JP5049944B2 - Aqueous dispersion, coating composition and painted body - Google Patents
Aqueous dispersion, coating composition and painted body Download PDFInfo
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- JP5049944B2 JP5049944B2 JP2008281195A JP2008281195A JP5049944B2 JP 5049944 B2 JP5049944 B2 JP 5049944B2 JP 2008281195 A JP2008281195 A JP 2008281195A JP 2008281195 A JP2008281195 A JP 2008281195A JP 5049944 B2 JP5049944 B2 JP 5049944B2
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- Prior art keywords
- acid
- aqueous dispersion
- mass
- olefin polymer
- polymer
- Prior art date
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- 239000006185 dispersion Substances 0.000 title claims description 100
- 239000008199 coating composition Substances 0.000 title claims description 30
- 229920000098 polyolefin Polymers 0.000 claims description 134
- 229920001155 polypropylene Polymers 0.000 claims description 72
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- 239000012968 metallocene catalyst Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 90
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 39
- 239000002245 particle Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 30
- 229920000642 polymer Polymers 0.000 description 22
- -1 fatty acid salt Chemical class 0.000 description 20
- 239000004033 plastic Substances 0.000 description 19
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- 238000006116 polymerization reaction Methods 0.000 description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- 239000000178 monomer Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229940096992 potassium oleate Drugs 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 6
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- 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 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- 229920000298 Cellophane Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 2
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 2
- 238000010137 moulding (plastic) Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002987 primer (paints) Substances 0.000 description 2
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- GCORITRBZMICMI-CMDGGOBGSA-N (e)-dodec-4-enoic acid Chemical compound CCCCCCC\C=C\CCC(O)=O GCORITRBZMICMI-CMDGGOBGSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
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- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
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- 239000006082 mold release agent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- 238000011002 quantification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
本発明は、結晶化度が低いプロピレン系重合体を主成分とする水性分散体、その水性分散体を含む塗料組成物、およびその塗料組成物を塗装した塗装体に関する。 The present invention relates to an aqueous dispersion mainly composed of a propylene-based polymer having a low crystallinity, a coating composition containing the aqueous dispersion, and a coated body coated with the coating composition.
ポリオレフィン樹脂は軽量且つ安価、良成形性、耐溶剤性が高いため、近年、車輌用樹脂として多く採用されている。
ところで、ポリオレフィン樹脂の成形体に対して塗装や接着を行う場合には、従来はトルエンやキシレン等の芳香族系有機溶剤に溶解させた塩素化ポリオレフィンを含有する塗料や接着剤が多く用いられてきた。しかしながら、近年の環境への配慮から、溶剤も塩素も含有しない塗料や接着剤、あるいは、プライマーの成分として使用できる水性の分散体がユーザーから求められている。
そこで、特許文献１では、酸変性ポリオレフィンと変性澱粉と乳化剤とを含み、ｐＨが６以上の水性分散体が提案されている。
By the way, in the case of coating or bonding to a molded article of polyolefin resin, conventionally, many paints and adhesives containing chlorinated polyolefin dissolved in an aromatic organic solvent such as toluene and xylene have been used. It was. However, in recent years, due to environmental considerations, users have demanded aqueous dispersions that can be used as components of paints, adhesives, or primers that do not contain solvents or chlorine.
Therefore, Patent Document 1 proposes an aqueous dispersion having an acid-modified polyolefin, a modified starch, and an emulsifier, and having a pH of 6 or more.
しかしながら、特許文献１に記載の水性分散体は、溶剤型の塗料や接着剤程の密着性を発揮することはなかった。特に、基材がポリオレフィン成形体である場合には、密着性が低かった。また、特許文献１に記載の水性分散体は、得られる塗膜の耐水性も不充分であった。
本発明は、前記事情を鑑みてなされたものであり、有機溶剤および塩素原子含有ポリマーを含まないにもかかわらず、各種基材、特にプラスチック成形体（中でも車輌内外装用ポリオレフィン成形体）に対して密着性が高く、得られる皮膜の耐水性に優れる水性分散体を提供することを目的とする。また、その水性分散体を含む塗料組成物およびその塗料組成物が塗装されて形成された皮膜を有する塗装体を提供することを目的とする。
However, the aqueous dispersion described in Patent Document 1 did not exhibit adhesion as much as solvent-type paints and adhesives. In particular, when the substrate was a polyolefin molded product, the adhesion was low. Moreover, the water-based dispersion described in Patent Document 1 has insufficient water resistance of the resulting coating film.
The present invention has been made in view of the above circumstances, and for various substrates, particularly plastic molded articles (especially polyolefin molded articles for vehicle interior / exterior) despite not including an organic solvent and a chlorine atom-containing polymer. An object is to provide an aqueous dispersion having high adhesion and excellent water resistance of the resulting film. It is another object of the present invention to provide a coating composition containing the aqueous dispersion and a coated body having a film formed by coating the coating composition.
本発明は、以下の態様を包含する。
［１］ プロピレン系重合体（Ａ）１００質量部に対して、５〜２０質量部の酸変性オレフィン系重合体（Ｂ）と、１〜１０質量部の界面活性剤（Ｃ）と、０．５〜２０質量部の水（Ｄ）とを含有する水性分散体であって、
プロピレン系重合体（Ａ）は、プロピレン単位８０〜８９質量％とα−オレフィン単位１１〜２０質量％とを含有する共重合体で、結晶化度が８〜１６％、質量平均分子量が１５０，０００〜２５０，０００、分子量分布Ｍｗ／Ｍｎが１．５〜３．５であり、
酸変性オレフィン系重合体（Ｂ）は、プロピレン単位６０〜９０質量％とエチレン単位および／または１−ブテン単位１０〜４０質量％とを含有するオレフィン系重合体に、エチレン性不飽和カルボン酸またはその無水物が結合された酸変性オレフィン系重合体で、質量平均分子量が４０，０００〜１００，０００、酸価が２０〜８０ｍｇＫＯＨ／ｇ、結晶化度が０．１〜１６％であることを特徴とする水性分散体
［２］ 前記プロピレン系重合体（Ａ）を構成するα−オレフィン単位がエチレン単位であることを特徴とする［１］に記載の水性分散体
［３］ 前記プロピレン系重合体（Ａ）がメタロセン系触媒を用いて重合されたことを特徴とする［１］または［２］に記載の水性分散体
［４］ 前記界面活性剤（Ｃ）がアニオン性界面活性剤であることを特徴とする［１］〜［３］のいずれかに記載の水性分散体
［５］ ［１］〜［４］のいずれかに記載の水性分散体を含むことを特徴とする塗料組成物。
［６］ 基材と、該基材の表面に［５］に記載の塗料組成物が塗装されて形成された皮膜とを有することを特徴とする塗装体。
The present invention includes the following aspects.
[1] 5 to 20 parts by mass of an acid-modified olefin polymer (B), 1 to 10 parts by mass of a surfactant (C) with respect to 100 parts by mass of the propylene polymer (A); An aqueous dispersion containing 5 to 20 parts by weight of water (D),
The propylene polymer (A) is a copolymer containing 80 to 89% by mass of propylene units and 11 to 20% by mass of α-olefin units, having a crystallinity of 8 to 16% and a mass average molecular weight of 150, 000-250,000, molecular weight distribution Mw / Mn is 1.5-3.5,
The acid-modified olefin polymer (B) is an olefin polymer containing 60 to 90% by mass of propylene units and 10 to 40% by mass of ethylene units and / or 1-butene units. The acid-modified olefin polymer to which the anhydride is bonded has a mass average molecular weight of 40,000 to 100,000, an acid value of 20 to 80 mgKOH / g, and a crystallinity of 0.1 to 16%. Aqueous dispersion [2] The aqueous dispersion [3] according to [1], wherein the α-olefin unit constituting the propylene polymer (A) is an ethylene unit. The aqueous dispersion [4] according to [1] or [2], wherein the polymer (A) is polymerized using a metallocene catalyst. The surfactant (C) is an anionic surfactant A coating composition comprising the aqueous dispersion according to any one of [1] to [3], wherein the aqueous dispersion according to any one of [1] to [3] is included. object.
[6] A coated body comprising a base material and a film formed by coating the surface of the base material with the coating composition according to [5].
本発明の水性分散体および塗料組成物は、有機溶剤および塩素原子含有ポリマーを含まないにもかかわらず、各種基材、特にプラスチック成形体に対して密着性が高く、得られる皮膜の耐水性に優れる。
本発明の塗装体は、基材に対する密着性および耐水性に優れる皮膜を有する。
Although the aqueous dispersion and coating composition of the present invention do not contain an organic solvent and a chlorine atom-containing polymer, the aqueous dispersion and the coating composition have high adhesion to various substrates, particularly plastic molded articles, and the water resistance of the resulting film is improved. Excellent.
The coated body of the present invention has a film excellent in adhesion to a substrate and water resistance.
「水性分散体」
本発明の水性分散体は、プロピレン系重合体（Ａ）と酸変性オレフィン系重合体（Ｂ）と界面活性剤（Ｃ）と水を含有するものである。
"Aqueous dispersion"
The aqueous dispersion of the present invention contains a propylene polymer (A), an acid-modified olefin polymer (B), a surfactant (C), and water.
（プロピレン系重合体（Ａ））
プロピレン系重合体（Ａ）は、プロピレン単位８０〜８９質量％とα−オレフィン単位１１〜２０質量％とを含有する共重合体である。
プロピレン系重合体（Ａ）におけるプロピレン単位含有率が８０質量％未満であると、得られる塗料組成物より形成した皮膜の密着性が低くなり、また、得られる皮膜の耐水性が低下する。プロピレン単位含有率が８９質量％を超える場合も、得られる塗料組成物より形成した皮膜の密着性および耐水性が低下する。
また、プロピレン系重合体（Ａ）における好ましいプロピレン単位含有率は８２〜８７質量％である。
(Propylene polymer (A))
The propylene polymer (A) is a copolymer containing 80 to 89% by mass of propylene units and 11 to 20% by mass of α-olefin units.
When the propylene unit content in the propylene-based polymer (A) is less than 80% by mass, the adhesion of the film formed from the resulting coating composition is lowered, and the water resistance of the obtained film is lowered. Even when the propylene unit content exceeds 89% by mass, the adhesion and water resistance of the film formed from the resulting coating composition are lowered.
Moreover, the preferable propylene unit content rate in a propylene polymer (A) is 82-87 mass%.
プロピレン系重合体（Ａ）のα−オレフィン成分としては、例えば、エチレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン等が挙げられる。それらの中でもエチレンが好ましい。α−オレフィンがエチレンであれば、得られる塗料組成物から形成した皮膜のベタツキやタックを防止できる。 Examples of the α-olefin component of the propylene polymer (A) include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and the like. Of these, ethylene is preferred. If the α-olefin is ethylene, stickiness and tackiness of the film formed from the coating composition obtained can be prevented.
