JPH04122771A - Polyamide composition - Google Patents
Polyamide compositionInfo
- Publication number
- JPH04122771A JPH04122771A JP2242629A JP24262990A JPH04122771A JP H04122771 A JPH04122771 A JP H04122771A JP 2242629 A JP2242629 A JP 2242629A JP 24262990 A JP24262990 A JP 24262990A JP H04122771 A JPH04122771 A JP H04122771A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- parts
- polyolefin resin
- modified polyolefin
- nylon
- 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
- 239000000203 mixture Substances 0.000 title claims description 16
- 239000004952 Polyamide Substances 0.000 title claims description 9
- 229920002647 polyamide Polymers 0.000 title claims description 9
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 23
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 7
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 abstract description 11
- 229920002292 Nylon 6 Polymers 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract 2
- 229920005749 polyurethane resin Polymers 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 13
- 239000000956 alloy Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- -1 polypropylene Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000008188 pellet Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229920000554 ionomer Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229920000305 Nylon 6,10 Polymers 0.000 description 3
- 229920000572 Nylon 6/12 Polymers 0.000 description 3
- 229920000577 Nylon 6/66 Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WLQXEFXDBYHMRG-UPHRSURJSA-N (z)-4-(oxiran-2-ylmethoxy)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1CO1 WLQXEFXDBYHMRG-UPHRSURJSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920000393 Nylon 6/6T Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- OAKHANKSRIPFCE-UHFFFAOYSA-L calcium;2-methylprop-2-enoate Chemical compound [Ca+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O OAKHANKSRIPFCE-UHFFFAOYSA-L 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 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
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 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
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ポリアミド組成物に関し、さらに詳しくは、
ポリアミド樹脂と変性ポリオレフィン系樹脂からなるア
ロイで、塗膜との密着力の大きいポリアミド組成物に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyamide composition, and more particularly,
This invention relates to a polyamide composition that is an alloy consisting of a polyamide resin and a modified polyolefin resin and has a high adhesion to a coating film.
ポリアミド樹脂は、その耐熱特性１機械的特性の優れた
点に着目し、自動車外装用部品、例えばエアソボイラー
、ホイールキャンプ、バンパー、フードルーバー、サイ
ドシールなどへの利用が拡大されつつある。ポリアミド
樹脂のもうひとつの特性として吸水性があり、吸水によ
る寸法変化が欠点になる場合が多々ある。最近では、ポ
リアミド樹脂に変性ポリフェニレンオキサイドや変性ポ
リプロピレンなどでアロイ化し、低吸水材料の開発がさ
かんに行われている。Polyamide resins are being used increasingly for automotive exterior parts, such as air boilers, wheel camps, bumpers, hood louvers, and side seals, due to their excellent heat resistance and mechanical properties. Another characteristic of polyamide resin is water absorption, and dimensional changes due to water absorption are often a drawback. Recently, the development of low water absorption materials by alloying polyamide resin with modified polyphenylene oxide, modified polypropylene, etc. has been actively conducted.
ところで、自動車外装用部品のホイールキャップやバン
パーなどは、車体との一体塗装ではなくオフライン塗装
が一般的である。オフライン塗装の塗料としては、美観
、耐候性、耐薬品性、耐衝撃性などが優れているところ
から広く、ウレタン樹脂塗料が使用されているが、この
塗料はポリアミド樹脂と変性ポリオレフィン樹脂のアロ
イに対して密着性が低いため、直接塗装することができ
ない。これは、ポリオレフィン樹脂は無極性で高結晶性
のため塗膜との密着性が極めて悪いためとされ、塗装を
行う際は、クロム酸混液処理、プラズマ処理などの前処
理を行うか、塩素化オレフィン系のプライマー処理が必
要とされている。そのためポリアミド樹脂と変性ポリオ
レフィン樹脂のアロイの成形品の場合も塗料を塗布する
際には、塩素化オレフィン系のプライマーを塗布し、次
に上塗り用塗料を塗布するという方法で行われているの
が現状である。Incidentally, automotive exterior parts such as wheel caps and bumpers are generally painted off-line rather than integrally with the vehicle body. Urethane resin paint is widely used as a paint for off-line painting due to its excellent appearance, weather resistance, chemical resistance, impact resistance, etc., but this paint is an alloy of polyamide resin and modified polyolefin resin. On the other hand, it cannot be painted directly because of its poor adhesion. This is said to be because polyolefin resin is non-polar and highly crystalline, so it has extremely poor adhesion to the paint film. Olefin-based primer treatment is required. Therefore, when applying paint to molded products made from alloys of polyamide resin and modified polyolefin resin, the method used is to apply a chlorinated olefin primer and then apply a top coat. This is the current situation.
