JP4713159B2 - Laser welding thermoplastic resin composition and synthetic resin parts using the same - Google Patents
Laser welding thermoplastic resin composition and synthetic resin parts using the same Download PDFInfo
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- JP4713159B2 JP4713159B2 JP2005001390A JP2005001390A JP4713159B2 JP 4713159 B2 JP4713159 B2 JP 4713159B2 JP 2005001390 A JP2005001390 A JP 2005001390A JP 2005001390 A JP2005001390 A JP 2005001390A JP 4713159 B2 JP4713159 B2 JP 4713159B2
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- thermoplastic resin
- laser welding
- resin composition
- Prior art date
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- 229920005992 thermoplastic resin Polymers 0.000 title claims description 70
- 238000003466 welding Methods 0.000 title claims description 67
- 239000011342 resin composition Substances 0.000 title claims description 46
- 229920003002 synthetic resin Polymers 0.000 title claims description 12
- 239000000057 synthetic resin Substances 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims description 93
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 32
- 229920002554 vinyl polymer Polymers 0.000 claims description 32
- 229920000578 graft copolymer Polymers 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 25
- -1 acrylate ester Chemical class 0.000 claims description 25
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 20
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 18
- 229920000800 acrylic rubber Polymers 0.000 claims description 16
- 229920000058 polyacrylate Polymers 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 229920006037 cross link polymer Polymers 0.000 claims description 12
- 239000006096 absorbing agent Substances 0.000 claims description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
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- 150000002009 diols Chemical class 0.000 claims description 3
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- 239000000975 dye Substances 0.000 description 23
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- 150000004670 unsaturated fatty acids Chemical class 0.000 description 9
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 9
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 7
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 6
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 6
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 6
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 6
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 4
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 4
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 4
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- 239000004925 Acrylic resin Substances 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
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- 125000005397 methacrylic acid ester group Chemical group 0.000 description 4
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- 239000011591 potassium Substances 0.000 description 4
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- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 3
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 3
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- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
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- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 3
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- XBGNYAOLZNHWDC-UHFFFAOYSA-N 2-sulfanylnaphthalen-1-ol Chemical class C1=CC=C2C(O)=C(S)C=CC2=C1 XBGNYAOLZNHWDC-UHFFFAOYSA-N 0.000 description 1
- VMKYTRPNOVFCGZ-UHFFFAOYSA-N 2-sulfanylphenol Chemical compound OC1=CC=CC=C1S VMKYTRPNOVFCGZ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- XURABDHWIADCPO-UHFFFAOYSA-N 4-prop-2-enylhepta-1,6-diene Chemical compound C=CCC(CC=C)CC=C XURABDHWIADCPO-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229920001895 acrylonitrile-acrylic-styrene Polymers 0.000 description 1
- 239000000654 additive Substances 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
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 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 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical compound C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
- B29C65/16—Laser beams
- B29C65/1603—Laser beams characterised by the type of electromagnetic radiation
- B29C65/1612—Infrared [IR] radiation, e.g. by infrared lasers
- B29C65/1616—Near infrared radiation [NIR], e.g. by YAG lasers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
- B29C65/16—Laser beams
- B29C65/1677—Laser beams making use of an absorber or impact modifier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
- B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
- B29C66/7375—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured
- B29C66/73753—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being partially cured, i.e. partially cross-linked, partially vulcanized
- B29C66/73754—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being partially cured, i.e. partially cross-linked, partially vulcanized the to-be-joined areas of both parts to be joined being partially cured
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
- B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
- B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
- B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
- B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
- B29C66/73921—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic characterised by the materials of both parts being thermoplastics
Description
本発明は、レーザー溶着用熱可塑性樹脂組成物に関するものであり、特に、溶着部に発生するバリなど外観が良好なレーザー溶着用熱可塑性樹脂組成物に関する。また、そのレーザー溶着用熱可塑性樹脂組成物を用いた合成樹脂製部品に関する。 The present invention relates to a laser welding thermoplastic resin composition, and more particularly, to a laser welding thermoplastic resin composition having a good appearance such as a burr generated at a welded portion. The present invention also relates to a synthetic resin part using the laser welding thermoplastic resin composition.
二輪車や四輪車で使用されているテールランプ、ストップランプなどのランプ類、メーターケース等は、樹脂からなる部品同士を組み合わせてつくられている。樹脂部品を組み合わせる際の接合方法としては、接着剤による方法のほかに、熱板溶着、振動溶着などの方法がある。これらの方法は、熱板との接触あるいは摩擦によって樹脂部品の一部を溶融させて接合するものであり、接着剤を塗布する手間や接着剤が硬化する時間を省くことができるため、生産性に優れた方法である。また、近年、接合する樹脂部分にレーザー光を、照射し、接合部分の樹脂に発生する吸収発熱を利用し、接着するレーザー溶着が提案されるようになってきた。一般的には、レーザー溶着は、従来の溶着方法と異なり、接合部分以外への、加熱がなく、溶着面は、きれいなものとなることが、知らされている。 Lamps such as tail lamps and stop lamps used in motorcycles and automobiles, meter cases, and the like are made by combining parts made of resin. As a joining method when combining resin parts, there are methods such as hot plate welding and vibration welding in addition to a method using an adhesive. These methods melt and bond a part of the resin parts by contact with the hot plate or friction, and can save time and effort for applying the adhesive and curing the adhesive. It is an excellent method. In recent years, laser welding has been proposed in which a resin portion to be bonded is irradiated with a laser beam and absorbed heat generated in the resin at the bonded portion is used for bonding. In general, it is known that laser welding is different from the conventional welding methods in that there is no heating to a portion other than the joining portion, and the welding surface is clean.
しかしながら、レーザー溶着によって樹脂部品を接合する方法は、実用例が、少なく、溶着条件など生産性を含めた工法の確立が今後望まれている。レーザー溶着では、レーザー光を、いかに効率良く樹脂同士の接触面に照射し発熱量を制御するかが重要とされている。 However, there are few practical examples of methods for joining resin parts by laser welding, and establishment of a construction method including productivity such as welding conditions is desired in the future. In laser welding, it is important to control the amount of heat generated by efficiently irradiating laser light onto the contact surface between resins.
レーザ光が、必要以上に照射されると、発熱により接着性は、増すが、外観は樹脂の溶融により、低下する問題が発生する。
これらを解決する方法として、特開２００４−１８２８３５号公報には、樹脂の組成を最適化する方法が提案されている。しかし、この場合は、他の特性とのバランスを考慮すると十分な効果が得られにくい。また、一般的には、カーボンを添加し、レーザー光の吸収量を制御する方法も知られているが、吸収量が強くなりすぎる傾向があることと、色相が黒色に限定されたものとなる。
When the laser beam is irradiated more than necessary, the adhesiveness increases due to heat generation, but the appearance deteriorates due to the melting of the resin.
As a method for solving these problems, JP 2004-182835 A proposes a method for optimizing the resin composition. However, in this case, it is difficult to obtain a sufficient effect considering the balance with other characteristics. In general, a method of adding carbon and controlling the amount of absorption of laser light is also known, but the amount of absorption tends to be too strong, and the hue is limited to black. .
本発明は、上記のように、レーザー溶着によってランプハウジングとレンズといった合成樹脂製部品を接合したときに発生する外観不具合を改善するレーザー溶着用熱可塑性樹脂組成物を提供することにある。また、そのレーザー溶着用熱可塑性樹脂組成物を用いた合成樹脂製部品を提供する。 An object of the present invention is to provide a laser welding thermoplastic resin composition that improves appearance defects that occur when a synthetic resin part such as a lamp housing and a lens is joined by laser welding as described above. In addition, a synthetic resin part using the thermoplastic resin composition for laser welding is provided.