プロピレン系重合体（Ａ）の結晶化度は８〜１６％であり、好ましくは１０〜１４％である。プロピレン系重合体（Ａ）の結晶化度が１６％を超えると、得られる塗料組成物から形成した皮膜の密着性が低くなり、８％未満であると、得られる塗料組成物から形成した皮膜の耐水性が低下する。
ここで、結晶化度は、Ｘ線回折を測定して求めた結晶のピーク面積の割合である。
The degree of crystallinity of the propylene polymer (A) is 8 to 16%, preferably 10 to 14%. When the crystallinity of the propylene-based polymer (A) exceeds 16%, the adhesion of the coating formed from the resulting coating composition is lowered, and when it is less than 8%, the coating formed from the resulting coating composition. The water resistance of is reduced.
Here, the degree of crystallinity is the ratio of the peak area of the crystal obtained by measuring X-ray diffraction.
プロピレン系重合体（Ａ）の質量平均分子量は１５０，０００〜２５０，０００の範囲であり、好ましくは１７０，０００〜２３０，０００の範囲である。プロピレン系重合体（Ａ）の質量平均分子量が２５０，０００を超えると、得られる塗料組成物から形成した皮膜の密着性が低くなり、１５０，０００未満であると、得られる塗料組成物から形成した皮膜の耐水性が低下する。 The mass average molecular weight of the propylene polymer (A) is in the range of 150,000 to 250,000, preferably in the range of 170,000 to 230,000. When the mass average molecular weight of the propylene polymer (A) exceeds 250,000, the adhesion of the film formed from the resulting coating composition is lowered, and when it is less than 150,000, it is formed from the obtained coating composition. The water resistance of the coated film decreases.
プロピレン系重合体（Ａ）の分子量分布Ｍｗ／Ｍｎは１．５〜３．５の範囲であり、好ましくは２．０〜２．８の範囲である。プロピレン系重合体（Ａ）の分子量分布が３．５を超えても１．５未満であっても、成形体に塗布した後、乾燥して得られる皮膜の密着性が低下する。
本発明における質量平均分子量Ｍｗおよび数平均分子量は、ゲルパーミエーションクロマトグラフィを用いて測定し、標準ポリスチレンで換算した値である。
The molecular weight distribution Mw / Mn of the propylene polymer (A) is in the range of 1.5 to 3.5, preferably in the range of 2.0 to 2.8. Even if the molecular weight distribution of the propylene-based polymer (A) is more than 3.5 or less than 1.5, the adhesion of a film obtained by drying after applying to a molded product is lowered.
The mass average molecular weight Mw and the number average molecular weight in the present invention are values measured by gel permeation chromatography and converted to standard polystyrene.
プロピレン系重合体（Ａ）を製造する方法としては、特開２００４−１１５７１２号公報に記載されているようなメタロセン系触媒を用いる方法が好ましい。メタロセン系触媒はマルチサイト触媒であるチーグラー・ナッタ触媒とは異なり、触媒活性が均一であるために、結晶化度、組成分布、分子量を任意に制御することが可能である。
メタロセン系触媒を用いて製造したプロピレン系重合体（Ａ）を用いた場合、チーグラー・ナッタ触媒を用いて製造したプロピレン系重合体（Ａ）を用いた場合には、皮膜の密着性と耐水性が低下する傾向にある。
As a method for producing the propylene polymer (A), a method using a metallocene catalyst as described in JP-A No. 2004-115712 is preferable. Unlike the Ziegler-Natta catalyst, which is a multi-site catalyst, the metallocene catalyst has a uniform catalytic activity, so that the crystallinity, composition distribution, and molecular weight can be arbitrarily controlled.
When a propylene polymer (A) produced using a metallocene catalyst is used, and when a propylene polymer (A) produced using a Ziegler-Natta catalyst is used, film adhesion and water resistance Tend to decrease.
メタロセン系触媒としては、シクロペンタジエニル骨格を少なくとも１個有する周期表第４族〜第６族の遷移金属の錯体を挙げることができる。例えば、特開平９−１５１２０５号公報に記載されたメタロセン系触媒を用いることができる。 Examples of the metallocene catalyst include complexes of transition metals belonging to Groups 4 to 6 of the periodic table having at least one cyclopentadienyl skeleton. For example, a metallocene catalyst described in JP-A-9-151205 can be used.
プロピレン系重合体（Ａ）の組成は、プロピレン系重合体（Ａ）重合時のプロピレンモノマーとα−オレフィンモノマーの供給量を適宜変更することにより、調節できる。またプロピレン系重合体（Ａ）の質量平均分子量と結晶化度の調整方法としては、重合時に水素ガスを使用して制御する方法、モノマー濃度を制御する方法、重合温度を制御する方法等が挙げられる。 The composition of the propylene polymer (A) can be adjusted by appropriately changing the supply amount of the propylene monomer and the α-olefin monomer during the polymerization of the propylene polymer (A). Examples of the method for adjusting the mass average molecular weight and crystallinity of the propylene polymer (A) include a method of controlling by using hydrogen gas during polymerization, a method of controlling the monomer concentration, and a method of controlling the polymerization temperature. It is done.
（酸変性オレフィン系重合体（Ｂ））
酸変性オレフィン系重合体（Ｂ）としては、オレフィン系重合体にカルボン酸またはカルボン酸無水物が結合された変性物が挙げられる。カルボン酸としては、例えば、（メタ）アクリル酸等が挙げられ、カルボン酸無水物としては、例えば、無水マレイン酸等が挙げられる。
(Acid-modified olefin polymer (B))
Examples of the acid-modified olefin polymer (B) include a modified product in which a carboxylic acid or a carboxylic acid anhydride is bonded to the olefin polymer. Examples of the carboxylic acid include (meth) acrylic acid, and examples of the carboxylic acid anhydride include maleic anhydride.
酸変性オレフィン系重合体（Ｂ）は、プロピレン単位６０〜９０質量％とエチレン単位および／または１−ブテン単位１０〜４０質量％とを含有する。プロピレン単位含有率が６０質量％未満であっても９０質量％を超えても、得られる塗料組成物から形成した皮膜の密着性および耐水性が低くなる。
また、酸変性オレフィン系重合体（Ｂ）における好ましいプロピレン単位含有率は６３〜８４質量％である。
The acid-modified olefin polymer (B) contains 60 to 90% by mass of propylene units and 10 to 40% by mass of ethylene units and / or 1-butene units. Even if the propylene unit content is less than 60% by mass or more than 90% by mass, the adhesion and water resistance of a film formed from the coating composition obtained are lowered.
Moreover, the preferable propylene unit content rate in an acid-modified olefin type polymer (B) is 63-84 mass%.
酸変性オレフィン系重合体（Ｂ）の酸価は２０〜８０ｍｇＫＯＨ／ｇであり、好ましくは４０〜６０ｍｇＫＯＨ／ｇである。ここでいう酸価は、酸変性オレフィン系重合体１ｇを中和するのに必要な水酸化カリウムのｍｇ数である。酸価が２０ｍｇＫＯＨ／ｇ未満であっても８０ｍｇＫＯＨ／ｇを超えても、得られる塗料組成物から形成した皮膜の密着性および耐水性が低くなる。 The acid value of the acid-modified olefin polymer (B) is 20 to 80 mgKOH / g, preferably 40 to 60 mgKOH / g. The acid value here is the number of mg of potassium hydroxide required to neutralize 1 g of the acid-modified olefin polymer. Even if the acid value is less than 20 mgKOH / g or more than 80 mgKOH / g, the adhesion and water resistance of the film formed from the resulting coating composition are lowered.
酸変性オレフィン系重合体（Ｂ）の質量平均分子量は４０，０００〜１００，０００であり、好ましくは６０，０００〜８０，０００である。酸変性オレフィン系重合体（Ｂ）の質量平均分子量が４０，０００未満であっても１００，０００を超えても、得られる塗料組成物から形成した皮膜の密着性および耐水性が低下する。 The mass average molecular weight of the acid-modified olefin polymer (B) is 40,000 to 100,000, preferably 60,000 to 80,000. Even if the mass average molecular weight of the acid-modified olefin polymer (B) is less than 40,000 or more than 100,000, the adhesion and water resistance of a film formed from the resulting coating composition are lowered.
酸変性オレフィン系重合体（Ｂ）の結晶化度は０．１〜１６％である。酸変性オレフィン系重合体（Ｂ）の結晶化度が１６％を超えると、得られる塗料組成物から形成した皮膜の密着性が低くなり、０．１％未満であると、塗料組成物から形成した皮膜の耐水性が低下する。 The crystallinity of the acid-modified olefin polymer (B) is 0.1 to 16%. When the degree of crystallinity of the acid-modified olefin polymer (B) exceeds 16%, the adhesion of the film formed from the resulting coating composition is lowered, and when it is less than 0.1%, it is formed from the coating composition. The water resistance of the coated film decreases.
酸変性オレフィン系重合体（Ｂ）の量は、プロピレン系重合体（Ａ）１００質量部に対して５〜２０質量部であり、好ましくは１０〜１５質量部である。酸変性ポリオレフィン（Ｂ）の量が５質量部未満であると、プロピレン系重合体（Ａ）を分散させることができないため、水性分散体が得られず、２０質量部を超えると、得られる塗料組成物から形成した皮膜の密着性および耐水性が低下する。 The amount of the acid-modified olefin polymer (B) is 5 to 20 parts by mass, preferably 10 to 15 parts by mass with respect to 100 parts by mass of the propylene polymer (A). If the amount of the acid-modified polyolefin (B) is less than 5 parts by mass, the propylene-based polymer (A) cannot be dispersed, so that an aqueous dispersion cannot be obtained. The adhesion and water resistance of the film formed from the composition are lowered.
酸変性オレフィン系重合体（Ｂ）の製造方法についてはオレフィン系重合体を製造する重合工程と、予め製造したオレフィン系重合体をエチレン性不飽和カルボン酸またはその無水物で変性する変性工程の２つの工程を有する。 The method for producing the acid-modified olefin polymer (B) includes a polymerization step for producing an olefin polymer, and a modification step for modifying the olefin polymer produced in advance with an ethylenically unsaturated carboxylic acid or its anhydride. It has one process.
