方向に配向し、液状でも結晶性
を示すいわゆる液晶性を示す。Unlike generally known thermoplastic polyesters such as polybutylene terephthalate and polyethylene terephthalate, liquid crystalline polyester is made of a rigid polymer, and its molecular chains are difficult to bend and maintain a rod shape even in the molten state. It has little entanglement, is oriented in one direction when subjected to a slight shear stress, and exhibits so-called liquid crystallinity, which means that it exhibits crystallinity even in liquid form.
斯かる液晶性ポリエステルについても一般に行われてい
る射出成形加工法を適用することはできるが、成形品の
表面は強い配向のため表層部は剥離し毛羽立ちを生じ易
く、そのままでは接着、塗装、メツキによる２次加工が
できない。Although the commonly used injection molding processing method can be applied to such liquid crystalline polyester, the surface of the molded product is highly oriented, so the surface layer tends to peel off and become fluffy, and if left as is, it will not be possible to bond, paint, or plate it. secondary processing is not possible.
そこで、従来一般の樹脂に用いられている様な薬品によ
る表面粗面化処理を行うことが考えられるが、表面は化
学的には極めて不活性で親和性のある適切な溶剤がなく
、表層の配向層を取り除き表面を粗面化することができ
ない。Therefore, surface roughening treatment using chemicals such as those conventionally used for general resins may be considered, but the surface is extremely inert chemically and there is no suitable solvent with affinity for the surface layer. It is not possible to remove the alignment layer and roughen the surface.
一方、熱的には液晶性ポリエステルは、一般金属の熱線
膨張係数に匹敵する低い線膨張係数を示し、耐熱的には
２６０℃のハンダ浴に１０秒間浸漬しても異常を生じな
い等の特徴を有し、この特性を生かして、金属と接着剤
による結合をさせた部品やメツキを付与した基板への用
途を目的として前記表面特性を改善した表面処理方法が
求められていたが、未だ満足のいく方法は知られていな
い。On the other hand, thermally, liquid crystalline polyester exhibits a low linear expansion coefficient comparable to that of general metals, and has characteristics such as heat resistance such as no abnormality even when immersed in a 260°C solder bath for 10 seconds. There has been a need for a surface treatment method that takes advantage of this property and improves the surface properties for applications such as parts bonded to metals with adhesives and plated substrates, but this method has not yet been satisfied. There is no known method of climbing.
〔問題点を解決するための手段）
本発明者等はこの様な液晶性ポリエステルの熱的に有益
な特徴を生かし、物理的・化学的性質を損なうことなし
に化学的に表面を活性なものとし、且つ剥離し易い表層
を発生させない方法について鋭意研究した結果、液晶性
ポリエステルに特定の無機充填材５〜８０重量％（対組
成物全量）を含有せしめた組成物からなる成形品をミエ
ッチンダ液としてのア゛ルカリ金属の水酸化物又はアル
カリ土類金属の水酸化物を主成分とする水溶液に接触処
理せしめるという、特定の材料組成と特定のエツチング
液の組み合わせ条件を採用すれば、液晶性ポリエステル
樹脂成形品の表面加工性が極めて向上することを見出し
、本発明を完成するに至った。[Means for Solving the Problems] The present inventors took advantage of the thermally beneficial characteristics of liquid crystalline polyester to create a material that chemically activates the surface without impairing its physical or chemical properties. As a result of intensive research into a method that does not generate a surface layer that is easy to peel off, molded products made of a composition containing 5 to 80% by weight (based on the total amount of the composition) of a specific inorganic filler in liquid crystalline polyester were prepared using Mietchinda liquid. If a combination of a specific material composition and a specific etching solution is used, such as contact treatment with an aqueous solution containing an alkali metal hydroxide or an alkaline earth metal hydroxide as a main component, liquid crystallinity can be achieved. The present inventors have discovered that the surface workability of polyester resin molded products is significantly improved, and have completed the present invention.
本発明で用いられる無機充填材とは、周期律表ＩＩａ、
［ｂ、ＩＩＩａ、Ｉ’Ｖａ、Ｖａ族元素からなる群より
選ばれた１種又は２種以上の元素を含むものであれば何
れのものでも良いが、特に周期律表ＩＩａ又はｎｂ族元
素の酸化物、硫酸塩、リン酸塩及び珪酸塩からなる群よ
り選ばれる１種又は２種以上が好ましい。The inorganic fillers used in the present invention include periodic table IIa,
[Any element may be used as long as it contains one or more elements selected from the group consisting of elements of groups IIa or Va of the periodic table, but in particular elements of group IIa or nb of the periodic table. One or more selected from the group consisting of oxides, sulfates, phosphates, and silicates are preferred.
周期律表■族の元素の酸化物とは、酸化マグネシウム、
酸化カルシウム、酸化バリウム、酸化亜鉛等の如き化合
物であり、リン酸塩とはリン酸マグネシウム、リン酸カ
ルシウム、リン酸バリウム、リン酸亜鉛、ピロリン酸マ
グネシウム、ピロリン酸カルシウム等の如き化合物であ
り、硫酸塩とは硫酸マグネシウム、硫酸力ルンウム、硫
酸バリウム等の化合物であり、珪酸塩とは珪酸マグネシ
ウム、珪酸カルシウム、珪酸アルミニウム、カオリン、
タルク、クレー、珪藻土、ウオラストナイト等の化合物
である。Oxides of elements in group ■ of the periodic table include magnesium oxide,
These are compounds such as calcium oxide, barium oxide, zinc oxide, etc. Phosphates are compounds such as magnesium phosphate, calcium phosphate, barium phosphate, zinc phosphate, magnesium pyrophosphate, calcium pyrophosphate, etc. are compounds such as magnesium sulfate, aluminum sulfate, and barium sulfate, and silicates include magnesium silicate, calcium silicate, aluminum silicate, kaolin,
Compounds such as talc, clay, diatomaceous earth, and wollastonite.
これらの無機充填材は、特に２次加工としてメツキを行
う場合の表面処理法に好ましく用いられ、特にリン酸塩
が好適である。又、２次加工として塗装を行う場合の表
面処理法には前記無機充填材の他に周期律表ＩＩＩａ、
Ｉ’Ｖａ、Ｖａ族元素、その元素の酸化物からなる群よ
り選ばれた１種又は２種以上も好ましい。特に、亜鉛、
アルミニウム、スズ、鉛等の両性金属及びその金属の酸
化物が好ましい。These inorganic fillers are preferably used in surface treatment methods, particularly when plating is performed as a secondary process, and phosphates are particularly suitable. In addition to the above-mentioned inorganic fillers, in addition to the above-mentioned inorganic fillers, the surface treatment method used when painting is performed as a secondary process includes materials from the periodic table IIIa,
One or more selected from the group consisting of I'Va, Va group elements, and oxides of these elements are also preferred. In particular, zinc
Amphoteric metals such as aluminum, tin, lead, and oxides of these metals are preferred.