本発明者は、レーザー溶着によって形成される溶着部の外観を改善するために検討を行った結果、特に、レーザー光を、効率よく吸収し、レーザー光による発熱量を制御し、溶着部の外観不具合を改善できることを見出し、本発明にいたった。
本発明は、［１］ 下記の（ａ１−１）存在下に（ａ１−２）を重合して得られた架橋アクリルゴム（ａ１）に、さらに下記の（ａ２）をグラフト重合したグラフト共重合体（Ａ）と、波長７５０〜８５０ｎｍで吸収性を示す赤外吸収剤を含有してなるレーザー溶着用熱可塑性樹脂組成物。
（ａ１−１）少なくとも、分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体と、芳香族ビニル単量体とを共重合した共重合体からなる架橋重合体粒子、
（ａ１−２）アクリル酸エステル、分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体、分子内にアリル基を有する単量体の混合物、
（ａ２）芳香族ビニル単量体、シアン化ビニル単量体、（メタ）アクリル酸エステル単量体、その他のビニル単量体からなる群より選ばれた少なくとも一種の単量体。
［２］ グラフト共重合体（Ａ）が、（ａ１）１０〜９０重量部に（ａ２）１０〜９０重量部（ただし（ａ１）と（ａ２）の合計が１００重量部）をグラフト重合したものであり、熱可塑性樹脂組成物中の熱可塑性樹脂成分は、グラフト共重合体（Ａ）単独か、（Ａ）とその他の熱可塑性樹脂（Ｂ）からなり、その混合比が、グラフト共重合体（Ａ）１０〜１００重量部、熱可塑性樹脂（Ｂ）０〜９０重量部（ただし（Ａ）と（Ｂ）の合計が１００重量部）である上記［１］記載のレーザー溶着用熱可塑性樹脂組成物。
また、本発明は、［３］ 波長７５０〜８５０ｎｍで吸収性を示す赤外吸収剤の含有量が、グラフト共重合体（Ａ）と熱可塑性樹脂（Ｂ）の混合割合１００重量部に対して０．００１〜１重量部であることを特徴とする上記［１］または［２］に記載のレーザー溶着用熱可塑性樹脂組成物である。
また、本発明は、［４］ 分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体の使用量が、アクリル酸エステル１００重量部に対して０．１〜１０重量部であることを特徴とする上記［１］ないし上記［３］のいずれかに記載のレーザー溶着用熱可塑性樹脂組成物である。
また、本発明は、［５］ 分子内にアリル基を有する単量体の使用量が、アクリル酸エステル１００重量部に対して０．０１〜１０重量部であることを特徴とする上記［１］ないし上記［４］のいずれかに記載のレーザー溶着用熱可塑性樹脂組成物である。
また、本発明は、［６］ 分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体が、分子内に２個の水酸基を有するジオールのジ（メタ）アクリル酸エステルであることを特徴とする上記［１］ないし上記［５］のいずれかに記載のレーザー溶着用熱可塑性樹脂組成物である。
また、本発明は、［７］ 分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体が、アルキレンジオールのジ（メタ）アクリル酸エステルであることを特徴とする上記［１］ないし上記［５］のいずれかに記載のレーザー溶着用熱可塑性樹脂組成物である。
また、本発明は、［８］ グラフト共重合体（Ａ）と熱可塑性樹脂（Ｂ）の混合割合が、（Ａ）と（Ｂ）の合計１００重量部に対して架橋アクリルゴム（ａ１）が１０〜５０重量部になるように決定された割合であることを特徴とする上記［１］ないし上記［７］のいずれかに記載のレーザー溶着用熱可塑性樹脂組成物である。
また、本発明は、［９］ 熱可塑性樹脂（Ｂ）が、芳香族ビニル単量体、シアン化ビニル単量体、（メタ）アクリル酸エステル単量体、その他のビニル単量体からなる群より選ばれた少なくとも一種の単量体を重合してなるものである上記［１］ないし上記［８］のいずれかに記載のレーザー溶着用熱可塑性樹脂組成物である。
また、本発明は、［１０］ ２個以上の樹脂成形品がレーザー溶着法によって一体化された合成樹脂製部品であって、樹脂成形品のうち１個以上が上記［１］ないし上記［９］のいずれかに記載のレーザー溶着用熱可塑性樹脂組成物からなることを特徴とする合成樹脂製部品である。
本発明では、（メタ）アクリロイル基は、メタアクリロイル基またはアクリロイル基を意味し、また、（メタ）アクリル酸は、メタアクリル酸またはアクリル酸を意味する。
As a result of studies conducted by the present inventors to improve the appearance of the welded portion formed by laser welding, in particular, the laser beam is efficiently absorbed, the amount of heat generated by the laser light is controlled, and the appearance of the welded portion is determined. The present inventors have found that the problem can be improved and have arrived at the present invention.
The present invention provides [1] graft copolymer obtained by graft polymerization of the following (a2) to the crosslinked acrylic rubber (a1) obtained by polymerizing (a1-2) in the presence of the following (a1-1): A laser welding thermoplastic resin composition comprising the coalesced (A) and an infrared absorbent exhibiting absorption at a wavelength of 750 to 850 nm.
(A1-1) Crosslinked polymer particles comprising a copolymer obtained by copolymerizing at least a monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule and an aromatic vinyl monomer,
(A1-2) acrylic acid ester, monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule, mixture of monomers having allyl groups in the molecule,
(A2) At least one monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylic acid ester monomers, and other vinyl monomers.
[2] Graft copolymer (A) obtained by graft polymerization of (a1) 10 to 90 parts by weight (a2) 10 to 90 parts by weight (provided the total of (a1) and (a2) is 100 parts by weight) The thermoplastic resin component in the thermoplastic resin composition is composed of the graft copolymer (A) alone or (A) and another thermoplastic resin (B), and the mixing ratio thereof is the graft copolymer. (A) 10 to 100 parts by weight, thermoplastic resin (B) 0 to 90 parts by weight (however, the sum of (A) and (B) is 100 parts by weight) The laser welding thermoplastic resin according to the above [1] Composition.
In the present invention, [3] the content of the infrared absorber that absorbs at a wavelength of 750 to 850 nm is 100 parts by weight of the mixing ratio of the graft copolymer (A) and the thermoplastic resin (B). The thermoplastic resin composition for laser welding according to the above [1] or [2], which is 0.001 to 1 part by weight.
In addition, the present invention provides: [4] The amount of the monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule is 0.1 to 10 parts by weight with respect to 100 parts by weight of the acrylate ester. The thermoplastic resin composition for laser welding according to any one of [1] to [3] above, wherein the thermoplastic resin composition is a laser welding thermoplastic resin composition.
[5] In the above [1], the amount of the monomer having an allyl group in the molecule is 0.01 to 10 parts by weight with respect to 100 parts by weight of the acrylate ester. ] The thermoplastic resin composition for laser welding according to any one of [4] above.
The present invention also provides [6] a di (meth) acrylic acid ester of a diol in which a monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule has two hydroxyl groups in the molecule. The thermoplastic resin composition for laser welding according to any one of the above [1] to [5], wherein the thermoplastic resin composition is a laser welding thermoplastic resin composition.
Further, the present invention provides [7] wherein the monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule is a di (meth) acrylic acid ester of alkylene diol. 1] to the thermoplastic resin composition for laser welding according to any one of [5] above .
Also, the present invention provides [8] Graft copolymer mixing ratio of (A) and the thermoplastic resin (B), (A) and the crosslinked acrylic rubber per 100 parts by weight of (B) (a1) The thermoplastic resin composition for laser welding according to any one of [1] to [ 7 ] above, wherein the ratio is determined so as to be 10 to 50 parts by weight.
In the present invention, the [ 9 ] thermoplastic resin (B) is composed of an aromatic vinyl monomer, a vinyl cyanide monomer, a (meth) acrylic acid ester monomer, and other vinyl monomers. The thermoplastic resin composition for laser welding according to any one of the above [1] to [ 8 ], which is obtained by polymerizing at least one monomer selected from the above.
Further, the present invention is [10] two or more of the resin molded article is an integral synthetic resin component by laser welding method, one or more of the resin molded article is above [1] to the [9 ] A synthetic resin part comprising the thermoplastic resin composition for laser welding according to any one of the above.
In the present invention, a (meth) acryloyl group means a methacryloyl group or an acryloyl group, and (meth) acrylic acid means methacrylic acid or acrylic acid.