重合工程でのオレフィン系重合体の製造方法では、プロピレン系重合体（Ａ）の重合方法と同様の方法や特開平１０−２７３５７０号公報に記載された方法のように、プロピレンモノマーとエチレンモノマー、あるいは１−ブテンモノマーの供給量を適宜変更することによりオレフィン系重合体の組成を容易に調節できる。
オレフィン系重合体の質量平均分子量と結晶化度の調整方法は、プロピレン系重合体（Ａ）の重合方法と同様に、重合時に水素ガスを使用する方法、モノマー濃度を制御する方法、重合温度を制御する方法などが適用される。
In the production method of the olefin polymer in the polymerization step, as in the method similar to the polymerization method of the propylene polymer (A) and the method described in JP-A-10-273570, a propylene monomer and an ethylene monomer, Alternatively, the composition of the olefin polymer can be easily adjusted by appropriately changing the supply amount of the 1-butene monomer.
The method for adjusting the mass average molecular weight and crystallinity of the olefin polymer is the same as the method for polymerizing the propylene polymer (A), the method using hydrogen gas during the polymerization, the method for controlling the monomer concentration, and the polymerization temperature. The control method is applied.
酸変性オレフィン系重合体（Ｂ）を製造する際の変性工程は、重合工程で得たオレフィン系重合体をエチレン性不飽和カルボン酸またはその無水物で変性して酸変性オレフィン系重合体を得る工程である。具体的には、エチレン性不飽和カルボン酸またはその無水物をオレフィン系重合体の主鎖にグラフト反応させる工程である。
エチレン性不飽和カルボン酸または無水物としては、フマル酸、マレイン酸、イタコン酸、シトラコン酸、アコニット酸、およびこれらの無水物が挙げられる。これらは１種を単独で用いてもよいし、２種以上を組み合わせてもよい。
In the modification step for producing the acid-modified olefin polymer (B), the olefin polymer obtained in the polymerization step is modified with an ethylenically unsaturated carboxylic acid or its anhydride to obtain an acid-modified olefin polymer. It is a process. Specifically, it is a step of graft-reacting ethylenically unsaturated carboxylic acid or its anhydride to the main chain of the olefin polymer.
Ethylenically unsaturated carboxylic acids or anhydrides include fumaric acid, maleic acid, itaconic acid, citraconic acid, aconitic acid, and anhydrides thereof. These may be used individually by 1 type and may combine 2 or more types.
エチレン性不飽和カルボン酸またはその無水物をオレフィン系重合体の主鎖にグラフト反応させる工程では、ラジカル重合開始剤を用いることが好ましい。ラジカル重合開始剤としては、有機過酸化物、アゾニトリルから適宜選択して使用できる。
有機過酸化物としては、ジ（ｔ−ブチルパーオキシ）シクロヘキサンなどのパーオキシケタール類、クメンヒドロキシパーオキシドなどのハイドロパーオキシド類、ジ（ｔ−ブチル）パーオキシドなどのジアルキルパーオキサイド類、ベンゾイルパーオキシドなどのジアシルパーオキサイド類が挙げられる。
アゾニトリルとしては、アゾイソブチロニトリル、アゾイソプロピロニトリル等が挙げられる。
これらラジカル重合開始剤は１種を単独で用いても構わないし、２種以上を組み合わせてもよい。
In the step of graft-reacting the ethylenically unsaturated carboxylic acid or its anhydride to the main chain of the olefin polymer, it is preferable to use a radical polymerization initiator. As the radical polymerization initiator, an organic peroxide or an azonitrile can be appropriately selected and used.
Organic peroxides include peroxyketals such as di (t-butylperoxy) cyclohexane, hydroperoxides such as cumene hydroxyperoxide, dialkyl peroxides such as di (t-butyl) peroxide, and benzoyl peroxide. And diacyl peroxides such as oxides.
Examples of the azonitrile include azoisobutyronitrile and azoisopropylonitrile.
These radical polymerization initiators may be used alone or in combination of two or more.
グラフト反応させる方法は、本発明を満たす重合体を製造できれば、いかなる方法であってもよい。例えば、溶液中で加熱攪拌して反応させる方法、無溶媒で溶融加熱攪拌して反応させる方法、押出機で加熱混練して反応させる方法等が挙げられる。それらの中でも押出機を用いてグラフト重合する方法は溶媒を使用する必要がなく、溶媒留去工程が不要であり、さらにグラフト重合工程に時間を有しないためエネルギー的に有利な点で好適である。 The method for grafting may be any method as long as a polymer satisfying the present invention can be produced. For example, a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, a method of reacting by heating and kneading with an extruder, and the like can be mentioned. Among them, the method of graft polymerization using an extruder does not require the use of a solvent, does not require a solvent distillation step, and further has no time in the graft polymerization step, which is preferable in terms of energy advantage. .
（界面活性剤（Ｃ））
界面活性剤（Ｃ）としては、ノニオン性界面活性剤やアニオン性界面活性剤、高分子乳化剤等が挙げられ、その中でも、より耐水性に優れる皮膜を形成させることができる点から、アニオン性界面活性剤が好ましい。例えば、第１級高級脂肪酸塩、第２級高級脂肪酸塩、第１級高級アルコール硫酸エステル塩、第２級高級アルコール硫酸エステル塩、第１級高級アルキルスルホン酸塩、第２級高級アルキルスルホン酸塩、高級アルキルジスルホン酸塩、スルホン化高級脂肪酸塩、高級脂肪酸硫酸エステル塩、高級脂肪酸エステルスルホン酸塩、高級アルコールエーテルの硫酸エステル塩、高級アルコールエーテルのスルホン酸塩、高級脂肪酸アミドのアルキロール化硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルフェノールスルホン酸塩、アルキルナフタリンスルホン酸塩、アルキルベンゾイルイミダゾールスルホン酸塩などが挙げられる。
上記のアニオン性界面活性剤を構成する高級脂肪酸としては、カプリン酸、ウンデカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、マーガリン酸、ステアリン酸、アラキン酸等の飽和脂肪酸、リンデル酸、ツズ酸、ペトロセリン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸等の不飽和脂肪酸と、これらの混合物が挙げられる。
高級脂肪酸と塩を形成するための元素としては、ナトリウム、カリウム等のアルカリ金属が挙げられる。
アニオン性界面活性剤は１種を単独で使用してもよいし、２種以上を組合せて使用してもよい。
(Surfactant (C))
Examples of the surfactant (C) include nonionic surfactants, anionic surfactants, polymer emulsifiers, etc. Among them, an anionic interface can be formed from the point that a film having better water resistance can be formed. An activator is preferred. For example, primary higher fatty acid salt, secondary higher fatty acid salt, primary higher alcohol sulfate ester salt, secondary higher alcohol sulfate ester salt, primary higher alkyl sulfonate salt, secondary higher alkyl sulfonic acid Salts, higher alkyl disulfonates, sulfonated higher fatty acid salts, higher fatty acid sulfates, higher fatty acid ester sulfonates, higher alcohol ether sulfates, higher alcohol ether sulfonates, higher fatty acid amides alkylolated Examples thereof include sulfate ester salts, alkylbenzene sulfonates, alkylphenol sulfonates, alkylnaphthalene sulfonates, and alkylbenzoylimidazole sulfonates.
Examples of higher fatty acids constituting the anionic surfactant include capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, and other saturated fatty acids, Linderic acid, Tuzic acid, Examples include unsaturated fatty acids such as petroceric acid, oleic acid, linoleic acid, linolenic acid, and arachidonic acid, and mixtures thereof.
Examples of elements for forming salts with higher fatty acids include alkali metals such as sodium and potassium.
An anionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.
界面活性剤（Ｃ）の量は、プロピレン系重合体（Ａ）１００質量部に対して１〜１０質量部であり、好ましくは３〜５質量部である。界面活性剤（Ｃ）の量が１質量部未満であると、水性分散体を得ることができず、１０質量部を超えると、得られる塗料組成物から形成した皮膜の密着性および耐水性が低くなる。 The amount of the surfactant (C) is 1 to 10 parts by mass, preferably 3 to 5 parts by mass with respect to 100 parts by mass of the propylene polymer (A). When the amount of the surfactant (C) is less than 1 part by mass, an aqueous dispersion cannot be obtained, and when it exceeds 10 parts by mass, the adhesion and water resistance of the film formed from the resulting coating composition are reduced. Lower.
水性分散体中の水（Ｄ）は転相時に必要な水であり、プロピレン系重合体（Ａ）１００質量部に対して、０．５〜２０質量部である。
なお、水（Ｄ）の量が前記範囲である水性分散体の固形分濃度は８４質量％以上であり、実質的に固体である。そのため、この水性分散体を既存の塗工方法を適用するため、あるいは、他の薬剤を混合しやすくするためには、粘度を適切な範囲にする目的で、水性分散体に４０質量部以上の希釈水を添加し、希釈して、固形分濃度が１０〜６０質量％の水性分散液とすることが好ましい。
Water (D) in the aqueous dispersion is water necessary for phase inversion, and is 0.5 to 20 parts by mass with respect to 100 parts by mass of the propylene-based polymer (A).
In addition, solid content concentration of the aqueous dispersion whose quantity of water (D) is the said range is 84 mass% or more, and is substantially solid. Therefore, in order to apply the existing coating method to this aqueous dispersion or to easily mix other chemicals, the aqueous dispersion has an amount of 40 parts by mass or more for the purpose of setting the viscosity within an appropriate range. It is preferable to add dilution water and dilute to obtain an aqueous dispersion having a solid content concentration of 10 to 60% by mass.
（水性分散体の製造方法）
本発明における水性分散体の製造方法は特に限定されないが、例えば、プロピレン系重合体（Ａ）と酸変性オレフィン系重合体（Ｂ）と界面活性剤（Ｃ）に水および水以外の溶媒を添加して混合物を調製した後、該混合物から水以外の溶媒を留去する方法が挙げられる。また、プロピレン系重合体（Ａ）と酸変性オレフィン系重合体（Ｂ）と界面活性剤（Ｃ）が溶融する温度以上で溶融させた後に水を添加する方法が挙げられる。これらの中でも、後者の方法が好ましい。後者の方法であれば、貯蔵安定性の高い水性分散体を得ることができる上に、得られた水性分散体から形成した塗膜の密着性および耐水性をより高くできる。また、水以外の溶媒を留去する必要がなく、消費エネルギーの点から有利である。
(Method for producing aqueous dispersion)
The method for producing the aqueous dispersion in the present invention is not particularly limited. For example, water and a solvent other than water are added to the propylene polymer (A), the acid-modified olefin polymer (B), and the surfactant (C). Then, after preparing the mixture, a method of distilling off the solvent other than water from the mixture can be mentioned. Moreover, the method of adding water, after making it melt above the temperature which a propylene polymer (A), an acid-modified olefin polymer (B), and surfactant (C) fuse | melt is mentioned. Among these, the latter method is preferable. With the latter method, an aqueous dispersion having high storage stability can be obtained, and adhesion and water resistance of a coating film formed from the obtained aqueous dispersion can be further increased. Further, it is not necessary to distill off a solvent other than water, which is advantageous in terms of energy consumption.