これらの無機充填材の配合量は液晶性ポリエステル樹脂
組成物全量に対して５〜８０重量％、好ましくは２０〜
７０重量％である。５重量％夫満では成形品表面に不均
質な流れマークが発生し、成形品表層は粘着テープを表
面に貼り付は引き剥がすと容易に薄皮状の剥がれが生じ
、又表面処理品はエツチングのムラを生じる。一方、８
０重量％を超えると樹脂の流動性が低下し、表面の良好
な成形品が得られず、エツチングにより表面にざらつき
を生じてしまうと同時に成形品の機械的強度も低下して
しまい好ましくない。The blending amount of these inorganic fillers is 5 to 80% by weight, preferably 20 to 80% by weight based on the total amount of the liquid crystalline polyester resin composition.
It is 70% by weight. At 5% by weight, uneven flow marks occur on the surface of the molded product, and when the adhesive tape is attached to the surface of the molded product, a thin film easily peels off when the tape is peeled off. Causes unevenness. On the other hand, 8
If it exceeds 0% by weight, the fluidity of the resin will decrease, making it impossible to obtain a molded product with a good surface, causing roughness on the surface due to etching, and at the same time reducing the mechanical strength of the molded product, which is not preferable.
又、無機充填材は微粉状であるのが好ましく、その粒径
は平均粒径０．０１〜１００μｍの範囲、好ましくは０
．１〜３０μｍ１更に好ましくは０．５〜１０μｍが適
切である。０．０１μｍ未満では分散不良により成形品
表面に凝集塊が生じ易く、１００μｍを超えるとエツチ
ング後の表面の面粗度が大きくなり、良い外観が得られ
ない。Further, the inorganic filler is preferably in the form of fine powder, and the particle size thereof is in the range of 0.01 to 100 μm, preferably 0.01 to 100 μm.
．． A suitable thickness is 1 to 30 μm, more preferably 0.5 to 10 μm. If it is less than 0.01 μm, aggregates are likely to form on the surface of the molded product due to poor dispersion, and if it exceeds 100 μm, the roughness of the surface after etching becomes large and a good appearance cannot be obtained.
本発明におけるエツチング処理液であるアルカリ金属の
水酸化物又はアルカリ土類金属の水酸化物を主成分とす
る水溶液とは、水酸化ナトリウム、水酸化カリウム、水
酸化リチウム等のアルカリ金属の水酸化物の水溶液、水
酸化ストロンチウム、水酸化バリウム等のアルカリ土類
金属の水酸化物の水溶液であり、好ましくは水酸化カリ
ウム水溶液である。この水溶液は、更に液晶性ポリエス
テルの表面分解物を溶解し、かつアルカリ水溶液に可溶
な有機溶媒、例えばメチルアルコール、エチルアルコー
ル、イソプロピルアルコーノへイソフチルアルコール等
ノアルコール、テトラヒドロフランの様なフラン化合物
、エチルアミン、ジメチルアミン、トリメチルアミン、
プロピルアミン、アニリン、ピリジン、ホルムアミド等
の窒素化合物、クロロベンゼン、０−ジクロロベンゼン
等の芳香族ハロゲン化炭化水素等の中から選ばれた１種
又は２種以上の溶剤を添加し、複合液として用いること
ができる。In the present invention, an aqueous solution containing an alkali metal hydroxide or an alkaline earth metal hydroxide as a main component, which is an etching solution, refers to an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. An aqueous solution of an alkaline earth metal hydroxide such as strontium hydroxide or barium hydroxide, preferably an aqueous potassium hydroxide solution. This aqueous solution further dissolves the surface decomposition product of the liquid crystalline polyester and contains an organic solvent soluble in the alkaline aqueous solution, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, isophyl alcohol, and a furan compound such as tetrahydrofuran. , ethylamine, dimethylamine, trimethylamine,
One or more solvents selected from nitrogen compounds such as propylamine, aniline, pyridine, and formamide, and aromatic halogenated hydrocarbons such as chlorobenzene and 0-dichlorobenzene are added and used as a composite liquid. be able to.
また、かかる水溶液で液晶性ポリエステル成形品をエツ
チング処理するに当たり、エツチング液への浸漬処理条
件はエツチング液の組成に応じ適宜最適条件が探索、選
択されるが、−船釣な処理条件は前記水酸化物２０〜６
０重量％の水溶液を用い、３０〜８０℃で３〜１２０分
の範囲で、好ましくは水酸化物４０〜５０重量％水溶液
を用い４０〜６０℃で１０〜３０分である。特に好まし
い処理条件例を示せば水酸化カリウ゛ムの約４５重量％
水溶液で、６０℃×３０分程度の処理が適当である。In addition, when etching a liquid crystalline polyester molded product with such an aqueous solution, optimal conditions for immersion in the etching solution are searched and selected as appropriate depending on the composition of the etching solution. Oxide 20-6
A 0% by weight aqueous solution is used at 30-80°C for 3-120 minutes, preferably a 40-50% by weight aqueous hydroxide solution is used at 40-60°C for 10-30 minutes. An example of particularly preferred treatment conditions is approximately 45% by weight of potassium hydroxide.
Treatment with an aqueous solution at 60° C. for about 30 minutes is appropriate.
本発明における液晶性ポリエステルとは、溶融加工性ポ
リエステルで、溶融状態でポリマー分子鎖が規則的な平
行配列をとる性質を有している。分子がこのように配列
した状態をしばしば液晶状態または液晶性物質のネマチ
ック相という。このようなポリマー分子は、一般に細長
く、偏平で、分子の長軸に沿ってかなり剛性が高く、普
通は同軸または平行のいずれかの関係にある複数の連鎖
伸長結合を有しているようなポリマーからなる。The liquid crystalline polyester in the present invention is a melt-processable polyester, and has the property that polymer molecular chains are regularly arranged in parallel in a molten state. The state in which the molecules are arranged in this way is often called the liquid crystal state or the nematic phase of liquid crystal materials. Such polymer molecules are generally elongated, oblate, fairly rigid along the long axis of the molecule, and have multiple chain extensions, usually in either coaxial or parallel relationships. Consisting of
異方性溶融相の性質は、直交偏光子を利用した慣用の偏
光検査法により確認することができる。より具体的には
、異方性溶融相の確認は、Ｌｅｉｔｚ偏光顕微鏡を使用
し、Ｌｅｉｔｚホットステージにのせた溶融試料を窒素
雲囲気下で４０倍の倍率で観察することにより実施でき
る。上記ポリマーは光学的に異方性である。すなわち、
直交偏光子の間で検査したときに光を透過させる。The nature of the anisotropic melt phase can be confirmed by conventional polarization testing using crossed polarizers. More specifically, the anisotropic melt phase can be confirmed by using a Leitz polarization microscope and observing a melt sample placed on a Leitz hot stage at a magnification of 40 times under a nitrogen cloud atmosphere. The polymer is optically anisotropic. That is,
Transmits light when examined between orthogonal polarizers.
試料が光学的に異方性であると、たとえ静止状態であっ
ても偏光は透過する。If the sample is optically anisotropic, polarized light will pass through it even if it is at rest.