本発明におけるレーザー溶着用熱可塑性樹脂組成物を用いることによって、レーザー溶着時のバリなど目立たなくなり、溶着部の外観の良好な自動車用ランプ等の合成樹脂製部品が得られる。また、本発明のレーザー溶着用熱可塑性樹脂組成物を用い、レーザー溶着によりレーザー溶着時にバリ、あるいは、空隙の発生など外観の不具合が改善され、また、作業性が向上し、樹脂成形品同士の接合強度も十分な合成樹脂製部品を製造できる。 By using the thermoplastic resin composition for laser welding according to the present invention, it is possible to obtain a synthetic resin part such as an automobile lamp having a good appearance of the welded portion, which does not stand out such as burrs during laser welding. In addition, using the laser welding thermoplastic resin composition of the present invention, laser welding improves the appearance defects such as burrs or voids during laser welding, improves workability, Synthetic resin parts with sufficient bonding strength can be manufactured.
本発明のレーザー溶着用熱可塑性樹脂組成物は、下記の（ａ１−１）存在下に（ａ１−２）を重合して得られた架橋アクリルゴム（ａ１）に、さらに下記の（ａ２）をグラフト重合したグラフト共重合体（Ａ）と所望により熱可塑性樹脂（Ｂ）と、波長７５０〜８５０ｎｍで吸収性を示す赤外吸収剤を含有してなることを特徴としている。これによって、レーザー溶着時に発生するバリなど、外観不良が低減できる。
（ａ１−１）架橋重合体粒子、
（ａ１−２）アクリル酸エステル、分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体、分子内にアリル基を有する単量体の混合物、
（ａ２）芳香族ビニル単量体、シアン化ビニル単量体、（メタ）アクリル酸エステル単量体、その他のビニル単量体からなる群より選ばれた少なくとも一種の単量体。
各成分の割合としては、グラフト共重合体（Ａ）が、（ａ１）１０〜９０重量部に、（ａ２）１０〜９０重量部（ただし（ａ１）と（ａ２）の合計が１００重量部）をグラフト重合したものであり、この（Ａ）成分単独か、この（Ａ）成分１００〜１０重量部に、その他の熱可塑性樹脂（Ｂ）を０〜９０重量部配合したもの（ただし（Ａ）と（Ｂ）の合計が１００重量部）であることが、耐衝撃性、耐候性等の効果が高く好ましい。
The thermoplastic resin composition for laser welding of the present invention further comprises the following (a2) to the crosslinked acrylic rubber (a1) obtained by polymerizing (a1-2) in the presence of the following (a1-1). It is characterized by containing a graft copolymer (A) obtained by graft polymerization, a thermoplastic resin (B) if necessary, and an infrared absorber exhibiting absorption at a wavelength of 750 to 850 nm. Thereby, appearance defects such as burrs generated during laser welding can be reduced.
(A1-1) crosslinked polymer particles,
(A1-2) acrylic acid ester, monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule, mixture of monomers having allyl groups in the molecule,
(A2) At least one monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylic acid ester monomers, and other vinyl monomers.
As a ratio of each component, the graft copolymer (A) is (a1) 10 to 90 parts by weight, (a2) 10 to 90 parts by weight (however, the total of (a1) and (a2) is 100 parts by weight) The component (A) alone or 100 to 10 parts by weight of the component (A) and 0 to 90 parts by weight of the other thermoplastic resin (B) (provided that (A) And (B) is preferably 100 parts by weight) because the effects such as impact resistance and weather resistance are high.
以下、本発明の詳細について説明する。
本発明におけるレーザー溶着用熱可塑性樹脂組成物に用いる架橋重合体粒子（ａ１−１）は、アクリルゴムの核としてはたらくものである。その成分は、架橋構造を有する重合体であれば特に限定されず、ポリスチレン、ＡＳ樹脂などのスチレン系樹脂、アクリル樹脂、ポリ酢酸ビニルなどが例として挙げられる。これらは、一種類単独または二種以上を混合して使用することができる。
Details of the present invention will be described below.
The crosslinked polymer particles (a1-1) used in the thermoplastic resin composition for laser welding in the present invention serve as the core of acrylic rubber. The component is not particularly limited as long as it is a polymer having a crosslinked structure, and examples thereof include styrene resins such as polystyrene and AS resin, acrylic resins, and polyvinyl acetate. These can be used individually by 1 type or in mixture of 2 or more types.
本発明における架橋重合体粒子（ａ１−１）として、分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体０．５〜１００重量部、芳香族ビニル単量体、シアン化ビニル単量体、（メタ）アクリル酸エステル単量体、その他のビニル単量体からなる群より選ばれた少なくとも一種の単量体０〜９９．５重量部(ただし、単量体の合計が１００重量部)を共重合してなる架橋重合体粒子を用いることが好ましい。 As the crosslinked polymer particles (a1-1) in the present invention, 0.5 to 100 parts by weight of a monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule, an aromatic vinyl monomer, cyan 0 to 99.5 parts by weight of at least one monomer selected from the group consisting of vinyl fluoride monomers, (meth) acrylic acid ester monomers, and other vinyl monomers (however, the total of the monomers It is preferable to use crosslinked polymer particles obtained by copolymerization of
前記した分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体は、架橋剤として働くものであり、例としては、エチレングリコールジアクリレート、１，３−ブタンジオールジアクリレート、１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、アクリル変成ポリジメチルシロキサンなどのアクリル酸エステル、エチレングリコールジメタクリレート、１，３−ブタンジオールジメタクリレート、１，４−ブタンジオールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールヘキサメタクリレート、メタクリル変成ポリジメチルシロキサンなどのメタクリル酸エステル、ジビニルベンゼンなどの芳香族ビニル化合物などが挙げられる。これらは一種類単独または二種以上を混合して使用することができる。 The monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule serves as a crosslinking agent, and examples thereof include ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, Acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, acrylic modified polydimethylsiloxane, ethylene glycol dimethacrylate 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, Examples include trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, methacrylic acid esters such as methacryl-modified polydimethylsiloxane, and aromatic vinyl compounds such as divinylbenzene. These can be used individually by 1 type or in mixture of 2 or more types.
前記した分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体の使用量は、前記のように、共重合する芳香族ビニル単量体、シアン化ビニル単量体、（メタ）アクリル酸エステル単量体、その他のビニル単量体からなる群より選ばれた少なくとも一種の単量体０〜９９．５重量部(ただし、単量体の合計が１００重量部)となるよう、０．５重量部〜１００重量部であると好ましい。０．５重量部未満であると、架橋が不十分であり、押出、成形などの溶融加工時に粒子の形状を保持できないおそれがある。 As described above, the amount of the monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule is such that the copolymerized aromatic vinyl monomer, vinyl cyanide monomer, ( At least one monomer selected from the group consisting of (meth) acrylic acid ester monomers and other vinyl monomers is 0 to 99.5 parts by weight (however, the total of the monomers is 100 parts by weight). Thus, 0.5 to 100 parts by weight is preferable. If it is less than 0.5 parts by weight, crosslinking is insufficient and the shape of the particles may not be maintained during melt processing such as extrusion and molding.
前記芳香族ビニル単量体としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、クロロスチレン、ブロモスチレンなどのうち、一種類単独または二種以上を混合して使用することができる。 As the aromatic vinyl monomer, one kind or a mixture of two or more kinds of styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, chlorostyrene, bromostyrene and the like are used. can do.
前記シアン化ビニル単量体としては、アクリロニトリル、メタクリロニトリルなどのうち、一種類単独または二種を混合して使用することができる。 As the vinyl cyanide monomer, one kind or a mixture of two kinds of acrylonitrile, methacrylonitrile and the like can be used.
前記（メタ）アクリル酸エステル単量体としては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチルなどのアクリル酸エステル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチルなどのメタクリル酸エステルが挙げられる。これらは、一種類単独または二種以上を混合して使用することができる。 Examples of the (meth) acrylic acid ester monomer include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. The methacrylic acid ester of this is mentioned. These can be used individually by 1 type or in mixture of 2 or more types.