また、塩素化オレフィン系の樹脂は耐候性が悪いため、
上塗り用塗料としては使用が難しいとされている。In addition, chlorinated olefin resins have poor weather resistance, so
It is said to be difficult to use as a top coat paint.
〔発明の目的］
本発明は、ウレタン樹脂塗膜との密着力の大きいポリア
ミド樹脂と変性ポリオレフィン樹脂アロイのポリアミド
組成物を提供する。[Object of the Invention] The present invention provides a polyamide composition of a polyamide resin and a modified polyolefin resin alloy that has high adhesion to a urethane resin coating.
すなわち、本発明は、
（Ａ）ポリアミド樹脂１００重重部、
（Ｂ）変成ポリオレフィン樹脂５〜４００重量部及び
（Ｃ）前記ポリアミド樹脂と変性ポリオレフィン樹脂と
の全使用量１００重量部当り
０．３〜５０重量部の割合となる使用
量の周期律表第１族〜第■族金属の金
属化合物とからなることを特徴とする
ポリアミド組成物である。That is, the present invention comprises (A) 100 parts by weight of polyamide resin, (B) 5 to 400 parts by weight of modified polyolefin resin, and (C) 0.3 to 100 parts by weight of the total amount of the polyamide resin and modified polyolefin resin used. This is a polyamide composition characterized by comprising a metal compound of a metal from Group 1 to Group Ⅰ of the periodic table in an amount of 50 parts by weight.
本発明のポリアミド樹脂の具体例としては、ナイロン６
、ナイロン１１．ナイロン１２などのポリラクタム類、
ナイロン６６、ナイロン６１０゜ナイロン６１２などの
ジカルボン酸とジアミンとから得られるポリアミド類、
ナイロン６／６６゜ナイロン６／６１０．ナイロン６／
１２．ナイロン６／６１２．ナイロン６／６６／６１０
．ナイロン６／６６／Ｉ ２．ナイロン６／６Ｔ（Ｔ：
テレフタル酸成分）などの共重合ポリアミド類、これら
の混合物などが挙げられる。Specific examples of the polyamide resin of the present invention include nylon 6
, nylon 11. polylactams such as nylon 12,
Polyamides obtained from dicarboxylic acids and diamines such as nylon 66, nylon 610° and nylon 612,
Nylon 6/66° Nylon 6/610. Nylon 6/
12. Nylon 6/612. Nylon 6/66/610
．． Nylon 6/66/I 2. Nylon 6/6T (T:
Examples include copolyamides such as terephthalic acid (terephthalic acid component), mixtures thereof, and the like.