上記の如き異方性溶融相を形成するポリマーの構成成分
としては
■ 芳香族ジカルボン酸、脂環族ジカルボン酸の１つま
たはそれ以上からなるもの
■ 芳香族ジオーノベ脂環族ジオール、脂肪族ジオール
の１つまたはそれ以上からなるもの■ 芳香族ヒドロキ
シカルボン酸の１つまたはそれ以上からなるもの
■ 芳香族チオールカルボン酸の１つまたはそれ以上か
らなるもの
■ 芳香族ジチオール、芳香族チオールフェノールの１
つまたはそれ以上からなるもの■ 芳香族ヒドロキシア
ミン、芳香族ジアミンの１つまたはそれ以上からなるも
の
等から選ばれ、異方性溶融相を形成するポリマーは
■）■と■からなるポリエステル
■）■だけからなるポリエステル
■）■と■と■からなるポリエステル
■）■だけからなるポリチオールエステルＶ）■と■か
らなるポリチオールエステル■）■と■と■からなるポ
リチオールエステル■）■と■と■からなるポリエステ
ルアミド■）■と■と■と■からなるポリエステルアミ
ド
等の組み合わせから構成される異方性溶融相を形成する
ポリエステルである。Constituent components of the polymer that forms the anisotropic melt phase as described above include: - one or more of aromatic dicarboxylic acids and alicyclic dicarboxylic acids; Consists of one or more aromatic hydroxycarboxylic acids; Consists of one or more aromatic thiol carboxylic acids; Aromatic dithiol, aromatic thiol phenol.
Polyesters consisting of one or more of aromatic hydroxyamines and aromatic diamines and forming an anisotropic melt phase are polyesters consisting of ■)■ and ■■) Polyester consisting of only ■ Polyester consisting of ■) ■, ■ and ■ ■) Polythiol ester consisting only of ■ V) Polythiol ester consisting of ■ and ■ ■) Polythiol ester consisting of ■ and ■ ■) ■ and ■ It is a polyester that forms an anisotropic melt phase composed of a combination of polyester amide consisting of ■), ■, polyester amide consisting of ■, and ■.
更に上記の成分の組み合わせの範鴫には含まれないが、
異方性溶融相を形成するポリマーには芳香族ポリアゾメ
チンが含まれ、かかるポリマーの具体例としては、ポリ
にトリロー２＝メチル−１，４−フェニレンニトリロ
メチリジン−１，４−フェニレンメチリジン）；ポリ
にトリロー２−メチル−１，４−フェニレンニトリロメ
チリジン−１，４−フェニレンメチリジン）；およびポ
リ にトリロー２−クロロ−１，４−フェニレンニトリ
ロメチリジン−１，４−フェニレンメチリジン）が挙げ
られる。Furthermore, although not included in the above combination of ingredients,
Polymers that form an anisotropic melt phase include aromatic polyazomethines; specific examples of such polymers include polytrilo-2=methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine. ) ; poly
trilo-2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine); Can be mentioned.
更に上記の成分の組み合わせの範躊には含まれないが、
異方性溶融相を形成するポリマーとしてポリエステルカ
ーボネートが含まれる。これは本質的に４−オキシベン
ゾイル単位、ジオキシフェニル単位、ジオキシカルボニ
ル単位及びテレフタロイル単位からなるものがある。In addition, although not included in the category of combinations of ingredients listed above,
Polyester carbonate is included as a polymer that forms an anisotropic melt phase. It may consist essentially of 4-oxybenzoyl units, dioxyphenyl units, dioxycarbonyl units and terephthaloyl units.
本発明で用いるのに好適な異方性溶融相を形成するポリ
マーである上記Ｉ） 、ＩＩ） 、ＩＩＩ）のポリエス
テル及び■）のポリエステルアミドは、縮合により所要
の反復単位を形成する官能基を有している有機モノマー
化合物同士を反応させることのできる多様なエステル形
成法により生成させることができる。たとえば、これら
の有機モノマー化合物の官能基はカルボン酸基、ヒドロ
キシル基、エステル基、アシルオキシ基、酸ハロゲン化
物、アミン基などでよい。上記有機モノマー化合物は、
溶融アシドリシス法により熱交換流体を存在させずに反
応させることができる。この方法ではモノマーをまず一
緒に加熱して反応物質の溶融溶液を形成する。反応を続
けていくと固体のポリマー粒子が液中に懸濁するように
なる。縮合の最終段階で副生じた揮発物（例、酢酸また
は水）の除去を容易にするために真空を適用してもよい
。The polyesters I), II), and III) and the polyesteramide (ii) above, which are polymers that form an anisotropic melt phase suitable for use in the present invention, contain functional groups that form the required repeating units by condensation. It can be produced by various ester formation methods that allow the organic monomer compounds that are present to react with each other. For example, the functional groups of these organic monomer compounds may be carboxylic acid groups, hydroxyl groups, ester groups, acyloxy groups, acid halides, amine groups, and the like. The above organic monomer compound is
The melt acidolysis method allows the reaction to occur without the presence of a heat exchange fluid. In this method, the monomers are first heated together to form a molten solution of the reactants. As the reaction continues, solid polymer particles become suspended in the liquid. Vacuum may be applied to facilitate removal of by-product volatiles (eg acetic acid or water) during the final stage of condensation.
また、スラリー重合法も本発明に用いるのに好適な液晶
性ポリエステルの形成に採用できる。Additionally, slurry polymerization methods can also be employed to form liquid crystalline polyesters suitable for use in the present invention.
この方法では、固体生成物は熱交換媒質中に懸濁した状
態で得られる。In this process, a solid product is obtained in suspension in a heat exchange medium.
本発明に使用するのに適した液晶性ポリマーは、一般溶
剤には実質的に不溶である傾向を示し、したがって溶液
加工には不向きである。しかし、既に述べたように、こ
れらのポリマーは普通の溶融加工法により容易に加工す
ることができる。Liquid crystalline polymers suitable for use in the present invention tend to be substantially insoluble in common solvents and are therefore unsuitable for solution processing. However, as previously mentioned, these polymers can be readily processed using conventional melt processing methods.
本発明で用いるのに好適な液晶性ポリエステルは一般に
重量平均分子量が約２．０００〜２００．０００、好ま
しくは約１０．０００〜５０．０００、特に好ましくは
約２０．０００〜２５．０００である。一方、好適な完
全芳香族ポリエステルアミドは一般に分子量が約５、０
００〜５０．０００、好ましくは約１０．０００〜３０
．０００、例えば１５．０００〜１７．０００である。Liquid crystalline polyesters suitable for use in the present invention generally have a weight average molecular weight of about 2.000 to 200.000, preferably about 10.000 to 50.000, particularly preferably about 20.000 to 25.000. . On the other hand, suitable fully aromatic polyester amides generally have a molecular weight of about 5.0
00-50,000, preferably about 10,000-30
．． 000, for example 15.000 to 17.000.
かかる分子量の測定は、ゲルパーミェーションクロマト
クラフィーならびにその他のポ゛リマ一の溶液形成を伴
わない標準的測定法、たとえば圧縮成形フィルムについ
て赤外分光法により末端基を定量することにより実施で
きる。また、ペンタフルオロフェノール溶液にして光散
乱法を用いて分子量を測定することもできる。Such molecular weight measurements are performed by gel permeation chromatography as well as other standard methods of measuring polymers that do not involve solution formation, such as quantification of end groups by infrared spectroscopy on compression molded films. can. Alternatively, the molecular weight can be measured using a light scattering method using a pentafluorophenol solution.