上記特定のプロピレン系重合体（Ａ）と酸変性ポリオレフィン系重合体（Ｂ）を含有する本発明の水性分散体は、有機溶剤および塩素原子含有ポリマーを含まないにもかかわらず、各種基材、特にプラスチック成形体に対して密着性が高い。また、該水性分散体から得られる皮膜は耐水性に優れる。 Although the aqueous dispersion of the present invention containing the specific propylene polymer (A) and the acid-modified polyolefin polymer (B) does not contain an organic solvent and a chlorine atom-containing polymer, In particular, it has high adhesion to plastic moldings. A film obtained from the aqueous dispersion is excellent in water resistance.
「塗料組成物」
本発明の塗料組成物は、上記水性分散体と、必要に応じて、副資材とを含む。
（副資材）
副資材としては、例えば、カチオン性界面活性剤、ノニオン性界面活性剤等の分散剤、乳化剤、安定化剤、湿潤剤、増粘剤、起泡剤、消泡剤、ゲル化剤、老化防止剤、軟化剤、可塑剤、充填剤、着色剤、付香剤、粘着防止剤、離型剤、造膜助剤、レベリング剤、ポリオレフィン樹脂エマルション、塩素化ポリオレフィン樹脂エマルション、アクリル樹脂やウレタン樹脂等の水性樹脂エマルション等が挙げられる。
"Paint composition"
The coating composition of this invention contains the said aqueous dispersion and an auxiliary material as needed.
(Auxiliary materials)
Examples of auxiliary materials include dispersants such as cationic surfactants and nonionic surfactants, emulsifiers, stabilizers, wetting agents, thickeners, foaming agents, antifoaming agents, gelling agents, and anti-aging agents. Agent, softener, plasticizer, filler, colorant, flavoring agent, anti-sticking agent, mold release agent, film-forming aid, leveling agent, polyolefin resin emulsion, chlorinated polyolefin resin emulsion, acrylic resin, urethane resin, etc. And an aqueous resin emulsion.
上述した塗料組成物は、上記水性分散体を含有するため、各種基材に対する密着性および皮膜の耐水性に優れる。このような塗料組成物は、車輌内外装用のプライマー塗料として適している。 Since the coating composition mentioned above contains the said aqueous dispersion, it is excellent in the adhesiveness with respect to various base materials, and the water resistance of a film | membrane. Such a coating composition is suitable as a primer coating for vehicle interior and exterior.
「塗装体」
本発明の塗装体は、基材と、該基材の表面に上記塗料組成物が塗装されて形成された皮膜とを有するものである。
基材としては、例えば、プラスチック成形体、金属成形体、金属酸化物成形体、木質成形体、紙、繊維織物等が挙げられる。これらの中でも、本発明の高い密着性の効果がとりわけ発揮されることから、プラスチック成形体が好ましい。さらには、プラスチック成形体としては、ポリエチレン、ポリプロピレン等のポリオレフィンの成形体であって、インストルメントパネル、表皮材、センターコンソール等の車輌内装用ポリオレフィン成形体が好ましい。
車輌内外装用ポリオレフィン成形体には、ポリエチレンおよびポリプロピレン以外の他のポリオレフィン（例えば、エチレン−プロピレン共重合体ゴム等）、無機フィラー（例えば、タルク、ガラス繊維、炭酸カルシウム等）、安定剤、着色剤などの各種添加剤が含まれていてもよい。車輌内外装用ポリオレフィン成形体各種添加剤が含まれる場合においても、発揮される効果は同等である。
"Paint body"
The coated body of the present invention has a base material and a film formed by coating the coating composition on the surface of the base material.
Examples of the base material include a plastic molded body, a metal molded body, a metal oxide molded body, a wood molded body, paper, and a textile fabric. Among these, a plastic molded body is preferable because the high adhesion effect of the present invention is particularly exhibited. Furthermore, the plastic molded body is a molded body of polyolefin such as polyethylene or polypropylene, and is preferably a polyolefin molded body for vehicle interior such as an instrument panel, a skin material, or a center console.
For polyolefin molded articles for vehicle interior / exterior, polyolefins other than polyethylene and polypropylene (for example, ethylene-propylene copolymer rubber), inorganic fillers (for example, talc, glass fiber, calcium carbonate, etc.), stabilizers, colorants Various additives such as may be contained. Even when various additives for polyolefin molded articles for vehicle interior / exterior are included, the effect exerted is the same.
皮膜の厚さは、目的に応じて適宜選択されるが、１〜５０μｍであることが好ましい。皮膜の厚さが１μｍ以上であれば、皮膜の機能を充分に発揮させることができ、５０μｍ以下であれば、容易に皮膜を形成できる。
塗料組成物の塗装方法としては、例えば、各種塗工機を用いる方法、スプレーを用いる方法、刷毛塗りなどの方法を用いることができる。
The thickness of the film is appropriately selected according to the purpose, but is preferably 1 to 50 μm. If the thickness of the film is 1 μm or more, the function of the film can be sufficiently exhibited, and if it is 50 μm or less, the film can be easily formed.
As a coating method of the coating composition, for example, a method using various coating machines, a method using a spray, a method such as brush coating can be used.
本発明の塗装体は、上記塗料組成物が塗装された皮膜を有するため、基材に対する密着性および耐水性に優れる皮膜を有する。 Since the coated body of the present invention has a film coated with the coating composition, it has a film excellent in adhesion to the substrate and water resistance.
以下、本発明を実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、以下の例において「％」は「質量％」のことを意味する。
プロピレン系重合体（Ａ）および酸変性オレフィン系重合体（Ｂ）の特性（各単量体単位の量、質量平均分子量、結晶化度、酸価、平均粒子径）は、下記のようにして測定した。
○プロピレン系重合体（Ａ）および酸変性オレフィン系重合体（Ｂ）の前駆体であるオレフィン系重合体の単量体単位の定量：重ベンゼンに溶解させた後、高分解能フーリエ変換核磁気共鳴装置ＪＮＭ−ＡＬ４００型（日本電子（株）製）を用いて、１Ｈ，１３Ｃ−ＮＭＲスペクトルの測定結果に基づき算出した。具体的には、１３Ｃ−ＮＭＲスペクトルにおいて、プロピレン単量体単位由来のメチル炭素のスペクトル強度と１−ブテン単量体単位由来のメチル炭素スペクトルとの強度比からプロピレン単量体単位とエチレン単量体、１−ブテン単量体単位のそれぞれの含有量（単位：モル％）を求め、組成比を算出した。
○プロピレン系重合体（Ａ）および酸変性オレフィン系重合体（Ｂ）の前駆体であるオレフィン系重合体および酸変性オレフィン系重合体（Ｂ）の質量平均分子量測定：ウォーターズ社製、アライアンスＧＰＣ Ｖ２０００型（標準物質；ポリスチレン, 溶媒；オルトジクロロベンゼン, 測定温度；１４０℃， 溶媒流速；１ｍＬ／分）により測定した。
○プロピレン系重合体（Ａ）および酸変性オレフィン系重合体（Ｂ）の結晶化度：理学電機（株）製、広角Ｘ線回折装置ＲＡＤ−ＲＸ型により求めた。
○酸変性オレフィン系重合体（Ｂ）の酸価の測定方法；酸変性オレフィン系重合体２００ｍｇとクロロホルム４８００ｍｇを１０ｍｌのサンプル瓶に入れて５０℃で３０分加熱し完全に溶解させた。ＮａＣｌ、光路長０．５ｍｍの液体セルにクロロホルムを入れ、バックグラウンドとした。次に溶解した酸変性オレフィン系重合体（Ｂ）液体セルに入れ、ＦＴ−ＩＲ（日本分光社製）を用いて、積算回数３２回にて赤外吸収スペクトルを測定した。無水マレイン酸のグラフト率は、無水マレイン酸をクロロホルムに溶解した溶液を測定し、検量線を作成したものを用いて計算した。カルボニル基の吸収ピーク（１７８０ｃｍ−１付近の極大ピーク、１７５０〜１８１３ｃｍ−１）の面積から、別途作成した検量線に基づき、重合体中の酸成分含有量を算出した。算出した酸成分含有量／（１００−酸成分含有量）×１／９７（グラフトされた無水マレイン酸１分子当りの分子量）×２当量（グラフトされた１分子の無水マレイン酸が中和された時のカルボン酸基数）×５７（ＫＯＨ分子量）×１０００から酸価を算出した。
○平均粒子径測定：日機装社製のマイクロトラック（ナノトラック１５０）（測定溶媒；純水）を用いて体積基準の平均粒子径を測定した。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example. In the following examples, “%” means “mass%”.
The characteristics (amount of each monomer unit, mass average molecular weight, crystallinity, acid value, average particle diameter) of the propylene polymer (A) and the acid-modified olefin polymer (B) are as follows: It was measured.
○ Quantification of monomer units of olefin polymers that are precursors of propylene polymers (A) and acid-modified olefin polymers (B): high-resolution Fourier transform nuclear magnetic resonance after dissolution in heavy benzene It calculated based on the measurement result of < 1 > H, < 13 > C-NMR spectrum using apparatus JNM-AL400 type | mold (JEOL Co., Ltd. product). Specifically, in the 13 C-NMR spectrum, the propylene monomer unit and the ethylene unit are determined from the intensity ratio of the spectrum intensity of the methyl carbon derived from the propylene monomer unit and the methyl carbon spectrum derived from the 1-butene monomer unit. The content of each of the monomer and 1-butene monomer units (unit: mol%) was determined, and the composition ratio was calculated.
○ Mass average molecular weight measurement of olefin polymer and acid-modified olefin polymer (B) which are precursors of propylene polymer (A) and acid-modified olefin polymer (B): Alliance GPC V2000, manufactured by Waters It was measured by a mold (standard substance; polystyrene, solvent; orthodichlorobenzene, measurement temperature: 140 ° C., solvent flow rate: 1 mL / min).
O Crystallinity of propylene polymer (A) and acid-modified olefin polymer (B): Determined by a wide-angle X-ray diffractometer RAD-RX, manufactured by Rigaku Corporation.