その他のビニル単量体としては、アクリル酸、メタクリル酸、オレイン酸、マレイン酸、フマル酸などの不飽和脂肪酸、無水アクリル酸、無水メタクリル酸、無水マレイン酸などの不飽和脂肪酸無水物、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、メタクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミドなどの不飽和脂肪酸のアミド、Ｎ−メチルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−フェニルマレイミドなどのマレイミド、酢酸ビニル、酪酸ビニル、安息香酸ビニルなどのビニルエステルなどが挙げられる。これらは、一種類単独または二種以上を混合して使用することができる。 Other vinyl monomers include unsaturated fatty acids such as acrylic acid, methacrylic acid, oleic acid, maleic acid and fumaric acid, unsaturated fatty acid anhydrides such as acrylic anhydride, methacrylic anhydride and maleic anhydride, acrylamide, N, N-dimethylacrylamide, amide of unsaturated fatty acid such as methacrylamide, N, N-dimethylmethacrylamide, maleimide such as N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, vinyl acetate, vinyl butyrate, benzoate And vinyl esters such as vinyl acid. These can be used individually by 1 type or in mixture of 2 or more types.
本発明の架橋重合体粒子の製造方法としては、乳化重合、懸濁重合など単量体組成物が分散した状態で重合を行う方法、架橋重合体を粉砕する方法などが挙げられる。これらの中で、分散状態の架橋重合体粒子を容易に得ることができる乳化重合、懸濁重合が好ましい。 Examples of the method for producing the crosslinked polymer particles of the present invention include a method in which the monomer composition is dispersed, such as emulsion polymerization and suspension polymerization, and a method in which the crosslinked polymer is pulverized. Among these, emulsion polymerization and suspension polymerization that can easily obtain dispersed polymer particles in a dispersed state are preferable.
本発明における架橋アクリルゴム（ａ１）は、上記架橋重合体粒子（ａ１−１）の存在下に、（ａ１−２）アクリル酸エステル、分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体および分子内にアリル基を有する単量体を共重合して得られる。上記アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸イソアミル、アクリル酸イソデシル、アクリル酸ラウリル、アクリル酸−２−エチルヘキシル、アクリル酸−２−エトキシエチルなどが挙げられる。これらは、一種類単独または二種以上を混合して使用することができる。 The crosslinked acrylic rubber (a1) in the present invention comprises (a1-2) an acrylate ester in the presence of the crosslinked polymer particles (a1-1), and two or more (meth) acryloyl groups or vinyl groups in the molecule. And a monomer having an allyl group in the molecule. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isoamyl acrylate, isodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, and 2-ethoxyethyl acrylate. Is mentioned. These can be used individually by 1 type or in mixture of 2 or more types.
本発明における（ａ１−２）の分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体は、上記アクリル酸エステルを重合する際に架橋剤としてはたらくものである。このような架橋剤の例としては、エチレングリコールジアクリレート、１，３−ブタンジオールジアクリレート、１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、アクリル変成ポリジメチルシロキサンなどのアクリル酸エステル、エチレングリコールジメタクリレート、１，３−ブタンジオールジメタクリレート、１，４−ブタンジオールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールヘキサメタクリレート、メタクリル変成ポリジメチルシロキサンなどのメタクリル酸エステル、ジビニルベンゼンなどの芳香族ビニル化合物などが挙げられる。これらの中でも特に、エチレングリコールジアクリレート、１，３−ブタンジオールジアクリレート、１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、エチレングリコールジメタクリレート、１，３−ブタンジオールジメタクリレート、１，４−ブタンジオールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレートなどの、分子内に２個の水酸基を有するジオールのジ（メタ）アクリル酸エステルが好ましい。さらには、エチレングリコールジアクリレート、１，３−ブタンジオールジアクリレート、１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、エチレングリコールジメタクリレート、１，３−ブタンジオールジメタクリレート、１，４−ブタンジオールジメタクリレート、１，６−ヘキサンジオールジメタクリレートなどのアルキレンジオールのジ（メタ）アクリル酸エステルを用いることがより好ましい。 The monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule (a1-2) in the present invention serves as a crosslinking agent when the acrylate ester is polymerized. Examples of such crosslinkers include ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate. Acrylic esters such as acrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, acrylic modified polydimethylsiloxane, ethylene glycol dimethacrylate 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, , 6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate Methacrylic acid esters such as methacryl-modified polydimethylsiloxane, and aromatic vinyl compounds such as divinylbenzene. Among these, especially ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate Acrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Has two hydroxyl groups in the molecule, such as polyethylene glycol dimethacrylate and neopentyl glycol dimethacrylate. Di (meth) acrylic acid esters are preferred diols that. Further, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1 It is more preferable to use di (meth) acrylic acid esters of alkylene diols such as 1,4-butanediol dimethacrylate and 1,6-hexanediol dimethacrylate.
分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体の使用量は、アクリル酸エステル１００重量部に対して、０．１〜１０重量部が好ましい。使用量が０．１重量部未満であると、架橋度が不足し、レーザー溶着外観の改善効果が見られない。使用量が１０重量部を超えると架橋度が高くなりすぎて衝撃強度が低下してしまうおそれがある。 As for the usage-amount of the monomer which has a 2 or more (meth) acryloyl group or vinyl group in a molecule | numerator, 0.1-10 weight part is preferable with respect to 100 weight part of acrylic ester. If the amount used is less than 0.1 parts by weight, the degree of crosslinking is insufficient, and the effect of improving the laser welding appearance is not observed. If the amount used exceeds 10 parts by weight, the degree of crosslinking becomes too high and the impact strength may be reduced.
本発明における（ａ１−２）の分子内にアリル基を有する単量体は、一般にグラフト化剤として機能するものであり、例としては、アリルメタクリレート、ジシクロペンタジエニルアクリレート、ジシクロペンタジエニルオキシエチルアクリレート、ジシクロペンタジエニルメタクリレート、ジシクロペンタジエニルオキシエチルメタクリレート、ジアリルフタレート、トリアリルイソシアヌレートなどが挙げられる。これらの使用量は、アクリル酸エステル１００重量部に対して、０．０１〜１０重量部が好ましい。使用量が０．０１重量部未満であると、十分にグラフト共重合せず、衝撃強度が低下するおそれがある。使用量が１０重量部を超えると架橋度が高くなりすぎて衝撃強度が低下してしまうおそれがある。 The monomer having an allyl group in the molecule (a1-2) in the present invention generally functions as a grafting agent. Examples thereof include allyl methacrylate, dicyclopentadienyl acrylate, and dicyclopentadiene. Examples include enyloxyethyl acrylate, dicyclopentadienyl methacrylate, dicyclopentadienyloxyethyl methacrylate, diallyl phthalate and triallyl isocyanurate. The amount of these used is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the acrylic ester. If the amount used is less than 0.01 parts by weight, the graft copolymerization is not sufficient and the impact strength may be reduced. If the amount used exceeds 10 parts by weight, the degree of crosslinking becomes too high and the impact strength may be reduced.
本発明の架橋アクリルゴム（ａ１）における下記（ａ１−１）と（ａ１−２）の比率は、（ａ１−１）と（ａ１−２）の合計（すなわち（ａ１）の総量）を１００重量部としたときに（ａ１−１）が５〜８０重量部であることが好ましく、１０〜５０重量部であることがより好ましい。（ａ１−１）が５重量部未満であると衝撃強度が不足し、８０重量部を超えると耐候性および耐衝撃性が不足する傾向にある。
（ａ１−１）架橋重合体粒子、
（ａ１−２）アクリル酸エステル、分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体、分子内にアリル基を有する単量体の混合物。
The ratio of the following (a1-1) and (a1-2) in the crosslinked acrylic rubber (a1) of the present invention is 100 weights of the sum of (a1-1) and (a1-2) (that is, the total amount of (a1)). Part (a1-1) is preferably 5 to 80 parts by weight, more preferably 10 to 50 parts by weight. When (a1-1) is less than 5 parts by weight, the impact strength is insufficient, and when it exceeds 80 parts by weight, the weather resistance and impact resistance tend to be insufficient.
(A1-1) crosslinked polymer particles,
(A1-2) An acrylic ester, a monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule, and a mixture of monomers having an allyl group in the molecule.