本発明で用いられる異方性溶融相を示すポリマーは、芳
香族ポリエステル及び芳香族ポリエステルアミドが好ま
しく、芳香族ポリエステル及び芳香族ポリエステルアミ
ドを同一分子鎖中に部分的に含むポリエステルも好まし
い例である。The polymer exhibiting an anisotropic melt phase used in the present invention is preferably an aromatic polyester or an aromatic polyester amide, and a polyester partially containing an aromatic polyester or an aromatic polyester amide in the same molecular chain is also a preferred example. .
それらを構成する化合物の好ましい例は、２゜６−ナフ
タレンジカルボン酸、２．６−ジヒドロキシナフタレン
、１．４−ジヒドロキシナフタレン及び６−ヒドロキシ
−２−ナフトエ酸等のすフタレン化合物、４．４’−ジ
フェニルジカルボン酸、４．４’−ジヒドロキシビフェ
ニル等のビフェニル化合物、下記一般式（１）、（ＩＩ
）又は（ＩＩＩ）で表わされる化合物：
（但し、Ｘ：アルキレン（Ｃ１〜Ｃ４）、アルキリデン
、−〇−、−３Ｏ−１−ＳＯ２−、−５−１−ＣＯ−よ
り−選ばれる基
ｙニー（ｃＨ２） ｈ−（ｎ＝１〜４）、罰（ＣＨ２）
ｈＯ−（ｎ・１〜４）より選ばれる基）
ｐ−ヒドロキシ安息香酸、テレフタル酸、ハイドロキノ
ン、ｐ−アミノフェノール及びｐ−フェニレンジアミン
等のパラ位置換のベンゼン化合物及びそれらの核置換ベ
ンゼン化合物（置換基は塩素、臭素、メチル、フェニノ
ベ １−フェニルエチルより選ばれる）、イソフタル酸
、レゾルシン等のメタ位置換のベンゼン化合物である。Preferred examples of the compounds constituting them are sphthalene compounds such as 2°6-naphthalene dicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, and 6-hydroxy-2-naphthoic acid; - diphenyldicarboxylic acid, biphenyl compounds such as 4,4'-dihydroxybiphenyl, the following general formulas (1), (II
) or (III): (However, X: a group selected from alkylene (C1 to C4), alkylidene, -〇-, -3O-1-SO2-, -5-1-CO- (cH2) h-(n=1-4), punishment (CH2)
hO-(n・1 to 4)) Para-substituted benzene compounds such as p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol, and p-phenylenediamine, and their nuclear-substituted benzene compounds ( The substituent is a meta-substituted benzene compound such as chlorine, bromine, methyl, or pheninobenzene (1-phenylethyl), isophthalic acid, or resorcinol.
又、本発明に使用される液晶性ポリエステルは、上述の
構成成分の他に同一分子鎖中に部分的に異方性溶融相を
示さないポリアルキレンテレフタレートであってもよい
。この場合のアルキル基の炭素数は２乃至４である。In addition to the above-mentioned constituent components, the liquid crystalline polyester used in the present invention may also be polyalkylene terephthalate that does not partially exhibit an anisotropic melt phase in the same molecular chain. In this case, the alkyl group has 2 to 4 carbon atoms.
上述の構成成分の内、ナフタレン化合物、ビフェニル化
合物、バラ位置換ベンゼン化合物より選ばれる１種若し
くは２種以上の化合物を必須の構成成分として含むもの
が更に好ましい例である。又、ｐ−位置換ベンゼン化合
物の内、ｐ−ヒドロキシ安息香酸、メチルハイドロキノ
ン及び１−フェニルエチルハイドロキノンは特に好まし
い例である。Among the above-mentioned constituents, those containing one or more compounds selected from naphthalene compounds, biphenyl compounds, and benzene compounds substituted at the bara position as essential constituents are more preferred examples. Among the p-substituted benzene compounds, p-hydroxybenzoic acid, methylhydroquinone and 1-phenylethylhydroquinone are particularly preferred examples.
本発明で用いられるのに特に好ましい異方性溶融相を形
成するポリエステルは、６−ヒドロキシ−２−ナフトイ
ノペ２，６−シヒドロキシナフタレン及び２．６−ジカ
ルボキシナフタレン等のナフタレン部分含有反復単位を
約１０モル％以上の量で含有するものである。好ましい
ポリエステルアミドは上述ナフタレン部分と４−アミノ
フェノール又は１，４−フェニレンジアミンよりなる部
分との反復単位を含有するものである。Particularly preferred anisotropic melt phase forming polyesters for use in the present invention include repeating units containing naphthalene moieties such as 6-hydroxy-2-naphthoinope 2,6-dihydroxynaphthalene and 2,6-dicarboxynaphthalene. It is contained in an amount of about 10 mol% or more. Preferred polyesteramides are those containing repeating units of the naphthalene moiety described above and a moiety consisting of 4-aminophenol or 1,4-phenylenediamine.
尚、上記■）〜■）の構成成分となる化合物の具体例及
び本発明で用いられるのに好ましい異方性溶融相を形成
するポリエステルの具体例については特開昭６１−６９
８６６号公報に記載されている。For specific examples of the compounds constituting the above-mentioned components (1) to (3) and specific examples of polyesters forming an anisotropic melt phase that are preferable for use in the present invention, see JP-A-61-69.
It is described in Publication No. 866.
本発明においては、種々の特性を改良する目的で、上記
特定の無機充填材に加え、更に他の各種の併用無機物を
配合することができる。かかる併用無機物は機械的特性
、耐熱性、寸法安定性（耐変形、そり）等の性質に優れ
た成形品を得るためには配合することが好ましく、これ
には目的に応じて繊維状、粉粒状、板状の併用無機物が
用いられる。In the present invention, in addition to the above-mentioned specific inorganic filler, various other concomitant inorganic substances may be blended for the purpose of improving various properties. It is preferable to incorporate such inorganic substances in order to obtain molded products with excellent properties such as mechanical properties, heat resistance, and dimensional stability (deformation resistance, warping). Particulate and plate-like inorganic materials are used.
繊維状無機物としては、ガラス繊維、炭素繊維、アスベ
スト繊維、シリカ繊維、シリカ・アルミナ繊維、アルミ
ナ繊維、ジルコニア繊維、窒化硼素繊維、態化珪素繊維
、硼素繊維、チタン酸カリ繊維、更にステンレス、アル
ミニウム、チタン、銅、真鍮等の金属の繊維状物などの
無機繊維状物質が挙げられる。Examples of fibrous inorganic materials include glass fiber, carbon fiber, asbestos fiber, silica fiber, silica/alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon fiber, boron fiber, potassium titanate fiber, stainless steel, and aluminum. Examples include inorganic fibrous materials such as fibrous materials of metals such as titanium, copper, and brass.