Method for measuring acid value of acid-modified olefin polymer (B): 200 mg of acid-modified olefin polymer and 4800 mg of chloroform were placed in a 10 ml sample bottle and heated at 50 ° C. for 30 minutes to completely dissolve. Chloroform was placed in a liquid cell with NaCl and an optical path length of 0.5 mm as a background. Next, it was put into a dissolved acid-modified olefin polymer (B) liquid cell, and an infrared absorption spectrum was measured at a total number of 32 times using FT-IR (manufactured by JASCO Corporation). The graft ratio of maleic anhydride was calculated using a calibration curve prepared by measuring a solution of maleic anhydride dissolved in chloroform. From the area of the absorption peak of the carbonyl group (maximum peak near 1780 cm −1 , 1750 to 1813 cm −1 ), the acid component content in the polymer was calculated based on a separately prepared calibration curve. Calculated acid component content / (100-acid component content) × 1/97 (molecular weight per grafted maleic anhydride molecule) × 2 equivalents (one grafted maleic anhydride was neutralized) The acid value was calculated from the number of carboxylic acid groups at the time) × 57 (KOH molecular weight) × 1000.
Average particle diameter measurement: The volume-based average particle diameter was measured using Microtrack (Nanotrack 150) (measuring solvent: pure water) manufactured by Nikkiso Co., Ltd.
以下の実施例、比較例において、（Ａ）成分として、下記の（Ａ−１）〜（Ａ−９）を用いた。
プロピレン系重合体（Ａ−１）：
１０００ｍＬ丸底フラスコに、脱イオン水１１０ｍＬ、硫酸マグネシウム・７水和物２２．２ｇおよび硫酸１８．２ｇを採取し、攪拌して溶解させた。これにより得た溶液に、市販の造粒モンモリロナイト１６．７ｇを分散させ、１００℃まで昇温し、２時間攪拌を行った。その後、室温まで冷却し、得られたスラリーを濾過してウェットケーキを回収した。回収したウェットケーキを１０００ｍＬ丸底フラスコにて、脱塩水５００ｍＬにて再度スラリー化し、濾過を行った。この操作を２回繰り返した。最終的に得られたケーキを、窒素雰囲気下１１０℃で一晩乾燥して、化学処理モンモリロナイト１３．３ｇを得た。
得られた化学処理モンモリロナイト４．４ｇに、トリエチルアルミニウムのトルエン溶液（０．４ｍｍｏｌ／ｍＬ）２０ｍＬを加え、室温で１時間攪拌した。この懸濁液にトルエン８０ｍＬを加え、攪拌後、上澄みを除いた。この操作を２回繰り返した後、トルエンを加えて、粘土スラリー（スラリー濃度＝９９ｍｇ粘土／ｍＬ）を得た。別のフラスコに、トリイソブチルアルミニウム０．２ｍｍｏｌを採取し、ここで得られた粘土スラリー１９ｍＬおよびジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−５，６，７，８−テトラヒドロ−１−アズレニル）ハフニウム］１３１ｍｇ（５７μｍｏｌ）のトルエン希釈液を加え、室温で１０分間攪拌し、触媒スラリーを得た。
次いで、内容積２４リットルの誘導攪拌式オートクレーブ内に液体プロピレン２．４８Ｌおよび液体エチレン０．４５Ｌを導入した。室温で、上記触媒スラリーを全量導入し、８５℃まで昇温し重合時全圧を０．７５ＭＰａ、水素濃度４００ｐｐｍで一定に保持しながら、同温度で２時間攪拌を継続した。攪拌終了後、未反応プロピレンを放出して重合を停止した。オートクレーブを開放してポリマーのトルエン溶液を全量回収し、溶媒並びに粘土残渣を除去して、プロピレン−エチレン共重合体トルエン溶液を得た。得られたプロピレン−エチレン共重合体をプロピレン系重合体（Ａ−１）とした。
プロピレン系重合体（Ａ−１）のエチレン単位量は１５％、質量平均分子量Ｍｗは１６０，０００（ポリスチレン換算）、結晶化度は１０％であった。
In the following examples and comparative examples, the following (A-1) to (A-9) were used as the component (A).
Propylene polymer (A-1):
In a 1000 mL round bottom flask, 110 mL of deionized water, 22.2 g of magnesium sulfate heptahydrate and 18.2 g of sulfuric acid were collected and dissolved by stirring. In this solution, 16.7 g of commercially available granulated montmorillonite was dispersed, heated to 100 ° C., and stirred for 2 hours. Then, it cooled to room temperature and filtered the obtained slurry, and collect | recovered the wet cake. The collected wet cake was slurried again with 500 mL of demineralized water in a 1000 mL round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried at 110 ° C. overnight under a nitrogen atmosphere to obtain 13.3 g of chemically treated montmorillonite.
To 4.4 g of the obtained chemically treated montmorillonite, 20 mL of a toluene solution of triethylaluminum (0.4 mmol / mL) was added and stirred at room temperature for 1 hour. To the suspension, 80 mL of toluene was added, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / mL). In a separate flask, 0.2 mmol of triisobutylaluminum was collected, and 19 mL of the clay slurry obtained here and dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-5,6,7,8 -Tetrahydro-1-azulenyl) hafnium] 131 mg (57 μmol) of toluene diluted solution was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry.
Next, 2.48 L of liquid propylene and 0.45 L of liquid ethylene were introduced into an induction stirring autoclave having an internal volume of 24 liters. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 85 ° C., and the stirring was continued for 2 hours at the same temperature while keeping the total pressure during polymerization at 0.75 MPa and a hydrogen concentration of 400 ppm. After completion of the stirring, unreacted propylene was released to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and the clay residue were removed to obtain a propylene-ethylene copolymer toluene solution. The obtained propylene-ethylene copolymer was used as a propylene polymer (A-1).
The propylene polymer (A-1) had an ethylene unit amount of 15%, a mass average molecular weight Mw of 160,000 (polystyrene conversion), and a crystallinity of 10%.
プロピレン系重合体（Ａ−２）〜（Ａ−９）：
重合条件を表１に示したように変更した以外は、プロピレン系重合体（Ａ−１）と同様にしてプロピレン系重合体（Ａ−２）〜（Ａ−９）を製造した。
Propylene polymers (A-2) to (A-9):
Propylene polymers (A-2) to (A-9) were produced in the same manner as the propylene polymer (A-1) except that the polymerization conditions were changed as shown in Table 1.
プロピレン系重合体（Ａ−１０）：
重合触媒にシクロペンタジエニルを添加しなかった（すなわち、トリエチルアルミニウム［３ＥｔＡｌ］のみを触媒として用いた）以外は、プロピレン系重合体（Ａ−１）と同様の方法により、プロピレン系重合体（Ａ−１０）を得た。
Propylene polymer (A-10):
A propylene polymer (A-1) was prepared in the same manner as the propylene polymer (A-1) except that cyclopentadienyl was not added to the polymerization catalyst (that is, only triethylaluminum [3EtAl] was used as a catalyst). A-10) was obtained.
プロピレン系重合体（Ａ−１）〜（Ａ−１０）における各単量体の組成、結晶化度、質量平均分子量を表２，３に示す。 Tables 2 and 3 show the composition, crystallinity, and mass average molecular weight of each monomer in the propylene polymers (A-1) to (A-10).
酸変性オレフィン系重合体（Ｂ）は、重合工程にて、プロピレン系重合体（Ａ）を製造したのと同様の方法で酸変性オレフィン系重合体（Ｂ）の前駆体であるオレフィン系重合体を製造し、変性工程にて、該オレフィン系重合体を変性することにより得た。以下、具体的に手順を示す。 The acid-modified olefin polymer (B) is an olefin polymer that is a precursor of the acid-modified olefin polymer (B) in the same manner as the production of the propylene polymer (A) in the polymerization step. This was obtained by modifying the olefin polymer in the modification step. The procedure is specifically shown below.
酸変性オレフィン系重合体（Ｂ−１）：
（ｉ）重合工程
１０００ｍＬ丸底フラスコに、脱イオン水１１０ｍＬ、硫酸マグネシウム・７水和物２２．２ｇおよび硫酸１８．２ｇを採取し、攪拌下に溶解させた。この溶液に、市販の造粒モンモリロナイト１６．７ｇを分散させ、１００℃まで昇温し、２時間攪拌を行った。その後、室温まで冷却し、得られたスラリーを濾過してウェットケーキを回収した。回収したケーキを１０００ｍＬ丸底フラスコにて、脱塩水５００ｍＬにて再度スラリー化し、濾過を行った。この操作を２回繰り返した。最終的に得られたケーキを、窒素雰囲気下１１０℃で終夜乾燥し、化学処理モンモリロナイト１３．３ｇを得た。
得られた化学処理モンモリロナイト４．４ｇに、トリエチルアルミニウムのトルエン溶液（０．４ｍｍｏｌ／ｍＬ）２０ｍＬを加え、室温で１時間攪拌した。この懸濁液にトルエン８０ｍＬを加え、攪拌後、上澄みを除いた。この操作を２回繰り返した後、トルエンを加えて、粘土スラリー（スラリー濃度＝９９ｍｇ粘土／ｍＬ）を得た。別のフラスコに、トリイソブチルアルミニウム０．２ｍｍｏｌを採取し、ここで得られた粘土スラリー１９ｍＬおよびジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−５，６，７，８−テトラヒドロ−１−アズレニル）ハフニウム］１３１ｍｇ（５７μｍｏｌ）のトルエン希釈液を加え、室温で１０分間攪拌し、触媒スラリーを得た。
次いで、内容積２４リットルの誘導攪拌式オートクレーブ内に液体プロピレン２．４８Ｌおよび液体エチレン０．８３Ｌを導入した。室温で、上記触媒スラリーを全量導入し、８５℃まで昇温し重合時全圧を０．７５ＭＰａ、水素濃度４００ｐｐｍで一定に保持しながら、同温度で２時間攪拌を継続した。攪拌終了後、未反応プロピレンを放出して重合を停止した。オートクレーブを開放してポリマーのトルエン溶液を全量回収し、溶媒並びに粘土残渣を除去して、酸変性オレフィン系重合体の前駆体であるオレフィン系重合体のトルエン溶液を得た。得られたオレフィン系重合体のエチレン単位量は２５％、質量平均分子量Ｍｗは８０，０００（ポリスチレン換算）、結晶化度は１０％であった。
Acid-modified olefin polymer (B-1):
(I) Polymerization step 110 mL of deionized water, 22.2 g of magnesium sulfate heptahydrate and 18.2 g of sulfuric acid were collected in a 1000 mL round bottom flask and dissolved under stirring. In this solution, 16.7 g of commercially available granulated montmorillonite was dispersed, heated to 100 ° C., and stirred for 2 hours. Then, it cooled to room temperature and filtered the obtained slurry, and collect | recovered the wet cake. The collected cake was slurried again with 500 mL of demineralized water in a 1000 mL round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried at 110 ° C. overnight under a nitrogen atmosphere to obtain 13.3 g of chemically treated montmorillonite.