本発明のポリオレフィン樹脂の具体例としては、高圧法
ポリエチレン、中低圧法ポリエチレン、ポリプロピレン
などのポリオレフィン、エチレンプロピレン・コポリマ
ー、エチレン−酢酸ビニル・コポリマーなどのオレフィ
ン共重合体などが挙げられ、また変性剤としては、不飽
和カルボン酸またはその誘導体があげられる。不飽和カ
ルボン酸またはその誘導体としては、アクリル酸、フマ
ール酸、テトロヒドロフタル酸、イタコン酸、シトラコ
ン酸、クロドロ酸、イソクロドロ酸、ナジック酸■（エ
ンドシス−ビシクロ（２，２゜１〕ヘプト−５−エン−
２，３−ジカルボン酸）など不飽和カルボン酸またはそ
の誘導体、例えば酸ハライド、アミド、イシド、無水物
、エステルなどが挙げられ、具体的には、塩化マレニル
マレイミド、無水マレイン酸、無水シトラコン酸、アク
リル酸メチル、メタクリル酸メチル、マレイン酸モノメ
チル、マレイン酸ジメチル、グリシジルマレエートなど
が例示される。これらの中でポリオレフィン樹脂として
は、ポリプロピレン、エチレン−プロピレン・コポリマ
ーが機械特性として好ましい。変性剤としては、マレイ
ン酸または、これらの無水物が好ましい。Specific examples of the polyolefin resin of the present invention include polyolefins such as high-pressure polyethylene, medium-low pressure polyethylene, and polypropylene, olefin copolymers such as ethylene propylene copolymer, and ethylene-vinyl acetate copolymer, and modifiers. Examples include unsaturated carboxylic acids or derivatives thereof. Examples of unsaturated carboxylic acids or derivatives thereof include acrylic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, chlodroic acid, isochloroacid, nadic acid (endocys-bicyclo(2,2゜1)hept-5 -en-
2,3-dicarboxylic acid) or derivatives thereof, such as acid halides, amides, isides, anhydrides, esters, etc., specifically, maleylmaleimide chloride, maleic anhydride, citraconic anhydride. , methyl acrylate, methyl methacrylate, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like. Among these, polypropylene and ethylene-propylene copolymer are preferred as the polyolefin resin in terms of mechanical properties. As the modifier, maleic acid or anhydride thereof is preferred.
本発明の周期律表第■族〜第■族金属の金属化金物の具
体例としてはＮａ、Ｃｕ、Ｍｇ、に、Ｃａ、Ｚｎ、Ｓｒ
、Ｂａ、ＡＩの酸化物、水酸化物、炭素塩、硫酸塩、酢
酸塩、不飽和カルボン酸塩を挙げることができる。好ま
しくはメタクリル酸２ｎ、メタクリル酸Ｃａ、酢酸マグ
ネシウムなどを挙げることができる。Specific examples of metallized metals of Groups 1 to 2 of the periodic table of the present invention include Na, Cu, Mg, Ca, Zn, and Sr.
, Ba, and AI oxides, hydroxides, carbon salts, sulfates, acetates, and unsaturated carboxylates. Preferred examples include methacrylic acid 2n, Ca methacrylate, and magnesium acetate.
このポリアミド樹脂と変性ポリオレフィン樹脂アロイに
は、ゴム類、熱可塑性樹脂などが含まれてもよい。この
ゴム類の例としては、エチレンプロピレンゴム、アクリ
ロニトリルブタジェンゴム、スチレン−ブタジェンブロ
ック共重合ゴム及びその水素添加物、スチレン−イソプ
レンブロック共重合ゴム及びその水素添加物、及びこれ
らのカルボン酸変性物やこれらの混合物を挙げることが
できる。また、熱可塑性樹脂の例としては、アクリルニ
トリル−ブタジェン−スチレン共重合体、アイオノマー
樹脂、及びこれらの混合物を挙げることができる。アイ
オノマーの代表的な例としては、エチレン、プロピレン
、ブチレンなどの不飽和炭化水素と、マレイン酸、アク
リル酸、メタクリル酸などの不飽和カルボン酸との共重
合体、または上記不飽和炭化水素、不飽和カルボン酸、
及び不飽和カルボン酸のアルキルエステルの共重合体が
金属イオンにそって架橋されている熱可塑性樹脂を挙げ
ることができる。The polyamide resin and modified polyolefin resin alloy may contain rubbers, thermoplastic resins, and the like. Examples of these rubbers include ethylene propylene rubber, acrylonitrile butadiene rubber, styrene-butadiene block copolymer rubber and hydrogenated products thereof, styrene-isoprene block copolymer rubber and hydrogenated products thereof, and carboxylic acid modified rubbers thereof. Examples include substances and mixtures thereof. Examples of thermoplastic resins include acrylonitrile-butadiene-styrene copolymers, ionomer resins, and mixtures thereof. Typical examples of ionomers include copolymers of unsaturated hydrocarbons such as ethylene, propylene, and butylene and unsaturated carboxylic acids such as maleic acid, acrylic acid, and methacrylic acid; saturated carboxylic acid,
and thermoplastic resins in which copolymers of alkyl esters of unsaturated carboxylic acids are crosslinked along metal ions.