一方、粉粒状無機物としては、カーボンブラック、黒鉛
、シリカ、石英粉末、ガラスピーズ、ミルドガラスファ
イバー、ガラスバルーン、ガラス粉、酸化鉄、三酸化ア
ンチモン、アルミナの如き金属の酸化物、その他フェラ
イト、炭化珪素、窒化珪素、窒化硼素等が挙げられる。On the other hand, powdery inorganic substances include carbon black, graphite, silica, quartz powder, glass beads, milled glass fibers, glass balloons, glass powder, iron oxide, antimony trioxide, metal oxides such as alumina, other ferrites, and carbonized Examples include silicon, silicon nitride, boron nitride, and the like.
又、板状無機物としては、マイカ、ガラスフレーク、各
種の金属箔等が挙げられる。In addition, examples of the plate-like inorganic material include mica, glass flakes, and various metal foils.
これらの併用無機物は一種又は二種以上併用することが
できる。These inorganic substances can be used alone or in combination.
特に好ましく用いられる併用無機物は繊維状物質、特に
ガラス繊維であり、その配合量は成形品組成物の全重量
に対し、１〜６０重量％の範囲であり、好ましくは５〜
４０重量％である。ただし、前記無機充填材と併用無機
物との総記合量が成形品組成物中の８５重量％を越える
ことは成形加工性及び各種の物性面から好ましくない。Particularly preferably used inorganic substances are fibrous substances, especially glass fibers, and the amount thereof is in the range of 1 to 60% by weight, preferably 5 to 60% by weight, based on the total weight of the molded article composition.
It is 40% by weight. However, it is not preferable for the total amount of the inorganic filler and the combined inorganic substance to exceed 85% by weight of the molded article composition from the viewpoint of moldability and various physical properties.
又、繊維状物質のみを単一充填したものは表面粗度がや
や大きくなり、装飾を目的とするメツキには不適切であ
る。併用する物質としては、直径１〜３０μｍ１長さ５
μｍ〜１ｍｍ 、好ましくは１０μｍ〜１００μｍの範
囲にあるもの、特にガラス繊維を前記無機充填材に組み
合わせると、予想に反し成形品の表面は一層均一化して
、成形品上に導電性回路を形成するためのメツキの密着
力は向上することが見出された。表面粗度と材料の機械
的物性のバランスの面からガラス繊維と微粉状ガラスの
中間に当たるミルドファイバーガラスが特に好ましい。Moreover, a single filling of only fibrous material has a rather large surface roughness, making it unsuitable for plating for decorative purposes. The material to be used in combination is 1 to 30 μm in diameter, 5 in length.
When a filler in the range of μm to 1 mm, preferably 10 μm to 100 μm, especially glass fiber, is combined with the inorganic filler, the surface of the molded article unexpectedly becomes more uniform and conductive circuits are formed on the molded article. It was found that the adhesion of the metal plating was improved. Milled fiber glass, which is between glass fiber and fine powder glass, is particularly preferred in terms of the balance between surface roughness and mechanical properties of the material.
これらの無機充填材及び併用無機物の使用にあたっては
必要ならば収束剤又は表面処理剤を使用することが望ま
しい。When using these inorganic fillers and concomitant inorganic substances, it is desirable to use a sizing agent or a surface treatment agent if necessary.
本発明組成物には従来使用されている核剤を併用しても
悪影響はない。There is no adverse effect when the composition of the present invention is used in combination with a conventionally used nucleating agent.
更に本発明の組成物、は、本発明の範囲でその意図する
目的を損なわない程度に他の熱可塑性樹脂を補助的に添
加したものであってもよい。Furthermore, the composition of the present invention may be supplemented with other thermoplastic resins within the scope of the present invention to the extent that the intended purpose thereof is not impaired.
この場合に使用する熱可塑性樹脂は特に限定されないが
、例を示すと、ポリエチレン、ポリプロピレン等のポリ
オレフィン、ポリアセタール（ホモ又はコポリマー）、
ポリスチレン、ポリ塩化ビニル、ポリアクリル酸エステ
ル、及びそれらの共重合体、ポリアミド、ポリカーボネ
ート、ＡＢＳ、ポリフェニレンオキシド、ポリフェニレ
ンスルフィド、フッ素樹脂等を挙げることができる。ま
たこれらの熱可塑性樹脂は２種以上混合して使用するこ
とができる。The thermoplastic resin used in this case is not particularly limited, but examples include polyolefins such as polyethylene and polypropylene, polyacetal (homo or copolymer),
Examples include polystyrene, polyvinyl chloride, polyacrylic acid ester, and copolymers thereof, polyamide, polycarbonate, ABS, polyphenylene oxide, polyphenylene sulfide, and fluororesin. Further, two or more of these thermoplastic resins can be used in combination.
更に一般の熱可塑性樹脂及び熱硬化性樹脂に添加される
公知の物質、即ち、可塑剤、酸化防止剤や紫外線吸収剤
等の安定剤、帯電防止剤、表面処理剤、界面活性剤、難
燃剤、染料や顔料等の着色剤及び流動性や離型性の改善
のための滑剤、潤滑剤及び結晶化促進剤（核剤）等もそ
の目的とする要求性能に応じ適宜使用することができる
。Furthermore, known substances added to general thermoplastic resins and thermosetting resins, such as plasticizers, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, surface treatment agents, surfactants, and flame retardants. Coloring agents such as dyes and pigments, lubricants, lubricants, and crystallization promoters (nucleating agents) for improving fluidity and mold releasability can also be used as appropriate depending on the desired performance requirements.
また、本発明においてはエツチングの前、後又は同時に
公知の方法で成形品を処理することも可能である。例え
ばエツチング前又は後の成形品の加熱処理、温水処理或
いは特定の化合物を含有した溶液への浸漬処理等である
。かかるエツチング後の処理はエツチング液の中和、洗
浄、乾燥等の工程と兼ねることもできる。Furthermore, in the present invention, it is also possible to treat the molded article by a known method before, after, or simultaneously with etching. For example, the molded article may be heated before or after etching, treated with warm water, or immersed in a solution containing a specific compound. Such post-etching treatment can also serve as steps such as neutralization of the etching solution, washing, and drying.
以上述べた様に、本発明の液晶性ポリエステル樹脂成形
品の表面処理法によれば、当該樹脂の表層剥離を容易に
起こさず、均一で緻密な表面構造を持ち、塗料、接着剤
との結合性が高く、更にはメツキの密着力を強め、これ
まで熱可塑性樹脂では困難であった金属との熱膨張係数
の差による高温剥離を生じることもなく、ハンダ浸漬（
処理時間約１０秒）も可能となり、外装部品はもとより
、プリント配線基板を対象とした用途への展開が可能と
なった。As described above, according to the surface treatment method for liquid crystalline polyester resin molded products of the present invention, the surface layer of the resin does not easily peel off, has a uniform and dense surface structure, and has good bonding with paints and adhesives. It has high properties, and furthermore, it strengthens the adhesion of plating, and it does not cause high-temperature peeling due to the difference in thermal expansion coefficient with metal, which was difficult to do with thermoplastic resins, and it can be used for solder immersion (
The processing time is approximately 10 seconds), making it possible to apply the process not only to exterior parts but also to printed wiring boards.