To 4.4 g of the obtained chemically treated montmorillonite, 20 mL of a toluene solution of triethylaluminum (0.4 mmol / mL) was added and stirred at room temperature for 1 hour. To the suspension, 80 mL of toluene was added, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / mL). In a separate flask, 0.2 mmol of triisobutylaluminum was collected, and 19 mL of the clay slurry obtained here and dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-5,6,7,8 -Tetrahydro-1-azulenyl) hafnium] 131 mg (57 μmol) of toluene diluted solution was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry.
Next, 2.48 L of liquid propylene and 0.83 L of liquid ethylene were introduced into an induction stirring autoclave having an internal volume of 24 liters. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 85 ° C., and the stirring was continued for 2 hours at the same temperature while keeping the total pressure during polymerization at 0.75 MPa and a hydrogen concentration of 400 ppm. After completion of the stirring, unreacted propylene was released to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and clay residue were removed to obtain a toluene solution of an olefin polymer that is a precursor of the acid-modified olefin polymer. The obtained olefin polymer had an ethylene unit amount of 25%, a mass average molecular weight Mw of 80,000 (polystyrene conversion), and a crystallinity of 10%.
（ii）変性工程
上記オレフィン系重合体１００質量部に、無水マレイン酸６質量部、ジ−ｔ−ブチルパーオキシド３質量部を、１７０℃に設定した二軸押出機を用いて反応させた。その際、押出機内を脱気して、残留する未反応物を除去した。
この反応により得られた酸変性オレフィン系重合体（Ｂ−１）は、質量平均分子量５０，０００、無水マレイン酸のグラフト質量が４質量％（酸価５０ｍｇＫＯＨ／ｇ）であった。
(Ii) Modification Step 6 parts by mass of maleic anhydride and 3 parts by mass of di-t-butyl peroxide were reacted with 100 parts by mass of the olefin polymer using a twin screw extruder set at 170 ° C. At that time, the inside of the extruder was deaerated to remove residual unreacted substances.
The acid-modified olefin polymer (B-1) obtained by this reaction had a mass average molecular weight of 50,000 and a maleic anhydride graft mass of 4% by mass (acid value 50 mgKOH / g).
酸変性オレフィン系重合体（Ｂ−２）〜（Ｂ−７），（Ｂ−１０）〜（Ｂ−１５），（Ｂ−１８），（Ｂ−１９）：
重合条件を表４に示すように変更して得たオレフィン系重合体を前駆体として用いたこと以外は、酸変性オレフィン系重合体（Ｂ−１）の製造と同様にして、酸変性オレフィン系重合体（Ｂ−２）〜（Ｂ−７），（Ｂ−１０）〜（Ｂ−１５），（Ｂ−１８），（Ｂ−１９）を得た（表５〜７参照）。
Acid-modified olefin polymers (B-2) to (B-7), (B-10) to (B-15), (B-18), (B-19):
The acid-modified olefin type is the same as the production of the acid-modified olefin polymer (B-1) except that the olefin polymer obtained by changing the polymerization conditions as shown in Table 4 is used as a precursor. Polymers (B-2) to (B-7), (B-10) to (B-15), (B-18), and (B-19) were obtained (see Tables 5 to 7).
酸変性オレフィン系重合体（Ｂ−８）：
無水マレイン酸を４質量部に変更した以外は、酸変性オレフィン系重合体（Ｂ−１）の製造と同様にして、酸変性オレフィン系重合体（Ｂ−８）を得た（表６参照）。
Acid-modified olefin polymer (B-8):
An acid-modified olefin polymer (B-8) was obtained in the same manner as in the production of the acid-modified olefin polymer (B-1) except that maleic anhydride was changed to 4 parts by mass (see Table 6). .
酸変性オレフィン系重合体（Ｂ−９）：
無水マレイン酸を８質量部に変更した以外は、酸変性オレフィン系重合体（Ｂ−１）の製造と同様にして、酸変性オレフィン系重合体（Ｂ−９）を得た（表６参照）。
Acid-modified olefin polymer (B-9):
An acid-modified olefin polymer (B-9) was obtained in the same manner as in the production of the acid-modified olefin polymer (B-1) except that maleic anhydride was changed to 8 parts by mass (see Table 6). .
酸変性オレフィン系重合体（Ｂ−１６）：
無水マレイン酸を２質量部に変更した以外は、酸変性オレフィン系重合体（Ｂ−１）の製造と同様にして、酸変性オレフィン系重合体（Ｂ−１６）を得た（表７参照）。
Acid-modified olefin polymer (B-16):
An acid-modified olefin polymer (B-16) was obtained in the same manner as in the production of the acid-modified olefin polymer (B-1) except that maleic anhydride was changed to 2 parts by mass (see Table 7). .
酸変性オレフィン系重合体（Ｂ−１７）：
無水マレイン酸を１０質量部に変更した以外は、酸変性オレフィン系重合体（Ｂ−１）の製造と同様にして、酸変性オレフィン系重合体（Ｂ−１７）を得た（表７参照）。
Acid-modified olefin polymer (B-17):
An acid-modified olefin polymer (B-17) was obtained in the same manner as in the production of the acid-modified olefin polymer (B-1) except that maleic anhydride was changed to 10 parts by mass (see Table 7). .
（実施例１）
プロピレン系重合体（Ａ−１）と、プロピレン系重合体１００質量部に対して、１０質量部の酸変性オレフィン系重合体（Ｂ−２）と、プロピレン系重合体１００質量部に対して５質量部のオレイン酸カリウム（Ｃ−１）を、二軸押出機（スクリュー径；３０ｍｍ、Ｌ／Ｄ；４０、バレル温度；２３０℃）にその投入口から供給して溶融混練した。
また、該二軸押出機のベント部に設けた供給口より１４％の水酸化カリウム水溶液を、プロピレン系重合体（Ａ−１）と酸変性オレフィン系重合体（Ｂ−２）とオレイン酸カリウムの総質量に対して、１.８ＭＰａで３．５質量部を連続的に圧入した。そして、二軸押出機先端より押し出された固形状の水性分散体を、１６５質量部の温水中で分散させて、固形分濃度が４０％で、平均粒子径０．２１μｍの水性分散体を得た。
得られた水性分散体を車輌内外装用ポリオレフィン成形体に塗装し、乾燥して、皮膜を有する塗装体を得た。
得られた皮膜の密着性と耐水性を、以下のように評価した。その結果を表８に示す。
Example 1
10 parts by mass of the acid-modified olefin polymer (B-2) and 100 parts by mass of the propylene polymer with respect to 100 parts by mass of the propylene polymer (A-1) and the propylene polymer. A part by weight of potassium oleate (C-1) was supplied to the twin screw extruder (screw diameter; 30 mm, L / D; 40, barrel temperature; 230 ° C.) from the inlet and melt-kneaded.
In addition, a 14% aqueous potassium hydroxide solution from a supply port provided in the vent portion of the twin-screw extruder was converted into a propylene polymer (A-1), an acid-modified olefin polymer (B-2), and potassium oleate. 3.5 parts by mass were continuously pressed at 1.8 MPa with respect to the total mass. Then, the solid aqueous dispersion extruded from the tip of the twin-screw extruder is dispersed in 165 parts by mass of warm water to obtain an aqueous dispersion having a solid concentration of 40% and an average particle diameter of 0.21 μm. It was.
The obtained aqueous dispersion was coated on a polyolefin molded body for vehicle interior / exterior and dried to obtain a coated body having a film.
The adhesion and water resistance of the obtained film were evaluated as follows. The results are shown in Table 8.
［試験片の作製］
車輌内外装用のポリオレフィン成形体であるトヨタスーパーオレフィンポリマー素材（１００×１００ｍｍ、厚さ２ｍｍの平板）表面を脱脂処理した後、水性分散体を乾燥膜厚で１５μｍになるようにスプレー塗装した。そして、８０℃で２０分間乾燥し、室温で２４時間静置して皮膜を形成し、皮膜を形成した平板を試験片として用いた。
[Preparation of test piece]
After degreasing the surface of a Toyota super olefin polymer material (100 × 100 mm, 2 mm thick flat plate), which is a polyolefin molded body for vehicle interior and exterior, the aqueous dispersion was spray coated to a dry film thickness of 15 μm. And it dried at 80 degreeC for 20 minute (s), and left still at room temperature for 24 hours, the film was formed, and the flat plate in which the film was formed was used as a test piece.
［密着性試験］
ＪＩＳ Ｋ５４００に準拠して、セロハンテープを用いて剥離試験を行った。２ｍｍ間隔で２５個のマス目を形成させた後、それらのマス目にセロハンテープを密着させた後、引き剥がし、残存したマス目の数を記録した。残存したマス目の数が２０マス以上であれば密着性に優れる。
[Adhesion test]
In accordance with JIS K5400, a peel test was performed using a cellophane tape. After forming 25 cells at intervals of 2 mm, cellophane tape was adhered to these cells and then peeled off, and the number of cells remaining was recorded. If the number of remaining cells is 20 cells or more, the adhesion is excellent.
［耐水性試験］
ステンレス製のカゴの中に入れた試験片を、４０℃の温水中に完全に浸漬し、１０日間放置した。その後、温水中から取出し、外観に異常が認められなければ、引き続き、上記密着性試験と同様の試験を行った。残存したマス目の数が２０マス以上であれば耐水性に優れる。
[Water resistance test]
The specimen placed in a stainless steel basket was completely immersed in warm water at 40 ° C. and left for 10 days. Thereafter, the test was taken out from the warm water, and if no abnormality was observed in the appearance, the same test as the adhesion test was subsequently performed. If the number of remaining squares is 20 squares or more, the water resistance is excellent.
（実施例２）
プロピレン系重合体（Ａ−１）をプロピレン系重合体（Ａ−２）に変更した以外は実施例１と同様にして、平均粒子径０．２６μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表８に示す。
(Example 2)
An aqueous dispersion having an average particle size of 0.26 μm was obtained in the same manner as in Example 1 except that the propylene polymer (A-1) was changed to the propylene polymer (A-2). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 8.
（実施例３）
プロピレン系重合体（Ａ−１）をプロピレン系重合体（Ａ−３）に変更した以外は実施例１と同様にして、平均粒子径０．３０μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表８に示す。
(Example 3)
An aqueous dispersion having an average particle size of 0.30 μm was obtained in the same manner as in Example 1 except that the propylene polymer (A-1) was changed to the propylene polymer (A-3). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 8.