本発明で用いられるグラフト共重合体（Ａ）は、上記架橋アクリルゴム（ａ１）（好ましくは１０〜９０重量部）に、（ａ２）芳香族ビニル単量体、シアン化ビニル単量体、（メタ）アクリル酸エステル単量体、その他のビニル単量体からなる群より選ばれた少なくとも一種の単量体（好ましくは１０〜９０重量部。ただし（ａ１）と（ａ２）の合計が１００重量部。）をグラフト共重合して得られるものである。 The graft copolymer (A) used in the present invention is obtained by adding (a2) an aromatic vinyl monomer, a vinyl cyanide monomer, (a2) to the crosslinked acrylic rubber (a1) (preferably 10 to 90 parts by weight), At least one monomer selected from the group consisting of (meth) acrylic acid ester monomers and other vinyl monomers (preferably 10 to 90 parts by weight, provided that the total of (a1) and (a2) is 100% by weight. Part.) Is obtained by graft copolymerization.
前記（ａ２）の一種である芳香族ビニル単量体としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、クロロスチレン、ブロモスチレンなどのうち、一種類単独または二種以上を混合して使用することができる。 As the aromatic vinyl monomer which is a kind of the above (a2), one kind or two kinds of styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, chlorostyrene, bromostyrene and the like are used. A mixture of seeds or more can be used.
前記（ａ２）の一種であるシアン化ビニル単量体としては、アクリロニトリル、メタクリロニトリルなどのうち、一種類単独または二種を混合して使用することができる。 As the vinyl cyanide monomer which is a kind of the above (a2), one kind of acrylonitrile, methacrylonitrile or the like can be used alone or a mixture of two kinds can be used.
前記（ａ２）の一種である（メタ）アクリル酸エステル単量体としては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチルなどのアクリル酸エステル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチルなどのメタクリル酸エステルが挙げられる。これらは、一種類単独または二種以上を混合して使用することができる。 Examples of the (meth) acrylic acid ester monomer that is a kind of (a2) include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. And methacrylic acid esters such as propyl acid and butyl methacrylate. These can be used individually by 1 type or in mixture of 2 or more types.
前記（ａ２）の一種であるその他のビニル単量体としては、アクリル酸、メタクリル酸、オレイン酸、マレイン酸、フマル酸などの不飽和脂肪酸、無水アクリル酸、無水メタクリル酸、無水マレイン酸などの不飽和脂肪酸無水物、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、メタクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミドなどの不飽和脂肪酸のアミド、Ｎ−メチルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−フェニルマレイミドなどのマレイミド、酢酸ビニル、酪酸ビニル、安息香酸ビニルなどのビニルエステルなどが挙げられる。これらは、一種類単独または二種以上を混合して使用することができる。 Examples of the other vinyl monomer that is a kind of (a2) include unsaturated fatty acids such as acrylic acid, methacrylic acid, oleic acid, maleic acid, and fumaric acid, acrylic acid anhydride, methacrylic anhydride, maleic anhydride, and the like. Unsaturated fatty acid anhydride, amide of unsaturated fatty acid such as acrylamide, N, N-dimethylacrylamide, methacrylamide, N, N-dimethylmethacrylamide, maleimide such as N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide And vinyl esters such as vinyl acetate, vinyl butyrate and vinyl benzoate. These can be used individually by 1 type or in mixture of 2 or more types.
本発明で用いるグラフト共重合体（Ａ）において、架橋アクリルゴム（ａ１）にグラフト共重合する下記（ａ２）の組成は、（ａ２）１００重量部に対して芳香族ビニル化合物が４０重量部以上含まれていることが好ましい。４０重量部未満であると、共重合組成のバランスが良くない。また、その他のビニル単量体の量が２０重量部以下であることが好ましい。２０重量部を超えると相溶性の点で好ましくない。
（ａ２）芳香族ビニル単量体、シアン化ビニル単量体、（メタ）アクリル酸エステル単量体、その他のビニル単量体からなる群より選ばれた少なくとも一種の単量体。
In the graft copolymer (A) used in the present invention, the composition of the following (a2) graft copolymerized with the crosslinked acrylic rubber (a1) is (a2) 40 parts by weight or more of the aromatic vinyl compound with respect to 100 parts by weight. It is preferably included. When it is less than 40 parts by weight, the balance of the copolymer composition is not good. The amount of other vinyl monomers is preferably 20 parts by weight or less. Exceeding 20 parts by weight is not preferable in terms of compatibility.
(A2) At least one monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylic acid ester monomers, and other vinyl monomers.
本発明で用いるグラフト共重合体（Ａ）１００重量部に含有される架橋アクリルゴム（ａ１）の割合は、１０〜９０重量部とすることが好ましい。１０重量部未満であると衝撃強度が不足する傾向にあり、９０重量部を超えるとグラフト成分が少ないためにゴム成分の分散状態が悪くなり、衝撃強度が低下する傾向にある。 The proportion of the crosslinked acrylic rubber (a1) contained in 100 parts by weight of the graft copolymer (A) used in the present invention is preferably 10 to 90 parts by weight. When the amount is less than 10 parts by weight, the impact strength tends to be insufficient. When the amount exceeds 90 parts by weight, since the graft component is small, the dispersed state of the rubber component is deteriorated and the impact strength tends to be lowered.
本発明で用いるグラフト共重合体（Ａ）において、架橋アクリルゴム（ａ１）にグラフト共重合を行うとき、１段階で行っても２段階以上に分割してもよい。
グラフト共重合体（Ａ）の製造方法は、従来から知られている乳化重合法、懸濁重合法、塊状重合法、溶液重合法などのいずれの方法でもよいが、一般的には乳化重合法が好ましい。
In the graft copolymer (A) used in the present invention, when the cross-linked acrylic rubber (a1) is subjected to graft copolymerization, it may be performed in one step or divided into two or more steps.
The method for producing the graft copolymer (A) may be any conventionally known emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method, etc., but in general emulsion polymerization method Is preferred.
本発明のレーザー溶着用熱可塑性樹脂組成物は、組成物に含まれる熱可塑性樹脂が、グラフト共重合体（Ａ）１０〜１００重量部、熱可塑性樹脂（Ｂ）０〜９０重量部（ただし（Ａ）と（Ｂ）の合計が１００重量部）からなるものが好ましく、（Ａ）が１０〜９０重量部、（Ｂ）が９０〜１０重量部（ただし（Ａ）と（Ｂ）の合計が１００重量部）からなるものがより好ましい。グラフト共重合体（Ａ）の割合が１０重量部未満であると、衝撃強度の向上効果が現れにくい。 In the thermoplastic resin composition for laser welding of the present invention, the thermoplastic resin contained in the composition is 10 to 100 parts by weight of the graft copolymer (A), 0 to 90 parts by weight of the thermoplastic resin (B) (however ( A) and (B) are preferably composed of 100 parts by weight), (A) is 10 to 90 parts by weight, (B) is 90 to 10 parts by weight (however, the sum of (A) and (B) is 100 parts by weight) is more preferable. When the proportion of the graft copolymer (A) is less than 10 parts by weight, the impact strength improving effect is hardly exhibited.
グラフト共重合体（Ａ）と熱可塑性樹脂（Ｂ）の混合割合は、本発明のレーザー溶着用熱可塑性樹脂組成物中のゴム成分を構成する架橋アクリルゴム（ａ１）が全体の１０〜５０重量部になるように決定された割合であることが好ましい。架橋アクリルゴム（ａ１）が全体の１０重量部未満では衝撃強度が不足し、５０重量部を超えると樹脂の流動性、表面硬度、剛性が不足するおそれがある。 The mixing ratio of the graft copolymer (A) and the thermoplastic resin (B) is 10 to 50% by weight of the crosslinked acrylic rubber (a1) constituting the rubber component in the laser welding thermoplastic resin composition of the present invention. It is preferable that the ratio is determined so as to be a part. When the cross-linked acrylic rubber (a1) is less than 10 parts by weight, the impact strength is insufficient, and when it exceeds 50 parts by weight, the fluidity, surface hardness, and rigidity of the resin may be insufficient.