以下、実施例及び比較例をもって本発明の処理法を更に
具体的に説明するが、本発明にこれに限定されるもので
はない。Hereinafter, the treatment method of the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例１〜８、比較例１〜４
後述の液晶性ポリエステル樹脂Ａと表−１に示した充填
材とを押出機による溶融混練方法により混線分散させ、
ペレット化し、１４０℃で３時間の乾燥をした後、成形
機により１５０〜１６０℃に温調された金型を用いて試
験片を成形し、成形した平板を以下の要領で種々の表面
特性を試験した。結果を表−１に示す。Examples 1 to 8, Comparative Examples 1 to 4 The liquid crystalline polyester resin A described below and the filler shown in Table 1 were cross-dispersed by a melt-kneading method using an extruder, and
After pelletizing and drying at 140°C for 3 hours, a test piece was molded using a mold whose temperature was controlled at 150-160°C using a molding machine, and various surface properties of the molded flat plate were measured as follows. Tested. The results are shown in Table-1.
（１）表面の配向から生じる表層の剥離性成形した平板
の上にセロハンテープにチバン■製、１３ｍｍ巾）を貼
りつけ、指で加圧（約５００ｇ） Ｌ、た後、テープを
９０°の角度で引き剥がし表層のピーリング性を目視に
て判定した。(1) Peelability of surface layer caused by surface orientation Paste cellophane tape (manufactured by Chiban ■, 13 mm width) on the molded flat plate, press it with your fingers (approximately 500 g), and then rotate the tape at a 90° angle. The peelability of the surface layer was visually judged by peeling off the sample at different angles.
評 価 ◎・・・表層剥離全くなし○・・・表層剥
離始どなし
△・・・部分的に表層剥離
×・・・テープ面に殆ど付着して表
層剥離を起こす
（２）゛ 成形品のフローマーク又は不均一フローの程
度
成形品表面を目視にて評価した。Evaluation ◎... No peeling of the surface layer at all ○... No beginning of peeling of the surface layer △... Partial peeling of the surface layer ×... Most of the tape adheres to the surface and causes peeling of the surface layer (2)゛ of the molded product The degree of flow marks or uneven flow was visually evaluated on the surface of the molded product.
評 価 ◎・・・均一表面
○・・・はぼ均一表面
△・・・部分的にフローマークアリ
×・・・全体にフローマーク発生
（３）エツチング処理による表面粗度のバラツキ成形品
をアルカリ脱脂液（奥野製薬工業■製ニースクリンＡ２
２０）中に６０℃にて５分間浸漬し、十分脱脂した後水
洗し、水酸化カリウムの４５重量％濃度の水溶液中で６
０℃にて３０分間エツチング処理した。エツチング処理
した成形品は水洗後塩酸の５重量％溶液で室温にて３分
間浸漬処理することにより、表面に付着したアルカリ分
を中和し水洗した上、８０℃で１５分間熱風循環炉で乾
燥した。エツチング前処理を終えた成形品の表面の粗度
を調べる目的で表面粗度計（小板研究所製５ｕｒｆｃｏ
ｒ＋ｊｅｒＳＥ３Ｃ）でエツチング面の３ケ所について
最大粗度を測定した。Evaluation ◎... Uniform surface ○... Barely uniform surface △... Flow marks partially ×... Flow marks generated throughout (3) Variations in surface roughness due to etching treatment Molded products are treated with alkali Degreasing liquid (Nice Clean A2 manufactured by Okuno Pharmaceutical Co., Ltd.)
20) for 5 minutes at 60°C, thoroughly degreased, washed with water, and soaked in a 45% by weight aqueous solution of potassium hydroxide.
Etching treatment was performed at 0°C for 30 minutes. After washing the etched molded product with water, it was immersed in a 5% by weight solution of hydrochloric acid at room temperature for 3 minutes to neutralize the alkaline content adhering to the surface, washed with water, and dried in a hot air circulation oven at 80°C for 15 minutes. did. In order to check the surface roughness of the molded product after etching pretreatment, we used a surface roughness meter (5urfco manufactured by Koita Research Institute).
The maximum roughness was measured at three locations on the etched surface.
（４）表面処理した成形品の接着性
成形したＡＳＴＭ引張試験片を（３）項と同様にエツチ
ング処理した後、エポキシ系接着剤（セメダインＥＰ−
００７，２液型）をダンベル試験片の中央で二分した各
々の先端部（重なり部の長さｌ ｃｍ） に塗布して貼
り合わせ、室温で２４時間放置後、万能試験機により引
張荷重を測定し、１ｃｍ’当たりの剪断強さを求め、引
張剪断強さとして示した。(4) Adhesion of surface-treated molded products After etching the molded ASTM tensile test pieces in the same manner as in item (3), an epoxy adhesive (CEMEDINE EP-
007, 2-liquid type) was applied to the tips of each of the two halves of the dumbbell test piece (length of the overlapping part 1 cm) and pasted together, and after being left at room temperature for 24 hours, the tensile load was measured using a universal testing machine. Then, the shear strength per 1 cm' was determined and expressed as tensile shear strength.
（５）表面処理した成形品のメツキ密着強さエツチング
処理した平板（５０Ｘ ７０ Ｘ ３ｍｍ）を下記要領
にてメツキした後、カッターナイフで１ｃｍ巾の帯状カ
ットを入れ先端を９０°の角度にめくり上げ、先端部を
バネばかりでつかみ引き剥がす力をメツキ密着強さ（ｋ
ｇ／ｃｍ） として示した。(5) Plating adhesion strength of surface-treated molded products After plating the etched flat plate (50 x 70 x 3 mm) as described below, cut a 1 cm wide strip with a cutter knife and turn the tip at a 90° angle. The strength of adhesion (k
g/cm).
くメツキ処理法〉
（水 洗） １
（湯洗又は水洗） １
（水 洗） １
（水 洗） １
■
（水 洗） １
（希硫酸） １
（希硫酸） １
［至可巨７Ｉ口］
］野製薬工業■製“エースタリンＡ２２０”６０℃×５
分間
Ｚ酸化カリウム水溶液 ４５重量％
６０℃Ｘ３０分間
１酸 ５重量％
２５℃×３分間
１酸 ５重量％
一り℃×２分間
（厚み４０μｍ）
実施例９〜１３
実施例２において液晶性ポリエステルＡの代わりに液晶
性ポリエステルＢ−Ｆを用いた他は同様にして平板を成
形し、同様の評価をして表−２の結果を得た。Scratching treatment method> (Water washing) 1 (Hot water washing or water washing) 1 (Water washing) 1 (Water washing) 1 ■ (Water washing) 1 (Dilute sulfuric acid) 1 (Dilute sulfuric acid) 1 [The largest 7I opening] ] “Acetalin A220” manufactured by No Pharmaceutical Industry ■ 60℃ x 5
Minute Z potassium oxide aqueous solution 45% by weight 60°C x 30 minutes 1 acid 5% by weight 25°C x 3 minutes 1 acid 5% by weight 1°C x 2 minutes (thickness 40 μm) Examples 9 to 13 Liquid crystalline polyester A in Example 2 A flat plate was molded in the same manner except that liquid crystalline polyester B-F was used instead of , and the same evaluation was performed to obtain the results shown in Table 2.