（実施例４）
酸変性オレフィン系重合体（Ｂ−２）を酸変性オレフィン系重合体（Ｂ−１）に変更した以外は実施例２と同様にして、平均粒子径０．３２μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表９に示す。
Example 4
An aqueous dispersion having an average particle size of 0.32 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-2) was changed to the acid-modified olefin polymer (B-1). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 9.
（実施例５）
酸変性オレフィン系重合体（Ｂ−２）を酸変性オレフィン系重合体（Ｂ−３）に変更した以外は実施例２と同様にして、平均粒子径０．３０μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表９に示す。
(Example 5)
An aqueous dispersion having an average particle size of 0.30 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-2) was changed to the acid-modified olefin polymer (B-3). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 9.
（実施例６）
酸変性オレフィン系重合体（Ｂ−２）を酸変性オレフィン系重合体（Ｂ−４）に変更した以外は実施例２と同様にして、平均粒子径０．３５μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表９に示す。
(Example 6)
An aqueous dispersion having an average particle size of 0.35 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-2) was changed to the acid-modified olefin polymer (B-4). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 9.
（実施例７）
酸変性オレフィン系重合体（Ｂ−２）を酸変性オレフィン系重合体（Ｂ−５）に変更した以外は実施例２と同様にして、平均粒子径０．３１μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表９に示す。
(Example 7)
An aqueous dispersion having an average particle size of 0.31 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-2) was changed to the acid-modified olefin polymer (B-5). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 9.
（実施例８）
酸変性オレフィン系重合体（Ｂ−２）を酸変性オレフィン系重合体（Ｂ−６）に変更した以外は実施例２と同様にして、平均粒子径０．３１μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表９に示す。
(Example 8)
An aqueous dispersion having an average particle size of 0.31 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-2) was changed to the acid-modified olefin polymer (B-6). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 9.
（実施例９）
酸変性オレフィン系重合体（Ｂ−２）を酸変性オレフィン系重合体（Ｂ−７）に変更した以外は実施例２と同様にして、平均粒子径０．３９μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表９に示す。
Example 9
An aqueous dispersion having an average particle size of 0.39 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-2) was changed to the acid-modified olefin polymer (B-7). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 9.
（実施例１０）
酸変性オレフィン系重合体（Ｂ−２）を酸変性オレフィン系重合体（Ｂ−８）に変更した以外は実施例２と同様にして、平均粒子径０．２９μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表９に示す。
(Example 10)
An aqueous dispersion having an average particle size of 0.29 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-2) was changed to the acid-modified olefin polymer (B-8). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 9.
（実施例１１）
酸変性オレフィン系重合体（Ｂ−２）を酸変性オレフィン系重合体（Ｂ−９）に変更した以外は実施例２と同様にして、平均粒子径０．３１μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表９に示す。
(Example 11)
An aqueous dispersion having an average particle size of 0.31 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-2) was changed to the acid-modified olefin polymer (B-9). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 9.
（実施例１２）
酸変性オレフィン系重合体（Ｂ−２）を酸変性オレフィン系重合体（Ｂ−１０）に変更した以外は実施例２と同様にして、平均粒子径０．３１μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表９に示す。
(Example 12)
An aqueous dispersion having an average particle size of 0.31 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-2) was changed to the acid-modified olefin polymer (B-10). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 9.
（実施例１３）
酸変性オレフィン系重合体（Ｂ−２）を酸変性オレフィン系重合体（Ｂ−１１）に変更した以外は実施例２と同様にして、平均粒子径０．３９μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表９に示す。
(Example 13)
An aqueous dispersion having an average particle size of 0.39 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-2) was changed to the acid-modified olefin polymer (B-11). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 9.
（実施例１４）
酸変性オレフィン系重合体（Ｂ−２）の添加量を６質量部に変更した以外は実施例２と同様にして、平均粒子径０．５０μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１０に示す。
(Example 14)
An aqueous dispersion having an average particle size of 0.50 μm was obtained in the same manner as in Example 2 except that the addition amount of the acid-modified olefin polymer (B-2) was changed to 6 parts by mass. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 10.
（実施例１５）
酸変性オレフィン系重合体（Ｂ−２）の添加量を１８質量部に変更した以外は実施例２と同様にして、平均粒子径０．２８μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１０に示す。
(Example 15)
An aqueous dispersion having an average particle size of 0.28 μm was obtained in the same manner as in Example 2 except that the addition amount of the acid-modified olefin polymer (B-2) was changed to 18 parts by mass. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 10.
（実施例１６）
オレイン酸カリウム（Ｃ−１）の添加量を２質量部に変更した以外は実施例２と同様にして、平均粒子径０．６８μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１０に示す。
(Example 16)
An aqueous dispersion having an average particle size of 0.68 μm was obtained in the same manner as in Example 2 except that the amount of potassium oleate (C-1) added was changed to 2 parts by mass. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 10.
（実施例１７）
オレイン酸カリウム（Ｃ−１）の添加量を９質量部に変更した以外は実施例２と同様にして、平均粒子径０．２９μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１０に示す。
(Example 17)
An aqueous dispersion having an average particle size of 0.29 μm was obtained in the same manner as in Example 2 except that the amount of potassium oleate (C-1) was changed to 9 parts by mass. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 10.
（実施例１８）
オレイン酸カリウム（Ｃ−１）の代わりにエマルゲン９２０（花王（株）製、ノニオン性界面活性剤）（Ｃ−２）を使用した以外は実施例２と同様にして、平均粒子径２．１μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性の評価をした。その結果を表１０に示す。
(Example 18)
An average particle size of 2.1 μm was obtained in the same manner as in Example 2 except that Emulgen 920 (manufactured by Kao Corporation, nonionic surfactant) (C-2) was used instead of potassium oleate (C-1). An aqueous dispersion of was obtained. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 10.
（比較例１）
プロピレン系重合体（Ａ−１）の代わりにプロピレン系重合体（Ａ−４）を使用した以外は実施例１と同様にして、平均粒子径０．３２μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１１に示す。
(Comparative Example 1)
An aqueous dispersion having an average particle size of 0.32 μm was obtained in the same manner as in Example 1 except that the propylene polymer (A-4) was used instead of the propylene polymer (A-1). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 11.
（比較例２）
プロピレン系重合体（Ａ−１）の代わりにプロピレン系重合体（Ａ−５）を使用した以外は実施例１と同様にして、平均粒子径０．３０μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１１に示す。
(Comparative Example 2)
An aqueous dispersion having an average particle size of 0.30 μm was obtained in the same manner as in Example 1 except that the propylene polymer (A-5) was used instead of the propylene polymer (A-1). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 11.
（比較例３）
プロピレン系重合体（Ａ−１）の代わりにプロピレン系重合体（Ａ−６）を使用した以外は実施例１と同様にして、平均粒子径０．３５μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１１に示す。
(Comparative Example 3)
An aqueous dispersion having an average particle size of 0.35 μm was obtained in the same manner as in Example 1 except that the propylene polymer (A-6) was used instead of the propylene polymer (A-1). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 11.
（比較例４）
プロピレン系重合体（Ａ−１）の代わりにプロピレン系重合体（Ａ−７）を使用した以外は実施例１と同様にして、平均粒子径０．４０μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１１に示す。
(Comparative Example 4)
An aqueous dispersion having an average particle size of 0.40 μm was obtained in the same manner as in Example 1 except that the propylene polymer (A-7) was used instead of the propylene polymer (A-1). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 11.
（比較例５）
プロピレン系重合体（Ａ−１）の代わりにプロピレン系重合体（Ａ−８）を使用した以外は実施例１と同様にして、平均粒子径０．３６μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１１に示す。
(Comparative Example 5)
An aqueous dispersion having an average particle size of 0.36 μm was obtained in the same manner as in Example 1 except that the propylene polymer (A-8) was used instead of the propylene polymer (A-1). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 11.
（比較例６）
プロピレン系重合体（Ａ−１）の代わりにプロピレン系重合体（Ａ−９）を使用した以外は実施例１と同様にして、平均粒子径０．３７μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１１に示す。
(Comparative Example 6)
An aqueous dispersion having an average particle size of 0.37 μm was obtained in the same manner as in Example 1 except that the propylene polymer (A-9) was used instead of the propylene polymer (A-1). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 11.
（比較例７）
プロピレン系重合体（Ａ−１）の代わりにプロピレン系重合体（Ａ−１０）を使用した以外は実施例１と同様にして、平均粒子径０．３７μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１１に示す。
(Comparative Example 7)
An aqueous dispersion having an average particle size of 0.37 μm was obtained in the same manner as in Example 1 except that the propylene polymer (A-10) was used instead of the propylene polymer (A-1). Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 11.
（比較例８）
酸変性オレフィン系重合体（Ｂ−２）の代わりに酸変性オレフィン系重合体（Ｂ−１２）を使用した以外は実施例２と同様にして、平均粒子径０．３２μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１２に示す。
(Comparative Example 8)
An aqueous dispersion having an average particle size of 0.32 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-12) was used instead of the acid-modified olefin polymer (B-2). It was. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 12.
（比較例９）
酸変性オレフィン系重合体（Ｂ−２）の代わりに酸変性オレフィン系重合体（Ｂ−１３）を使用した以外は実施例２と同様にして、平均粒子径０．３４μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１２に示す。
(Comparative Example 9)
An aqueous dispersion having an average particle size of 0.34 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-13) was used instead of the acid-modified olefin polymer (B-2). It was. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 12.
（比較例１０）
酸変性オレフィン系重合体（Ｂ−２）の代わりに酸変性オレフィン系重合体（Ｂ−１４）を使用した以外は実施例２と同様にして、平均粒子径０．３１μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１２に示す。
(Comparative Example 10)
An aqueous dispersion having an average particle size of 0.31 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-14) was used instead of the acid-modified olefin polymer (B-2). It was. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 12.
（比較例１１）
酸変性オレフィン系重合体（Ｂ−２）の代わりに酸変性オレフィン系重合体（Ｂ−１５）を使用した以外は実施例２と同様にして、平均粒子径０．３３μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１２に示す。
(Comparative Example 11)
An aqueous dispersion having an average particle size of 0.33 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-15) was used instead of the acid-modified olefin polymer (B-2). It was. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 12.
（比較例１２）
酸変性オレフィン系重合体（Ｂ−２）の代わりに酸変性オレフィン系重合体（Ｂ−１６）を使用した以外は実施例２と同様にして、平均粒子径０．３２μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１２に示す。
(Comparative Example 12)
An aqueous dispersion having an average particle size of 0.32 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-16) was used instead of the acid-modified olefin polymer (B-2). It was. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 12.