本発明で使用する熱可塑性樹脂（Ｂ）の種類は特に制限されないが、ポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂、ＡＡＳ樹脂、ＡＥＳ樹脂などのスチレン系樹脂、ナイロン６６、ナイロン６などのポリアミド樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレートなどのポリエステル樹脂、塩化ビニル樹脂、ポリカーボネート樹脂、アクリル樹脂などの熱可塑性樹脂が挙げられる。また、これらの樹脂の混合物、変性体も含まれる。これらの中でも、スチレン系樹脂を主成分として用いることが好ましい。 The type of the thermoplastic resin (B) used in the present invention is not particularly limited, but styrene resins such as polystyrene, AS resin, ABS resin, AAS resin and AES resin, polyamide resins such as nylon 66 and nylon 6, polyethylene terephthalate And thermoplastic resins such as polyester resins such as polybutylene terephthalate, vinyl chloride resins, polycarbonate resins, and acrylic resins. Also included are mixtures and modified products of these resins. Among these, it is preferable to use a styrene resin as a main component.
本発明で使用する熱可塑性樹脂（Ｂ）として、芳香族ビニル単量体、シアン化ビニル単量体、（メタ）アクリル酸エステル単量体、その他のビニル単量体からなる群より選ばれた少なくとも一種の単量体を重合してなるものを使用することができる。前記芳香族ビニル単量体としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、クロロスチレン、ブロモスチレンなどのうち、一種類単独または二種以上を混合して使用することができる。 The thermoplastic resin (B) used in the present invention was selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylic acid ester monomers, and other vinyl monomers. Those obtained by polymerizing at least one monomer can be used. As the aromatic vinyl monomer, one kind or a mixture of two or more kinds of styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, chlorostyrene, bromostyrene and the like are used. can do.
前記シアン化ビニル単量体としては、アクリロニトリル、メタクリロニトリルなどのうち、一種類単独または二種を混合して使用することができる。 As the vinyl cyanide monomer, one kind or a mixture of two kinds of acrylonitrile, methacrylonitrile and the like can be used.
前記（メタ）アクリル酸エステル単量体としては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチルなどのアクリル酸エステル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチルなどのメタクリル酸エステルが挙げられる。これらは、一種類単独または二種以上を混合して使用することができる。 Examples of the (meth) acrylic acid ester monomer include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. The methacrylic acid ester of this is mentioned. These can be used individually by 1 type or in mixture of 2 or more types.
その他のビニル単量体としては、アクリル酸、メタクリル酸、オレイン酸、マレイン酸、フマル酸などの不飽和脂肪酸、無水アクリル酸、無水メタクリル酸、無水マレイン酸などの不飽和脂肪酸無水物、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、メタクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミドなどの不飽和脂肪酸のアミド、Ｎ−メチルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−フェニルマレイミドなどのマレイミド、酢酸ビニル、酪酸ビニル、安息香酸ビニルなどのビニルエステルなどが挙げられる。これらは、一種類単独または二種以上を混合して使用することができる。 Other vinyl monomers include unsaturated fatty acids such as acrylic acid, methacrylic acid, oleic acid, maleic acid and fumaric acid, unsaturated fatty acid anhydrides such as acrylic anhydride, methacrylic anhydride and maleic anhydride, acrylamide, N, N-dimethylacrylamide, amide of unsaturated fatty acid such as methacrylamide, N, N-dimethylmethacrylamide, maleimide such as N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, vinyl acetate, vinyl butyrate, benzoate And vinyl esters such as vinyl acid. These can be used individually by 1 type or in mixture of 2 or more types.
上記重合体または共重合体の製造方法は、従来から知られている乳化重合法、懸濁重合法、塊状重合法、溶液重合法などのいずれの方法でもよい。また、これらの方法を組み合わせた方法でもよい。 The method for producing the polymer or copolymer may be any conventionally known emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method and the like. Moreover, the method which combined these methods may be sufficient.
本発明で、使用される波長７５０〜８５０ｎｍで吸収性を示す赤外吸収剤としては、縮合多環系の着色剤、銅化合物などがあり、これらは、一種類単独または二種以上を混合して使用することができる。波長７５０〜８５０ｎｍで吸収性を示す赤外吸収剤の含有量は、グラフト共重合体（Ａ）と熱可塑性樹脂（Ｂ）の混合割合１００重量部に対して０．００１〜１重量部であると好ましい。０．００１重量部未満では、レーザー吸収量が十分でなく、溶着性が低下する。また、１重量部を超えて使用しても、効果は変わらない。
赤外吸収剤は、吸収した赤外線を熱に変換する機能を有する染料又は顔料である。
染料としては、市販の染料及び例えば「染料便覧」（有機合成化学協会編集、昭和４５年刊）、「特殊機能色素」（池森・住谷編集、１９８６年（株）シーエムシー発行）、「機能性色素の化学」（檜垣編集、１９８１年（株）シーエムシー発行）、「色素ハンドブック」（大河、平嶋、松岡、北尾編集、講談社発行）等の文献に記載されている公知のものが利用できる。具体的には、アゾ系染料、金属錯塩アゾ系染料、ピラゾロンアゾ系染料、ナフトキノン系染料、アントラキノン系染料、キノリン系色素、フタロシアニン系染料、カルボニウム系染料、キノンイミン系染料、メチン系染料、シアニン系染料、スクワリリウム系色素、ピリリウムまたはチオピリリウム系色素、ピリリウム系塩、アズレニウム系色素、クロコニウム系色素、インドール系色素、ベンゾチアゾール系色素、金属チオレート系錯体、チオールニッケル系色素、メルカプトフェノール系色素、メルカプトナフトール系色素、トリアリルメタン系色素、インモニウムまたはジインモニウム系色素、金属錯塩系色素等の染料、カーボンブラック、人造黒鉛、天然黒鉛、チタン、クロム等の金属、硫化銅、硫化鉛、三硫化モリブデン、黒色チタン、イモニウム系化合物、ジイモニウム系化合物、アミニウム化合物、Ｆｅ2+および／またはＣｕ2+を含有するガラス系材料、酸化スズ、酸化亜鉛、酸化バナジウム、酸化タングステン等の金属酸化物、チタンカーバイト等の金属炭化物、金属ホウ化物、金属水酸化物、金属硫酸塩、金属炭酸塩、金属珪酸塩、金属硝酸塩及び金属錯化合物等が挙げられる。本発明では、縮合多環系の着色剤、銅化合物が好ましい。
In the present invention, infrared absorbers having absorption at a wavelength of 750 to 850 nm include condensed polycyclic colorants, copper compounds, and the like. These may be used alone or in combination of two or more. Can be used. The content of the infrared absorber that absorbs at a wavelength of 750 to 850 nm is 0.001 to 1 part by weight with respect to 100 parts by weight of the mixing ratio of the graft copolymer (A) and the thermoplastic resin (B). And preferred. If it is less than 0.001 part by weight, the laser absorption amount is not sufficient, and the weldability is lowered. Moreover, even if it uses exceeding 1 weight part, an effect does not change.
An infrared absorber is a dye or pigment having a function of converting absorbed infrared rays into heat.
Examples of the dye include commercially available dyes, for example, “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, published in 1970), “Special Functional Colors” (edited by Ikemori / Sumitani, published by CMC Corporation in 1986), “Functional Colors”. No. Chemistry (edited by Higaki, published by CMC Co., Ltd. in 1981), “Dye Handbook” (edited by Taiga, Hirashima, Matsuoka, Kitao, published by Kodansha), etc., can be used. Specifically, azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, quinoline dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes Dyes, squarylium dyes, pyrylium or thiopyrylium dyes, pyrylium salts, azurenium dyes, croconium dyes, indole dyes, benzothiazole dyes, metal thiolate complexes, thiol nickel dyes, mercaptophenol dyes, mercaptonaphthols Type dyes, triallylmethane dyes, dyes such as immonium or diimmonium dyes, metal complex dyes, carbon black, artificial graphite, natural graphite, titanium, chromium and other metals, copper sulfide, lead sulfide, molybdenum trisulfide, Black Emissions, immonium based compounds, diimmonium-based compounds, aminium compounds, glass-based material containing Fe 2+ and / or Cu 2+, tin oxide, zinc oxide, vanadium oxide, metal oxides such as tungsten oxide, titanium carbide, etc. Metal carbides, metal borides, metal hydroxides, metal sulfates, metal carbonates, metal silicates, metal nitrates, and metal complex compounds. In the present invention, a condensed polycyclic colorant and a copper compound are preferable.