実施例１４〜１９
実施例４で用いた材料について５０Ｘ７０Ｘ３ｍｍの平
板を成形し、各種エツチング液を使って表面処理性を評
価したところ、表−３の結果を得た。Examples 14 to 19 A flat plate of 50 x 70 x 3 mm was molded using the material used in Example 4, and its surface treatability was evaluated using various etching solutions, and the results shown in Table 3 were obtained.
実施例２０
実施例９で得られたメッキ品のメツキ部を１０ｍｍ巾の
帯状にカットし、２６０℃のハンダ浴に１０秒間浸漬し
た後、メツキの密着性を評価したところ、密着力はｌ、
５ｋｇ／ｃｍあり殆ど密着力の低下がなかった。Example 20 The plated part of the plated product obtained in Example 9 was cut into a 10 mm wide strip and immersed in a 260°C solder bath for 10 seconds, and the adhesion of the plate was evaluated.The adhesion was 1,
At 5 kg/cm, there was almost no decrease in adhesion.
実施例２１〜２４、比較例５〜７
液晶性ポリエステル樹脂Ａと表−４に示した充填材とを
実施例１と同様にしてペレット化し試験片を成形した。Examples 21 to 24, Comparative Examples 5 to 7 Liquid crystalline polyester resin A and the filler shown in Table 4 were pelletized in the same manner as in Example 1 to form test pieces.
成形した試験片について、実施例１と同様に表層の剥離
性を、又その他の試験については下記の要領で測定した
。結果を表−４に示す。Regarding the molded test pieces, the peelability of the surface layer was measured in the same manner as in Example 1, and other tests were measured in the following manner. The results are shown in Table 4.
（６）材料強度
成形した試験片の引張強度をＡＳＴＩ、ｌ Ｄ ６３ｇ
により測定した。(6) Material strength The tensile strength of the molded test piece is ASTI, l D 63g
It was measured by
（７）表面処理した成形品の塗装性
成形品を（３）項と同様にエツチング処理した後、市販
のウレタン塗料（関西ペイント■製、レタンＰＧ６０）
を乾燥膜厚で３０±１０μｍになるように塗布し、１０
０℃で６０分間乾燥した後、室温にて１日放置し、塗膜
の付着強さをゴバン目セロハンテープ剥離による方法で
評価した。ゴバン目の大きさは１ｍｍ角×１００個とし
、評価結果はゴバン目残存数／ゴバン目総数で表した。(7) Paintability of surface-treated molded product After etching the molded product in the same manner as in (3), apply a commercially available urethane paint (manufactured by Kansai Paint ■, Rethan PG60).
was applied to a dry film thickness of 30 ± 10 μm, and
After drying at 0° C. for 60 minutes, it was left to stand at room temperature for one day, and the adhesion strength of the coating film was evaluated by peeling with cellophane tape. The size of the squares was 1 mm square x 100, and the evaluation results were expressed as the number of remaining squares/total number of squares.
比較例８．９
実施例２において液晶性を示さない通常の熱可塑性ポリ
エステルとしてポリブチレンテレフタレート （ＰＢＴ
） Ｃポリプラスチックス■製「ジュラネックス」）
を用い、同等処方材料について同等の評価をした。また
、比較例９として充填材を含まないＰＢＴについても同
等に比較評価した。結果を表−５に示す。Comparative Example 8.9 In Example 2, polybutylene terephthalate (PBT) was used as a normal thermoplastic polyester that does not exhibit liquid crystallinity.
) “DURANEX” manufactured by C Polyplastics ■)
was used to evaluate equivalent prescription materials. Further, as Comparative Example 9, PBT containing no filler was similarly evaluated. The results are shown in Table-5.
ＰＢＴの場合は無充填では表面に強い配向もなく、容易
に水酸化カリウノ、て表面エンチングを受け、ガラス繊
維を含む充填材により逆に配向性が生じ、エツチング面
は液晶性ポリエステルより粗化が速く表面の荒れが大き
くなり、良好な外観の塗装品、メッキ品は得られなかっ
た。In the case of unfilled PBT, there is no strong orientation on the surface, and the surface is easily etched by potassium hydroxide, whereas fillers containing glass fiber cause the opposite orientation, and the etched surface is rougher than that of liquid crystalline polyester. The surface roughness quickly became large, and a painted or plated product with a good appearance could not be obtained.
尚、実施例で使用した液晶性ポリエステルは下記の構成
単位を有するものである。The liquid crystalline polyester used in the examples has the following structural units.
＝６０／２０／２０ ＝７０／１５／１５ ＝ ６０／２０／２０ 出願人代理人 古 谷 馨=60/20/20 =70/15/15 = 60/20/20 Applicant's agent Kaoru Furutani
Claims (1)
に周期律表IIａ、IIｂ、IIIａ、IVａ、Ｖａ族元素から
なる群より選ばれた１種又は２種以上の元素を含む無機
充填材を組成物全重量に対して５〜８０重量％含有せし
めてなる液晶性ポリエステル樹脂組成物からなる成形品
を、アルカリ金属の水酸化物又はアルカリ土類金属の水
酸化物を主成分とする水溶液に接触処理せしめることを
特徴とする液晶性ポリエステル樹脂成形品の表面処理法
。 ２ 無機充填材が周期律表IIａ又はIIｂ族元素の酸化物
、硫酸塩、リン酸塩及び珪酸塩からなる群より選ばれた
１種又は２種以上の無機充填材である特許請求の範囲第
１項記載の液晶性ポリエステル樹脂成形品の表面処理法
。 ３ 無機充填材が周期律表IIIａ、IVａ、Ｖａ族元素及
びその酸化物からなる群より選ばれた１種又は２種以上
の無機充填材である特許請求の範囲第１項記載の液晶性
ポリエステル樹脂成形品の表面処理法。 ４ 無機充填材が平均粒径０．０１〜１００μｍの範囲
の微粉状である特許請求の範囲第１項〜３項の何れか１
項に記載の液晶性ポリエステル樹脂成形品の表面処理法
。 ５ 成形品が、上記無機充填材の他に更に直径が１〜３
０μｍ、長さ５μｍ〜１ｍｍの範囲にある繊維状無機物
を、成形品組成物の全重量に対して１〜６０重量％配合
した組成物からなる特許請求の範囲第１〜４項の何れか
１項に記載の液晶性ポリエステル樹脂成形品の表面処理
法。[Scope of Claims] 1. One or more elements selected from the group consisting of Group IIa, IIb, IIIa, IVa, and Va elements of the Periodic Table in a melt-processable polyester capable of forming an anisotropic melt phase. A molded article made of a liquid crystalline polyester resin composition containing 5 to 80% by weight of an inorganic filler containing an alkali metal hydroxide or an alkaline earth metal hydroxide based on the total weight of the composition. A method for surface treatment of liquid crystalline polyester resin molded articles, characterized by contact treatment with an aqueous solution containing the main component. 2. Claim No. 2, wherein the inorganic filler is one or more inorganic fillers selected from the group consisting of oxides, sulfates, phosphates, and silicates of group IIa or IIb elements of the periodic table. A method for surface treatment of a liquid crystalline polyester resin molded article according to item 1. 3. The liquid crystalline polyester according to claim 1, wherein the inorganic filler is one or more inorganic fillers selected from the group consisting of IIIa, IVa, and Va group elements of the periodic table and their oxides. Surface treatment method for resin molded products. 4. Any one of claims 1 to 3, wherein the inorganic filler is in the form of fine powder with an average particle size in the range of 0.01 to 100 μm.