さらに、このポリアミド樹脂と変性ポリオレフィン樹脂
アロイには所望に応じ無機充填剤を配合し補強すること
もできる。この無機充填剤の具体例としては、炭酸カル
シウム、ケイ酸カルシウム（ワラストナイト）、タルク
、カオリン、マイカ、酸化チタン、アルミナ、シリカ、
フェライト、炭酸などの粉末や、ガラス繊維、炭素繊維
、金属繊維、ホウ素繊維、チタン酸カリウム繊維、セラ
ミック繊維などの繊維を挙げることができる。無機充填
剤は、単独でまたは２種以上を組合わせて用いてもよい
。Furthermore, the polyamide resin and modified polyolefin resin alloy can be reinforced with an inorganic filler, if desired. Specific examples of this inorganic filler include calcium carbonate, calcium silicate (wollastonite), talc, kaolin, mica, titanium oxide, alumina, silica,
Examples include powders such as ferrite and carbonic acid, and fibers such as glass fibers, carbon fibers, metal fibers, boron fibers, potassium titanate fibers, and ceramic fibers. The inorganic fillers may be used alone or in combination of two or more.
周期律表第１族〜第■族金属の金属化合物はポリアミド
樹脂と変性ポリオレフィン系樹脂との全使用量１００重
量部当たり、０．３〜５０重量部好ましくは０．７〜１
０重量部含有するように添加する。０．３未満ではウレ
タン樹脂塗料との密着性を改良する効果が不十分である
。５０重量部を超えて添加しても塗装密着性は同等であ
りコストアップにつながり好ましくない。The metal compound of Groups 1 to 2 of the periodic table is used in an amount of 0.3 to 50 parts by weight, preferably 0.7 to 1 part by weight, per 100 parts by weight of the total amount of polyamide resin and modified polyolefin resin.
Add so as to contain 0 parts by weight. If it is less than 0.3, the effect of improving the adhesion with the urethane resin paint is insufficient. Even if it is added in an amount exceeding 50 parts by weight, the coating adhesion remains the same, which is not preferable as it increases the cost.
また、すでに、塗膜密着性を改良するポリアミド組成物
として、特開昭５９−１８７５６号広報に記載されてい
るトリアジン類を組み合わせて用いてもよい。Furthermore, triazines already described in JP-A-59-18756 may be used in combination as a polyamide composition for improving coating film adhesion.