グラフト共重合体（Ａ）と熱可塑性樹脂（Ｂ）を混合する方法は、ラテックス状態での混合、溶液状態での混合、パウダ状態での混合、ペレット状に加工してからの混合などいずれの方法でもよく、混合された後、バンバリ−ミキサー、単軸押出機、２軸押出機などで溶融混練することが好ましい。 The method of mixing the graft copolymer (A) and the thermoplastic resin (B) may be any of mixing in a latex state, mixing in a solution state, mixing in a powder state, mixing after processing into a pellet form, etc. A method may be used, and after mixing, melt kneading is preferably performed with a Banbury mixer, a single screw extruder, a twin screw extruder or the like.
本発明のレーザー溶着用熱可塑性樹脂組成物には、上記のほかに、着色、耐熱性向上、耐候性向上、成形性向上などの目的で、着色剤、熱安定剤、光安定剤、紫外線吸収剤、難燃剤、滑剤、離型剤、可塑剤、帯電防止剤など一般に用いられている添加剤を添加することができる。 In addition to the above, the thermoplastic resin composition for laser welding of the present invention includes a coloring agent, a thermal stabilizer, a light stabilizer, and an ultraviolet absorber for the purpose of coloring, improving heat resistance, improving weather resistance, and improving moldability. Commonly used additives such as an agent, a flame retardant, a lubricant, a release agent, a plasticizer, and an antistatic agent can be added.
本発明の合成樹脂製部品は、２個以上の樹脂成形品がレーザー溶着法によって一体化された合成樹脂製部品であって、樹脂成形品のうち１個以上が本発明のレーザー溶着用熱可塑性樹脂組成物からなることを特徴とする。このものでは、溶着部の外観に優れ、かつ作業性が向上し、樹脂成形品同士の接合強度も十分なものになる。 The synthetic resin part of the present invention is a synthetic resin part in which two or more resin molded products are integrated by a laser welding method, and one or more of the resin molded products are thermoplastic for laser welding of the present invention. It consists of a resin composition. In this case, the appearance of the welded portion is excellent, the workability is improved, and the bonding strength between the resin molded products is sufficient.
本発明のレーザー溶着用熱可塑性樹脂組成物を用いて成形品を製造する場合、成形方法は特に限定されないが、一般的には射出成形、押出成形などの方法が適用される。 When a molded product is produced using the thermoplastic resin composition for laser welding of the present invention, the molding method is not particularly limited, but generally methods such as injection molding and extrusion molding are applied.
以下、実施例により本発明を具体的に説明するが、本発明の範囲を制限するものではない。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
（架橋重合体粒子（ラテックス）の製造）
純水１８０重量部に牛脂脂肪酸カリウム１重量部を添加し、そこにスチレン１００重量部、アリルメタクリレート０．０５重量部、１，６−ヘキサンジオールジアクリレート２重量部を混合したものを入れ、撹拌混合し、窒素置換しながら６０℃に昇温した。昇温後、過硫酸カリウム０．４重量部を純水２０重量部に溶解した溶液を加え、４時間撹拌を続けた後、冷却した。このときの反応率は９８％であった。
(Production of crosslinked polymer particles (latex))
1 part by weight of beef tallow fatty acid potassium is added to 180 parts by weight of pure water, and a mixture of 100 parts by weight of styrene, 0.05 parts by weight of allyl methacrylate and 2 parts by weight of 1,6-hexanediol diacrylate is added to the mixture and stirred. The mixture was mixed and heated to 60 ° C. while being purged with nitrogen. After the temperature increase, a solution obtained by dissolving 0.4 parts by weight of potassium persulfate in 20 parts by weight of pure water was added, and the mixture was stirred for 4 hours and then cooled. The reaction rate at this time was 98%.
（架橋アクリルゴム（ａ１）の製造）
上記架橋重合体粒子（ラテックス）６０重量部（固形分２０重量部）、純水２００重量部、牛脂脂肪酸カリウム０．８重量部、アクリル酸ブチル８０重量部、アリルメタクリレート０．０４重量部、１，６−ヘキサンジオールジアクリレート０．８重量部を撹拌混合し、窒素置換しながら６０℃に昇温した。昇温後、過硫酸カリウム０．１６重量部を純水８重量部に溶解した溶液を加え、３時間撹拌を続けた後、冷却した。このときの反応率は９７％であった。
(Production of cross-linked acrylic rubber (a1))
60 parts by weight of the crosslinked polymer particles (latex) (20 parts by weight of solid content), 200 parts by weight of pure water, 0.8 parts by weight of potassium tallow fatty acid, 80 parts by weight of butyl acrylate, 0.04 parts by weight of allyl methacrylate, 1 , 6-Hexanediol diacrylate 0.8 parts by weight was stirred and mixed, and the temperature was raised to 60 ° C. while purging with nitrogen. After the temperature rise, a solution prepared by dissolving 0.16 parts by weight of potassium persulfate in 8 parts by weight of pure water was added, and the mixture was stirred for 3 hours and then cooled. The reaction rate at this time was 97%.
（グラフト共重合体（Ａ）の製造）
上記架橋アクリルゴム（ラテックス）１９５重量部、純水１６．５重量部、牛脂脂肪酸カリウム０．１７５重量部、スチレン３重量部、アクリロニトリル１．５重量部、アリルメタクリレート０．１重量部、クメンヒドロパーオキサイド０．０１６重量部を撹拌混合し、窒素置換しながら７０℃に昇温した。昇温後、ピロリン酸ナトリウム０．２重量部および硫酸鉄(II)０．００４重量部を純水１２重量部に溶解した溶液を加え、１時間撹拌した。続けて、スチレン２４重量部、アクリロニトリル９．３重量部、tert‐ドデシルメルカプタン０．１６重量部、純水１５重量部、牛脂脂肪酸カリウム０．５重量部、クメンヒドロパーオキサイド０．０７重量部の混合物を２時間かけて滴下した。滴下終了後１時間温度を保持し、冷却した。このときの反応率は９５％であった。合成したグラフト共重合体（Ａ）ラテックスを硫酸アルミニウム水溶液中に滴下し、できたスラリーを脱水、乾燥して、グラフト共重合体（Ａ）パウダを得た。
(Production of graft copolymer (A))
195 parts by weight of the above-mentioned crosslinked acrylic rubber (latex), 16.5 parts by weight of pure water, 0.175 part by weight of beef tallow fatty acid potassium, 3 parts by weight of styrene, 1.5 parts by weight of acrylonitrile, 0.1 part by weight of allyl methacrylate, cumene hydro 0.016 part by weight of peroxide was mixed with stirring, and the temperature was raised to 70 ° C. while replacing with nitrogen. After the temperature rise, a solution prepared by dissolving 0.2 parts by weight of sodium pyrophosphate and 0.004 parts by weight of iron (II) sulfate in 12 parts by weight of pure water was added and stirred for 1 hour. Subsequently, 24 parts by weight of styrene, 9.3 parts by weight of acrylonitrile, 0.16 parts by weight of tert-dodecyl mercaptan, 15 parts by weight of pure water, 0.5 parts by weight of beef tallow fatty acid potassium, 0.07 parts by weight of cumene hydroperoxide The mixture was added dropwise over 2 hours. After completion of dropping, the temperature was maintained for 1 hour and cooled. The reaction rate at this time was 95%. The synthesized graft copolymer (A) latex was dropped into an aluminum sulfate aqueous solution, and the resulting slurry was dehydrated and dried to obtain a graft copolymer (A) powder.