The method for surface treatment of liquid crystalline polyester resin molded products as described in 2. 5 The molded product has a diameter of 1 to 3 in addition to the above inorganic filler.
Any one of claims 1 to 4, comprising a composition containing 1 to 60% by weight of a fibrous inorganic substance having a length of 0 μm and a length of 5 μm to 1 mm based on the total weight of the molded article composition. The method for surface treatment of liquid crystalline polyester resin molded products as described in 2.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62249196A JPH0819251B2 (en) | 1987-10-02 | 1987-10-02 | Surface treatment method for liquid crystalline polyester resin moldings |
| DE19883884546 DE3884546T3 (en) | 1987-10-02 | 1988-05-18 | Process for the surface treatment of objects made of liquid crystalline polyester resin. |
| EP19880304473 EP0311232B2 (en) | 1987-10-02 | 1988-05-18 | Process for surface treatment of moldings of liquid-crystalline polyester resin |
| AT88304473T ATE95210T1 (en) | 1987-10-02 | 1988-05-18 | PROCESS FOR SURFACE TREATMENT OF OBJECTS MADE OF LIQUID CRYSTALLINE POLYESTER RESIN. |
| US07/198,255 US4997724A (en) | 1987-10-02 | 1988-05-25 | Process for surface treatment of moldings of liquid-crystalline polyester resin |
| KR1019880006133A KR910005863B1 (en) | 1987-10-02 | 1988-05-25 | Process for surface treatment of moldings of liquid-crystalline polyester resin |
| HK195496A HK195496A (en) | 1987-10-02 | 1996-10-24 | Process for surface treatment of moldings of liquid-crystalline polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62249196A JPH0819251B2 (en) | 1987-10-02 | 1987-10-02 | Surface treatment method for liquid crystalline polyester resin moldings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0192241A true JPH0192241A (en) | 1989-04-11 |
| JPH0819251B2 JPH0819251B2 (en) | 1996-02-28 |
Family
ID=17189333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62249196A Expired - Lifetime JPH0819251B2 (en) | 1987-10-02 | 1987-10-02 | Surface treatment method for liquid crystalline polyester resin moldings |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0819251B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01123857A (en) * | 1987-11-06 | 1989-05-16 | Toray Ind Inc | Highly melting-resistant polyarylate resin and its production |
| JPH03140235A (en) * | 1989-10-27 | 1991-06-14 | Sankyo Kasei Co Ltd | Manufacture of resin molded product |
| JP2007119518A (en) * | 2005-10-25 | 2007-05-17 | Polyplastics Co | High-dielectric constant resin composition for plating |
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|---|---|---|---|---|
| JPS536374A (en) * | 1976-07-06 | 1978-01-20 | Minolta Camera Kk | Method of treating thermoplastic polyester resin for electroless plating |
| JPS5468877A (en) * | 1977-11-09 | 1979-06-02 | Polyplastics Kk | Method of plating thermoplastic polyester |
| JPS55133431A (en) * | 1979-04-03 | 1980-10-17 | Kuraray Co Ltd | Polyester film having roughened surface and its manufacture |
| JPS5710641A (en) * | 1980-06-24 | 1982-01-20 | Sumitomo Chem Co Ltd | Wholly aromatic copolyester resin composition |
| JPS58123587U (en) * | 1982-02-17 | 1983-08-23 | 富士通株式会社 | coaxial multi connector |
| JPS596623U (en) * | 1982-07-05 | 1984-01-17 | ミツミ電機株式会社 | Knob mounting structure |
| JPS59176333A (en) * | 1983-03-28 | 1984-10-05 | Kanegafuchi Chem Ind Co Ltd | Surface modification of polyester |
| JPS59210950A (en) * | 1983-05-16 | 1984-11-29 | Toyobo Co Ltd | Metal-plated polyester molding and production thereof |
| JPS6040163A (en) * | 1983-07-27 | 1985-03-02 | ヘキスト・セラニーズ・コーポレーション | Improved sealing method for electronic parts |
| JPS6244580A (en) * | 1985-08-23 | 1987-02-26 | Toray Ind Inc | Production of surface metallized polybutylene telephthalate resin molding |
| JPS6254073A (en) * | 1985-09-02 | 1987-03-09 | Polyplastics Co | Surface-metallized resin molding |
| JPS6257429A (en) * | 1985-09-05 | 1987-03-13 | Mitsui Toatsu Chem Inc | Composite material |
-
1987
- 1987-10-02 JP JP62249196A patent/JPH0819251B2/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS536374A (en) * | 1976-07-06 | 1978-01-20 | Minolta Camera Kk | Method of treating thermoplastic polyester resin for electroless plating |
| JPS5468877A (en) * | 1977-11-09 | 1979-06-02 | Polyplastics Kk | Method of plating thermoplastic polyester |
| JPS55133431A (en) * | 1979-04-03 | 1980-10-17 | Kuraray Co Ltd | Polyester film having roughened surface and its manufacture |
| JPS5710641A (en) * | 1980-06-24 | 1982-01-20 | Sumitomo Chem Co Ltd | Wholly aromatic copolyester resin composition |
| JPS58123587U (en) * | 1982-02-17 | 1983-08-23 | 富士通株式会社 | coaxial multi connector |
| JPS596623U (en) * | 1982-07-05 | 1984-01-17 | ミツミ電機株式会社 | Knob mounting structure |
| JPS59176333A (en) * | 1983-03-28 | 1984-10-05 | Kanegafuchi Chem Ind Co Ltd | Surface modification of polyester |
| JPS59210950A (en) * | 1983-05-16 | 1984-11-29 | Toyobo Co Ltd | Metal-plated polyester molding and production thereof |
| JPS6040163A (en) * | 1983-07-27 | 1985-03-02 | ヘキスト・セラニーズ・コーポレーション | Improved sealing method for electronic parts |
| JPS6244580A (en) * | 1985-08-23 | 1987-02-26 | Toray Ind Inc | Production of surface metallized polybutylene telephthalate resin molding |
| JPS6254073A (en) * | 1985-09-02 | 1987-03-09 | Polyplastics Co | Surface-metallized resin molding |
| JPS6257429A (en) * | 1985-09-05 | 1987-03-13 | Mitsui Toatsu Chem Inc | Composite material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01123857A (en) * | 1987-11-06 | 1989-05-16 | Toray Ind Inc | Highly melting-resistant polyarylate resin and its production |
| JPH03140235A (en) * | 1989-10-27 | 1991-06-14 | Sankyo Kasei Co Ltd | Manufacture of resin molded product |
| JP2007119518A (en) * | 2005-10-25 | 2007-05-17 | Polyplastics Co | High-dielectric constant resin composition for plating |
| JP4727381B2 (en) * | 2005-10-25 | 2011-07-20 | ポリプラスチックス株式会社 | High dielectric resin composition for plating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0819251B2 (en) | 1996-02-28 |
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