この発明のポリアミド組成物を調整する方法、すなわち
金属化合物含有ポリアミド樹脂と変性ポリオレフィン樹
脂アロイの調整方法は特に制限がなく、公知の配合方法
のいずれも採用することがでいる。配合方法の例として
は、ポリアミド樹脂と変性ポリオレフィン樹脂と金属化
合物をトライブレンドする方法、このトライブレンド物
を溶融混合押し出してペレットとする方法、所定量以上
の金属化合物を練りこんだマスターペレットを調整し、
これを希釈用ポリアミド樹脂と変性ポリオレフィン樹脂
アロイ材料にトライブレンドする方法。あるいはポリア
ミド樹脂重合時またはポリオレフィン樹脂重合時に金属
化合物を添加しアロイとして使用する方法などが挙げら
れる。The method for preparing the polyamide composition of the present invention, that is, the method for preparing the metal compound-containing polyamide resin and the modified polyolefin resin alloy, is not particularly limited, and any known blending method may be employed. Examples of blending methods include tri-blending a polyamide resin, modified polyolefin resin, and metal compound, melting and extruding this tri-blend to form pellets, and preparing master pellets in which a predetermined amount or more of a metal compound is kneaded. death,
A method of tri-blending this with polyamide resin for dilution and modified polyolefin resin alloy material. Alternatively, a method may be mentioned in which a metal compound is added during polymerization of polyamide resin or polyolefin resin and used as an alloy.
本発明のポリアミド樹脂と変性ポリオレフィン樹脂アロ
イ組成物は、要求される特性に応じて他の添加剤、例え
ば耐熱剤、紫外線吸収剤を含む耐候剤、難燃剤、帯電防
止剤、滑剤、可塑剤、核剤発泡剤１着色剤、安定剤、カ
ップリング剤などを含有することができる。The polyamide resin and modified polyolefin resin alloy composition of the present invention may contain other additives depending on the required properties, such as heat resisters, weathering agents including ultraviolet absorbers, flame retardants, antistatic agents, lubricants, plasticizers, The nucleating agent and blowing agent 1 may contain a coloring agent, a stabilizer, a coupling agent, etc.
本発明のポリアミド樹脂と変性ポリオレフィン樹脂アロ
イ組成物は、公知の成形方法、例えば、射出成形、押し
出し成形、プロー成形、圧縮成形などによって各種成形
品に成形することができる。The polyamide resin and modified polyolefin resin alloy composition of the present invention can be molded into various molded products by known molding methods such as injection molding, extrusion molding, blow molding, and compression molding.
［実施例］ 次に実施例及び比較例を示す。[Example] Next, examples and comparative examples will be shown.
なお、実施例及び比較例中の塗膜密着性評価に用いた塗
料及び塗膜密着性の測定方法は、次のとおりである。In addition, the paint used for the evaluation of paint film adhesion in Examples and Comparative Examples and the method of measuring paint film adhesion are as follows.
（１）塗料
ウレタン樹脂塗料（オリジン電気株式会社製、オリジブ
レートＺホワイト）（オリジン電気株式会社製、オリジ
ブレートＺシルバーメタリック）を専用硬化剤及び専用
シンナーで希釈。(1) Paint Urethane resin paint (manufactured by Origin Electric Co., Ltd., Origiblate Z White) (manufactured by Origin Electric Co., Ltd., Origiblate Z Silver Metallic) is diluted with a special hardening agent and a special thinner.
（２）密着性
ＪＩＳＫ５４００−１９７９に準し、１ｍｍｍｍ角目盤
目試験い、剥離しない面積割合を求めた。(2) Adhesion In accordance with JIS K5400-1979, a 1 mm mm square cut test was carried out to determine the area ratio at which no peeling occurred.
（１００／１００＝剥離しない面積割合７１ｍｍ角×１
００基盤目）
以下の試験において「部」はすべて「重量部」を示す。(100/100 = area ratio without peeling 71mm square x 1
00 base) In the following tests, all "parts" indicate "parts by weight."
実施例１〜１０
ナイロン６．１００部と変性ポリプロピレン、４５部に
メタクリル酸亜鉛１．５部をトライブレンドした混合物
を押出機を用いてペレットを得た。Examples 1 to 10 Pellets were obtained from a tri-blend mixture of 6.100 parts of nylon, 45 parts of modified polypropylene, and 1.5 parts of zinc methacrylate using an extruder.
この材料を射出成形し、平板（長さ１２５ｍｍ。This material was injection molded into a flat plate (length 125 mm).