（熱可塑性樹脂（Ｂ）の製造）
純水１５０重量部、１０重量％リン酸カルシウム水分散液３重量部、１２．５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液０．０４重量部を撹拌混合し、そこに、スチレン７０重量部、アクリロニトリル３０重量部、tert−ドデシルメルカプタン０．２重量部、ジラウロイルパーオキサイド０．５重量部、１，１−ビス（tert−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン０．０５重量部の混合物を添加した。これを６５℃で８時間、さらに１１０℃で２時間懸濁重合を行い、冷却後脱水・乾燥して、熱可塑性樹脂（Ｂ）を得た。得られた樹脂の重量平均分子量をＧＰＣで測定したところ、スチレン換算で１５０，０００であった。
(Manufacture of thermoplastic resin (B))
150 parts by weight of pure water 3 parts by weight of a 10% by weight calcium phosphate aqueous dispersion and 0.04 part by weight of a 12.5% by weight aqueous sodium dodecylbenzenesulfonate solution are mixed with stirring, and 70 parts by weight of styrene and 30 parts by weight of acrylonitrile are mixed there. , Tert-dodecyl mercaptan 0.2 parts by weight, dilauroyl peroxide 0.5 parts by weight, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane 0.05 parts by weight Added. This was subjected to suspension polymerization at 65 ° C. for 8 hours and further at 110 ° C. for 2 hours, cooled, dehydrated and dried to obtain a thermoplastic resin (B). When the weight average molecular weight of the obtained resin was measured by GPC, it was 150,000 in terms of styrene.
（レーザー溶着用熱可塑性樹脂組成物の製造）
上記の方法で合成したグラフト共重合体（Ａ）２５重量部と熱可塑性樹脂（Ｂ）７５重量部を配合し、多環縮合系化合物（C52H68Ｎ4O4、有本化学工業（株）製 商品名：ＳＤＯ−８） ０．２重量部、滑剤 ０．５重量部を添加し、２軸押出機で混練してペレットにした。このペレットを射出成形機で成形し、物性評価用試験片を作製した。
(Manufacture of thermoplastic resin composition for laser welding)
25 parts by weight of the graft copolymer (A) synthesized by the above method and 75 parts by weight of the thermoplastic resin (B) are blended, and a polycyclic condensed compound (C 52 H 68 N 4 O 4 , Arimoto Chemical Industry ( Co., Ltd. product name: SDO-8) 0.2 parts by weight and 0.5 parts by weight of a lubricant were added and kneaded with a twin screw extruder into pellets. This pellet was molded with an injection molding machine to produce a test piece for evaluating physical properties.
（アイゾット衝撃強度の評価）
上記で作製した物性評価用試験片を用いて衝撃強度を測定した。衝撃強度は、アイゾット衝撃試験を用い、ＡＳＴＭ−Ｄ２５６に準拠して行った。その測定結果を表１に示した。
(Evaluation of Izod impact strength)
The impact strength was measured using the physical property evaluation test piece prepared above. The impact strength was measured according to ASTM-D256 using an Izod impact test. The measurement results are shown in Table 1.
（レーザー溶着外観の評価）
射出成形機を使用して、前記ペレットからレーザー溶着外観評価用の試験片を作製した。同様に、アクリル樹脂を用いて試験片を作製した。
これらの試験片をアクリル樹脂が上部になるように、重ね合わせ、レーザー溶着機（ファインデバイス社製FDT-840-30-6型）を使用して、以下の条件でレーザー溶着を行い、溶着部の外観を目視評価した。
溶着条件
レーザー出力：２０Ｗ
レーザー波長：８４０ｎｍ
幅：０.６ｍｍ
レーザー溶着外観の評価結果を表１に示した。ここで、レーザー溶着外観は、溶着部の外観を良い順に、◎、○、×の三段階で評価した。
(Evaluation of laser welding appearance)
A test piece for laser welding appearance evaluation was produced from the pellets using an injection molding machine. Similarly, a test piece was prepared using an acrylic resin.
These test pieces are stacked so that the acrylic resin is on top, and laser welding is performed using a laser welding machine (FDT-840-30-6 manufactured by Fine Devices) under the following conditions. The appearance of was visually evaluated.
Welding conditions Laser output: 20W
Laser wavelength: 840 nm
Width: 0.6mm
The evaluation results of the laser welding appearance are shown in Table 1. Here, the appearance of laser welding was evaluated in three stages of ◎, ○, and X in the order of good appearance of the welded portion.
（実施例２、比較例１）
実施例１と同様にして、多環縮合系化合物（C52H68Ｎ4O4、有本化学工業（株）製 商品名：ＳＤＯ−８） ０．５重量部とした場合を、実施例２とし、また、赤外吸収剤を配合しない熱可性樹脂組成物を比較例１として物性評価用試験片を作製した。これらを、実施例１と同様に評価し、その結果を表１に示した。
(Example 2, Comparative Example 1)
In the same manner as in Example 1, the polycyclic condensed compound (C 52 H 68 N 4 O 4 , Arimoto Chemical Industry Co., Ltd., trade name: SDO-8) was used in an amount of 0.5 parts by weight. 2 and a thermosetting resin composition containing no infrared absorber was used as Comparative Example 1 to produce a physical property evaluation test piece. These were evaluated in the same manner as in Example 1, and the results are shown in Table 1.
表１に示したように、本発明のグラフト重合したグラフト共重合体（Ａ）と、熱可塑性樹脂（Ｂ）からなるレーザー溶着用熱可塑性樹脂組成物に赤外吸収剤を含有した実施例１、２は、衝撃強度が高く、耐衝撃性があり、レーザー溶着した際に、バリや空隙の発生がみられず外観に優れる。これに対し、赤外吸収剤を含有しない比較例１は、レーザー溶着しない。 As shown in Table 1, Example 1 in which an infrared absorber is contained in a laser welding thermoplastic resin composition comprising the graft-polymerized graft copolymer (A) of the present invention and a thermoplastic resin (B). No. 2 has high impact strength and impact resistance, and is excellent in appearance without the occurrence of burrs or voids when laser welded. On the other hand, the comparative example 1 which does not contain an infrared absorber does not laser-weld.
Claims (10)
（ａ１−１）少なくとも、分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体と、芳香族ビニル単量体とを共重合した共重合体からなる架橋重合体粒子、
（ａ１−２）アクリル酸エステル、分子内に２個以上の（メタ）アクリロイル基またはビニル基を有する単量体、分子内にアリル基を有する単量体の混合物、
（ａ２）芳香族ビニル単量体、シアン化ビニル単量体、（メタ）アクリル酸エステル単量体、その他のビニル単量体からなる群より選ばれた少なくとも一種の単量体。 A crosslinked acrylic rubber (a1) obtained by polymerizing (a1-2) in the presence of the following (a1-1), and a graft copolymer (A) obtained by graft polymerization of the following (a2); A thermoplastic resin composition for laser welding, comprising an infrared absorber having absorbency at 850 nm.
(A1-1) Crosslinked polymer particles comprising a copolymer obtained by copolymerizing at least a monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule and an aromatic vinyl monomer,
(A1-2) acrylic acid ester, monomer having two or more (meth) acryloyl groups or vinyl groups in the molecule, mixture of monomers having allyl groups in the molecule,
(A2) At least one monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylic acid ester monomers, and other vinyl monomers.
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| JP4853710B2 (en) * | 2006-11-22 | 2012-01-11 | 住友金属鉱山株式会社 | Laser-absorbing light-absorbing resin composition, light-absorbing resin molded body, and method for producing light-absorbing resin molded body |
| CN102149772B (en) * | 2008-09-10 | 2013-05-22 | 日本A&L株式会社 | Thermoplastic resin composition for vehicular lamp housing |
| JP6424351B2 (en) | 2016-02-12 | 2018-11-21 | ユーエムジー・エービーエス株式会社 | Thermoplastic resin composition |
| JP6812217B2 (en) * | 2016-11-25 | 2021-01-13 | テクノＵｍｇ株式会社 | Thermoplastic resin composition and molded products using it |
| WO2019208353A1 (en) * | 2018-04-23 | 2019-10-31 | 株式会社クラレ | Composition having excellent curability |
| CN114891467A (en) * | 2022-06-10 | 2022-08-12 | 广东汇齐新材料有限公司 | Laser-weldable hot melt adhesive film and preparation method thereof |
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