（比較例１３）
酸変性オレフィン系重合体（Ｂ−２）の代わりに酸変性オレフィン系重合体（Ｂ−１７）を使用した以外は実施例２と同様にして、平均粒子径０．３５μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１２に示す。
(Comparative Example 13)
An aqueous dispersion having an average particle size of 0.35 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-17) was used instead of the acid-modified olefin polymer (B-2). It was. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 12.
（比較例１４）
酸変性オレフィン系重合体（Ｂ−２）の代わりに酸変性オレフィン系重合体（Ｂ−１８）を使用した以外は実施例２と同様にして、平均粒子径０．３２μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１２に示す。
(Comparative Example 14)
An aqueous dispersion having an average particle size of 0.32 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-18) was used instead of the acid-modified olefin polymer (B-2). It was. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 12.
（比較例１５）
酸変性オレフィン系重合体（Ｂ−２）の代わりに酸変性オレフィン系重合体（Ｂ−１９）を使用した以外は施例２と同様にして、平均粒子径０．３１μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１２に示す。
(Comparative Example 15)
An aqueous dispersion having an average particle size of 0.31 μm was obtained in the same manner as in Example 2 except that the acid-modified olefin polymer (B-19) was used instead of the acid-modified olefin polymer (B-2). It was. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 12.
（比較例１６）
酸変性オレフィン系重合体（Ｂ−２）の添加量を３質量部に変更した以外は実施例２と同様にして、水性分散体を得ようとしたが、得ることができなかった。
(Comparative Example 16)
An aqueous dispersion was obtained in the same manner as in Example 2 except that the amount of the acid-modified olefin polymer (B-2) was changed to 3 parts by mass, but it could not be obtained.
（比較例１７）
酸変性オレフィン系重合体（Ｂ−２）の添加量を２５質量部に変更した以外は実施例２と同様にして、平均粒子径０．２８μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１３に示す。
(Comparative Example 17)
An aqueous dispersion having an average particle size of 0.28 μm was obtained in the same manner as in Example 2 except that the addition amount of the acid-modified olefin polymer (B-2) was changed to 25 parts by mass. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 13.
（比較例１８）
オレイン酸カリウム（Ｃ−１）の添加量を０．５質量部に変更した以外は実施例２と同様にして、水性分散体を得ようとしたが、得ることができなかった。
(Comparative Example 18)
An aqueous dispersion was obtained in the same manner as in Example 2 except that the addition amount of potassium oleate (C-1) was changed to 0.5 parts by mass, but could not be obtained.
（比較例１９）
オレイン酸カリウム（Ｃ−１）の添加量を１５質量部に変更した以外は実施例２と同様にして、平均粒子径０．８５μｍの水性分散体を得た。そして、実施例１と同様にして密着性および耐水性を評価した。その結果を表１３に示す。
(Comparative Example 19)
An aqueous dispersion having an average particle diameter of 0.85 μm was obtained in the same manner as in Example 2 except that the amount of potassium oleate (C-1) added was changed to 15 parts by mass. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 13.
本願請求項１に係る発明の範囲にある実施例１〜１８の水性分散体では、プラスチック成形体に対して密着性が高く、得られる皮膜の耐水性に優れていた。 In the aqueous dispersions of Examples 1 to 18 within the scope of the invention according to claim 1 of the present application, the adhesiveness to the plastic molding was high, and the water resistance of the resulting film was excellent.
プロピレン系重合体（Ａ）のエチレン単位含有量が２０％を超える比較例１の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
プロピレン系重合体（Ａ）のエチレン単位含有量が１１％未満の比較例２の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
プロピレン系重合体（Ａ）の結晶化度が１６％を超える比較例３の水性分散体では、プラスチック成形体に対する密着性が低かった。
プロピレン系重合体（Ａ）の結晶化度が８％未満の比較例４の水性分散体では、皮膜の耐水性が低かった。
プロピレン系重合体（Ａ）の質量平均分子量が１５万未満の比較例５の水性分散体では、皮膜の耐水性が低かった。
プロピレン系重合体（Ａ）の結晶化度が２５万を超える比較例６の水性分散体では、プラスチック成形体に対する密着性が低かった。
プロピレン系重合体（Ａ）が非メタロセン系触媒を用いて得た重合体である比較例７の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
In the aqueous dispersion of Comparative Example 1 in which the ethylene unit content of the propylene-based polymer (A) exceeds 20%, the adhesion to the plastic molded article was low and the water resistance was also low.
In the aqueous dispersion of Comparative Example 2 in which the ethylene unit content of the propylene polymer (A) was less than 11%, the adhesion to the plastic molded article was low and the water resistance was also low.
In the aqueous dispersion of Comparative Example 3 in which the degree of crystallinity of the propylene-based polymer (A) exceeds 16 %, the adhesion to the plastic molded article was low.
In the aqueous dispersion of Comparative Example 4 in which the crystallinity of the propylene polymer (A) was less than 8 %, the water resistance of the film was low.
In the aqueous dispersion of Comparative Example 5 in which the mass average molecular weight of the propylene polymer (A) was less than 150,000, the water resistance of the film was low.
In the aqueous dispersion of Comparative Example 6 in which the crystallinity of the propylene-based polymer (A) exceeded 250,000 , the adhesion to the plastic molded article was low.
The aqueous dispersion of Comparative Example 7 in which the propylene polymer (A) was a polymer obtained using a nonmetallocene catalyst had low adhesion to the plastic molded article and low water resistance.
酸変性オレフィン系重合体（Ｂ）のエチレン単位含有量が４０％を超える比較例８の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
酸変性オレフィン系重合体（Ｂ）のエチレン単位含有量が１０％未満の比較例９の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
酸変性オレフィン系重合体（Ｂ）の質量平均分子量が４万未満の比較例１０の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
酸変性オレフィン系重合体（Ｂ）の質量平均分子量が１０万を超える比較例１１の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
酸変性オレフィン系重合体（Ｂ）の酸価が２０ｍｇＫＯＨ／ｇ未満の比較例１２の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
酸変性オレフィン系重合体（Ｂ）の酸価が８０ｍｇＫＯＨ／ｇを超える比較例１３の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
酸変性オレフィン系重合体（Ｂ）の結晶化度が０．１％未満の比較例１４の水性分散体では、耐水性が低かった。
酸変性オレフィン系重合体（Ｂ）の結晶化度が１６％を超える比較例１５の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
In the aqueous dispersion of Comparative Example 8 in which the ethylene unit content of the acid-modified olefin polymer (B) exceeds 40%, the adhesion to the plastic molded article was low, and the water resistance was also low.
In the aqueous dispersion of Comparative Example 9 in which the ethylene unit content of the acid-modified olefin polymer (B) was less than 10%, the adhesion to the plastic molded article was low and the water resistance was also low.
In the aqueous dispersion of Comparative Example 10 in which the mass average molecular weight of the acid-modified olefin polymer (B) was less than 40,000, the adhesion to the plastic molded article was low and the water resistance was also low.
In the aqueous dispersion of Comparative Example 11 in which the mass average molecular weight of the acid-modified olefin polymer (B) exceeded 100,000, the adhesion to the plastic molded article was low and the water resistance was also low.
In the aqueous dispersion of Comparative Example 12 in which the acid value of the acid-modified olefin polymer (B) was less than 20 mgKOH / g, the adhesion to the plastic molded article was low and the water resistance was also low.
In the aqueous dispersion of Comparative Example 13 in which the acid value of the acid-modified olefin polymer (B) exceeds 80 mgKOH / g, the adhesion to the plastic molded article is low and the water resistance is also low.
In the aqueous dispersion of Comparative Example 14 in which the crystallinity of the acid-modified olefin polymer (B) was less than 0.1%, the water resistance was low.
In the aqueous dispersion of Comparative Example 15 in which the crystallinity of the acid-modified olefin polymer (B) exceeded 16%, the adhesion to the plastic molded article was low and the water resistance was also low.
酸変性オレフィン系重合体（Ｂ）の添加量が５質量部未満の比較例１６では、水性分散体が得られなかった。
酸変性オレフィン系重合体（Ｂ）の添加量が２５質量部を超える比較例１７の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
界面活性剤（Ｃ）の添加量が１質量部未満の比較例１８では、水性分散体が得られなかった。
界面活性剤（Ｃ）の添加量が１０質量部を超える比較例１９の水性分散体では、プラスチック成形体に対する密着性が低く、耐水性も低かった。
In Comparative Example 16 in which the addition amount of the acid-modified olefin polymer (B) was less than 5 parts by mass , an aqueous dispersion was not obtained.
In the aqueous dispersion of Comparative Example 17 in which the addition amount of the acid-modified olefin polymer (B) exceeds 25 parts by mass, the adhesion to the plastic molded article is low and the water resistance is also low.
In Comparative Example 18 in which the addition amount of the surfactant (C) was less than 1 part by mass , an aqueous dispersion was not obtained.
In the aqueous dispersion of Comparative Example 19 in which the amount of the surfactant (C) added exceeded 10 parts by mass, the adhesion to the plastic molded article was low and the water resistance was also low.
Claims (6)
プロピレン系重合体（Ａ）は、プロピレン単位８０〜８９質量％とα−オレフィン単位１１〜２０質量％とを含有する共重合体で、結晶化度が８〜１６％、質量平均分子量が１５０，０００〜２５０，０００、分子量分布Ｍｗ／Ｍｎが１．５〜３．５であり、
酸変性オレフィン系重合体（Ｂ）は、プロピレン単位６０〜９０質量％とエチレン単位および／または１−ブテン単位１０〜４０質量％とを含有するオレフィン系重合体に、エチレン性不飽和カルボン酸またはその無水物が結合された酸変性オレフィン系重合体で、質量平均分子量が４０，０００〜１００，０００、酸価が２０〜８０ｍｇＫＯＨ／ｇ、結晶化度が０．１〜１６％であることを特徴とする水性分散体 5 to 20 parts by mass of the acid-modified olefin polymer (B), 1 to 10 parts by mass of the surfactant (C), and 0.5 to 20 parts per 100 parts by mass of the propylene polymer (A). An aqueous dispersion containing parts by weight of water (D),
The propylene polymer (A) is a copolymer containing 80 to 89% by mass of propylene units and 11 to 20% by mass of α-olefin units, having a crystallinity of 8 to 16% and a mass average molecular weight of 150, 000-250,000, molecular weight distribution Mw / Mn is 1.5-3.5,
The acid-modified olefin polymer (B) is an olefin polymer containing 60 to 90% by mass of propylene units and 10 to 40% by mass of ethylene units and / or 1-butene units. The acid-modified olefin polymer to which the anhydride is bonded has a mass average molecular weight of 40,000 to 100,000, an acid value of 20 to 80 mgKOH / g, and a crystallinity of 0.1 to 16%. Aqueous dispersion characterized
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