幅７５ｍｍ、厚さ３ｍｍ）を作製した。この平板にウレ
タン樹脂塗料をエアスプレィ−塗装し室温で１０分間放
置後、８０°Ｃで３０分加熱硬化し塗装物を得た。この
塗装物の塗膜厚みは４０μｍであった。この塗装物の密
着性を測定した結果を第１表に示す。75 mm in width and 3 mm in thickness). This flat plate was air-sprayed with a urethane resin paint, left to stand at room temperature for 10 minutes, and then heated and cured at 80°C for 30 minutes to obtain a coated product. The coating thickness of this coated product was 40 μm. Table 1 shows the results of measuring the adhesion of this coated product.
また、メタクリル酸亜鉛の量を変量させた結果及びトリ
アジン類（メラミン）併用結果を実施例２３．４．５と
して第１表に示す。Further, the results of varying the amount of zinc methacrylate and the results of using triazines (melamine) are shown in Table 1 as Example 23.4.5.
実施例６，７，８，９．１０にメタクリル酸亜鉛のかわ
りにメタクリル酸カルシウム、酢酸カルシウム、硫酸マ
グネシウム、酸化亜鉛、水酸化マグネシウムを添加した
以外は実施例１と同様にペレット及び塗装物を作成し密
着性を測定した。Pellets and coated products were prepared in the same manner as in Example 1, except that calcium methacrylate, calcium acetate, magnesium sulfate, zinc oxide, and magnesium hydroxide were added in place of zinc methacrylate in Examples 6, 7, 8, 9, and 10. The adhesion was measured.
また、比較のためにメタクリル酸亜鉛未含有物の結果を
比較例１とし第１表に示す。For comparison, the results of the product not containing zinc methacrylate are shown in Table 1 as Comparative Example 1.
実施例１１及び比較例２
実施例１のメタクリル酸亜鉛１．５部、ナイロン６と変
性ポリプロピレン、ガラス繊維を添加混合し、メタクリ
ル酸亜鉛１．５部、ガラス繊維含有１０部のペレットを
調整した。このペレットを用い、実施例１と同様にして
塗装物を作成し密着性を測定した。結果を実施例１１と
し第２表に示す。また、比較のためにメタクリル酸亜鉛
未含有物の結果を比較例２とし第２表に示す。Example 11 and Comparative Example 2 1.5 parts of zinc methacrylate from Example 1, nylon 6, modified polypropylene, and glass fiber were added and mixed to prepare pellets containing 1.5 parts of zinc methacrylate and 10 parts of glass fiber. . Using this pellet, a coated article was prepared in the same manner as in Example 1, and the adhesion was measured. The results are shown in Table 2 as Example 11. Further, for comparison, the results of the product not containing zinc methacrylate are shown in Table 2 as Comparative Example 2.
実施例１２及び比較例３
実施例１１のガラス繊維の代わりにケイ酸カルシウムを
用いる以外実施例１と同様にして塗装物を作成し密着性
を測定した。結果を実施例１２とし第２表に示す。また
、比較のためにメタクリル酸亜鉛未含有物の結果を比較
例３とし、第２表に示す。Example 12 and Comparative Example 3 Painted objects were prepared in the same manner as in Example 1, except that calcium silicate was used instead of the glass fiber of Example 11, and the adhesion was measured. The results are shown in Table 2 as Example 12. Further, for comparison, the results of the product not containing zinc methacrylate are referred to as Comparative Example 3 and are shown in Table 2.
実施例１３及び比較例４
実施例１のメタクリル酸亜鉛１．５部、ナイロン６と変
性ポリプロピレンに、アイオノマー樹脂（三井ポリケミ
カル社製、ハイミラン１７０６）を添加混合し、押出機
を用いてメタクリル酸亜鉛１．５部、アイオノマー樹脂
含有１０部のペレットに調整した。このペレットを用い
、実施例１と同様にして塗装物を作成し密着性を測定し
た。結果を実施例１３とし、第２表に示す。また、比較
のためにメタクリル酸亜鉛未含有物の結果を比較例４と
し、第２表に示す。Example 13 and Comparative Example 4 An ionomer resin (Himilan 1706, manufactured by Mitsui Polychemical Co., Ltd.) was added and mixed to 1.5 parts of zinc methacrylate of Example 1, nylon 6, and modified polypropylene, and methacrylic acid was added using an extruder. The pellets were adjusted to contain 1.5 parts of zinc and 10 parts of ionomer resin. Using this pellet, a coated article was prepared in the same manner as in Example 1, and the adhesion was measured. The results are referred to as Example 13 and are shown in Table 2. For comparison, the results of the product not containing zinc methacrylate are referred to as Comparative Example 4 and are shown in Table 2.
Claims (1)
の全使用量１００重量部当り ０．３〜５０重量部の割合となる使用 量の周期律表第 I 族〜第III族金属の金 属化合物とからなることを特徴とする ポリアミド組成物。Scope of Claims: (A) 100 parts by weight of polyamide resin, (B) 5 to 400 parts by weight of modified polyolefin resin, and (C) 0.3 to 100 parts by weight of the total amount of the polyamide resin and modified polyolefin resin used. 1. A polyamide composition comprising a metal compound of a metal from Group I to Group III of the Periodic Table in an amount of 50 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2242629A JP2668741B2 (en) | 1990-09-14 | 1990-09-14 | Polyamide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2242629A JP2668741B2 (en) | 1990-09-14 | 1990-09-14 | Polyamide composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04122771A true JPH04122771A (en) | 1992-04-23 |
| JP2668741B2 JP2668741B2 (en) | 1997-10-27 |
Family
ID=17091896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2242629A Expired - Fee Related JP2668741B2 (en) | 1990-09-14 | 1990-09-14 | Polyamide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2668741B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997019131A1 (en) * | 1995-11-21 | 1997-05-29 | E.I. Du Pont De Nemours And Company | Moldable thermoplastic resin composition |
| WO2020122054A1 (en) * | 2018-12-11 | 2020-06-18 | バンドー化学株式会社 | Crosslinked rubber composition and rubber product using same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01315462A (en) * | 1988-03-28 | 1989-12-20 | Ems Inventa Ag | Polyamide molding material and production thereof |
| JPH0224355A (en) * | 1988-07-12 | 1990-01-26 | Tonen Sekiyukagaku Kk | Fiber-reinforced polymer composition |
| JPH02208359A (en) * | 1989-02-09 | 1990-08-17 | Showa Denko Kk | Polyamide resin composition |
| JPH04100858A (en) * | 1990-08-18 | 1992-04-02 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomer composition and rubber member for refrigerator prepared therefrom |
-
1990
- 1990-09-14 JP JP2242629A patent/JP2668741B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01315462A (en) * | 1988-03-28 | 1989-12-20 | Ems Inventa Ag | Polyamide molding material and production thereof |
| JPH0224355A (en) * | 1988-07-12 | 1990-01-26 | Tonen Sekiyukagaku Kk | Fiber-reinforced polymer composition |
| JPH02208359A (en) * | 1989-02-09 | 1990-08-17 | Showa Denko Kk | Polyamide resin composition |
| JPH04100858A (en) * | 1990-08-18 | 1992-04-02 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomer composition and rubber member for refrigerator prepared therefrom |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997019131A1 (en) * | 1995-11-21 | 1997-05-29 | E.I. Du Pont De Nemours And Company | Moldable thermoplastic resin composition |
| WO2020122054A1 (en) * | 2018-12-11 | 2020-06-18 | バンドー化学株式会社 | Crosslinked rubber composition and rubber product using same |
| JPWO2020122054A1 (en) * | 2018-12-11 | 2021-10-28 | バンドー化学株式会社 | Crosslinked rubber composition and rubber products using it |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2668741B2 (en) | 1997-10-27 |
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